WorldWideScience

Sample records for solid lithium-ion electrolyte

  1. Lithium-ion batteries having conformal solid electrolyte layers

    Science.gov (United States)

    Kim, Gi-Heon; Jung, Yoon Seok

    2014-05-27

    Hybrid solid-liquid electrolyte lithium-ion battery devices are disclosed. Certain devices comprise anodes and cathodes conformally coated with an electron insulating and lithium ion conductive solid electrolyte layer.

  2. Lithium-ion transport in inorganic solid state electrolyte

    International Nuclear Information System (INIS)

    Gao Jian; Li Hong; Zhao Yu-Sheng; Shi Si-Qi

    2016-01-01

    An overview of ion transport in lithium-ion inorganic solid state electrolytes is presented, aimed at exploring and designing better electrolyte materials. Ionic conductivity is one of the most important indices of the performance of inorganic solid state electrolytes. The general definition of solid state electrolytes is presented in terms of their role in a working cell (to convey ions while isolate electrons), and the history of solid electrolyte development is briefly summarized. Ways of using the available theoretical models and experimental methods to characterize lithium-ion transport in solid state electrolytes are systematically introduced. Then the various factors that affect ionic conductivity are itemized, including mainly structural disorder, composite materials and interface effects between a solid electrolyte and an electrode. Finally, strategies for future material systems, for synthesis and characterization methods, and for theory and calculation are proposed, aiming to help accelerate the design and development of new solid electrolytes. (topical review)

  3. Solid Lithium Ion Conductors (SLIC) for Lithium Solid State Batteries

    Data.gov (United States)

    National Aeronautics and Space Administration — To identify the most lithium-ion conducting solid electrolytes for lithium solid state batteries from the emerging types of solid electrolytes, based on a...

  4. Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

    Energy Technology Data Exchange (ETDEWEB)

    Kartini, Evvy [Center for Science and Technology of Advanced Materials – National Nuclear Energy Agency, Kawasan Puspiptek Serpong, Tangerang Selatan15314, Banten (Indonesia); Manawan, Maykel [Post Graduate Program of Materials Science, University of Indonesia, Jl.Salemba Raya No.4, Jakarta 10430 (Indonesia)

    2016-02-08

    With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say “the most important emerging energy technology” is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner’s cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes

  5. Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

    International Nuclear Information System (INIS)

    Kartini, Evvy; Manawan, Maykel

    2016-01-01

    With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say “the most important emerging energy technology” is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner’s cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes

  6. Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

    Science.gov (United States)

    Kartini, Evvy; Manawan, Maykel

    2016-02-01

    With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say "the most important emerging energy technology" is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner's cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes

  7. Review on solid electrolytes for all-solid-state lithium-ion batteries

    Science.gov (United States)

    Zheng, Feng; Kotobuki, Masashi; Song, Shufeng; Lai, Man On; Lu, Li

    2018-06-01

    All-solid-state (ASS) lithium-ion battery has attracted great attention due to its high safety and increased energy density. One of key components in the ASS battery (ASSB) is solid electrolyte that determines performance of the ASSB. Many types of solid electrolytes have been investigated in great detail in the past years, including NASICON-type, garnet-type, perovskite-type, LISICON-type, LiPON-type, Li3N-type, sulfide-type, argyrodite-type, anti-perovskite-type and many more. This paper aims to provide comprehensive reviews on some typical types of key solid electrolytes and some ASSBs, and on gaps that should be resolved.

  8. Lithium carbon batteries with solid polymer electrolyte; Accumulateur lithium carbone a electrolyte solide polymere

    Energy Technology Data Exchange (ETDEWEB)

    Andrieu, X.; Boudin, F. [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

    1996-12-31

    The lithium carbon batteries studied in this paper use plasticized polymer electrolytes made with passive polymer matrix swollen by a liquid electrolyte with a high ionic conductivity (> 10{sup -3} S/cm at 25 deg. C). The polymers used to prepare the gels are polyacrylonitrile (PAN) and vinylidene poly-fluoride (PVdF). The electrochemical and physical properties of these materials are analyzed according to their composition. The behaviour of solid electrolytes with different materials of lithium ion insertion (graphite and LiNiO{sub 2}) are studied and compared to liquid electrolytes. The parameters taken into account are the reversible and irreversible capacities, the cycling performance and the admissible current densities. Finally, complete lithium ion batteries with gelled electrolytes were manufactured and tested. (J.S.) 2 refs.

  9. Lithium carbon batteries with solid polymer electrolyte; Accumulateur lithium carbone a electrolyte solide polymere

    Energy Technology Data Exchange (ETDEWEB)

    Andrieu, X; Boudin, F [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

    1997-12-31

    The lithium carbon batteries studied in this paper use plasticized polymer electrolytes made with passive polymer matrix swollen by a liquid electrolyte with a high ionic conductivity (> 10{sup -3} S/cm at 25 deg. C). The polymers used to prepare the gels are polyacrylonitrile (PAN) and vinylidene poly-fluoride (PVdF). The electrochemical and physical properties of these materials are analyzed according to their composition. The behaviour of solid electrolytes with different materials of lithium ion insertion (graphite and LiNiO{sub 2}) are studied and compared to liquid electrolytes. The parameters taken into account are the reversible and irreversible capacities, the cycling performance and the admissible current densities. Finally, complete lithium ion batteries with gelled electrolytes were manufactured and tested. (J.S.) 2 refs.

  10. Design and Characterisation of Solid Electrolytes for All-Solid-State Lithium Batteries

    DEFF Research Database (Denmark)

    Sveinbjörnsson, Dadi Þorsteinn

    The development of all-solid-state lithium batteries, in which the currently used liquid electrolytes are substituted for solid electrolyte materials, could lead to safer batteries offering higher energy densities and longer cycle lifetimes. Designing suitable solid electrolytes with sufficient...... chemical and electrochemical stability, high lithium ion conduction and negligible electronic conduction remains a challenge. The highly lithium ion conducting LiBH4-LiI solid solution is a promising solid electrolyte material. Solid solutions with a LiI content of 6.25%-50% were synthesised by planetary......-rich microstructures during ball milling is found to significantly influence the conductivity of the samples. The long-range diffusion of lithium ions was measured using quasi-elastic neutron scattering. The solid solutions are found to exhibit two-dimensional conduction in the hexagonal plane of the crystal structure...

  11. Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte.

    Science.gov (United States)

    Ganapathy, Swapna; van Eck, Ernst R H; Kentgens, Arno P M; Mulder, Fokko M; Wagemaker, Marnix

    2011-12-23

    The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Solid polymer electrolyte lithium batteries

    Science.gov (United States)

    Alamgir, Mohamed; Abraham, Kuzhikalail M.

    1993-01-01

    This invention pertains to Lithium batteries using Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride).

  13. Single- and double-ion type cross-linked polysiloxane solid electrolytes for lithium cells

    Science.gov (United States)

    Tsutsumi, Hiromori; Yamamoto, Masahiro; Morita, Masayuki; Matsuda, Yoshiharu; Nakamura, Takashi; Asai, Hiroyuki

    Polymeric solid electrolytes, that have poly(dimethylsiloxane) (PMS) backbone and cross-linked network, were applied to a rechargeable lithium battery system. Single- (PMS-Li) and double-ion type (PMS-LiClO 4) electrolytes were prepared from the same prepolymers. Lithium electrode in the both electrolytes showed reversible stripping and deposition of lithium. Intercalation and deintercalation processes of lithium ion between lithium-manganese composite oxide (Li xMnO 2) electrode and the electrolytes were also confirmed by cyclic voltammetry, however, peak current decreased with several cycles in both cases. The model cell, Li/PMS-Li/Li xMnO 2 cell had 1.4 mA h g -1 (per 1 g of active material, current density: 3.77 μA cm -2), and the Li/PMS-LiClO 4/Li xMnO 2 cell had 1.6 mA h g -1 (current density: 75.3 μA cm -2).

  14. Fabrication of All-Solid-State Lithium-Ion Cells Using Three-Dimensionally Structured Solid Electrolyte Li7La3Zr2O12 Pellets

    International Nuclear Information System (INIS)

    Shoji, Mao; Munakata, Hirokazu; Kanamura, Kiyoshi

    2016-01-01

    All-solid-state lithium-ion batteries using Li + -ion conducting ceramic electrolytes have been focused on as attractive future batteries for electric vehicles and renewable energy conversion systems because high safety can be realized due to non-flammability of ceramic electrolytes. In addition, a higher volumetric energy density than that of current lithium-ion batteries is expected since the all-solid-state lithium-ion batteries can be made in bipolar cell configurations. However, the special ideas and techniques based on ceramic processing are required to construct the electrochemical interface for all-solid-state lithium-ion batteries since the battery development has been done so far based on liquid electrolyte system over 100 years. As one of the promising approaches to develop practical all-solid-state batteries, we have been focusing on three-dimensionally (3D) structured cell configurations such as an interdigitated combination of 3D pillars of cathode and anode, which can be realized by using solid electrolyte membranes with hole-array structures. The application of such kinds of 3D structures effectively increases the interface between solid electrode and solid electrolyte per unit volume, lowering the internal resistance of all-solid-state lithium-ion batteries. In this study, Li 6.25 Al 0.25 La 3 Zr 2 O 12 (LLZAl), which is a Al-doped Li 7 La 3 Zr 2 O 12 (LLZ) with Li + -ion conductivity of ~10 –4 S ⋅cm −1 at room temperature and high stability against lithium-metal, was used as a solid electrolyte, and its pellets with 700 μm depth holes in 700 μm × 700 μm area were fabricated to construct 3D-structured all-solid-state batteries with LiCoO 2 /LLZAl/lithium-metal configuration. It is expected that the LiCoO 2 –LLZAl interface is formed by point-to-point contact even when the LLZAl pellet with 3D hole-array structure is applied. Therefore, Li 3 BO 3 , which is a mechanically soft solid electrolyte with a low melting point at around 700

  15. Recent advances in solid polymer electrolytes for lithium batteries

    Institute of Scientific and Technical Information of China (English)

    Qingqing Zhang; Kai Liu; Fei Ding; Xingjiang Liu

    2017-01-01

    Solid polymer electrolytes are light-weight,flexible,and non-flammable and provide a feasible solution to the safety issues facing lithium-ion batteries through the replacement of organic liquid electrolytes.Substantial research efforts have been devoted to achieving the next generation of solid-state polymer lithium batteries.Herein,we provide a review of the development of solid polymer electrolytes and provide comprehensive insights into emerging developments.In particular,we discuss the different molecular structures of the solid polymer matrices,including polyether,polyester,polyacrylonitrile,and polysiloxane,and their interfacial compatibility with lithium,as well as the factors that govern the properties of the polymer electrolytes.The discussion aims to give perspective to allow the strategic design of state-of-the-art solid polymer electrolytes,and we hope it will provide clear guidance for the exploration of high-performance lithium batteries.

  16. Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

    International Nuclear Information System (INIS)

    Sakamoto, Y.; Ishii, Y.; Kawasaki, S.

    2016-01-01

    Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

  17. Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Sakamoto, Y.; Ishii, Y.; Kawasaki, S., E-mail: kawasaki.shinji@nitech.ac.jp [Nagoya Institute of Technology, Gokiso, Showa, Nagoya, Aichi (Japan)

    2016-07-06

    Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

  18. Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface

    NARCIS (Netherlands)

    Yu, C.; Ganapathy, S.; van Eck, Ernst R H; Wang, H.; Basak, S.; Li, Z.; Wagemaker, M.

    2017-01-01

    Solid-state batteries potentially offer increased lithium-ion battery energy density and safety as required for large-scale production of electrical vehicles. One of the key challenges toward high-performance solid-state batteries is the large impedance posed by the electrode-electrolyte

  19. Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

    Science.gov (United States)

    Teran, Alexander Andrew

    Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid

  20. Cathode solid electrolyte interface’s function originated from salt type additives in lithium ion batteries

    International Nuclear Information System (INIS)

    Kaneko, Yu; Park, Juyeon; Yokotsuji, Hokuto; Odawara, Makoto; Takase, Hironari; Ue, Makoto; Lee, Maeng-Eun

    2016-01-01

    Highlights: • Our chemical analysis determines the important functional groups of cathode’s solid electrolyte interface originated from salt type additives. • Our quantum chemical calculation reveals the redox character of the additives and their candidate chemical components of the solid electrolyte interface. • Our molecular dynamics simulation reproduces the selective lithium ion translocation and protective layer formation as the solid electrolyte interface function. - Abstract: This is the study about the cathode’s solid electrolyte interface (SEI) formation mechanism of salt type additives (STAs) and its function. To address this issue, we performed several types of chemical analysis and computer simulation techniques. In order to reveal the redox nature and oxidative decomposition dynamics, the electrolyte (EL) solution dynamics by Quantum mechanics and Molecular mechanics (QM/MM) method was applied. The estimation of SEI chemical components agrees with our chemical analyses data and other group’s reports. The molecular dynamics simulation of sub micro second sampling indicates that the SEI phase induced from STAs functions as a lithium ion selective translocation media and protective coating layer against the degradation of the solvent molecules. The results give us an insight how to design additive’s chemical structure to improve longevity of the cell in the high voltage regime.

  1. Fabrication of All-Solid-State Lithium-Ion Cells Using Three-Dimensionally Structured Solid Electrolyte Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} Pellets

    Energy Technology Data Exchange (ETDEWEB)

    Shoji, Mao; Munakata, Hirokazu; Kanamura, Kiyoshi, E-mail: kanamura@tmu.ac.jp [Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Tokyo (Japan)

    2016-08-30

    All-solid-state lithium-ion batteries using Li{sup +}-ion conducting ceramic electrolytes have been focused on as attractive future batteries for electric vehicles and renewable energy conversion systems because high safety can be realized due to non-flammability of ceramic electrolytes. In addition, a higher volumetric energy density than that of current lithium-ion batteries is expected since the all-solid-state lithium-ion batteries can be made in bipolar cell configurations. However, the special ideas and techniques based on ceramic processing are required to construct the electrochemical interface for all-solid-state lithium-ion batteries since the battery development has been done so far based on liquid electrolyte system over 100 years. As one of the promising approaches to develop practical all-solid-state batteries, we have been focusing on three-dimensionally (3D) structured cell configurations such as an interdigitated combination of 3D pillars of cathode and anode, which can be realized by using solid electrolyte membranes with hole-array structures. The application of such kinds of 3D structures effectively increases the interface between solid electrode and solid electrolyte per unit volume, lowering the internal resistance of all-solid-state lithium-ion batteries. In this study, Li{sub 6.25}Al{sub 0.25}La{sub 3}Zr{sub 2}O{sub 12} (LLZAl), which is a Al-doped Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} (LLZ) with Li{sup +}-ion conductivity of ~10{sup –4} S ⋅cm{sup −1} at room temperature and high stability against lithium-metal, was used as a solid electrolyte, and its pellets with 700 μm depth holes in 700 μm × 700 μm area were fabricated to construct 3D-structured all-solid-state batteries with LiCoO{sub 2}/LLZAl/lithium-metal configuration. It is expected that the LiCoO{sub 2}–LLZAl interface is formed by point-to-point contact even when the LLZAl pellet with 3D hole-array structure is applied. Therefore, Li{sub 3}BO{sub 3}, which is a

  2. Lithium-Ion Electrolytes Containing Flame Retardant Additives for Increased Safety Characteristics

    Science.gov (United States)

    Smart, Marshall C. (Inventor); Smith, Kiah A. (Inventor); Bugga, Ratnakumar V. (Inventor); Prakash, Surya G. (Inventor); Krause, Frederick Charles (Inventor)

    2014-01-01

    The invention discloses various embodiments of Li-ion electrolytes containing flame retardant additives that have delivered good performance over a wide temperature range, good cycle life characteristics, and improved safety characteristics, namely, reduced flammability. In one embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a fluorinated co-solvent, a flame retardant additive, and a lithium salt. In another embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a flame retardant additive, a solid electrolyte interface (SEI) film forming agent, and a lithium salt.

  3. Electrolytes for lithium and lithium-ion batteries

    CERN Document Server

    Jow, T Richard; Borodin, Oleg; Ue, Makoto

    2014-01-01

    Electrolytes for Lithium and Lithium-ion Batteries provides a comprehensive overview of the scientific understanding and technological development of electrolyte materials in the last?several years. This book covers key electrolytes such as LiPF6 salt in mixed-carbonate solvents with additives for the state-of-the-art Li-ion batteries as well as new electrolyte materials developed recently that lay the foundation for future advances.?This book also reviews the characterization of electrolyte materials for their transport properties, structures, phase relationships, stabilities, and impurities.

  4. Modulation of solid electrolyte interphase of lithium-ion batteries by LiDFOB and LiBOB electrolyte additives

    Science.gov (United States)

    Huang, Shiqiang; Wang, Shuwei; Hu, Guohong; Cheong, Ling-Zhi; Shen, Cai

    2018-05-01

    Solid-electrolyte interphase (SEI) layer is an organic-inorganic composite layer that allows Li+ transport across but blocks electron flow across and prevents solvent diffusing to electrode surface. Morphology, thickness, mechanical and chemical properties of SEI are important for safety and cycling performance of lithium-ion batteries. Herein, we employ a combination of in-situ AFM and XPS to investigate the effects of two electrolyte additives namely lithium difluoro(oxalate)borate (LiDFOB) and lithium bis(oxalato)borate (LiBOB) on SEI layer. LiDFOB is found to result in a thin but hard SEI layer containing more inorganic species (LiF and LiCO3); meanwhile LiBOB promotes formation of a thick but soft SEI layer containing more organic species such as ROCO2Li. Findings from present study will help development of electrolyte additives that promote formation of good SEI layer.

  5. A New All-Solid-State Hyperbranched Star Polymer Electrolyte for Lithium Ion Batteries: Synthesis and Electrochemical Properties

    International Nuclear Information System (INIS)

    Wang, Ailian; Xu, Hao; Zhou, Qian; Liu, Xu; Li, Zhengyao; Gao, Rui; Wu, Na; Guo, Yuguo; Li, Huayi; Zhang, Liaoyun

    2016-01-01

    Highlights: • A new hyperbranched multi-arm star polymer was successfully synthesized. • The star polymer electrolyte has good thermal stability and forming-film property. • The ion conductivity electrolyte can reach 8.3 × 10"−"5 S cm"−"1 at room temperature. • The star polymer electrolyte has wide electrochemical windows of 4.7 V. - Abstract: A new hyperbranched multi-arm star polymer with hyperbranched polystyrene (HBPS) as core and polymethyl methacrylate-block-poly(ethylene glycol) methyl ether methacrylate(PMMA-b-PPEGMA) as arms was firstly synthesized by atom transfer radical polymerization. The obtained hyperbranched multi-arm star polymer (HBPS-(PMMA-b-PPEGMA)_x) exhibited good thermal stability with a thermal decomposition temperature of 372 °C. The transparent, free-standing, flexible polymer electrolyte film of the blending of HBPS-(PMMA-b-PPEGMA)_x and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) was successfully fabricated by a solution casting method. The ionic conductivity of the hyperbranched star polymer electrolyte with a molar ratio of [EO]/[Li] of 30 could reach 8.3 × 10"−"5 S cm"−"1 at 30 °C (with the content of PPEGMA of 83.7%), and 2.0 × 10"−"4 S cm"−"1 at 80 °C (with the content of PPEGMA of 51.6%). The effect of the concentration of lithium salts on ionic conductivity was also investigated. The obtained all-solid-state polymer electrolyte possessed a wide electrochemical stability window of 4.7 V (vs. Li"+/Li), and a lithium-ion transference number (t_L_i"+) up to 0.31. The interfacial impedance of the fabricated LiÔöépolymer electrolyteÔöéLi symmetric cell based on hyperbranched star multi-arm polymer electrolyte exhibited good interfacial compatibility between all-solid-state polymer electrolyte and electrodes. The excellent properties of the hyperbranched star polymer electrolyte made it attractive as solid-state polymer electrolyte for lithium-ion batteries.

  6. Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

    Science.gov (United States)

    DeSilva, J .H. S. R.; Udinwe, V.; Sideris, P. J.; Smart, M. C.; Krause, F. C.; Hwang, C.; Smith, K. A.; Greenbaum, S. G.

    2012-01-01

    Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

  7. Polarization behavior of lithium electrode in polymetric solid electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Matsuda, Yoshiharu (Dept. of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi Univ., Ube (Japan)); Morita, Masayuki (Dept. of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi Univ., Ube (Japan)); Tsutsumi, Hiromori (Dept. of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi Univ., Ube (Japan))

    1993-04-15

    Complexes of novel polymer matrices and lithium salts have been prepared as polymeric solid electrolytes for lithium batteries. Poly(ethylene oxide)-grafted poly(methylmethacrylate) (PEO-PMMA) and poly(methylsiloxane) (PMS) were used as the matrices. The conductance behavior of the complexes and the basic polarization characteristics of the lithium electrode in the polymeric electrolytes were studied. As high conductivities as 10[sup -3] S cm[sup -1] were obtained at room temperature for the PMMA-based electrolytes containing some liquid plasticizer. Limiting current densities of 3 to 5 mA cm[sup -2] were observed for the anodic and cathodic polarization of the lithium electrode. The transport number of Li[sup +] was approximately unity in 'single-ion type' PMS-based electrolyte, in which the polarization curve of the lithium electrode showed no current hysteresis. (orig.)

  8. Highly Stable Lithium Metal Batteries Enabled by Regulating the Solvation of Lithium Ions in Nonaqueous Electrolytes.

    Science.gov (United States)

    Zhang, Xue-Qiang; Chen, Xiang; Cheng, Xin-Bing; Li, Bo-Quan; Shen, Xin; Yan, Chong; Huang, Jia-Qi; Zhang, Qiang

    2018-05-04

    Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO 3 ) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiN x O y on a working lithium metal anode with dendrite-free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO 3 electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first-principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes

    KAUST Repository

    Chan, Candace K.; Ruffo, Riccardo; Hong, Seung Sae; Cui, Yi

    2009-01-01

    Silicon nanowires (SiNWs) have the potential to perform as anodes for lithium-ion batteries with a much higher energy density than graphite. However, there has been little work in understanding the surface chemistry of the solid electrolyte

  10. Non-aqueous electrolytes for lithium ion batteries

    Science.gov (United States)

    Chen, Zonghai; Amine, Khalil

    2015-11-12

    The present invention is generally related to electrolytes containing anion receptor additives to enhance the power capability of lithium-ion batteries. The anion receptor of the present invention is a Lewis acid that can help to dissolve LiF in the passivation films of lithium-ion batteries. Accordingly, one aspect the invention provides electrolytes comprising a lithium salt; a polar aprotic solvent; and an anion receptor additive; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

  11. Recent Developments of All-Solid-State Lithium Secondary Batteries with Sulfide Inorganic Electrolytes.

    Science.gov (United States)

    Xu, Ruochen; Zhang, Shengzhao; Wang, Xiuli; Xia, Yan; Xia, Xinhui; Wu, Jianbo; Gu, Changdong; Tu, Jiangping

    2018-04-20

    Due to the increasing demand of security and energy density, all-solid-state lithium ion batteries have become the promising next-generation energy storage devices to replace the traditional liquid batteries with flammable organic electrolytes. In this Minireview, we focus on the recent developments of sulfide inorganic electrolytes for all-solid-state batteries. The challenges of assembling bulk-type all-solid-state batteries for industrialization are discussed, including low ionic conductivity of the present sulfide electrolytes, high interfacial resistance and poor compatibility between electrolytes and electrodes. Many efforts have been focused on the solutions for these issues. Although some progresses have been achieved, it is still far away from practical application. The perspectives for future research on all-solid-state lithium ion batteries are presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Solid composite electrolytes for lithium batteries

    Science.gov (United States)

    Kumar, Binod; Scanlon, Jr., Lawrence G.

    2000-01-01

    Solid composite electrolytes are provided for use in lithium batteries which exhibit moderate to high ionic conductivity at ambient temperatures and low activation energies. In one embodiment, a ceramic-ceramic composite electrolyte is provided containing lithium nitride and lithium phosphate. The ceramic-ceramic composite is also preferably annealed and exhibits an activation energy of about 0.1 eV.

  13. Facilely solving cathode/electrolyte interfacial issue for high-voltage lithium ion batteries by constructing an effective solid electrolyte interface film

    International Nuclear Information System (INIS)

    Xu, Jingjing; Xia, Qingbo; Chen, Fangyuan; Liu, Tao; Li, Li; Cheng, Xueyuan; Lu, Wei; Wu, Xiaodong

    2016-01-01

    The cathode/electrolyte interface stability is the key factor for the cyclic performance and the safety performance of lithium ion batteries. Suppression of consuming key elements in the electrode materials is essential in this concern. In this purpose, we investigate a facile strategy to solve interfacial issue for high-voltage lithium ion batteries by adding an oxidable fluorinated phosphate, Bis(2,2,2-trifluoroethyl) Phosphite (BTFEP), as a sacrificial additive in electrolyte. We demonstrate that BTFEP additive could be oxidized at slightly above 4.28 V which is a relatively lower voltage than that of solvents, and the oxidative products facilitate in-situ forming a stable solid electrolyte interphase (SEI) film on the cathode surface. The results manifest the SEI film validly restrains the generation of HF and the interfacial side reaction between high-voltage charged LiNi 0.5 Mn 1.5 O 4 (LNMO) and electrolyte, hence, the dissolution of Mn and Ni is effectively suppressed. Finally, the cyclic performance of LNMO after 200 cycles was remarkably improved from 68.4% in blank electrolyte to 95% in 1 wt% BTFEP-adding electrolyte.

  14. MultiLayer solid electrolyte for lithium thin film batteries

    Science.gov (United States)

    Lee, Se -Hee; Tracy, C. Edwin; Pitts, John Roland; Liu, Ping

    2015-07-28

    A lithium metal thin-film battery composite structure is provided that includes a combination of a thin, stable, solid electrolyte layer [18] such as Lipon, designed in use to be in contact with a lithium metal anode layer; and a rapid-deposit solid electrolyte layer [16] such as LiAlF.sub.4 in contact with the thin, stable, solid electrolyte layer [18]. Batteries made up of or containing these structures are more efficient to produce than other lithium metal batteries that use only a single solid electrolyte. They are also more resistant to stress and strain than batteries made using layers of only the stable, solid electrolyte materials. Furthermore, lithium anode batteries as disclosed herein are useful as rechargeable batteries.

  15. Solid polymer electrolytes

    Science.gov (United States)

    Abraham, Kuzhikalail M.; Alamgir, Mohamed; Choe, Hyoun S.

    1995-01-01

    This invention relates to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF.sub.3 SO.sub.2).sub.2, LiAsF.sub.6, and LiClO.sub.4.

  16. Electrochemical performance of all-solid-state lithium batteries using inorganic lithium garnets particulate reinforced PEO/LiClO4 electrolyte

    International Nuclear Information System (INIS)

    Cheng, Samson Ho-Sum; He, Kang-Qiang; Liu, Ying; Zha, Jun-Wei; Kamruzzaman, Md; Ma, Robin Lok-Wang; Dang, Zhi-Min; Li, Robert K.Y.; Chung, C.Y.

    2017-01-01

    All-solid-state batteries are proposed to have ultimate safety and higher power and energy densities over conventional lithium ion batteries with liquid electrolytes. The Li ion conductivity and interfacial resistance between electrolyte and electrodes are the major bottleneck of the development of all-solid-state batteries for practical uses. Here, we reported a novel composite electrolyte which is composed of uniform distributed Li ion conducting Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) fillers in PEO/LiClO 4 matrix. The EO:Li + ratio of 15:1 is being used to achieve lower interfacial resistance between electrolyte and electrodes through the melting process. The composite electrolyte is fabricated by simple solution casting method, which is more advantageous comparing with high temperature sintering or sol-gel method used in the fabrication of ceramic electrolytes. The composite electrolyte exhibits good Li ion conductivity of 4.8 × 10 −4 Scm −1 at 60 °C and excellent interfacial stability against Li metal. The all-solid-state lithium battery using this composite electrolyte shows a specific capacity of 140mAhg −1 and an unprecedentedly high capacity retention of 83% after 500 cycles at 60 °C and the rate of 1C. It is concluded that good electrode/electrolyte interfacial stability and contact as well as fast Li ion conductivity obtained by the addition of active garnet particulates to PEO/LiClO 4 matrix are essential criteria for good charge/discharge performance of all-solid-state lithium batteries.

  17. Solid state electrolytes for all-solid-state 3D lithium-ion batteries

    NARCIS (Netherlands)

    Kokal, I.

    2012-01-01

    The focus of this Ph.D. thesis is to understand the lithium ion motion and to enhance the Li-ionic conductivities in commonly known solid state lithium ion conductors by changing the structural properties and preparation methods. In addition, the feasibility for practical utilization of several

  18. Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Sengwa, R. J., E-mail: rjsengwa@rediffmail.com; Dhatarwal, Priyanka, E-mail: dhatarwalpriyanka@gmail.com; Choudhary, Shobhna, E-mail: shobhnachoudhary@rediffmail.com [Dielectric Research Laboratory, Department of Physics, Jai Narain Vyas University, Jodhpur – 342 005 (India)

    2016-05-06

    Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF{sub 4}) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governed by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10{sup −6} S cm{sup −1} which suggests the suitability of the SPE film for rechargeable lithium batteries.

  19. Novel Non-Vacuum Fabrication of Solid State Lithium Ion Battery Components

    Energy Technology Data Exchange (ETDEWEB)

    Oladeji, I. [Planar Energy Devices, Inc.; Wood, D. L. [ORNL; Wood, III, D. L.

    2012-10-19

    The purpose of this Cooperative Research and Development Agreement (CRADA) between Oak Ridge National Laboratory (ORNL) and Planar Energy Devices, Inc. was to develop large-scale electroless deposition and photonic annealing processes associated with making all-solid-state lithium ion battery cathode and electrolyte layers. However, technical and processing difficulties encountered in 2011 resulted in the focus of the CRADA being redirected solely to annealing of the cathode thin films. In addition, Planar Energy Devices de-emphasized the importance of annealing of the solid-state electrolytes within the scope of the project, but materials characterization of stabilized electrolyte layers was still of interest. All-solid-state lithium ion batteries are important to automotive and stationary energy storage applications because they would eliminate the problems associated with the safety of the liquid electrolyte in conventional lithium ion batteries. However, all-solid-state batteries are currently produced using expensive, energy consuming vacuum methods suited for small electrode sizes. Transition metal oxide cathode and solid-state electrolyte layers currently require about 30-60 minutes at 700-800°C vacuum processing conditions. Photonic annealing requires only milliseconds of exposure time at high temperature and a total of <1 min of cumulative processing time. As a result, these processing techniques are revolutionary and highly disruptive to the existing lithium ion battery supply chain. The current methods of producing all-solid-state lithium ion batteries are only suited for small-scale, low-power cells and involve high-temperature vacuum techniques. Stabilized LiNixMnyCozAl1-x-y-zO2 (NMCA) nanoparticle films were deposited onto stainless steel substrates using Planar Energy Devices’ streaming process for electroless electrochemical deposition (SPEED). Since successful SPEED trials were demonstrated by Planar Energy Devices with NMCA prior to 2010, this

  20. Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

    Science.gov (United States)

    West, William; Whitacre, Jay; Lim, James

    2008-01-01

    Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

  1. In-situ Mass Spectrometric Determination of Molecular Structural Evolution at the Solid Electrolyte Interphase in Lithium-Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Zihua; Zhou, Yufan; Yan, Pengfei; Vemuri, Venkata Rama Ses; Xu, Wu; Zhao, Rui; Wang, Xuelin; Thevuthasan, Suntharampillai; Baer, Donald R.; Wang, Chong M.

    2015-08-19

    Dynamic molecular evolution at solid/liquid electrolyte interface is always a mystery for a rechargeable battery due to the challenge to directly probe/observe the solid/liquid interface under reaction conditions, which in essence appears to be similarly true for all the fields involving solid/liquid phases, such as electrocatalysis, electrodeposition, biofuel conversion, biofilm, and biomineralization, We use in-situ liquid secondary ion mass spectroscopy (SIMS) for the first time to directly observe the molecular structural evolution at the solid electrode/liquid electrolyte interface for a lithium (Li)-ion battery under dynamic operating conditions. We have discovered that the deposition of Li metal on copper electrode leads to the condensation of solvent molecules around the electrode. Chemically, this layer of solvent condensate tends to deplete the salt anion and with low concentration of Li+ ions, which essentially leads to the formation of a lean electrolyte layer adjacent to the electrode and therefore contributes to the overpotential of the cell. This unprecedented molecular level dynamic observation at the solid electrode/liquid electrolyte interface provides vital chemical information that is needed for designing of better battery chemistry for enhanced performance, and ultimately opens new avenues for using liquid SIMS to probe molecular evolution at solid/liquid interface in general.

  2. Ion-ion and ion-solvent interactions in lithium imidazolide electrolytes studied by Raman spectroscopy and DFT models.

    Science.gov (United States)

    Scheers, Johan; Niedzicki, Leszek; Zukowska, Grażyna Z; Johansson, Patrik; Wieczorek, Władysław; Jacobsson, Per

    2011-06-21

    Molecular level interactions are of crucial importance for the transport properties and overall performance of ion conducting electrolytes. In this work we explore ion-ion and ion-solvent interactions in liquid and solid polymer electrolytes of lithium 4,5-dicyano-(2-trifluoromethyl)imidazolide (LiTDI)-a promising salt for lithium battery applications-using Raman spectroscopy and density functional theory calculations. High concentrations of ion associates are found in LiTDI:acetonitrile electrolytes, the vibrational signatures of which are transferable to PEO-based LiTDI electrolytes. The origins of the spectroscopic changes are interpreted by comparing experimental spectra with simulated Raman spectra of model structures. Simple ion pair models in vacuum identify the imidazole nitrogen atom of the TDI anion to be the most important coordination site for Li(+), however, including implicit or explicit solvent effects lead to qualitative changes in the coordination geometry and improved correlation of experimental and simulated Raman spectra. To model larger aggregates, solvent effects are found to be crucial, and we finally suggest possible triplet and dimer ionic structures in the investigated electrolytes. In addition, the effects of introducing water into the electrolytes-via a hydrate form of LiTDI-are discussed.

  3. Lithium dendrite and solid electrolyte interphase investigation using OsO4

    Science.gov (United States)

    Zier, Martin; Scheiba, Frieder; Oswald, Steffen; Thomas, Jürgen; Goers, Dietrich; Scherer, Torsten; Klose, Markus; Ehrenberg, Helmut; Eckert, Jürgen

    2014-11-01

    Osmium tetroxide (OsO4) staining, commonly used to enhance scattering contrast in electron microscopy of biologic tissue and polymer blends, has been adopted for studies of graphite anodes in lithium-ion batteries. OsO4 shows a coordinated reaction with components of the solid electrolyte interphase (SEI) and lithium dendrites, thereby increasing material contrast for scanning electron microscopy investigations. Utilizing the high affinity of lithium metal to react with osmium tetroxide it was possible to localize even small lithium deposits on graphite electrodes. In spite of their reaction with the OsO4 fume, the lithium dendrite morphology remains almost untouched by the staining procedure, offering information on the dendrite growth process. Correlating the quantity of osmium detected with the amount of residual ("dead") lithium of a discharged electrode, it was possible to obtain a practical measure for lithium plating and stripping efficiencies. EDX mappings allowed for a localization of electrochemically stripped lithium dendrites by their residual stained SEI shells. Cross sections, prepared by focused ion beam (FIB) of cycled graphite electrodes treated with OsO4, revealed important information about deposition and distribution of metallic lithium and the electrolyte reduction layer across the electrode.

  4. Realization of entirely solid lithium ion batteries; Realisation d`accumulateurs a ions lithium entierement solides

    Energy Technology Data Exchange (ETDEWEB)

    Brousse, T.; Marchand, R.; Fragnaud, P.; Schleich, D.M. [Laboratoire de Genie des Materiaux, ISITEM, 44 - Nantes (France); Bohnke, O. [Universite du Maine, 72 - Le Mans (France). Laboratoire des Fluorures; West, K. [Technical University of Denmark, Lyngby (Denmark). Dept. of Chemistry

    1996-12-31

    This paper presents a prototype of an entirely inorganic lithium ions battery cell. LiCoO{sub 2} thin film cathodes and Li{sub 4/3}Ti{sub 5/3}O{sub 4} thin film anodes have been deposited on Li{sub 3x}La{sub 2/3-x}TiO{sub 3} sintered solid electrolyte pellets and the performances of these battery cells have been tested. (J.S.) 5 refs.

  5. Realization of entirely solid lithium ion batteries; Realisation d`accumulateurs a ions lithium entierement solides

    Energy Technology Data Exchange (ETDEWEB)

    Brousse, T; Marchand, R; Fragnaud, P; Schleich, D M [Laboratoire de Genie des Materiaux, ISITEM, 44 - Nantes (France); Bohnke, O [Universite du Maine, 72 - Le Mans (France). Laboratoire des Fluorures; West, K [Technical University of Denmark, Lyngby (Denmark). Dept. of Chemistry

    1997-12-31

    This paper presents a prototype of an entirely inorganic lithium ions battery cell. LiCoO{sub 2} thin film cathodes and Li{sub 4/3}Ti{sub 5/3}O{sub 4} thin film anodes have been deposited on Li{sub 3x}La{sub 2/3-x}TiO{sub 3} sintered solid electrolyte pellets and the performances of these battery cells have been tested. (J.S.) 5 refs.

  6. Flexible poly(ethylene carbonate)/garnet composite solid electrolyte reinforced by poly(vinylidene fluoride-hexafluoropropylene) for lithium metal batteries

    Science.gov (United States)

    He, Zijian; Chen, Long; Zhang, Bochen; Liu, Yongchang; Fan, Li-Zhen

    2018-07-01

    Solid-state electrolytes with high ionic conductivities, great flexibility, and easy processability are needed for high-performance solid-state rechargeable lithium batteries. In this work, we synthesize nanosized cubic Li6.25Al0.25La3Zr2O12 (LLZO) by solution combustion method and develop a flexible garnet-based composite solid electrolyte composed of LLZO, poly(ethylene carbonate) (PEC), poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP) and lithium bis(fluorosulfonyl)imide (LiFSI)). In the flexible composite solid electrolytes, LLZO nanoparticles, as ceramic matrix, have a positive effect on ionic conductivities and lithium ion transference number (tLi+). PEC, as a fast ion-conducting polymer, possesses high tLi+ inherently. P(VdF-HFP), as a binder, can strengthen mechanical properties. Consequently, the as-prepared composite solid electrolyte demonstrates high tLi+ (0.82) and superb thermal stability (remaining LLZO matrix after burning). All-solid-state LiFePO4|Li cells assembled with the flexible composite solid electrolyte deliver a high initial discharge specific capacity of 121.4 mAh g-1 and good cycling stability at 55 °C.

  7. Lithium-Ion Electrolytes with Improved Safety Tolerance to High Voltage Systems

    Science.gov (United States)

    Smart, Marshall C. (Inventor); Bugga, Ratnakumar V. (Inventor); Prakash, Surya G. (Inventor); Krause, Frederick C. (Inventor)

    2015-01-01

    The invention discloses various embodiments of electrolytes for use in lithium-ion batteries, the electrolytes having improved safety and the ability to operate with high capacity anodes and high voltage cathodes. In one embodiment there is provided an electrolyte for use in a lithium-ion battery comprising an anode and a high voltage cathode. The electrolyte has a mixture of a cyclic carbonate of ethylene carbonate (EC) or mono-fluoroethylene carbonate (FEC) co-solvent, ethyl methyl carbonate (EMC), a flame retardant additive, a lithium salt, and an electrolyte additive that improves compatibility and performance of the lithium-ion battery with a high voltage cathode. The lithium-ion battery is charged to a voltage in a range of from about 2.0 V (Volts) to about 5.0 V (Volts).

  8. Development of all-solid lithium-ion battery using Li-ion conducting glass-ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Inda, Yasushi [Research and Development Department, Ohara-inc, 1-15-30 Oyama, Sagamihara, Kanagawa 229-1186 (Japan); Graduate School of Engineering, Iwate University, 4-3-5 Ueda, Morioka, Iwate 020-8551 (Japan); Katoh, Takashi [Research and Development Department, Ohara-inc, 1-15-30 Oyama, Sagamihara, Kanagawa 229-1186 (Japan); Baba, Mamoru [Graduate School of Engineering, Iwate University, 4-3-5 Ueda, Morioka, Iwate 020-8551 (Japan)

    2007-12-06

    We have developed a high performance lithium-ion conducting glass-ceramics. This glass-ceramics has the crystalline form of Li{sub 1+x+y}Al{sub x}Ti{sub 2-x}Si{sub y}P{sub 3-y}O{sub 12} with a NASICON-type structure, and it exhibits a high lithium-ion conductivity of 10{sup -3} S cm{sup -1} or above at room temperature. Moreover, since this material is stable in the open atmosphere and even to exposure to moist air, it is expected to be applied for various uses. One of applications of this material is as a solid electrolyte for a lithium-ion battery. Batteries were developed by combining a LiCoO{sub 2} positive electrode, a Li{sub 4}Ti{sub 5}O{sub 12} negative electrode, and a composite electrolyte. The battery using the composite electrolyte with a higher conductivity exhibited a good charge-discharge characteristic. (author)

  9. Electrolyte Suitable for Use in a Lithium Ion Cell or Battery

    Science.gov (United States)

    McDonald, Robert C. (Inventor)

    2014-01-01

    Electrolyte suitable for use in a lithium ion cell or battery. According to one embodiment, the electrolyte includes a fluorinated lithium ion salt and a solvent system that solvates lithium ions and that yields a high dielectric constant, a low viscosity and a high flashpoint. In one embodiment, the solvent system includes a mixture of an aprotic lithium ion solvating solvent and an aprotic fluorinated solvent.

  10. Electrolytes for Wide Operating Temperature Lithium-Ion Cells

    Science.gov (United States)

    Smart, Marshall C. (Inventor); Bugga, Ratnakumar V. (Inventor)

    2016-01-01

    Provided herein are electrolytes for lithium-ion electrochemical cells, electrochemical cells employing the electrolytes, methods of making the electrochemical cells and methods of using the electrochemical cells over a wide temperature range. Included are electrolyte compositions comprising a lithium salt, a cyclic carbonate, a non-cyclic carbonate, and a linear ester and optionally comprising one or more additives.

  11. Solid-state lithium battery

    Science.gov (United States)

    Ihlefeld, Jon; Clem, Paul G; Edney, Cynthia; Ingersoll, David; Nagasubramanian, Ganesan; Fenton, Kyle Ross

    2014-11-04

    The present invention is directed to a higher power, thin film lithium-ion electrolyte on a metallic substrate, enabling mass-produced solid-state lithium batteries. High-temperature thermodynamic equilibrium processing enables co-firing of oxides and base metals, providing a means to integrate the crystalline, lithium-stable, fast lithium-ion conductor lanthanum lithium tantalate (La.sub.1/3-xLi.sub.3xTaO.sub.3) directly with a thin metal foil current collector appropriate for a lithium-free solid-state battery.

  12. Copper Antimonide Nanowire Array Lithium Ion Anodes Stabilized by Electrolyte Additives.

    Science.gov (United States)

    Jackson, Everett D; Prieto, Amy L

    2016-11-09

    Nanowires of electrochemically active electrode materials for lithium ion batteries represent a unique system that allows for intensive investigations of surface phenomena. In particular, highly ordered nanowire arrays produced by electrodeposition into anodic aluminum oxide templates can lead to new insights into a material's electrochemical performance by providing a high-surface-area electrode with negligible volume expansion induced pulverization. Here we show that for the Li-Cu x Sb ternary system, stabilizing the surface chemistry is the most critical factor for promoting long electrode life. The resulting solid electrolyte interphase is analyzed using a mix of electron microscopy, X-ray photoelectron spectroscopy, and lithium ion battery half-cell testing to provide a better understanding of the importance of electrolyte composition on this multicomponent alloy anode material.

  13. Electrolytes for lithium ion batteries

    Science.gov (United States)

    Vaughey, John; Jansen, Andrew N.; Dees, Dennis W.

    2014-08-05

    A family of electrolytes for use in a lithium ion battery. The genus of electrolytes includes ketone-based solvents, such as, 2,4-dimethyl-3-pentanone; 3,3-dimethyl 2-butanone(pinacolone) and 2-butanone. These solvents can be used in combination with non-Lewis Acid salts, such as Li.sub.2[B.sub.12F.sub.12] and LiBOB.

  14. Ion Transport and Structure in Polymer Electrolytes with Applications in Lithium Batteries

    Science.gov (United States)

    Chintapalli, Mahati

    When mixed with lithium salts, polymers that contain more than one chemical group, such as block copolymers and endgroup-functionalized polymers, are promising electrolyte materials for next-generation lithium batteries. One chemical group can provide good ion solvation and transport properties, while the other chemical group can provide secondary properties that improve the performance characteristics of the battery. Secondary properties of interest include non-flammability for safer lithium ion batteries and high mechanical modulus for dendrite resistance in high energy density lithium metal batteries. Block copolymers and other materials with multiple chemical groups tend to exhibit nanoscale heterogeneity and can undergo microphase separation, which impacts the ion transport properties. In block copolymers that microphase separate, ordered self-assembled structures occur on longer length scales. Understanding the interplay between structure at different length scales, salt concentration, and ion transport is important for improving the performance of multifunctional polymer electrolytes. In this dissertation, two electrolyte materials are characterized: mixtures of endgroup-functionalized, short chain perfluoropolyethers (PFPEs) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, and mixtures of polystyrene-block-poly(ethylene oxide) (PS- b-PEO; SEO) and LiTFSI. The PFPE/LiTFSI electrolytes are liquids in which the PFPE backbone provides non-flammability, and the endgroups resemble small molecules that solvate ions. In these electrolytes, the ion transport properties and nanoscale heterogeneity (length scale 1 nm) are characterized as a function of endgroup using electrochemical techniques, nuclear magnetic resonance spectroscopy, and wide angle X-ray scattering. Endgroups, especially those containing PEO segments, have a large impact on ionic conductivity, in part because the salt distribution is not homogenous; we find that salt partitions

  15. Solid-state graft copolymer electrolytes for lithium battery applications.

    Science.gov (United States)

    Hu, Qichao; Caputo, Antonio; Sadoway, Donald R

    2013-08-12

    Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 °C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed.

  16. Ionic Borate-Based Covalent Organic Frameworks: Lightweight Porous Materials for Lithium-Stable Solid State Electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Black, Hayden T; Harrison, Katharine Lee

    2016-10-01

    The synthesis and characterization of the first polyelectrolyte of intrinsic microporosity (PEIM) is described. The novel material was synthesized via reaction between the nitrile group in the polymer backbone and n-butyl lithium, effectively anchoring an imine anion to the porous framework while introducing a mobile lithium counterion. The PEIM was characterized by 13C, 1H, and 7Li NMR experiments, revealing quantitative conversion of the nitrile functionality to the anionic imine. Variable temperature 7Li NMR analysis of the dry PEIM and the electrolyteswollen PEIM revealed that lithium ion transport within the dry PEIM was largely due to interchain hopping of the Li+ ions, and that the mobility of polymer associated Li+ was reduced after swelling in electrolyte solution. Meanwhile, the swollen PEIM supported efficient transport of dissolved Li+ within the expanded pores. These results are discussed in the context of developing novel solid or solid-like lithium ion electrolytes using the new PEIM material.

  17. Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high performance solid state lithium batteries

    International Nuclear Information System (INIS)

    He, Weisheng; Cui, Zili; Liu, Xiaochen; Cui, Yanyan; Chai, Jingchao; Zhou, Xinhong; Liu, Zhihong; Cui, Guanglei

    2017-01-01

    The classic poly(ethylene oxide) (PEO) based solid polymer electrolyte suffers from poor ionic conductivity of ambient temperature, low lithium ion transference number and relatively narrow electrochemical window (<4.0 V vs. Li + /Li). Herein, the carbonate-linked PEO solid polymer such as poly(diethylene glycol carbonate) (PDEC) and poly(triethylene glycol carbonate) (PTEC) were explored to find out the feasibility of resolving above issues. It was proven that the optimized ionic conductivity of PTEC based electrolyte reached up to 1.12 × 10 −5 S cm −1 at 25 °C with a decent lithium ion transference number of 0.39 and a wide electrochemical window about 4.5 V vs. Li + /Li. In addition, the PTEC based Li/LiFePO 4 cell could be reversibly charged and discharged at 0.05 C-rates at ambient temperature. Moreover, the higher voltage Li/LiFe 0.2 Mn 0.8 PO 4 cell (cutoff voltage 4.35 V) possessed considerable rate capability and excellent cycling performance even at ambient temperature. Therefore, these carbonate-linked PEO electrolytes were demonstrated to be fascinating candidates for the next generation solid state lithium batteries simultaneously with high energy and high safety.

  18. Lithium Azide as an Electrolyte Additive for All-Solid-State Lithium-Sulfur Batteries.

    Science.gov (United States)

    Eshetu, Gebrekidan Gebresilassie; Judez, Xabier; Li, Chunmei; Bondarchuk, Oleksandr; Rodriguez-Martinez, Lide M; Zhang, Heng; Armand, Michel

    2017-11-27

    Of the various beyond-lithium-ion battery technologies, lithium-sulfur (Li-S) batteries have an appealing theoretical energy density and are being intensely investigated as next-generation rechargeable lithium-metal batteries. However, the stability of the lithium-metal (Li°) anode is among the most urgent challenges that need to be addressed to ensure the long-term stability of Li-S batteries. Herein, we report lithium azide (LiN 3 ) as a novel electrolyte additive for all-solid-state Li-S batteries (ASSLSBs). It results in the formation of a thin, compact and highly conductive passivation layer on the Li° anode, thereby avoiding dendrite formation, and polysulfide shuttling. It greatly enhances the cycling performance, Coulombic and energy efficiencies of ASSLSBs, outperforming the state-of-the-art additive lithium nitrate (LiNO 3 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. New Solid Polymer Electrolytes for Improved Lithium Batteries

    Science.gov (United States)

    Hehemann, David G.

    2002-01-01

    The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

  20. Electrospinning of Ceramic Solid Electrolyte Nanowires for Lithium-Ion Batteries with Enhanced Ionic Conductivity

    Science.gov (United States)

    Yang, Ting

    Solid electrolytes have great potential to address the safety issues of Li-ion batteries, but better synthesis methods are still required for ceramics electrolytes such as lithium lanthanum titanate (LLTO) and lithium lanthanum zirconate (LLZO). Pellets made from ceramic nanopowders using conventional sintering can be porous due to the agglomeration of nanoparticles (NPs). Electrospinning is a simple and versatile technique for preparing oxide ceramic nanowires (NWs) and was used to prepare electrospun LLTO and LLZO NWs. Pellets prepared from the electrospun LLTO NWs had higher density, less void space, and higher Li+ conductivity compared to those comprised of LLTO prepared with conventional sol-gel methods, which demonstrated the potential that electrospinning can provide towards improving the properties of sol-gel derived ceramics. Cubic phase LLZO was stabilized at room temperature in the form of electrospun NWs without extrinsic dopants. Bulk LLZO with tetragonal structure was transformed to the cubic phase using particle size reduction via ball milling. Heating conditions that promoted particle coalescence and grain growth induced a transformation from the cubic to tetragonal phase in both types of nanostructured LLZO. Composite polymer solid electrolyte was fabricated using LLZO NWs as the filler and showed an improved ionic conductivity at room temperature. Nuclear magnetic resonance studies show that LLZO NWs partially modify the polymer matrix and create preferential pathways for Li+ conduction through the modified polymer regions. Doping did not have significant effect on improving the overall conductivity as the interfaces played a predominant role. By comparing fillers with different morphologies and intrinsic conductivities, it was found that both NW morphology and high intrinsic conductivity are desired.

  1. Triethyl orthoformate as a new film-forming electrolytes solvent for lithium-ion batteries with graphite anodes

    International Nuclear Information System (INIS)

    Wang Lishi; Huang Yudai; Jia Dianzeng

    2006-01-01

    Triethyl orthoformate (TEOF) as a new solvent used in propylene carbonate (PC)-based electrolytes together with graphitic anodes in lithium-ion batteries has been investigated. It can be observed that TEOF was capable of suppressing the co-intercalation of PC solvated lithium-ions into the graphite layer during the first lithiation process and the irreversible discharge capacity of the first cycle is the smallest when using 1.0 M LiPF 6 in PC and TEOF at solvent ratio of 1:1 as the electrolytes. The CV, FTIR, EIS, SEM results show that the PC-based electrolytes containing the solvent TEOF can generate an effective solid electrolytes interphase (SEI) film during the first cycling process, and the film is probably mainly composed of ROCO 2 Li, ROLi, Li 2 CO 3 , etc. The formation of a stable passivating film on the graphite surface is believed to be the reason for the improved cell performance. All these results show that TEOF possesses a promising performance for use as an effective film-forming electrolytes solvent in lithium-ion batteries with graphitic anodes

  2. Artificial Solid Electrolyte Interphase-Protected LixSi Nanoparticles: An Efficient and Stable Prelithiation Reagent for Lithium-Ion Batteries.

    Science.gov (United States)

    Zhao, Jie; Lu, Zhenda; Wang, Haotian; Liu, Wei; Lee, Hyun-Wook; Yan, Kai; Zhuo, Denys; Lin, Dingchang; Liu, Nian; Cui, Yi

    2015-07-08

    Prelithiation is an important strategy to compensate for lithium loss in lithium-ion batteries, particularly during the formation of the solid electrolyte interphase (SEI) from reduced electrolytes in the first charging cycle. We recently demonstrated that LixSi nanoparticles (NPs) synthesized by thermal alloying can serve as a high-capacity prelithiation reagent, although their chemical stability in the battery processing environment remained to be improved. Here we successfully developed a surface modification method to enhance the stability of LixSi NPs by exploiting the reduction of 1-fluorodecane on the LixSi surface to form a continuous and dense coating through a reaction process similar to SEI formation. The coating, consisting of LiF and lithium alkyl carbonate with long hydrophobic carbon chains, serves as an effective passivation layer in the ambient environment. Remarkably, artificial-SEI-protected LixSi NPs show a high prelithiation capacity of 2100 mA h g(-1) with negligible capacity decay in dry air after 5 days and maintain a high capacity of 1600 mA h g(-1) in humid air (∼10% relative humidity). Silicon, tin, and graphite were successfully prelithiated with these NPs to eliminate the irreversible first-cycle capacity loss. The use of prelithiation reagents offers a new approach to realize next-generation high-energy-density lithium-ion batteries.

  3. Network type sp3 boron-based single-ion conducting polymer electrolytes for lithium ion batteries

    Science.gov (United States)

    Deng, Kuirong; Wang, Shuanjin; Ren, Shan; Han, Dongmei; Xiao, Min; Meng, Yuezhong

    2017-08-01

    Electrolytes play a vital role in modulating lithium ion battery performance. An outstanding electrolyte should possess both high ionic conductivity and unity lithium ion transference number. Here, we present a facile method to fabricate a network type sp3 boron-based single-ion conducting polymer electrolyte (SIPE) with high ionic conductivity and lithium ion transference number approaching unity. The SIPE was synthesized by coupling of lithium bis(allylmalonato)borate (LiBAMB) and pentaerythritol tetrakis(2-mercaptoacetate) (PETMP) via one-step photoinitiated in situ thiol-ene click reaction in plasticizers. Influence of kinds and content of plasticizers was investigated and the optimized electrolytes show both outstanding ionic conductivity (1.47 × 10-3 S cm-1 at 25 °C) and high lithium transference number of 0.89. This ionic conductivity is among the highest ionic conductivity exhibited by SIPEs reported to date. Its electrochemical stability window is up to 5.2 V. More importantly, Li/LiFePO4 cells with the prepared single-ion conducting electrolytes as the electrolyte as well as the separator display highly reversible capacity and excellent rate capacity under room temperature. It also demonstrates excellent long-term stability and reliability as it maintains capacity of 124 mA h g-1 at 1 C rate even after 500 cycles without obvious decay.

  4. All-solid-state lithium-ion and lithium metal batteries - paving the way to large-scale production

    Science.gov (United States)

    Schnell, Joscha; Günther, Till; Knoche, Thomas; Vieider, Christoph; Köhler, Larissa; Just, Alexander; Keller, Marlou; Passerini, Stefano; Reinhart, Gunther

    2018-04-01

    Challenges and requirements for the large-scale production of all-solid-state lithium-ion and lithium metal batteries are herein evaluated via workshops with experts from renowned research institutes, material suppliers, and automotive manufacturers. Aiming to bridge the gap between materials research and industrial mass production, possible solutions for the production chains of sulfide and oxide based all-solid-state batteries from electrode fabrication to cell assembly and quality control are presented. Based on these findings, a detailed comparison of the production processes for a sulfide based all-solid-state battery with conventional lithium-ion cell production is given, showing that processes for composite electrode fabrication can be adapted with some effort, while the fabrication of the solid electrolyte separator layer and the integration of a lithium metal anode will require completely new processes. This work identifies the major steps towards mass production of all-solid-state batteries, giving insight into promising manufacturing technologies and helping stakeholders, such as machine engineering, cell producers, and original equipment manufacturers, to plan the next steps towards safer batteries with increased storage capacity.

  5. Rational coating of Li7P3S11 solid electrolyte on MoS2 electrode for all-solid-state lithium ion batteries

    Science.gov (United States)

    Xu, R. C.; Wang, X. L.; Zhang, S. Z.; Xia, Y.; Xia, X. H.; Wu, J. B.; Tu, J. P.

    2018-01-01

    Large interfacial resistance between electrode and electrolyte limits the development of high-performance all-solid-state batteries. Herein we report a uniform coating of Li7P3S11 solid electrolyte on MoS2 to form a MoS2/Li7P3S11 composite electrode for all-solid-state lithium ion batteries. The as-synthesized Li7P3S11 processes a high ionic of 2.0 mS cm-1 at room temperature. Due to homogeneous union and reduced interfacial resistance, the assembled all-solid-state batteries with the MoS2/Li7P3S11 composite electrode exhibit higher reversible capacity of 547.1 mAh g-1 at 0.1 C and better cycling stability than the counterpart based on untreated MoS2. Our study provides a new reference for design/fabrication of advanced electrode materials for high-performance all-solid-state batteries.

  6. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes

    KAUST Repository

    Lu, Yingying; Tu, Zhengyuan; Archer, Lynden A.

    2014-01-01

    of these metals and their inability to form uniform electrodeposits on surfaces with inevitable defects. We report on electrodeposition of lithium in simple liquid electrolytes and in nanoporous solids infused with liquid electrolytes. We find that simple liquid

  7. Heteroaromatic-based electrolytes for lithium and lithium-ion batteries

    Science.gov (United States)

    Cheng, Gang; Abraham, Daniel P.

    2017-04-18

    The present invention provides an electrolyte for lithium and/or lithium-ion batteries comprising a lithium salt in a liquid carrier comprising heteroaromatic compound including a five-membered or six-membered heteroaromatic ring moiety selected from the group consisting of a furan, a pyrazine, a triazine, a pyrrole, and a thiophene, the heteroaromatic ring moiety bearing least one carboxylic ester or carboxylic anhydride substituent bound to at least one carbon atom of the heteroaromatic ring. Preferred heteroaromatic ring moieties include pyridine compounds, pyrazine compounds, pyrrole compounds, furan compounds, and thiophene compounds.

  8. Superconcentrated electrolytes for a high-voltage lithium-ion battery

    Science.gov (United States)

    Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro; Chiang, Ching Hua; Tateyama, Yoshitaka; Yamada, Atsuo

    2016-01-01

    Finding a viable electrolyte for next-generation 5 V-class lithium-ion batteries is of primary importance. A long-standing obstacle has been metal-ion dissolution at high voltages. The LiPF6 salt in conventional electrolytes is chemically unstable, which accelerates transition metal dissolution of the electrode material, yet beneficially suppresses oxidative dissolution of the aluminium current collector; replacing LiPF6 with more stable lithium salts may diminish transition metal dissolution but unfortunately encounters severe aluminium oxidation. Here we report an electrolyte design that can solve this dilemma. By mixing a stable lithium salt LiN(SO2F)2 with dimethyl carbonate solvent at extremely high concentrations, we obtain an unusual liquid showing a three-dimensional network of anions and solvent molecules that coordinate strongly to Li+ ions. This simple formulation of superconcentrated LiN(SO2F)2/dimethyl carbonate electrolyte inhibits the dissolution of both aluminium and transition metal at around 5 V, and realizes a high-voltage LiNi0.5Mn1.5O4/graphite battery that exhibits excellent cycling durability, high rate capability and enhanced safety. PMID:27354162

  9. Single-ion triblock copolymer electrolytes based on poly(ethylene oxide) and methacrylic sulfonamide blocks for lithium metal batteries

    Science.gov (United States)

    Porcarelli, Luca; Aboudzadeh, M. Ali; Rubatat, Laurent; Nair, Jijeesh R.; Shaplov, Alexander S.; Gerbaldi, Claudio; Mecerreyes, David

    2017-10-01

    Single-ion conducting polymer electrolytes represent the ideal solution to reduce concentration polarization in lithium metal batteries (LMBs). This paper reports on the synthesis and characterization of single-ion ABA triblock copolymer electrolytes comprising PEO and poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) blocks, poly(LiMTFSI). Block copolymers are prepared by reversible addition-fragmentation chain transfer polymerization, showing low glass transition temperature (-55 to 7 °C) and degree of crystallinity (51-0%). Comparatively high values of ionic conductivity are obtained (up to ≈ 10-4 S cm-1 at 70 °C), combined with a lithium-ion transference number close to unity (tLi+ ≈ 0.91) and a 4 V electrochemical stability window. In addition to these promising features, solid polymer electrolytes are successfully tested in lithium metal cells at 70 °C providing long lifetime up to 300 cycles, and stable charge/discharge cycling at C/2 (≈100 mAh g-1).

  10. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes

    KAUST Repository

    Lu, Yingying

    2014-08-10

    Rechargeable lithium, sodium and aluminium metal-based batteries are among the most versatile platforms for high-energy, cost-effective electrochemical energy storage. Non-uniform metal deposition and dendrite formation on the negative electrode during repeated cycles of charge and discharge are major hurdles to commercialization of energy-storage devices based on each of these chemistries. A long-held view is that unstable electrodeposition is a consequence of inherent characteristics of these metals and their inability to form uniform electrodeposits on surfaces with inevitable defects. We report on electrodeposition of lithium in simple liquid electrolytes and in nanoporous solids infused with liquid electrolytes. We find that simple liquid electrolytes reinforced with halogenated salt blends exhibit stable long-term cycling at room temperature, often with no signs of deposition instabilities over hundreds of cycles of charge and discharge and thousands of operating hours. We rationalize these observations with the help of surface energy data for the electrolyte/lithium interface and impedance analysis of the interface during different stages of cell operation. Our findings provide support for an important recent theoretical prediction that the surface mobility of lithium is significantly enhanced in the presence of lithium halide salts. Our results also show that a high electrolyte modulus is unnecessary for stable electrodeposition of lithium.

  11. PVDF-HFP-based porous polymer electrolyte membranes for lithium-ion batteries

    DEFF Research Database (Denmark)

    Miao, Ruiying; Liu, Bowen; Zhu, Zhongzheng

    2008-01-01

    As a potential electrolyte for lithium-ion batteries, a porous polymer electrolyte membrane based on poly(vinylidenefluoride-hexafluoropropylene) (PVDF-HFP) was prepared by a phase inversion method. The casting solution, effects of the solvent and non-solvent and addition of micron scale TiO2...... particles were investigated. The membranes were characterized by SEM, XRD, AC impedance, and charge/discharge tests. By using acetone as the solvent and water as the non-solvent, the prepared membranes showed good ability to absorb and retain the lithium ion containing electrolyte. Addition of micron TiO2...

  12. Secondary lithium solid polymer electrolyte cells

    International Nuclear Information System (INIS)

    Fix, K.A.; Sammells, A.F.

    1988-01-01

    A strategy for developing morphologically invariant lithium/solid polymer electrolyte interface is being investigated via the use of lithium intercalated electrodes. Emphasis is being placed upon the rutile material Li/sub x/WO/sub 2/ 0.1 < x < 1.0. An absence of shape change at this interface is expected to result in both long cycle life electrochemical cells and the simultaneous maintenance of small interelectrode spacing so that low IR losses can be maintained. During fabrication of cells investigated here both electrochemical and chemical lithium intercalation of WO/sub 2/ was pursued. In the case of larger WO/sub 2/ electrodes initially prepared for fully discharged state cells, electrochemical intercalation during cell charge was found to require significant time, and the reproducible achievement of complete uniform intercalation across the negative electrode became an issue. Emphasis was consequently placed upon cells fabricated using Li/sub x/WO/sub 2/ electrodes initially chemically intercalated by lithium prior to cell assembly. Previous work has demonstrated direct lithium intercalation of metal dichalcogenides using n-BuLi. Lithium activity in n-BuLi is, however, insufficient to achieve lithium intercalation of WO/sub 2//sup 4/. However, recent work has shown that WO/sub 2/ can be directly lithium intercalated upon immersion in lithium naphthalide. Li/sub x/WO/sub 2/ electrodes prepared in this work were intercalated using lithium naphthalide (0.8M) in 2MeTHF. Lithium intercalation was found to readily occur at room temperature, being initially rapid and slowing as bulk intercalation within the electrode proceeded. For electrodes intercalated in this manner, a relationship was identified between the degree of lithium intercalation and initial open-circuit potential in liquid non-aqueous electrolyte

  13. Membranes in Lithium Ion Batteries

    Science.gov (United States)

    Yang, Min; Hou, Junbo

    2012-01-01

    Lithium ion batteries have proven themselves the main choice of power sources for portable electronics. Besides consumer electronics, lithium ion batteries are also growing in popularity for military, electric vehicle, and aerospace applications. The present review attempts to summarize the knowledge about some selected membranes in lithium ion batteries. Based on the type of electrolyte used, literature concerning ceramic-glass and polymer solid ion conductors, microporous filter type separators and polymer gel based membranes is reviewed. PMID:24958286

  14. Membranes in Lithium Ion Batteries

    Directory of Open Access Journals (Sweden)

    Junbo Hou

    2012-07-01

    Full Text Available Lithium ion batteries have proven themselves the main choice of power sources for portable electronics. Besides consumer electronics, lithium ion batteries are also growing in popularity for military, electric vehicle, and aerospace applications. The present review attempts to summarize the knowledge about some selected membranes in lithium ion batteries. Based on the type of electrolyte used, literature concerning ceramic-glass and polymer solid ion conductors, microporous filter type separators and polymer gel based membranes is reviewed.

  15. Lithium-ion batteries fundamentals and applications

    CERN Document Server

    Wu, Yuping

    2015-01-01

    Lithium-Ion Batteries: Fundamentals and Applications offers a comprehensive treatment of the principles, background, design, production, and use of lithium-ion batteries. Based on a solid foundation of long-term research work, this authoritative monograph:Introduces the underlying theory and history of lithium-ion batteriesDescribes the key components of lithium-ion batteries, including negative and positive electrode materials, electrolytes, and separatorsDiscusses electronic conductive agents, binders, solvents for slurry preparation, positive thermal coefficient (PTC) materials, current col

  16. Recent progress in sulfide-based solid electrolytes for Li-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Liu, D., E-mail: liu.dongqiang@ireq.ca; Zhu, W.; Feng, Z.; Guerfi, A.; Vijh, A.; Zaghib, K.

    2016-11-15

    Graphical abstract: Li{sub 2}S-GeS{sub 2}-P{sub 2}S{sub 5} ternary diagram showing various sulphide compounds as solid electrolytes for Li-ion batteries. - Highlights: • Recent progress of sulfide-based solid electrolytes is described from point of view of structure. • Thio-LISICON type electrolytes exhibited high ionic conductivity due to their bcc sublattice and unique Li{sup +} diffusion pathway. • “Mixed-anion effect” is also an effective way to modify the energy landscape as well as the ionic conductivity. - Abstract: Sulfide-based ionic conductors are one of most attractive solid electrolyte candidates for all-solid-state batteries. In this review, recent progress of sulfide-based solid electrolytes is described from point of view of structure. In particular, lithium thio-phosphates such as Li{sub 7}P{sub 3}S{sub 11}, Li{sub 10}GeP{sub 2}S{sub 12} and Li{sub 11}Si{sub 2}PS{sub 12} etc. exhibit extremely high ionic conductivity of over 10{sup −2} S cm{sup −1} at room temperature, even higher than those of commercial organic carbonate electrolytes. The relationship between structure and unprecedented high ionic conductivity is delineated; some potential drawbacks of these electrolytes are also outlined.

  17. Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes

    KAUST Repository

    Chan, Candace K.

    2009-04-01

    Silicon nanowires (SiNWs) have the potential to perform as anodes for lithium-ion batteries with a much higher energy density than graphite. However, there has been little work in understanding the surface chemistry of the solid electrolyte interphase (SEI) formed on silicon due to the reduction of the electrolyte. Given that a good, passivating SEI layer plays such a crucial role in graphite anodes, we have characterized the surface composition and morphology of the SEI formed on the SiNWs using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). We have found that the SEI is composed of reduction products similar to that found on graphite electrodes, with Li2CO3 as an important component. Combined with electrochemical impedance spectroscopy, the results were used to determine the optimal cycling parameters for good cycling. The role of the native SiO2 as well as the effect of the surface area of the SiNWs on reactivity with the electrolyte were also addressed. © 2009 Elsevier B.V. All rights reserved.

  18. Structure and properties of solid polymer electrolyte based on chitosan and ZrO{sub 2} nanoparticle for lithium ion battery

    Energy Technology Data Exchange (ETDEWEB)

    Sudaryanto,, E-mail: dryanto@batan.go.id; Yulianti, Evi, E-mail: yulianti@batan.go.id [Center for Sains and Technology Advanced Materials – BATAN Kawasan Puspiptek Serpong, Tangerang Selatan, BantenV 15314 (Indonesia); Patimatuzzohrah, E-mail: pzohrah@yahoo.com [Department Of Physics, Mataram University, Jl. Majapahit 62, Mataram, NTB 83125 (Indonesia)

    2016-02-08

    In order to develop all solid lithium ion battery, study on the structure and properties of solid polymer electrolytes (SPE) based on chitosan has been done. The SPE were prepared by adding Zirconia (ZrO{sub 2}) nanoparticle and LiClO{sub 4} as lithium salt into the chitosan solution followed by casting method. Effect of the ZrO{sub 2} and salt concentration to the structure and properties of SPE were elaborated using several methods. The structure of the SPE cast film, were characterized mainly by using X-ray diffractometer (XRD). While the electrical properties of SPE were studied by electrochemical impedance spectrometer (EIS) and ion transference number measurement. XRD profiles show that the addition of ZrO{sub 2} and LiClO{sub 4} disrupts the crystality of chitosan. The decrease in sample crytalinity with the nanoparticle and salt addition may increase the molecular mobility result in the increasing sample conductivity and cathionic transference number as determined by EIS and ion transference number measurement, respectively. The highest ionic conductivity (3.58×10{sup −4} S cm{sup −1}) was obtained when 4 wt% of ZrO{sub 2} nanoparticle and 40 wt% of LiClO{sub 4} salt were added to the chitosan. The ion transference number with that composition was 0.55. It is high enough to be used as SPE for lithium ion battery.

  19. "Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries.

    Science.gov (United States)

    Suo, Liumin; Borodin, Oleg; Gao, Tao; Olguin, Marco; Ho, Janet; Fan, Xiulin; Luo, Chao; Wang, Chunsheng; Xu, Kang

    2015-11-20

    Lithium-ion batteries raise safety, environmental, and cost concerns, which mostly arise from their nonaqueous electrolytes. The use of aqueous alternatives is limited by their narrow electrochemical stability window (1.23 volts), which sets an intrinsic limit on the practical voltage and energy output. We report a highly concentrated aqueous electrolyte whose window was expanded to ~3.0 volts with the formation of an electrode-electrolyte interphase. A full lithium-ion battery of 2.3 volts using such an aqueous electrolyte was demonstrated to cycle up to 1000 times, with nearly 100% coulombic efficiency at both low (0.15 coulomb) and high (4.5 coulombs) discharge and charge rates. Copyright © 2015, American Association for the Advancement of Science.

  20. Non-aqueous electrolyte for lithium-ion battery

    Science.gov (United States)

    Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

    2014-04-15

    The present technology relates to stabilizing additives and electrolytes containing the same for use in electrochemical devices such as lithium ion batteries and capacitors. The stabilizing additives include triazinane triones and bicyclic compounds comprising succinic anhydride, such as compounds of Formulas I and II described herein.

  1. Design principles for solid-state lithium superionic conductors.

    Science.gov (United States)

    Wang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J; Kim, Jae Chul; Mo, Yifei; Ceder, Gerbrand

    2015-10-01

    Lithium solid electrolytes can potentially address two key limitations of the organic electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochemical stability. However, achieving a Li(+) conductivity in the solid state comparable to existing liquid electrolytes (>1 mS cm(-1)) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centred cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic conductivity, and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.

  2. Stability of the solid electrolyte Li{sub 3}OBr to common battery solvents

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, D.J. [Department of Engineering Technology, College of Engineering and Engineering Technology, Northern Illinois University, 301B Still Gym, DeKalb, IL 60115 (United States); Hubaud, A.A. [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439-4837 (United States); Vaughey, J.T., E-mail: vaughey@anl.gov [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439-4837 (United States)

    2014-01-01

    Graphical abstract: The stability of the anti-perovskite phase Li{sub 3}OBr has been assessed in a variety of battery solvents. - Highlights: • Lithium stable solid electrolyte Li{sub 3}OBr unstable to polar organic solvents. • Solvation with no dissolution destroys long-range structure. • Ion exchange with protons observed. - Abstract: Recently a new class of solid lithium ion conductors was reported based on the anti-perovskite structure, notably Li{sub 3}OCl and Li{sub 3}OBr. For many beyond lithium-ion battery uses, the solid electrolyte is envisioned to be in direct contact with liquid electrolytes and lithium metal. In this study we evaluated the stability of the Li{sub 3}OBr phase against common battery solvents electrolytes, including diethylcarbonate (DEC) and dimethylcarbonate (DMC), as well as a LiPF{sub 6} containing commercial electrolyte. In contact with battery-grade organic solvents, Li{sub 3}OBr was typically found to be insoluble but lost its crystallinity and reacted with available protons and in some cases with the solvent. A low temperature heat treatment was able to restore crystallinity of the samples; however evidence of proton ion exchange was conserved.

  3. Developments of Electrolyte Systems for Lithium-Sulfur Batteries: A Review

    Directory of Open Access Journals (Sweden)

    Zhan eLin

    2015-02-01

    Full Text Available With a theoretical specific energy 5 times higher than that of lithium-ion (Li-ion batteries (2,600 vs. ~500 Wh kg-1, lithium-sulfur (Li-S batteries have been considered as one of the most promising energy storage systems for the electrification of vehicles. However, both the polysulfide shuttle effects of the sulfur cathode and dendrite formation of the lithium anode are still key limitations to practical use of traditional Li-S batteries. In this review, we focus on the recent developments in electrolyte systems. First we start with a brief discussion on fundamentals of Li-S batteries and key challenges associated with traditional liquid cells. We then introduce the most recent progresses in liquid systems, including ether-based, carbonate-based, and ionic liquid-based electrolytes. And then we move on to the advances in solid systems, including polymer and non-polymer electrolytes. Finally, the opportunities and perspectives for future research in both the liquid and solid Li-S batteries are presented.

  4. Novel polymeric systems for lithium-ion batteries gel electrolytes

    International Nuclear Information System (INIS)

    Appetecchi, G.B.; Alessandrini, F.; Passerini, S.; Caporiccio, G.; Boutevin, B.; Guida-Pietrasanta, F.

    2004-01-01

    The investigation of chemically cross-linked, self-supporting gel-type electrolyte membranes, based on hybrid polyfluorosilicone polymers reinforced with nanosized silica, for lithium-ion battery systems is reported. The polyfluorosilicone materials were selected on the basis of their high chemical and thermal stabilities. The precursors were synthesized with functional groups capable to form inter-molecular cross-linking, thus obtaining three-dimensional polymer matrices. The latter were undergone to swelling processes in (non-aqueous, lithium salt containing) electrolytic solutions to obtain gel-type polymer electrolytes. Several kinds of membranes, based on different types of polyfluorosilicone precursor, were prepared and characterized in terms of swelling behavior, ionic conductivity and electrochemical stability. The properties of the swelled matrices were evaluated as a function of dipping time, temperature, kind of electrolytic solution and cross-linking initiator content

  5. Electrolyte compositions for lithium ion batteries

    Science.gov (United States)

    Sun, Xiao-Guang; Dai, Sheng; Liao, Chen

    2016-03-29

    The invention is directed in a first aspect to an ionic liquid of the general formula Y.sup.+Z.sup.-, wherein Y.sup.+ is a positively-charged component of the ionic liquid and Z.sup.- is a negatively-charged component of the ionic liquid, wherein Z.sup.- is a boron-containing anion of the following formula: ##STR00001## The invention is also directed to electrolyte compositions in which the boron-containing ionic liquid Y.sup.+Z.sup.- is incorporated into a lithium ion battery electrolyte, with or without admixture with another ionic liquid Y.sup.+X.sup.- and/or non-ionic solvent and/or non-ionic solvent additive.

  6. Single-ion polymer electrolyte membranes enable lithium-ion batteries with a broad operating temperature range.

    Science.gov (United States)

    Cai, Weiwei; Zhang, Yunfeng; Li, Jing; Sun, Yubao; Cheng, Hansong

    2014-04-01

    Conductive processes involving lithium ions are analyzed in detail from a mechanistic perspective, and demonstrate that single ion polymeric electrolyte (SIPE) membranes can be used in lithium-ion batteries with a wide operating temperature range (25-80 °C) through systematic optimization of electrodes and electrode/electrolyte interfaces, in sharp contrast to other batteries equipped with SIPE membranes that display appreciable operability only at elevated temperatures (>60 °C). The performance is comparable to that of batteries using liquid electrolyte of inorganic salt, and the batteries exhibit excellent cycle life and rate performance. This significant widening of battery operation temperatures coupled with the inherent flexibility and robustness of the SIPE membranes makes it possible to develop thin and flexible Li-ion batteries for a broad range of applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Truly quasi-solid-state lithium cells utilizing carbonate free polymer electrolytes on engineered LiFePO_4

    International Nuclear Information System (INIS)

    Nair, Jijeesh R.; Cíntora-Juárez, Daniel; Pérez-Vicente, Carlos; Tirado, José L.; Ahmad, Shahzada; Gerbaldi, Claudio

    2016-01-01

    Highlights: • Carbonate free truly quasi-solid-state polymer electrolytes for lithium batteries. • Simple and easy up scalable preparation by solvent free thermal curing. • LiFePO_4 cathode engineered by PEDOT:PSS interphase at the current collector. • Direct polymerization over the engineered electrode surface in one pot. • Stable lithium polymer cells operating in a wide temperature range. - Abstract: Stable and safe functioning of a Li-ion battery is the demand of modern generation. Herein, we are demonstrating the application of an in-situ free radical polymerisation process (thermal curing) to fabricate a polymer electrolyte that possesses mechanical robustness, high thermal stability, improved interfacial and ion transport characteristics along with stable cycling at ambient conditions. The polymer electrolyte is obtained by direct polymerization over the electrode surface in one pot starting from a reactive mixture comprising an ethylene oxide-based dimethacrylic oligomer (BDM), dimethyl polyethylene glycol (DPG) and lithium salt. Furthermore, an engineered cathode is used, comprising a LiFePO_4/PEDOT:PSS interface at the current collector that improves the material utilization at high rates and mitigates the corrosive effects of LiTFSI on aluminium current collector. The lithium cell resulting from the newly elaborated multiphase assembly of the composite cathode with the DPG-based carbonate-free polymer electrolyte film exhibits excellent reversibility upon prolonged cycling at ambient as well as elevated temperatures, which is found to be superior compared to previous reports on uncoated electrodes with polymer electrolytes.

  8. Ionic liquids as electrolytes for Li-ion batteries-An overview of electrochemical studies

    Science.gov (United States)

    Lewandowski, Andrzej; Świderska-Mocek, Agnieszka

    The paper reviews properties of room temperature ionic liquids (RTILs) as electrolytes for lithium and lithium-ion batteries. It has been shown that the formation of the solid electrolyte interface (SEI) on the anode surface is critical to the correct operation of secondary lithium-ion batteries, including those working with ionic liquids as electrolytes. The SEI layer may be formed by electrochemical transformation of (i) a molecular additive, (ii) RTIL cations or (iii) RTIL anions. Such properties of RTIL electrolytes as viscosity, conductivity, vapour pressure and lithium-ion transport numbers are also discussed from the point of view of their influence on battery performance.

  9. All-solid-state lithium-sulfur battery based on a nanoconfined LiBH4 electrolyte

    DEFF Research Database (Denmark)

    Das, Supti; Ngene, Peter; Norby, Poul

    2016-01-01

    In this work we characterize all-solid-state lithium-sulfur batteries based on nano-confined LiBH4 in mesoporous silica as solid electrolytes. The nano-confined LiBH4 has fast ionic lithium conductivity at room temperature, 0.1 mScm-1, negligible electronic conductivity and its cationic transport...... number (t+ = 0.96), close to unity, demonstrates a purely cationic conductor. The electrolyte has an excellent stability against lithium metal. The behavior of the batteries is studied by cyclic voltammetry and repeated charge/discharge cycles in galvanostatic conditions. The batteries show very good...

  10. Challenges and perspectives of garnet solid electrolytes for all solid-state lithium batteries

    Science.gov (United States)

    Liu, Qi; Geng, Zhen; Han, Cuiping; Fu, Yongzhu; Li, Song; He, Yan-bing; Kang, Feiyu; Li, Baohua

    2018-06-01

    Garnet Li7La3Zr2O12 (LLZO) solid electrolytes recently have attracted tremendous interest as they have the potential to enable all solid-state lithium batteries (ASSLBs) owing to high ionic conductivity (10-3 to 10-4 S cm-1), negligible electronic transport, wide potential window (up to 9 V), and good chemical stability. Here we present the key issues and challenges of LLZO in the aspects of ion conduction property, interfacial compatibility, and stability in air. First, different preparation methods of LLZO are reviewed. Then, recent progress about the improvement of ionic conductivity and interfacial property between LLZO and electrodes are presented. Finally, we list some emerging LLZO-based solid-state batteries and provide perspectives for further research. The aim of this review is to summarize the up-to-date developments of LLZO and lead the direction for future development which could enable LLZO-based ASSLBs.

  11. Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte

    International Nuclear Information System (INIS)

    Crowe, Adam J.; Bartlett, Bart M.

    2016-01-01

    With high elemental abundance, large volumetric capacity, and dendrite-free metal deposition, magnesium metal anodes offer promise in beyond-lithium-ion batteries. However, the increased charge density associated with the divalent magnesium-ion (Mg 2+ ), relative to lithium-ion (Li + ) hinders the ion-insertion and extraction processes within many materials and structures known for lithium-ion cathodes. As a result, many recent investigations incorporate known amounts of water within the electrolyte to provide temporary solvation of the Mg 2+ , improving diffusion kinetics. Unfortunately with the addition of water, compatibility with magnesium metal anodes disappears due to forming an ion-insulating passivating layer. In this short review, recent advances in solid state cathode materials for rechargeable magnesium-ion batteries are highlighted, with a focus on cathode materials that do not require water contaminated electrolyte solutions for ion insertion and extraction processes. - Graphical abstract: In this short review, we present candidate materials for reversible Mg-battery cathodes that are compatible with magnesium metal in water-free electrolytes. The data suggest that soft, polarizable anions are required for reversible cycling.

  12. Revealing the Solvation Structure and Dynamics of Carbonate Electrolytes in Lithium-Ion Batteries by Two-Dimensional Infrared Spectrum Modeling.

    Science.gov (United States)

    Liang, Chungwen; Kwak, Kyungwon; Cho, Minhaeng

    2017-12-07

    Carbonate electrolytes in lithium-ion batteries play a crucial role in conducting lithium ions between two electrodes. Mixed solvent electrolytes consisting of linear and cyclic carbonates are commonly used in commercial lithium-ion batteries. To understand how the linear and cyclic carbonates introduce different solvation structures and dynamics, we performed molecular dynamics simulations of two representative electrolyte systems containing either linear or cyclic carbonate solvents. We then modeled their two-dimensional infrared (2DIR) spectra of the carbonyl stretching mode of these carbonate molecules. We found that the chemical exchange process involving formation and dissociation of lithium-ion/carbonate complexes is responsible for the growth of 2DIR cross peaks with increasing waiting time. In addition, we also found that cyclic carbonates introduce faster dynamics of dissociation and formation of lithium-ion/carbonate complexes than linear carbonates. These findings provide new insights into understanding the lithium-ion mobility and its interplay with solvation structure and ultrafast dynamics in carbonate electrolytes used in lithium-ion batteries.

  13. Electrochemical Model for Ionic Liquid Electrolytes in Lithium Batteries

    International Nuclear Information System (INIS)

    Yoo, Kisoo; Deshpande, Anirudh; Banerjee, Soumik; Dutta, Prashanta

    2015-01-01

    ABSTRACT: Room temperature ionic liquids are considered as potential electrolytes for high performance and safe lithium batteries due to their very low vapor pressure and relatively wide electrochemical and thermal stability windows. Unlike organic electrolytes, ionic liquid electrolytes are molten salts at room temperature with dissociated cations and anions. These dissociated ions interfere with the transport of lithium ions in lithium battery. In this study, a mathematical model is developed for transport of ionic components to study the performance of ionic liquid based lithium batteries. The mathematical model is based on a univalent ternary electrolyte frequently encountered in ionic liquid electrolytes of lithium batteries. Owing to the very high concentration of components in ionic liquid, the transport of lithium ions is described by the mutual diffusion phenomena using Maxwell-Stefan diffusivities, which are obtained from atomistic simulation. The model is employed to study a lithium-ion battery where the electrolyte comprises ionic liquid with mppy + (N-methyl-N-propyl pyrrolidinium) cation and TFSI − (bis trifluoromethanesulfonyl imide) anion. For a moderate value of reaction rate constant, the electric performance results predicted by the model are in good agreement with experimental data. We also studied the effect of porosity and thickness of separator on the performance of lithium-ion battery using this model. Numerical results indicate that low rate of lithium ion transport causes lithium depleted zone in the porous cathode regions as the porosity decreases or the length of the separator increases. The lithium depleted region is responsible for lower specific capacity in lithium-ion cells. The model presented in this study can be used for design of optimal ionic liquid electrolytes for lithium-ion and lithium-air batteries

  14. Ionic Liquid-Doped Gel Polymer Electrolyte for Flexible Lithium-Ion Polymer Batteries

    Science.gov (United States)

    Zhang, Ruisi; Chen, Yuanfen; Montazami, Reza

    2015-01-01

    Application of gel polymer electrolytes (GPE) in lithium-ion polymer batteries can address many shortcomings associated with liquid electrolyte lithium-ion batteries. Due to their physical structure, GPEs exhibit lower ion conductivity compared to their liquid counterparts. In this work, we have investigated and report improved ion conductivity in GPEs doped with ionic liquid. Samples containing ionic liquid at a variety of volume percentages (vol %) were characterized for their electrochemical and ionic properties. It is concluded that excess ionic liquid can damage internal structure of the batteries and result in unwanted electrochemical reactions; however, samples containing 40–50 vol % ionic liquid exhibit superior ionic properties and lower internal resistance compared to those containing less or more ionic liquids.

  15. Effect of sulfolane on the performance of lithium bis(oxalato)borate-based electrolytes for advanced lithium ion batteries

    International Nuclear Information System (INIS)

    Li Shiyou; Zhao Yangyu; Shi Xinming; Li Bucheng; Xu Xiaoli; Zhao Wei; Cui Xiaoling

    2012-01-01

    Highlights: ► High purity of LiBOB is obtained by the compressing dry granulation method. ► LiBOB-SL/DEC electrolyte is an excellent candidate electrolyte for lithium ion batteries. ► It shows high oxidation potentials (>5.3 V) and satisfactory conductivities. ► In Li/MCMB cells, this novel electrolyte exhibits excellent film-forming characteristics and low impedances of the interface films. ► In LiFePO 4 /Li cells, this novel electrolyte exhibits stable cycle performance and high discharge voltage plateau (>3.35 V). - Abstract: Lithium bis(oxalato)borate (LiBOB) is a promising salt for lithium ion batteries. However, before applying in lithium ion batteries, it is necessary to prepare high purity LiBOB with a simple method, and find more appropriate solvent systems to exert the perfect electrochemical performance of LiBOB. In this paper, LiBOB is synthesized by the compressing dry granulation method, with the yield of 97%. Moreover, the electrochemical performances of LiBOB-sulfolane (SL)/diethyl carbonate (DEC) electrolyte are investigated. It shows high oxidation potentials (>5.3 V) and satisfactory conductivities, also the temperature dependence of the conductivity is well in accord with the Vogel–Tamman–Fulcher (VTF) behavior. When used in Li/MCMB (mesophase carbon microbeads) cells, this novel electrolyte exhibits not only excellent film-forming characteristics, but also low impedances of the interface films. When used in LiFePO 4 /Li cells, compared to the cell with the electrolyte system of LiBOB-EC/DEC electrolyte, LiBOB-SL/DEC electrolyte exhibit several advantages, such as more stable cycle performance, and higher discharge voltage plateau (>3.35 V).

  16. Solid-State NMR Study of New Copolymers as Solid Polymer Electrolytes

    Directory of Open Access Journals (Sweden)

    Jean-Christophe Daigle

    2018-01-01

    Full Text Available We report the analysis of comb-like polymers by solid-state NMR. The polymers were previously evaluated as solid-polymer-electrolytes (SPE for lithium-polymer-metal batteries that have suitable ionic conductivity at 60 °C. We propose to develop a correlation between 13C solid-state NMR measurements and phase segregation. 13C solid-state NMR is a perfect tool for differentiating polymer phases with fast or slow motions. 7Li was used to monitor the motion of lithium ions in the polymer, and activation energies were calculated.

  17. Novel polymeric systems for lithium ion batteries gel electrolytes

    International Nuclear Information System (INIS)

    Appetecchi, G.B.; Alessandrini, F.; Passerini, S.; Caporiccio, G.; Boutevin, B.; Guida-PietraSanta, F.

    2005-01-01

    Cross-linked, self-supporting, membranes for lithium ion battery gel electrolytes were obtained by cross-linking a mixture of polyfluorosilicone (PFSi) and polysilicone containing ethylene oxide (EO) units [P(Si-EO)]. The membranes were also reinforced with nanosized silica. The two polymer precursors were synthesized with functional groups capable to form inter-molecular cross-linking, thus obtaining three-dimensional, polymer matrices. The precursors were dissolved in a common solvent and cross-linked to obtain free-standing PFSi/P(Si-EO):SiO 2 composite films. The latter were undergone to swelling processes in (non-aqueous, aprotic, lithium salt containing) electrolytic solutions to obtain gel-type polymer electrolytes. The properties of the swelled PFSi/P(Si-EO):SiO 2 samples were evaluated as a function of the electrolytic solutions and the dipping time. The PFSi/P(Si-EO):SiO 2 membranes exhibited large swelling properties, high ionic conductivity and good electrochemical stability

  18. Ionic Liquid-Doped Gel Polymer Electrolyte for Flexible Lithium-Ion Polymer Batteries

    Directory of Open Access Journals (Sweden)

    Ruisi Zhang

    2015-05-01

    Full Text Available Application of gel polymer electrolytes (GPE in lithium-ion polymer batteries can address many shortcomings associated with liquid electrolyte lithium-ion batteries. Due to their physical structure, GPEs exhibit lower ion conductivity compared to their liquid counterparts. In this work, we have investigated and report improved ion conductivity in GPEs doped with ionic liquid. Samples containing ionic liquid at a variety of volume percentages (vol % were characterized for their electrochemical and ionic properties. It is concluded that excess ionic liquid can damage internal structure of the batteries and result in unwanted electrochemical reactions; however, samples containing 40–50 vol % ionic liquid exhibit superior ionic properties and lower internal resistance compared to those containing less or more ionic liquids.

  19. Solid lithium ion conductors for battery applications

    Energy Technology Data Exchange (ETDEWEB)

    Weppner, W.

    1985-01-15

    The phase equilibria and conductivities of the LiF-LiH, LiF-LiOH, LiF-Li/sub 2/O, Li/sub 2/S-Li/sub 2/O, Li/sub 2/S-LiCl and Li/sub 2/S-LiBr systems were investigated. All ternary single phases and two-phase mixtures are solid electrolytes which are thermodynamically stable in respect of reaction with elemental lithium (anode) and at practically useful, low lithium activities (cathode). The conductivity normally increases with decreasing thermodynamic stability and vice versa. The conductivity may be optimized in the case of solid solutions by selecting a composition with a decomposition voltage just above the value required by the cathode material employed. All materials are isotropic in structure and no dendrite formation was observed. This allows their use in rechargeable, thin film electrolyte batteries.

  20. Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

    DEFF Research Database (Denmark)

    Jongh, P. E. de; Blanchard, D.; Matsuo, M.

    2016-01-01

    A central goal in current battery research is to increase the safety and energy density of Li-ion batteries. Electrolytes nowadays typically consist of lithium salts dissolved in organic solvents. Solid electrolytes could facilitate safer batteries with higher capacities, as they are compatible...... electrolytes, discussing in detail LiBH4, strategies towards for fast room-temperature ionic conductors, alternative compounds, and first explorations of implementation of these electrolytes in all-solid-state batteries....

  1. Assessment of all-solid-state lithium-ion batteries

    Science.gov (United States)

    Braun, P.; Uhlmann, C.; Weiss, M.; Weber, A.; Ivers-Tiffée, E.

    2018-07-01

    All-solid-state lithium-ion batteries (ASSBs) are considered as next generation energy storage systems. A model might be very useful, which describes all contributions to the internal cell resistance, enables an optimization of the cell design, and calculates the performance of an open choice of cell architectures. A newly developed one-dimensional model for ASSBs is presented, based on a design concept which employs the use of composite electrodes. The internal cell resistance is calculated by linking two-phase transmission line models representing the composite electrodes with an ohmic resistance representing the solid electrolyte (separator). Thereby, electrical parameters, i.e. ionic and electronic conductivity, electrochemical parameters, i.e. charge-transfer resistance at interfaces and lithium solid-state diffusion, and microstructure parameters, i.e. electrode thickness, particle size, interface area, phase composition and tortuosity, are considered as the most important material and design parameters. Subsequently, discharge curves are simulated, and energy- and power-density characteristics of all-solid-state cell architectures are calculated. These model calculations are discussed and compared with experimental data from literature for a high power LiCoO2-Li10GeP2S12/Li10GeP2S12/Li4Ti5O12-Li10GeP2S12 cell.

  2. A structural study of solid electrolyte interface on negative electrode of lithium-Ion battery by electron microscopy.

    Science.gov (United States)

    Matsushita, Tadashi; Watanabe, Jiro; Nakao, Tatsuya; Yamashita, Seiichi

    2014-11-01

    For the last decades, the performance of the lithium-ion battery (LIB) has been significantly improved and its applications have been expanding rapidly. However, its performance has yet to be enhanced.In the lithium-ion battery development, it is important to elucidate the electrode structure change in detail during the charge and discharge cycling. In particular, solid electrolyte interface (SEI) formed by decomposition of the electrolytes on the graphite negative electrode surface should play an important role for battery properties. Therefore, it is essential to control the structure and composition of SEI to improve the battery performance. Here, we conducted a scanning electron microscope (SEM) and transmission electron microscope (TEM) study to elucidate the structures of the SEI during the charge and discharge process using LiNi1/3Co1/3Mn1/3O2 [1] cathode and graphite anode. [2] Since SEI is a lithium-containing compound with high activity, it was observed without being exposed to the atmosphere. The electrodes including SEI were sampled after dismantling batteries with cutoff voltages of 3V and 4.2V for the charge process and 3V for the discharge process. Fig.1 shows SEM images of the graphite electrode surface during the charge and discharge process. The change of the SEI structure during the process was clearly observed. Further, TEM images showed that the SEI grew thicker during the charge process and becomes thinner when discharged. These results with regard to the reversible SEI structure could give a new insight for the battery development.jmicro;63/suppl_1/i21/DFU056F1F1DFU056F1Fig. 1.SEM images of the graphite electrode surface:(a) before charge process;(b) with charge-cutoff voltage of 3.0V; (c) with charge-cutoff voltage of 4.2V; (d) with discharge-cutoff voltage of 3.0V. © The Author 2014. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  3. Wide-Temperature Electrolytes for Lithium-Ion Batteries.

    Science.gov (United States)

    Li, Qiuyan; Jiao, Shuhong; Luo, Langli; Ding, Michael S; Zheng, Jianming; Cartmell, Samuel S; Wang, Chong-Min; Xu, Kang; Zhang, Ji-Guang; Xu, Wu

    2017-06-07

    Formulating electrolytes with solvents of low freezing points and high dielectric constants is a direct approach to extend the service-temperature range of lithium (Li)-ion batteries (LIBs). In this study, we report such wide-temperature electrolyte formulations by optimizing the ethylene carbonate (EC) content in the ternary solvent system of EC, propylene carbonate (PC), and ethyl methyl carbonate (EMC) with LiPF 6 salt and CsPF 6 additive. An extended service-temperature range from -40 to 60 °C was obtained in LIBs with lithium nickel cobalt aluminum oxide (LiNi 0.80 Co 0.15 Al 0.05 O 2 , NCA) as cathode and graphite as anode. The discharge capacities at low temperatures and the cycle life at room temperature and elevated temperatures were systematically investigated together with the ionic conductivity and phase-transition behaviors. The most promising electrolyte formulation was identified as 1.0 M LiPF 6 in EC-PC-EMC (1:1:8 by wt) with 0.05 M CsPF 6 , which was demonstrated in both coin cells of graphite∥NCA and 1 Ah pouch cells of graphite∥LiNi 1/3 Mn 1/3 Co 1/3 O 2 . This optimized electrolyte enables excellent wide-temperature performances, as evidenced by the high capacity retention (68%) at -40 °C and C/5 rate, significantly higher than that (20%) of the conventional LIB electrolyte, and the nearly identical stable cycle life as the conventional LIB electrolyte at room temperature and elevated temperatures up to 60 °C.

  4. In-situ Plasticized Cross-linked Polymer Composite Electrolyte Enhanced with Lithium-ion Conducting Nanofibers for Ambient All-Solid-State Lithium-ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Chaoyi; Zhu, Pei; Jia, Hao; Zhu, Jiadeng; Selvan, R. Kalai; Li, Ya; Dong, Xia; Du, Zhuang; Angunawela, Indunil; Wu, Nianqiang; Dirican, Mahmut

    2018-04-29

    Solid electrolytes have been gaining attention recently for the development of next-generation Li-ion batteries due to the substantial improvements in stability and safety. Among various types of solid electrolytes, composite solid electrolytes (CSEs) exhibit both high ionic conductivity and excellent interfacial contact with the electrodes. Incorporating active nanofibers into the polymer matrix demonstrates an effective method to fabricate CSEs. However, current CSEs based on traditional poly(ethylene oxide) (PEO) polymer suffer from the poor ionic conductivity of PEO and agglomeration effect of inorganic fillers at high concentrations, which limit further improvements in Li+ conductivity and electrochemical stability. Herein, we synthesize a novel PEO based cross-linked polymer (CLP) as the polymer matrix with naturally amorphous structure and high room-temperature ionic conductivity of 2.40 × 10-4 S cm-1. Li0.3La0.557TiO3 (LLTO) nanofibers incorporated composite solid electrolytes (L-CLPCSE) exhibit enhanced ionic conductivity without showing filler agglomeration. The high content of Li-conductive nanofibers improves the mechanical strength, ensures the conductive networks, and increases the total Li+ conductivity to 3.31 × 10-4 S cm-1. The all-solid-state Li|LiFePO4 batteries with L-CLPCSE are able to deliver attractive specific capacity of 147 mAh g-1 at room temperature, and no evident dendrite is found at the anode/electrolyte interface after 100 cycles.

  5. All-Solid-State Lithium-Sulfur Battery based on a nanoconfined LiBH 4 Electrolyte

    NARCIS (Netherlands)

    Das, Supti; Ngene, Peter; Norby, Poul; Vegge, Tejs; de Jongh, P.E.; Blanchard, Didier

    2016-01-01

    In this work we characterize all-solid-state lithium-sulfur batteries based on nano-confined LiBH4in mesoporous silica as solid electrolytes. The nano-confined LiBH4has fast ionic lithium conductivity at room temperature, 0.1 mScm-1, negligible electronic conductivity and its cationic transport

  6. Non-Flammable, High Voltage Electrolytes for Lithium Ion Batteries, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — An electrolyte will be demonstrated for lithium ion batteries with increased range of charge and discharge voltages and with improved fire safety. Experimental...

  7. High flash point electrolyte for use in lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Isken, P.; Dippel, C.; Schmitz, R.; Schmitz, R.W.; Kunze, M.; Passerini, S.; Winter, M. [Institute of Physical Chemistry, Westfaelische Wilhelms-University Muenster, Corrensstrasse 28/30, 48149 Muenster (Germany); Lex-Balducci, A., E-mail: a.lex-balducci@uni-muenster.de [Institute of Physical Chemistry, Westfaelische Wilhelms-University Muenster, Corrensstrasse 28/30, 48149 Muenster (Germany)

    2011-09-01

    Highlights: > Substitution of linear carbonates in conventional electrolytes with adiponitrile allows the realization of high flash point electrolytes. > EC:ADN based electrolytes display a higher anodic stability than a conventional electrolyte based on EC:DEC. > Graphite and NCM electrodes used in combination with the EC:ADN based electrolyte display a performance comparable with that of conventional electrolytes. - Abstract: The high flash point solvent adiponitrile (ADN) was investigated as co-solvent with ethylene carbonate (EC) for use as lithium-ion battery electrolyte. The flash point of this solvent mixture was more than 110 deg. C higher than that of conventional electrolyte solutions involving volatile linear carbonate components, such as diethyl carbonate (DEC) or dimethyl carbonate (DMC). The electrolyte based on EC:ADN (1:1 wt) with lithium tetrafluoroborate (LiBF{sub 4}) displayed a conductivity of 2.6 mS cm{sup -1} and no aluminum corrosion. In addition, it showed higher anodic stability on a Pt electrode than the standard electrolyte 1 M lithium hexafluorophosphate (LiPF{sub 6}) in EC:DEC (3:7 wt). Graphite/Li half cells using this electrolyte showed excellent rate capability up to 5C and good cycling stability (more than 98% capacity retention after 50 cycles at 1C). Additionally, the electrolyte was investigated in NCM/Li half cells. The cells were able to reach a capacity of 104 mAh g{sup -1} at 5C and capacity retention of more than 97% after 50 cycles. These results show that an electrolyte with a considerably increased flash point with respect to common electrolyte systems comprising linear carbonates, could be realized without any negative effects on the electrochemical performance in Li-half cells.

  8. Atomic layer deposition of lithium phosphates as solid-state electrolytes for all-solid-state microbatteries

    International Nuclear Information System (INIS)

    Wang, Biqiong; Liu, Jian; Sun, Qian; Li, Ruying; Sun, Xueliang; Sham, Tsun-Kong

    2014-01-01

    Atomic layer deposition (ALD) has been shown as a powerful technique to build three-dimensional (3D) all-solid-state microbattery, because of its unique advantages in fabricating uniform and pinhole-free thin films in 3D structures. The development of solid-state electrolyte by ALD is a crucial step to achieve the fabrication of 3D all-solid-state microbattery by ALD. In this work, lithium phosphate solid-state electrolytes were grown by ALD at four different temperatures (250, 275, 300, and 325 °C) using two precursors (lithium tert-butoxide and trimethylphosphate). A linear dependence of film thickness on ALD cycle number was observed and uniform growth was achieved at all four temperatures. The growth rate was 0.57, 0.66, 0.69, and 0.72 Å/cycle at deposition temperatures of 250, 275, 300, and 325 °C, respectively. Furthermore, x-ray photoelectron spectroscopy confirmed the compositions and chemical structures of lithium phosphates deposited by ALD. Moreover, the lithium phosphate thin films deposited at 300 °C presented the highest ionic conductivity of 1.73 × 10 −8 S cm −1 at 323 K with ∼0.51 eV activation energy based on the electrochemical impedance spectroscopy. The ionic conductivity was calculated to be 3.3 × 10 −8 S cm −1 at 26 °C (299 K). (paper)

  9. Designing Artificial Solid-Electrolyte Interphases for Single-Ion and High-Efficiency Transport in Batteries

    KAUST Repository

    Tu, Zhengyuan; Choudhury, Snehashis; Zachman, Michael J.; Wei, Shuya; Zhang, Kaihang; Kourkoutis, Lena F.; Archer, Lynden A.

    2017-01-01

    energy storage technologies. In lithium-ion batteries, electrolytes with single- or near-single-ion conductivity reduce losses caused by ion polarization. In emergent lithium or sodium metal batteries, they maintain high conductivity at the anode

  10. Modeling all-solid-state Li-ion batteries

    NARCIS (Netherlands)

    Danilov, D.; Niessen, R.A.H.; Notten, P.H.L.

    2011-01-01

    A mathematical model for all-solid-state Li-ion batteries is presented. The model includes the charge transfer kinetics at the electrode/electrolyte interface, diffusion of lithium in the intercalation electrode, and diffusion and migration of ions in the electrolyte. The model has been applied to

  11. Electrochemical performances of lithium ion battery using alkoxides of group 13 as electrolyte solvent

    International Nuclear Information System (INIS)

    Kaneko, Fuminari; Masuda, Yuki; Nakayama, Masanobu; Wakihara, Masataka

    2007-01-01

    Tris(methoxy polyethylenglycol) borate ester (B-PEG) and aluminum tris(polyethylenglycoxide) (Al-PEG) were used as electrolyte solvent for lithium ion battery, and the electrochemical property of these electrolytes were investigated. These electrolytes, especially B-PEG, showed poor electrochemical stability, leading to insufficient discharge capacity and rapid degradation with cycling. These observations would be ascribed to the decomposition of electrolyte, causing formation of unstable passive layer on the surface of electrode in lithium ion battery at high voltage. However, significant improvement was observed by the addition of aluminum phosphate (AlPO 4 ) powder into electrolyte solvent. AC impedance technique revealed that the increase of interfacial resistance of electrode/electrolyte during cycling was suppressed by adding AlPO 4 , and this suppression could enhance the cell capabilities. We infer that dissolved AlPO 4 components formed electrochemically stable layer on the surface of electrode

  12. Efficient Electrolytes for Lithium-Sulfur Batteries

    Directory of Open Access Journals (Sweden)

    Natarajan eAngulakshmi

    2015-05-01

    Full Text Available This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium-sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium-sulfur batteries. The electrolytes for lithium-sulfur batteries are broadly classified as (i non-aqueous liquid electrolytes, (ii ionic liquids, (iii solid polymer and (iv glass-ceramic electrolytes. This article presents the properties, advantages and limitations of each type of electrolytes. Also the importance of electrolyte additives on the electrochemical performance of Li-S cells is discussed.

  13. Ion-conducting lithium bis(oxalato)borate-based polymer electrolytes

    Czech Academy of Sciences Publication Activity Database

    Reiter, Jakub; Dominko, R.; Nádherná, Martina; Jakubec, Ivo

    2009-01-01

    Roč. 189, č. 1 (2009), s. 133-138 ISSN 0378-7753 R&D Projects: GA MŠk LC523; GA AV ČR KJB400320701 Institutional research plan: CEZ:AV0Z40320502 Keywords : polymer electrolyte * 2-ethoxyethyl methacrylate * lithium -ion battery Subject RIV: CG - Electrochemistry Impact factor: 3.792, year: 2009

  14. Current status of environmental, health, and safety issues of lithium ion electric vehicle batteries

    Energy Technology Data Exchange (ETDEWEB)

    Vimmerstedt, L.J.; Ring, S.; Hammel, C.J.

    1995-09-01

    The lithium ion system considered in this report uses lithium intercalation compounds as both positive and negative electrodes and has an organic liquid electrolyte. Oxides of nickel, cobalt, and manganese are used in the positive electrode, and carbon is used in the negative electrode. This report presents health and safety issues, environmental issues, and shipping requirements for lithium ion electric vehicle (EV) batteries. A lithium-based electrochemical system can, in theory, achieve higher energy density than systems using other elements. The lithium ion system is less reactive and more reliable than present lithium metal systems and has possible performance advantages over some lithium solid polymer electrolyte batteries. However, the possibility of electrolyte spills could be a disadvantage of a liquid electrolyte system compared to a solid electrolyte. The lithium ion system is a developing technology, so there is some uncertainty regarding which materials will be used in an EV-sized battery. This report reviews the materials presented in the open literature within the context of health and safety issues, considering intrinsic material hazards, mitigation of material hazards, and safety testing. Some possible lithium ion battery materials are toxic, carcinogenic, or could undergo chemical reactions that produce hazardous heat or gases. Toxic materials include lithium compounds, nickel compounds, arsenic compounds, and dimethoxyethane. Carcinogenic materials include nickel compounds, arsenic compounds, and (possibly) cobalt compounds, copper, and polypropylene. Lithiated negative electrode materials could be reactive. However, because information about the exact compounds that will be used in future batteries is proprietary, ongoing research will determine which specific hazards will apply.

  15. Gelled Electrolyte Containing Phosphonium Ionic Liquids for Lithium-Ion Batteries

    Directory of Open Access Journals (Sweden)

    Mélody Leclère

    2018-06-01

    Full Text Available In this work, new gelled electrolytes were prepared based on a mixture containing phosphonium ionic liquid (IL composed of trihexyl(tetradecylphosphonium cation combined with bis(trifluoromethanesulfonimide [TFSI] counter anions and lithium salt, confined in a host network made from an epoxy prepolymer and amine hardener. We have demonstrated that the addition of electrolyte plays a key role on the kinetics of polymerization but also on the final properties of epoxy networks, especially thermal, thermo-mechanical, transport, and electrochemical properties. Thus, polymer electrolytes with excellent thermal stability (>300 °C combined with good thermo-mechanical properties have been prepared. In addition, an ionic conductivity of 0.13 Ms·cm−1 at 100 °C was reached. Its electrochemical stability was 3.95 V vs. Li0/Li+ and the assembled cell consisting in Li|LiFePO4 exhibited stable cycle properties even after 30 cycles. These results highlight a promising gelled electrolyte for future lithium ion batteries.

  16. Degradation of the solid electrolyte interphase induced by the deposition of manganese ions

    Science.gov (United States)

    Shin, Hosop; Park, Jonghyun; Sastry, Ann Marie; Lu, Wei

    2015-06-01

    The deposition of manganese ions dissolved from the cathode onto the interface between the solid electrolyte interphase (SEI) and graphite causes severe capacity fading in manganese oxide-based cells. The evolution of the SEI layer containing these Mn compounds and the corresponding instability of the layer are thoroughly investigated by artificially introducing soluble Mn ions into a 1 mol L-1 LiPF6 electrolyte solution. Deposition of dissolved Mn ions induces an oxygen-rich SEI layer that results from increased electrolyte decomposition, accelerating SEI growth. The spatial distribution of Mn shows that dissolved Mn ions diffuse through the porous layer and are deposited mostly at the inorganic layer/graphite interface. The Mn compound deposited on the anode, identified as MnF2, originates from a metathesis reaction between LiF and dissolved Mn ion. It is confirmed that ion-exchange reaction occurs in the inorganic layer, converting SEI species to Mn compounds. Some of the Mn is observed inside the graphite; this may cause surface structural disordering in the graphite, limiting lithium-ion intercalation. The continuous reaction that occurs at the inorganic layer/graphite interfacial regions and the modification of the original SEI layer in the presence of Mn ions are critically related to capacity fade and impedance rise currently plaguing Li-ion cells.

  17. New Insights of Graphite Anode Stability in Rechargeable Batteries: Li-Ion Coordination Structures Prevail over Solid Electrolyte Interphases

    KAUST Repository

    Ming, Jun

    2018-01-04

    Graphite anodes are not stable in most noncarbonate solvents (e.g., ether, sulfoxide, sulfone) upon Li ion intercalation, known as an urgent issue in present Li ions and next-generation Li–S and Li–O2 batteries for storage of Li ions within the anode for safety features. The solid electrolyte interphase (SEI) is commonly believed to be decisive for stabilizing the graphite anode. However, here we find that the solvation structure of the Li ions, determined by the electrolyte composition including lithium salts, solvents, and additives, plays a more dominant role than SEI in graphite anode stability. The Li ion intercalation desired for battery operation competes with the undesired Li+–solvent co-insertion, leading to graphite exfoliation. The increase in organic lithium salt LiN(SO2CF3)2 concentration or, more effectively, the addition of LiNO3 lowers the interaction strength between Li+ and solvents, suppressing the graphite exfoliation caused by Li+–solvent co-insertion. Our findings refresh the knowledge of the well-known SEI for graphite stability in metal ion batteries and also provide new guidelines for electrolyte systems to achieve reliable and safe Li–S full batteries.

  18. Atomic scale imaging of structural changes in solid electrolyte lanthanum lithium niobate upon annealing

    International Nuclear Information System (INIS)

    Hu, Xiaobing; Fisher, Craig A.J.; Kobayashi, Shunsuke; Ikuhara, Yumi H.; Fujiwara, Yasuyuki; Hoshikawa, Keigo; Moriwake, Hiroki; Kohama, Keiichi; Iba, Hideki; Ikuhara, Yuichi

    2017-01-01

    La (1-x)/3 Li x NbO 3 (LLNbO) is a promising electrolyte material for solid-state lithium-ion batteries because it is stable in contact with Li metal and contains a high concentration of intrinsic Li-ion vacancies. One strategy for improving its ionic conductivity and making it more competitive with other solid-state Li-ion electrolytes is to disorder the Li-ion vacancies by appropriate post-synthesis heat treatment, e.g., annealing. In this study, we examine the effects of annealing on single crystals of LLNbO with Li contents x = 0.07 and 0.13 based on simultaneous atomic resolution high angle annular dark field and annular bright field imaging methods using state-of-the-art aberration corrected scanning transmission electron microscopes. It is found that La modulation within A1 layers of the cation-deficient layered perovskite structure becomes more diffuse after annealing. In addition, some La atoms move to A-site positions and O4 window positions in the nominally vacant A2 layer, while O atom columns in this layer become rumpled in the [001] p direction, indicating that the NbO 6 octahedra are more heavily distorted after annealing. The observed crystal structure differences between as-prepared and annealed single crystals explain the drop in Li-ion conductivities of LLNbO single crystals after heat treatment.

  19. PEO nanocomposite polymer electrolyte for solid state symmetric ...

    Indian Academy of Sciences (India)

    cells/supercapacitors) to electro-chromic displays, smart windows and ... electrolytes and their usage in lithium ion rechargeable solid state batteries are well .... the experimental plot using the Arrhenius relationship σ = σ0exp(−Ea/kT) where ...

  20. Polymer Electrolytes for Lithium/Sulfur Batteries

    Directory of Open Access Journals (Sweden)

    The Nam Long Doan

    2012-08-01

    Full Text Available This review evaluates the characteristics and advantages of employing polymer electrolytes in lithium/sulfur (Li/S batteries. The main highlights of this study constitute detailed information on the advanced developments for solid polymer electrolytes and gel polymer electrolytes, used in the lithium/sulfur battery. This includes an in-depth analysis conducted on the preparation and electrochemical characteristics of the Li/S batteries based on these polymer electrolytes.

  1. Conductivity studies of PEG based polymer electrolyte for applications as electrolyte in ion batteries

    Science.gov (United States)

    Patil, Ravikumar V.; Praveen, D.; Damle, R.

    2018-05-01

    Development of lithium ion batteries employing solid polymer electrolytes as electrolyte material has led to efficient energy storage and usage in many portable devices. However, due to a few drawbacks like lower ionic conductivity of solid polymer electrolytes (SPEs), studies on SPEs for improvement in conductivity still have a good scope. In the present paper, we report the conductivity studies of a new SPE with low molecular weight poly ethylene glycol (PEG) as host polymer in which a salt with larger anion Lithium trifluro methane sulphonate (LTMS). XRD studies have revealed that the salt completely dissociates in the polymer giving a good stable electrolyte at lower salt concentration. Conductivity of the SPEs has been studied as a function of temperature and we reiterate that the conductivity is a thermally activated process and follows Arrhenius type behavior.

  2. Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode–Electrolyte Interface in Lithium-Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Han [Chemical; Maglia, Filippo [BMW Group, Munich 80788, Germany; Lamp, Peter [BMW Group, Munich 80788, Germany; Amine, Khalil [Chemical; Chen, Zonghai [Chemical

    2017-12-13

    Current developments of electrolyte additives to stabilize electrode-electrolyte interface in Li-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a “corrosion inhibitor film” that prevents severely attack and passivation from protons that generated from the solvent oxidation, even the decomposition of solvent cannot not mitigated. Effect of three exemplary electrolyte additives: (i) lithium difluoro(oxalato)borate (LiDFOB); (ii) 3-hexylthiophene (3HT); and (iii) tris(hexafluoro-iso-propyl)phosphate (HFiP), on LiNi0.6Mn0.2Co0.2O2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next generation high-energy density lithium-ion chemistries.

  3. Electrolytes for Low Impedance, Wide Operating Temperature Range Lithium-Ion Battery Module

    Science.gov (United States)

    Hallac, Boutros (Inventor); Krause, Frederick C. (Inventor); Jiang, Junwei (Inventor); Smart, Marshall C. (Inventor); Metz, Bernhard M. (Inventor); Bugga, Ratnakumar V. (Inventor)

    2018-01-01

    A lithium ion battery cell includes a housing, a cathode disposed within the housing, wherein the cathode comprises a cathode active material, an anode disposed within the housing, wherein the anode comprises an anode active material, and an electrolyte disposed within the housing and in contact with the cathode and anode. The electrolyte consists essentially of a solvent mixture, a lithium salt in a concentration ranging from approximately 1.0 molar (M) to approximately 1.6 M, and an additive mixture. The solvent mixture includes a cyclic carbonate, an non-cyclic carbonate, and a linear ester. The additive mixture consists essentially of lithium difluoro(oxalato)borate (LiDFOB) in an amount ranging from approximately 0.5 weight percent to approximately 2.0 weight percent based on the weight of the electrolyte, and vinylene carbonate (VC) in an amount ranging from approximately 0.5 weight percent to approximately 2.0 weight percent based on the weight of the electrolyte.

  4. Pyrrolidinium-based ionic liquid electrolyte with organic additive and LiTFSI for high-safety lithium-ion batteries

    International Nuclear Information System (INIS)

    Yang, Binbin; Li, Cuihua; Zhou, Junhui; Liu, Jianhong; Zhang, Qianling

    2014-01-01

    Highlights: • New ionic liquid electrolytes composed by PYR 13 TFSI and EC/DMC-5%VC. • Mixed electrolyte for use in high-safety lithium-ion batteries. • LiTFSI concentration in IL electrolyte greatly affects the rate capability of the cell. • The optimal mixed electrolyte is ideal for applications at high temperature. - Abstract: In this paper, we report on the physicochemical properties of mixed electrolytes based on an ionic liquid N-propyl-N-methylpyrrolidiniumbis (trifluoromethanesulfonyl) imide (PYR 13 TFSI), organic additives, and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) for high safety lithium-ion batteries. The proposed optimal content of ionic liquid in the mixed electrolyte is 65 vol%, which results in non- flammability, high thermal stability, a wide electrochemical window of 4.8 V, low viscosity, low bulk resistance and the lowest interface resistance to lithium anode. The effects of the concentration of LiTFSI in the above electrolyte are critical to the rate performance of the LiFePO 4 -based battery. We have found the suitable LiTFSI concentration (0.3 M) for good capacity retention and rate capability

  5. Polycarbonate-based polyurethane as a polymer electrolyte matrix for all-solid-state lithium batteries

    Science.gov (United States)

    Bao, Junjie; Shi, Gaojian; Tao, Can; Wang, Chao; Zhu, Chen; Cheng, Liang; Qian, Gang; Chen, Chunhua

    2018-06-01

    Four kinds of polycarbonate-based polyurethane with 8-14 wt% hard segments content are synthesized via reactions of polycarbonatediol, hexamethylene diisocyanate and diethylene glycol. The mechanical strength of the polyurethanes increase with the increase of hard segments content. Solid polymer electrolytes composed of the polycarbonate-based polyurethanes and LiTFSI exhibits fascinating characteristics for all-solid-state lithium batteries with a high ionic conductivity of 1.12 × 10-4 S cm-1 at 80 °C, an electrochemical stability window up to 4.5 V (vs. Li+/Li), excellent mechanical strength and superior interfacial stability against lithium metal. The all-solid-state batteries using LiFePO4 cathode can deliver high discharge capacities (161, 158, 134 and 93 mAh g-1 at varied rates of 0.2, 0.5, 1 and 2 C) at 80 °C and excellent cycling performance (with 91% capacity retention after 600 cycles at 1 C). All the results indicate that such a polyurethane-based solid polymer electrolyte can be a promising candidate for all-solid-state lithium batteries.

  6. Measurement of lithium ion transference numbers of electrolytes for lithium-ion batteries. A comparative study with five various methods.; Messung von Lithium-Ionen Ueberfuehrungszahlen an Elektrolyten fuer Lithium-Ionen Batterien. Eine vergleichende Studie mit fuenf verschiedenen Methoden

    Energy Technology Data Exchange (ETDEWEB)

    Zugmann, Sandra

    2011-03-30

    Transference numbers are decisive transport properties to characterize electrolytes. They state the fraction of a certain species at charge transport and are defined by the ratio of current Ii that is transported by the ionic species i to the total current I. They are very important for lithium-ion batteries, because they give information about the real lithium transport and the efficiency of the battery. If the transference number has a too small value, for example, the lithium cannot be ''delivered'' fast enough in the discharge process. This can lead to precipitation of the salt at the anode and to depletion of the electrolyte at the cathode. Currently only a few adequate measurement methods for non-aqueous lithium electrolytes exist. The aim of this work was the installation of measurement devices and the comparison of different methods of transference numbers for electrolytes in lithium-ion batteries. The advantages and disadvantages for every method should be analyzed and transference numbers of new electrolyte be measured. In this work a detailed comparison of different methods with electrochemical and spectroscopic factors was presented for the first time. The galvanostatic polarization, the potentiostatic polarization, the emf method, the determination by NMR and the determination by conductivity measurements were tested for their practical application and used for different lithium salts in several solvents. The results show clearly that the assumptions made for every method affect the measured transference number a lot. They can have different values depending on the used method and the concentration dependence can even have contrary tendencies for methods with electrochemical or spectroscopic aspects. The influence of ion pairs is the determining factor at the measurements. For a full characterization of electrolytes a complete set of transport parameters is necessary, including diffusion coefficients, conductivity, transference number and ideally

  7. Measurement of lithium ion transference numbers of electrolytes for lithium-ion batteries. A comparative study with five various methods.; Messung von Lithium-Ionen Ueberfuehrungszahlen an Elektrolyten fuer Lithium-Ionen Batterien. Eine vergleichende Studie mit fuenf verschiedenen Methoden

    Energy Technology Data Exchange (ETDEWEB)

    Zugmann, Sandra

    2011-03-30

    Transference numbers are decisive transport properties to characterize electrolytes. They state the fraction of a certain species at charge transport and are defined by the ratio of current Ii that is transported by the ionic species i to the total current I. They are very important for lithium-ion batteries, because they give information about the real lithium transport and the efficiency of the battery. If the transference number has a too small value, for example, the lithium cannot be ''delivered'' fast enough in the discharge process. This can lead to precipitation of the salt at the anode and to depletion of the electrolyte at the cathode. Currently only a few adequate measurement methods for non-aqueous lithium electrolytes exist. The aim of this work was the installation of measurement devices and the comparison of different methods of transference numbers for electrolytes in lithium-ion batteries. The advantages and disadvantages for every method should be analyzed and transference numbers of new electrolyte be measured. In this work a detailed comparison of different methods with electrochemical and spectroscopic factors was presented for the first time. The galvanostatic polarization, the potentiostatic polarization, the emf method, the determination by NMR and the determination by conductivity measurements were tested for their practical application and used for different lithium salts in several solvents. The results show clearly that the assumptions made for every method affect the measured transference number a lot. They can have different values depending on the used method and the concentration dependence can even have contrary tendencies for methods with electrochemical or spectroscopic aspects. The influence of ion pairs is the determining factor at the measurements. For a full characterization of electrolytes a complete set of transport parameters is necessary, including diffusion coefficients, conductivity, transference

  8. Solid polymer electrolyte on the basis of polyethylene carbonate-lithium perchlorate system

    International Nuclear Information System (INIS)

    Dukhanin, G.P.; Dumler, S.A.; Sablin, A.N.; Novakov, I.A.

    2009-01-01

    Reaction in the system polyethylene carbonate-lithium perchlorate was investigated by IR spectroscopy, differential thermal and X-ray structural analyses. Specific electric conductivity of the prepared composition has been measured. Solid polymer electrolytes on the basis of polyethylene carbonate have conducting properties as electrolytes on the basis of unmodified polyethylene oxide. Compositions of polyethylene carbonate : LiClO 4 =10 : 1Al 2 O 3 -ZrO 2 possess maximum value of electrical conductivity. Activation energies of the process is calculated for all investigated compositions, and dependence of these values from concentration of lithium perchlorate is established

  9. Nanoconfined LiBH4 as a Fast Lithium Ion Conductor

    DEFF Research Database (Denmark)

    Blanchard, Didier; Nale, Angeloclaudio; Sveinbjörnsson, Dadi Þorsteinn

    2015-01-01

    is associated with a fraction of the confined borohydride that shows no phase transition, and most likely located close to the interface with the SiO2 pore walls. These results point to a new strategy to design low-temperature ion conducting solids for application in all solid-state lithium ion batteries, which......Designing new functional materials is crucial for the development of efficient energy storage and conversion devices such as all solid-state batteries. LiBH 4 is a promising solid electrolyte for Li-ion batteries. It displays high lithium mobility, although only above 110 °C at which a transition...

  10. Lithium and sodium batteries with polysulfide electrolyte

    KAUST Repository

    Li, Mengliu

    2017-12-28

    A battery comprising: at least one cathode, at least one anode, at least one battery separator, and at least one electrolyte disposed in the separator, wherein the anode is a lithium metal or lithium alloy anode or an anode adapted for intercalation of lithium ion, wherein the cathode comprises material adapted for reversible lithium extraction from and insertion into the cathode, and wherein the separator comprises at least one porous, electronically conductive layer and at least one insulating layer, and wherein the electrolyte comprises at least one polysulfide anion. The battery provides for high energy density and capacity. A redox species is introduced into the electrolyte which creates a hybrid battery. Sodium metal and sodium-ion batteries also provided.

  11. Solid polymer electrolyte from phosphorylated chitosan

    Energy Technology Data Exchange (ETDEWEB)

    Fauzi, Iqbal, E-mail: arcana@chem.itb.ac.id; Arcana, I Made, E-mail: arcana@chem.itb.ac.id [Inorganic and Physical Chemistry Research Groups, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia)

    2014-03-24

    Recently, the need of secondary battery application continues to increase. The secondary battery which using a liquid electrolyte was indicated had some weakness. A solid polymer electrolyte is an alternative electrolytes membrane which developed in order to replace the liquid electrolyte type. In the present study, the effect of phosphorylation on to polymer electrolyte membrane which synthesized from chitosan and lithium perchlorate salts was investigated. The effect of the component’s composition respectively on the properties of polymer electrolyte, was carried out by analyzed of it’s characterization such as functional groups, ion conductivity, and thermal properties. The mechanical properties i.e tensile resistance and the morphology structure of membrane surface were determined. The phosphorylation processing of polymer electrolyte membrane of chitosan and lithium perchlorate was conducted by immersing with phosphoric acid for 2 hours, and then irradiated on a microwave for 60 seconds. The degree of deacetylation of chitosan derived from shrimp shells was obtained around 75.4%. Relative molecular mass of chitosan was obtained by viscometry method is 796,792 g/mol. The ionic conductivity of chitosan membrane was increase from 6.33 × 10{sup −6} S/cm up to 6.01 × 10{sup −4} S/cm after adding by 15 % solution of lithium perchlorate. After phosphorylation, the ionic conductivity of phosphorylated lithium chitosan membrane was observed 1.37 × 10{sup −3} S/cm, while the tensile resistance of 40.2 MPa with a better thermal resistance. On the strength of electrolyte membrane properties, this polymer electrolyte membrane was suggested had one potential used for polymer electrolyte in field of lithium battery applications.

  12. Comparative study of polymer matrices for gelled electrolytes of lithium batteries; Etude comparative de matrices polymeres pour electrolytes gelifies de batteries au lithium

    Energy Technology Data Exchange (ETDEWEB)

    Du Pasquier, A.; Sarrazin, C.; Fauvarque, J.F. [CNAM, 75 - Paris (France); Andrieu, X. [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

    1996-12-31

    A solid electrolyte for lithium batteries requires several properties: a good ionic conductivity of about 10{sup -3} S/cm at 298 deg. K, a high cationic transport number (greater than 0.5), a redox stability window higher than 4.5 V, a good stability of the interface with the lithium electrode, and a sufficient mechanical stability. The family of gelled or hybrid electrolytes seems to meet all these requirements. Thus, a systematic study of the gelling of an ethylene carbonate and lithium bistrifluorosulfonimide (LiTFSI) based electrolyte has been carried out. The polymers used for gel or pseudo-gel synthesis are POE, PMMA and PAN which represent 3 different cases of interaction with the electrolyte. All the properties mentioned above have been studied according to the nature of the polymer and to the concentration of lithium salt, showing the advantages and drawbacks of each polymer. The possibility of using some of these gels in lithium-ion batteries has been tested by lithium intercalation tests in UF2 graphite at the C/10 regime and by the cycling of LiCoO{sub 2}/UF{sub 2} batteries at the C/5 regime. Interesting performances have been obtained on Li/PPy batteries which can operate at the 7.5 C regime. (J.S.)

  13. Comparative study of polymer matrices for gelled electrolytes of lithium batteries; Etude comparative de matrices polymeres pour electrolytes gelifies de batteries au lithium

    Energy Technology Data Exchange (ETDEWEB)

    Du Pasquier, A; Sarrazin, C; Fauvarque, J F [CNAM, 75 - Paris (France); Andrieu, X [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

    1997-12-31

    A solid electrolyte for lithium batteries requires several properties: a good ionic conductivity of about 10{sup -3} S/cm at 298 deg. K, a high cationic transport number (greater than 0.5), a redox stability window higher than 4.5 V, a good stability of the interface with the lithium electrode, and a sufficient mechanical stability. The family of gelled or hybrid electrolytes seems to meet all these requirements. Thus, a systematic study of the gelling of an ethylene carbonate and lithium bistrifluorosulfonimide (LiTFSI) based electrolyte has been carried out. The polymers used for gel or pseudo-gel synthesis are POE, PMMA and PAN which represent 3 different cases of interaction with the electrolyte. All the properties mentioned above have been studied according to the nature of the polymer and to the concentration of lithium salt, showing the advantages and drawbacks of each polymer. The possibility of using some of these gels in lithium-ion batteries has been tested by lithium intercalation tests in UF2 graphite at the C/10 regime and by the cycling of LiCoO{sub 2}/UF{sub 2} batteries at the C/5 regime. Interesting performances have been obtained on Li/PPy batteries which can operate at the 7.5 C regime. (J.S.)

  14. Li-ion site disorder driven superionic conductivity in solid electrolytes: a first-principles investigation of β-Li3PS4

    International Nuclear Information System (INIS)

    Phani Dathar, Gopi Krishna; Balachandran, Janakiraman; Kent, Paul R. C.; Rondinone, Adam J.; Ganesh, P.

    2016-01-01

    The attractive safety and long-term stability of all solid-state batteries has added a new impetus to the discovery and development of solid electrolytes for lithium batteries. Recently several superionic lithium conducting solid electrolytes have been discovered. All the superionic lithium containing compounds (β-Li 3 PS 4 and Li 10 GeP 2 S 12 and oxides, predominantly in the garnet phase) have partially occupied sites. This naturally begs the question of understanding the role of partial site occupancies (or site disorder) in optimizing ionic conductivity in these family of solids. In this paper, we find that for a given topology of the host lattice, maximizing the number of sites with similar Li-ion adsorption energies, which gives partial site occupancy, is a natural way to increase the configurational entropy of the system and optimize the conductivity. For a given topology and density of Li-ion adsorption sites, the ionic conductivity is maximal when the number of mobile Li-ions are equal to the number of mobile vacancies, also the very condition for achieving maximal configurational entropy. We demonstrate applicability of this principle by elucidating the role of Li-ion site disorder and the local chemical environment in the high ionic conductivity of β-Li 3 PS 4 . In addition, for β-Li 3 PS 4 we find that a significant density of vacancies in the Li-ion sub-lattice (~25%) leads to sub-lattice melting at (~600 K) leading to a molten form for the Li-ions in an otherwise solid anionic host. This gives a lithium site occupancy that is similar to what is measured experimentally. We further show that quenching this disorder can improve conductivity at lower temperatures. As a consequence, we discover that (a) one can optimize ionic conductivity in a given topology by choosing a chemistry/composition that maximizes the number of mobile-carriers i.e. maximizing both mobile Li-ions and vacancies, and (b) when the concentration of vacancies becomes significant in

  15. Wide-Temperature Electrolytes for Lithium-Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Li, Qiuyan; Jiao, Shuhong; Luo, Langli; Ding, Michael S.; Zheng, Jianming; Cartmell, Samuel S.; Wang, Chong-Min; Xu, Kang; Zhang, Ji-Guang; Xu, Wu

    2017-05-26

    Formulating electrolytes with solvents of low freezing points and high dielectric constants is a direct approach to extend the service temperature range of lithium (Li)-ion batteries (LIBs), for which propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl butyrate (MB) are excellent candidates. In this work, we report such low temperature electrolyte formulations by optimizing the content of ethylene carbonate (EC) in the EC-PC-EMC ternary solvent system with LiPF6 salt and CsPF6 additive. An extended service temperature range from 40°C to 60°C was obtained in LIBs with lithium nickel cobalt aluminum mixed oxide (LiNi0.80Co0.15Al0.05O2, NCA) as cathode and graphite as anode. The discharge capacities at low temperatures and the cycle life at room and elevated temperatures were systematically investigated in association with the ionic conductivity and phase transition behaviors. The most promising electrolyte formulation was identified as 1.0 M LiPF6 in EC-PC-EMC (1:1:8 by wt.) with 0.05 M CsPF6, which was demonstrated in both coin cells of graphite||NCA and 1 Ah pouch cells of graphite||LiNi1/3Mn1/3Co1/3O2. This optimized electrolyte enables excellent wide-temperature performances, as evidenced by the 68% capacity retention at 40C and C/5 rate, and nearly identical stable cycle life at room and elevated temperatures up to 60C.

  16. Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

    Science.gov (United States)

    Smart, Marshall C. (Inventor); Bugga, Ratnakumar V. (Inventor); Surampudi, Subbarao (Inventor); Huang, Chen-Kuo (Inventor)

    2002-01-01

    Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

  17. Single-ion conducting diblock terpolymers for lithium-ion batteries

    Science.gov (United States)

    Morris, Melody; Epps, Thomas H., III

    Block polymer (BP) electrolytes provide an attractive route to overcome the competing constraints of high conductivity and mechanical/thermal stability in lithium-ion batteries through nanoscale self-assembly. For example, macromolecules can be engineered such that one domain conducts lithium ions and the other prevents lithium dendrite formation. Herein, we report on the behavior of a single-ion conducting BP electrolyte that was designed to facilitate the transport of lithium ions. These polymers differ from traditional salt-doped BP electrolytes, which require the addition of a lithium salt to bestow conductivity and typically suffer from substantial counterion motion that reduces efficiency. New single-ion BPs were synthesized, and the nanoscale morphologies were determined using small angle X-ray scattering and transmission electron microscopy. Electrolyte performance was measured using AC impedance spectroscopy and DC polarization, and the results were correlated to nanoscale morphology and ion content. Enhanced physical understanding of single-ion BPs was gained by connecting the ion mobility to the chemistry, chain structure, and ion content of the single-ion BP. These studies can be applied to other charged-neutral block polymers to elucidate the effects of ion content on self-assembly and macroscopic properties.

  18. Preparation of poly(acrylonitrile-butyl acrylate) gel electrolyte for lithium-ion batteries

    International Nuclear Information System (INIS)

    Tian Zheng; He Xiangming; Pu Weihua; Wan Chunrong; Jiang Changyin

    2006-01-01

    Poly(acrylonitrile-butyl acrylate) gel polymer electrolyte was prepared for lithium ion batteries. The preparation started with synthesis of poly(acrylonitrile-butyl acrylate) by radical emulsion polymerization, followed by phase inversion to produce microporous membrane. Then, the microporous gel polymer electrolytes (MGPEs) was prepared with the microporous membrane and LiPF 6 in ethylene carbonate/diethyl carbonate. The dry microporous membrane showed a fracture strength as high as 18.98 MPa. As-prepared gel polymer electrolytes presented ionic conductivity in excess of 3.0 x 10 -3 S cm -1 at ambient temperature and a decomposition voltage over 6.6 V. The results showed that the as-prepared gel polymer electrolytes were promising materials for Li-ion batteries

  19. Ultrashort pulsed laser ablation for decollation of solid state lithium-ion batteries

    Science.gov (United States)

    Hördemann, C.; Anand, H.; Gillner, A.

    2017-08-01

    Rechargeable lithium-ion batteries with liquid electrolytes are the main energy source for many electronic devices that we use in our everyday lives. However, one of the main drawbacks of this energy storage technology is the use of liquid electrolyte, which can be hazardous to the user as well as the environment. Moreover, lithium-ion batteries are limited in voltage, energy density and operating temperature range. One of the most novel and promising battery technologies available to overcome the above-mentioned drawbacks is the Solid-State Lithium-Ion Battery (SSLB). This battery type can be produced without limitations to the geometry and is also bendable, which is not possible with conventional batteries1 . Additionally, SSLBs are characterized by high volumetric and gravimetric energy density and are intrinsically safe since no liquid electrolyte is used2-4. Nevertheless, the manufacturing costs of these batteries are still high. The existing production-technologies are comparable to the processes used in the semiconductor industry and single cells are produced in batches with masked-deposition at low deposition rates. In order to decrease manufacturing costs and to move towards continuous production, Roll2Roll production methods are being proposed5, 6. These methods offer the possibility of producing large quantities of substrates with deposited SSLB-layers. From this coated substrate, single cells can be cut out. For the flexible decollation of SSLB-cells from the substrate, new manufacturing technologies have to be developed since blade-cutting, punching or conventional laser-cutting processes lead to short circuiting between the layers. Here, ultra-short pulsed laser ablation and cutting allows the flexible decollation of SSLBs. Through selective ablation of individual layers, an area for the cutting kerf is prepared to ensure a shortcut-free decollation.

  20. Current limit diagrams for dendrite formation in solid-state electrolytes for Li-ion batteries

    Science.gov (United States)

    Raj, R.; Wolfenstine, J.

    2017-03-01

    We build upon the concept that nucleation of lithium dendrites at the lithium anode-solid state electrolyte interface is instigated by the higher resistance of grain boundaries that raises the local electro-chemical potential of lithium, near the lithium-electrode. This excess electro-chemo-mechanical potential, however, is reduced by the mechanical back stress generated when the dendrite is formed within the electrolyte. These parameters are coalesced into an analytical model that prescribes a specific criterion for dendrite formation. The results are presented in the form of current limit diagrams that show the "safe" and "fail" regimes for battery function. A higher conductivity of the electrolyte can reduce dendrite formation.

  1. Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries

    Science.gov (United States)

    Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won

    2016-01-01

    Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842

  2. Designing Artificial Solid-Electrolyte Interphases for Single-Ion and High-Efficiency Transport in Batteries

    KAUST Repository

    Tu, Zhengyuan

    2017-09-21

    Substrates able to rectify transport of ions based on charge and/or size are ubiquitous in biological systems. Electrolytes and interphases that selectively transport electrochemically active ions are likewise of broad interest in all electrical energy storage technologies. In lithium-ion batteries, electrolytes with single- or near-single-ion conductivity reduce losses caused by ion polarization. In emergent lithium or sodium metal batteries, they maintain high conductivity at the anode and stabilize metal deposition by fundamental mechanisms. We report that 20- to 300-nm-thick, single-ion-conducting membranes deposited at the anode enable electrolytes with the highest combination of cation transference number, ionic conductivity, and electrochemical stability reported. By means of direct visualization we find that single-ion membranes also reduce dendritic deposition of Li in liquids. Galvanostatic measurements further show that the electrolytes facilitate long (3 mAh) recharge of full Li/LiNi0.8Co0.15Al0.05O2 (NCA) cells with high cathode loadings (3 mAh cm−2/19.9 mg cm−2) and at high current densities (3 mA cm−2).

  3. The effects of LiBOB additive for stable SEI formation of PP13TFSI-organic mixed electrolyte in lithium ion batteries

    International Nuclear Information System (INIS)

    An Yongxin; Zuo Pengjian; Cheng Xinqun; Liao Lixia; Yin Geping

    2011-01-01

    Highlights: → LiBOB as the additive of SEI formation. → LiBOB containing mixed electrolyte shows well thermal stability and safety. → LiBOB improves the electrochemical performance of PP13TFSI-organic mixture. - Abstract: A safe electrolyte system is prepared from N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP13TFSI), organic electrolyte (1 mol L -1 LiPF 6 /EC-DEC) and lithium bis (oxalato) borate (LiBOB). The additive of LiBOB enhances the stability of interface between electrolyte and anode. The LiBOB-containing mixed electrolytes show non-flammability and good compatibility with active materials. The performance of anode for lithium ion battery is successfully improved by LiBOB-containing mixed electrolytes, which shows 200 mA h g -1 reversible capacities at 0.3 C rate. The ionic conductivity and the lithium ion transference number in LiBOB-containing mixed electrolytes system also suits to application for lithium ion battery.

  4. Nanostructured electrolytes for stable lithium electrodeposition in secondary batteries.

    Science.gov (United States)

    Tu, Zhengyuan; Nath, Pooja; Lu, Yingying; Tikekar, Mukul D; Archer, Lynden A

    2015-11-17

    Secondary batteries based on lithium are the most important energy storage technology for contemporary portable devices. The lithium ion battery (LIB) in widespread commercial use today is a compromise technology. It compromises high energy, high power, and design flexibility for long cell operating lifetimes and safety. Materials science, transport phenomena, and electrochemistry in the electrodes and electrolyte that constitute such batteries are areas of active study worldwide because significant improvements in storage capacity and cell lifetime are required to meet new demands, including the electrification of transportation and for powering emerging autonomous aircraft and robotics technologies. By replacing the carbonaceous host material used as the anode in an LIB with metallic lithium, rechargeable lithium metal batteries (LMBs) with higher storage capacity and compatibility with low-cost, high-energy, unlithiated cathodes such as sulfur, manganese dioxide, carbon dioxide, and oxygen become possible. Large-scale, commercial deployment of LMBs are today limited by safety concerns associated with unstable electrodeposition and lithium dendrite formation during cell recharge. LMBs are also limited by low cell operating lifetimes due to parasitic chemical reactions between the electrode and electrolyte. These concerns are greater in rechargeable batteries that utilize other, more earth abundant metals such as sodium and to some extent even aluminum. Inspired by early theoretical works, various strategies have been proposed for alleviating dendrite proliferation in LMBs. A commonly held view among these early studies is that a high modulus, solid-state electrolyte that facilitates fast ion transport, is nonflammable, and presents a strong-enough physical barrier to dendrite growth is a requirement for any commercial LMB. Unfortunately, poor room-temperature ionic conductivity, challenging processing, and the high cost of ceramic electrolytes that meet the

  5. Preparation of poly(acrylonitrile-butyl acrylate) gel electrolyte for lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Tian Zheng [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); He Xiangming [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China)]. E-mail: hexm@tsinghua.edu.cn; Pu Weihua [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Wan Chunrong [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Jiang Changyin [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China)

    2006-10-25

    Poly(acrylonitrile-butyl acrylate) gel polymer electrolyte was prepared for lithium ion batteries. The preparation started with synthesis of poly(acrylonitrile-butyl acrylate) by radical emulsion polymerization, followed by phase inversion to produce microporous membrane. Then, the microporous gel polymer electrolytes (MGPEs) was prepared with the microporous membrane and LiPF{sub 6} in ethylene carbonate/diethyl carbonate. The dry microporous membrane showed a fracture strength as high as 18.98 MPa. As-prepared gel polymer electrolytes presented ionic conductivity in excess of 3.0 x 10{sup -3} S cm{sup -1} at ambient temperature and a decomposition voltage over 6.6 V. The results showed that the as-prepared gel polymer electrolytes were promising materials for Li-ion batteries.

  6. Electrospun polyimide-based fiber membranes as polymer electrolytes for lithium-ion batteries

    International Nuclear Information System (INIS)

    Wang, Qiujun; Song, Wei-Li; Wang, Luning; Song, Yu; Shi, Qiao; Fan, Li-Zhen

    2014-01-01

    Polymer electrolytes based on electrospun polyimide (PI) membranes are incorporated with electrolyte solution containing 1 mol L −1 LiPF 6 /ethylene carbonate/ethylmethyl carbonate/dimethyl carbonate to examine their potential application for lithium ion batteries. The as-electrospun non-woven membranes demonstrate a uniformly interconnected structure with an average fiber diameter of 800 nm. The membranes, showing superior thermal stability and flame retardant property compared to the commercial Celgard® membranes, exhibit high porosity and high uptake when activated with the liquid electrolyte. The resulting PI electrolytes (PIs) have a high ionic conductivity up to 2.0 × 10 −3 S cm −1 at 25 °C, and exhibit a high electrochemical stability potential more than 5.0 V (vs. Li/Li + ). They also possess excellent charge/discharge performance and capacity retention. The initial discharge capacities of the Li/PIs/Li 4 Ti 5 O 12 cells are 178.4, 167.4, 160.3, 148.3 and 135.9 mAh g −1 at the charge/discharge rates of 0.2 C, 1 C, 2 C, 5 C and 10 C, respectively. After 200 cycles at 5 C, a capacity around ∼146.8 mAh g −1 can be still achieved. The PI-based polymer electrolytes with strong mechanical properties and good electrochemical performance are proved to be promising electrolytes for lithium ion batteries

  7. PC based electrolytes with LiDFOB as an alternative salt for lithium-ion batteries

    Science.gov (United States)

    Knight, Brandon M.

    Lithium-ion batteries (LIBs) have been greatly sought after as a source of renewable energy storage. LIBs have a wide range of applications including but not limited portable electronic devices, electric vehicles, and power tools. As a direct result of their commercial viability an insatiable hunger for knowledge, advancement within the field of LIBs has been omnipresent for the last two decades. However, there are set backs evident within the LIB field; most notably the limitations of standard electrolyte formulations and LiPF6 lithium salt. The standard primary carbonate of ethylene carbonate (EC) has a very limited operating range due to its innate physical properties, and the LiPF6 salt is known to readily decompose to form HF which can further degrade LIB longevity. The goal of our research is to explore the use of a new primary salt LiDFOB in conjunction with a propylene carbonate based electrolyte to establish a more flexible electrolyte formulation by constructing coin cells and cycling them under various conditions to give a clear understanding of each formulation inherent performance capabilities. Our studies show that 1.2M LiDFOB in 3:7 PC/EMC + 1.5% VC is capable of performing comparably to the standard 1.2M LiPF6 in 3:7 EC/EMC at 25°C and the PC electrolyte also illustrates performance superior to the standard at 55°C. The degradation of lithium manganese spinel electrodes, including LiNi 0.5Mn1.5O4, is an area of great concern within the field of lithium ion batteries (LIBs). Manganese containing cathode materials frequently have problems associated with Mn dissolution which significantly reduces the cycle life of LIB. Thus the stability of the cathode material is paramount to the performance of Mn spinel cathode materials in LIBs. In an effort to gain a better understanding of the stability of LiNi0.5 Mn1.5O4 in common LiPF6/carbonate electrolytes, samples were stored at elevated temperature in the presence of electrolyte. Then after storage both

  8. Nonflammable perfluoropolyether-based electrolytes for lithium batteries

    Science.gov (United States)

    Wong, Dominica H. C.; Thelen, Jacob L.; Fu, Yanbao; Devaux, Didier; Pandya, Ashish A.; Battaglia, Vincent S.; Balsara, Nitash P.; DeSimone, Joseph M.

    2014-01-01

    The flammability of conventional alkyl carbonate electrolytes hinders the integration of large-scale lithium-ion batteries in transportation and grid storage applications. In this study, we have prepared a unique nonflammable electrolyte composed of low molecular weight perfluoropolyethers and bis(trifluoromethane)sulfonimide lithium salt. These electrolytes exhibit thermal stability beyond 200 °C and a remarkably high transference number of at least 0.91 (more than double that of conventional electrolytes). Li/LiNi1/3Co1/3Mn1/3O2 cells made with this electrolyte show good performance in galvanostatic cycling, confirming their potential as rechargeable lithium batteries with enhanced safety and longevity. PMID:24516123

  9. Solid state electrolyte composites based on complex hydrides and metal doped fullerenes/fulleranes for batteries and electrochemical applications

    Science.gov (United States)

    Zidan, Ragaiy; Teprovich, Jr., Joseph A.; Colon-Mercado, Hector R.; Greenway, Scott D.

    2018-05-01

    A LiBH4--C60 nanocomposite that displays fast lithium ionic conduction in the solid state is provided. The material is a homogenous nanocomposite that contains both LiBH4 and a hydrogenated fullerene species. In the presence of C60, the lithium ion mobility of LiBH4 is significantly enhanced in the as prepared state when compared to pure LiBH4. After the material is annealed the lithium ion mobility is further enhanced. Constant current cycling demonstrated that the material is stable in the presence of metallic lithium electrodes. The material can serve as a solid state electrolyte in a solid-state lithium ion battery.

  10. Methods for using atomic layer deposition to produce a film for solid state electrolytes and protective electrode coatings for lithium batteries

    Science.gov (United States)

    Elam, Jeffrey W.; Meng, Xiangbo

    2018-03-13

    A method for using atomic layer deposition to produce a film configured for use in an anode, cathode, or solid state electrolyte of a lithium-ion battery or a lithium-sulfur battery. The method includes repeating a cycle for a predetermined number of times in an inert atmosphere. The cycle includes exposing a substrate to a first precursor, purging the substrate with inert gas, exposing the substrate to a second precursor, and purging the substrate with inert gas. The film is a metal sulfide.

  11. Improvement of lithium-ion battery performance at low temperature by adopting polydimethylsiloxane-based electrolyte additives

    International Nuclear Information System (INIS)

    Kim, Kwang Man; Ly, Nguyen Vu; Won, Jung Ha; Lee, Young-Gi; Cho, Won Il; Ko, Jang Myoun; Kaner, Richard B.

    2014-01-01

    Three kinds of polydimethylsiloxane (PDMS)-based grafted and ungrafted copolymers such as poly[dimethylsiloxane-co-(siloxane-g-acrylate)] (PDMS-A), poly(dimethylsiloxane-co-phenylsiloxane) (PDMS-P), and poly[dimethylsiloxane-co-(siloxane-g-ethylene oxide)] (PDMS-EO) are used as additives to standard liquid electrolyte solutions to enhance the lithium-ion battery performance at low temperatures. Liquid electrolyte solutions with PDMS-based additives are electrochemically stable under 5.0 V and have adequate ionic conductivities of 10 −4 S cm −1 at -20 °C. Particularly, liquid electrolytes with PDMS-P and PDMS-EO exhibit higher ionic conductivities of around 5 × 10 −4 S cm −1 at -20 °C, indicating a specific resisting property against the freezing of the liquid electrolyte components. As a result, the addition of PDMS-based additives to liquid electrolytes improves the capacity retention ratio and rate-capability of lithium-ion batteries at low temperatures

  12. Analysis of the Deposit Layer from Electrolyte Side Reaction on the Anode of the Pouch Type Lithium Ion Polymer Batteries: The Effect of State of Charge and Charge Rate

    International Nuclear Information System (INIS)

    Agubra, Victor A.; Fergus, Jeffrey W.; Fu, Rujian; Choe, Song-yul

    2014-01-01

    Highlights: • Raising the battery cycling potential increased the rate of side reaction. • Growth of deposit layer thickness at the electrode/electrolyte interface at high SOC. • A significant amount of lithium was consumed in forming the deposit layer. • Some of the lithium were “trapped” in the graphite after the discharge cycle. - Abstract: The formation of the solid electrolyte interface (SEI) layer on the surface of the anode electrode of a lithium ion battery prevents further electrolyte decomposition reaction. However, at certain battery operating conditions, the SEI breakdown leading to more electrolyte decomposition reactions that form several species on the anode electrode surface. This paper focuses on the effect of battery potential and charge rate on the decomposition side reaction on the anode electrode of a lithium ion polymer battery, as a result of the breakdown of the SEI layer. The results from this study indicate that raising the state of charge (SOC) increases the rate of the electrolyte decomposition side reaction that resulted in formation of a thick deposit layer at the electrolyte/electrolyte interface. This deposit layer contains lithium that can no longer participate in the reversible electrochemical reaction. In addition, at high cycling potential and charge rates the amount of lithium in the graphite after complete cell discharge increased due to the entrapment of lithium in the graphite. The amount of irreversible capacity loss for the batteries cycled at high potential and current correlates with the amount of trapped lithium in the graphite and the growth of the deposit layer thickness at the electrode/electrolyte interface

  13. Redox Species-Based Electrolytes for Advanced Rechargeable Lithium Ion Batteries

    KAUST Repository

    Ming, Jun

    2016-08-15

    Seeking high-capacity cathodes has become an intensive effort in lithium ion battery research; however, the low energy density still remains a major issue for sustainable handheld devices and vehicles. Herein, we present a new strategy of integrating a redox species-based electrolyte in batteries to boost their performance. Taking the olivine LiFePO4-based battery as an example, the incorporation of redox species (i.e., polysulfide of Li2S8) in the electrolyte results in much lower polarization and superior stability, where the dissociated Li+/Sx2– can significantly speed up the lithium diffusion. More importantly, the presence of the S82–/S2– redox reaction further contributes extra capacity, making a completely new LiFePO4/Li2Sx hybrid battery with a high energy density of 1124 Wh kgcathode–1 and a capacity of 442 mAh gcathode–1. The marriage of appropriate redox species in an electrolyte for a rechargeable battery is an efficient and scalable approach for obtaining higher energy density storage devices.

  14. Synthesis and properties of new carboxyborate lithium salts as electrolytes for lithium-ion batteries

    International Nuclear Information System (INIS)

    Gładka, Dorota; Krajewski, Mariusz; Młynarska, Sandra; Galińska, Justyna; Zygadło-Monikowska, Ewa

    2017-01-01

    Bis(carboxytrifluoroborate lithium) salts [R(CH 2 COOBF 3 Li) 2 ] with oxyethylene groups R of oligomeric molar masses [R = O(CH 2 CH 2 O) n , where n = 3 or 11, BCB3 and BCB11, respectively] were synthesized via reaction of carboxylates salts with boron fluoride. The new salts were characterized by spectroscopic analysis. The physical properties of the salts were determined by oxyethylene chain length. For n = 3 the salt was crystalline with m p = 197 °C and for n = 11 it showed properties of an ionic liquid at ambient temperature. Their thermal stability was at least 250 °C. The values of lithium-ion transference numbers (T + ) of the solutions in polar aprotic solvents, determined by a well established steady-state technique, were in the range of 0.2–0.6. Electrochemical impedance spectroscopy analysis of solid polymer electrolytes (SPEs) based on PEO and studied salts with different concentration (from 24 to 94 wt %) was carried out. The ionic conductivity of SPEs was in the order of 10 −8 –10 −7 S cm −1 at room temperature and 10 −4 S cm −1 at 80 °C. A distinguishing feature of SPEs with the studied new salts is the high immobilization of anions, which causes almost a monoconducting character of charge transport. Lithium transference numbers (T + ) exceed 0.9.

  15. The Role of Sub- and Supercritical CO2 as "Processing Solvent" for the Recycling and Sample Preparation of Lithium Ion Battery Electrolytes.

    Science.gov (United States)

    Nowak, Sascha; Winter, Martin

    2017-03-06

    Quantitative electrolyte extraction from lithium ion batteries (LIB) is of great interest for recycling processes. Following the generally valid EU legal guidelines for the recycling of batteries, 50 wt % of a LIB cell has to be recovered, which cannot be achieved without the electrolyte; hence, the electrolyte represents a target component for the recycling of LIBs. Additionally, fluoride or fluorinated compounds, as inevitably present in LIB electrolytes, can hamper or even damage recycling processes in industry and have to be removed from the solid LIB parts, as well. Finally, extraction is a necessary tool for LIB electrolyte aging analysis as well as for post-mortem investigations in general, because a qualitative overview can already be achieved after a few minutes of extraction for well-aged, apparently "dry" LIB cells, where the electrolyte is deeply penetrated or even gellified in the solid battery materials.

  16. Enhanced cycling performance of a Li metal anode in a dimethylsulfoxide-based electrolyte using highly concentrated lithium salt for a lithium-oxygen battery

    Science.gov (United States)

    Togasaki, Norihiro; Momma, Toshiyuki; Osaka, Tetsuya

    2016-03-01

    Stable charge-discharge cycling behavior for a lithium metal anode in a dimethylsulfoxide (DMSO)-based electrolyte is strongly desired of lithium-oxygen batteries, because the Li anode is rapidly exhausted as a result of side reactions during cycling in the DMSO solution. Herein, we report a novel electrolyte design for enhancing the cycling performance of Li anodes by using a highly concentrated DMSO-based electrolyte with a specific Li salt. Lithium nitrate (LiNO3), which forms an inorganic compound (Li2O) instead of a soluble product (Li2S) on a lithium surface, exhibits a >20% higher coulombic efficiency than lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium perchlorate, regardless of the loading current density. Moreover, the stable cycling of Li anodes in DMSO-based electrolytes depends critically on the salt concentration. The highly concentrated electrolyte 4.0 M LiNO3/DMSO displays enhanced and stable cycling performance comparable to that of carbonate-based electrolytes, which had not previously been achieved. We suppose this enhancement is due to the absence of free DMSO solvent in the electrolyte and the promotion of the desolvation of Li ions on the solid electrolyte interphase surface, both being consequences of the unique structure of the electrolyte.

  17. Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries

    KAUST Repository

    Tu, Zhengyuan

    2015-11-17

    © 2015 American Chemical Society. ConspectusSecondary batteries based on lithium are the most important energy storage technology for contemporary portable devices. The lithium ion battery (LIB) in widespread commercial use today is a compromise technology. It compromises high energy, high power, and design flexibility for long cell operating lifetimes and safety. Materials science, transport phenomena, and electrochemistry in the electrodes and electrolyte that constitute such batteries are areas of active study worldwide because significant improvements in storage capacity and cell lifetime are required to meet new demands, including the electrification of transportation and for powering emerging autonomous aircraft and robotics technologies. By replacing the carbonaceous host material used as the anode in an LIB with metallic lithium, rechargeable lithium metal batteries (LMBs) with higher storage capacity and compatibility with low-cost, high-energy, unlithiated cathodes such as sulfur, manganese dioxide, carbon dioxide, and oxygen become possible. Large-scale, commercial deployment of LMBs are today limited by safety concerns associated with unstable electrodeposition and lithium dendrite formation during cell recharge. LMBs are also limited by low cell operating lifetimes due to parasitic chemical reactions between the electrode and electrolyte. These concerns are greater in rechargeable batteries that utilize other, more earth abundant metals such as sodium and to some extent even aluminum.Inspired by early theoretical works, various strategies have been proposed for alleviating dendrite proliferation in LMBs. A commonly held view among these early studies is that a high modulus, solid-state electrolyte that facilitates fast ion transport, is nonflammable, and presents a strong-enough physical barrier to dendrite growth is a requirement for any commercial LMB. Unfortunately, poor room-temperature ionic conductivity, challenging processing, and the high cost

  18. Chitosan-gold-Lithium nanocomposites as solid polymer electrolyte.

    Science.gov (United States)

    Begum, S N Suraiya; Pandian, Ramanathaswamy; Aswal, Vinod K; Ramasamy, Radha Perumal

    2014-08-01

    Lithium micro batteries are emerging field of research. For environmental safety biodegradable films are preferred. Recently biodegradable polymers have gained wide application in the field of solid polymer electrolytes. To make biodegradable polymers films plasticizers are usually used. However, use of plasticizers has disadvantages such as inhomogenities in phases and mechanical instability that will affect the performance of Lithium micro batteries. We have in this research used gold nanoparticles that are environmentally friendly, instead of plasticizers. Gold nanoparticles were directly template upon chitosan membranes by reduction process so as to enhance the interactions of Lithium with the polymer. In this article, for the first time the characteristics of Chitosan-gold-Lithium nanocomposite films are investigated. The films were prepared using simple solution casting technique. We have used various characterization tools such as Small Angle Neutron Scattering (SANS), XRD, FTIR, Raman, FESEM, and AFM, Light scattering, Dielectric and electrical conductivity measurements. Our investigations show that incorporation of gold results in enhancement of conductivity in Lithium containing Chitosan films. Also it affects the dielectric characteristics of the films. We conclude through various characterization tools that the enhancement in the conductivity was due to the retardation of crystal growth of lithium salt in the presence of gold nanoparticles. A model is proposed regarding the formation of the new nanocomposite. The conductivity of these biodegradable films is comparable to those of the current inorganic Lithium micro batteries. This new chitosan-Au-Li nanocomposite has potential applications in the field of Lithium micro batteries.

  19. Nitrile functionalized silyl ether with dissolved LiTFSI as new electrolyte solvent for lithium-ion batteries

    International Nuclear Information System (INIS)

    Pohl, Benjamin; Grünebaum, Mariano; Drews, Mathias; Passerini, Stefano; Winter, Martin; Wiemhöfer, Hans‑Dieter

    2015-01-01

    Highlights: • A new electrolyte based on a nitrile-silyl ether solvent and LiTFSI as lithium salt was successfully tested. • This electrolyte shows higher ionic conductivities as compared to earlier published silicon based solvents. • Due to the absence of ether groups, the electrochemical stability is extended to 5.4 V vs. Li/Li + . • With LiTFSI, the electrolyte can be cycled up to 4.15 V vs. Li/Li + without causing anodic aluminum dissolution. - Abstract: 3-((Trimethylsilyl) oxy) propionitrile is introduced as non-volatile solvent for lithium-ion battery electrolytes using LiTFSI as lithium salt. The thermal and chemical stability of the electrolytes offer an enhanced safety as compared to conventional volatile carbonate electrolytes. In cell tests, the investigated LiTFSI nitrile silyl ether electrolyte shows compatibility with LiFePO 4 , LiNi 0.33 Mn 0.33 Co 0.33 O 2 and graphite active materials.

  20. Power and Thermal Technologies for Air and Space. Delivery Order 0001: Single Ionic Conducting Solid-State Electrolyte

    National Research Council Canada - National Science Library

    Turner, Allen

    2005-01-01

    This report focuses on the development of a lithium-ion conducting channel as a solid-state electrolyte for rechargeable lithium batteries through the use of thin films of dilithium phthalocyanine (Li2Pc...

  1. Dynamic NMR studies of polymer electrolyte materials for application to lithium-ion batteries and fuel cells

    Science.gov (United States)

    Khalfan, Amish N.

    This dissertation investigates the structural and dynamical properties of polymer electrolyte materials for applications to lithium-ion batteries and fuel cells. The nuclear magnetic resonance (NMR) technique was used to characterize these materials. NMR aids in understanding the local environments of nuclei and the mobility of a molecular/ionic species. Five research projects were carried out, and they have been outlined in this work. NASA has developed rod-coil block copolymers for use as electrolytes in lithium-ion batteries. The copolymers exhibit a microphase separation within their structure leading to the formation of ionically conducting channels. We studied ion transport properties of the copolymers, and determined the predominant mechanism for transport to occur in the amorphous phase. Seven gel polymer electrolytes, each containing a mixture of LiBETI salt and organic solvents, were studied. Two of them incorporated BMI (1-n-butyl-3-methylimidazolium) ionic liquid. Ionic liquids are room temperature molten salts. BMI had been thought to enhance ion mobility. However, the BMI component was observed to restrict ion mobility. Gel polymer electrolytes containing LiTFSI salt and P13TFSI ionic liquid with or without the inclusion of ethylene carbonate (EC) were studied for application to lithium metal/air batteries, which have high theoretical energy densities. The addition of EC was found to improve lithium ion transport. The gels with EC therefore prove to be favorable for use as electrolytes in lithium metal/air batteries. Highly sulfonated poly(arylenethioethersulfone) (SPTES) membranes were examined for use in direct methanol fuel cells (DMFCs) as an alternative to the Nafion membrane. DMFCs use methanol as a fuel instead of reformed hydrogen as in conventional proton exchange membrane fuel cells. Compared to Nafion, the SPTES membranes were shown to retain water better at high temperatures and yield lower methanol diffusion. SPTES membranes with the

  2. The Effect of 1-Pentylamine as Solid Electrolyte Interphase Precursor on Lithium Metal Anodes

    International Nuclear Information System (INIS)

    Ding, Markus S.; Koch, Stephan L.; Passerini, Stefano

    2017-01-01

    Highlights: • Manufacturing of a well-controlled artificial SEI on lithium metal electrodes. • Native SEI-free lithium electrodes. • Lithium electrodes with decreased impedance and overpotential due to artificial SEI. • Process development to remove influence of native SEI. • 1-pentylamine in n-pentane as artificial SEI precursor for lithium metal. - Abstract: In this study, the formation of an artificial primary solid electrolyte interphase on a fresh Li surface, via reaction with 1-pentylamine (PA), is reported, allowing removing the influence of the metal electrode’s prior history. Electrochemical impedance spectroscopy, galvanostatic cycling, scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) are used in order to investigate the effect of PA as solid electrolyte interphase precursor on Li metal. It is shown that pretreating native SEI-free Li metal surfaces with 1 M PA in n-pentane sharply decreases the electrode impedance and overpotential with respect to the treatment with only n-pentane. The treatment with 1 M PA in n-pentane results in surface roughening, but no increase of dendrite formation upon cycling. However, the use of higher PA concentration (5 M) increases impedance and overpotential and leads to dendrite growth.

  3. Surface-protected LiCoO2 with ultrathin solid oxide electrolyte film for high-voltage lithium ion batteries and lithium polymer batteries

    Science.gov (United States)

    Yang, Qi; Huang, Jie; Li, Yejing; Wang, Yi; Qiu, Jiliang; Zhang, Jienan; Yu, Huigen; Yu, Xiqian; Li, Hong; Chen, Liquan

    2018-06-01

    Surface modification of LiCoO2 with the ultrathin film of solid state electrolyte of Li1.4Al0.4Ti1.6(PO4)3 (LATP) has been realized by a new and facile solution-based method. The coated LiCoO2 reveals enhanced structural and electrochemical stability at high voltage (4.5 V vs Li+/Li) in half-cell with liquid electrolyte. Transmission electron microscopy (TEM) images show that a dense LATP coating layer is covered on the surface of LiCoO2 uniformly with thickness of less than 20 nm. The LATP coating layer is proven to be able to prevent the direct contact between the cathode and the electrolyte effectively and thus to suppress the side reactions of liquid electrolyte with LiCoO2 surface at high charging voltage. As a result, dissolution of Co3+ has been largely suppressed over prolonged cycling as indicated by the X-ray photoelectron spectroscopy (XPS) measurements. Due to this surface passivating feature, the electrochemical performance of 0.5 wt% LATP modified LiCoO2 has also been evaluated in an all solid lithium battery with poly(ethylene oxide)-based polymer electrolyte. The cell exhibits 93% discharge capacity retention of the initial discharge capacity after 50 cycles at the charging cut-off voltage of 4.2 V, suggesting that the LATP coating layer is effective to suppress the oxidation of PEO at high voltage.

  4. Boronic ionogel electrolytes to improve lithium transport for Li-ion batteries

    International Nuclear Information System (INIS)

    Lee, Albert S.; Lee, Jin Hong; Hong, Soon Man; Lee, Jong-Chan; Hwang, Seung Sang; Koo, Chong Min

    2016-01-01

    Boron containing ionogels were fabricated through chemical crosslinking of boron allyloxide with polyethylene glycol dimethacrylate in an ionic liquid electrolyte solution to obtain mechanically robust gels. Because of the relatively small concentration of crosslinking agent required to fully solidify the ionic liquid electrolyte, good characters of high ionic conductivity, high thermal stability, and good electrochemical stability were observed. A spectroscopic investigation of the boronic ionogels revealed that the lithium mobility was noticeably enhanced compared with ionogels fabricated without the boronic crosslinker, leading to promising Li-ion battery performance at elevated temperatures.

  5. X-ray Raman spectroscopy of lithium-ion battery electrolyte solutions in a flow cell.

    Science.gov (United States)

    Ketenoglu, Didem; Spiekermann, Georg; Harder, Manuel; Oz, Erdinc; Koz, Cevriye; Yagci, Mehmet C; Yilmaz, Eda; Yin, Zhong; Sahle, Christoph J; Detlefs, Blanka; Yavaş, Hasan

    2018-03-01

    The effects of varying LiPF 6 salt concentration and the presence of lithium bis(oxalate)borate additive on the electronic structure of commonly used lithium-ion battery electrolyte solvents (ethylene carbonate-dimethyl carbonate and propylene carbonate) have been investigated. X-ray Raman scattering spectroscopy (a non-resonant inelastic X-ray scattering method) was utilized together with a closed-circle flow cell. Carbon and oxygen K-edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li + ion concentration in the solvent manifests itself as a blue-shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K-edge results agree with previous soft X-ray absorption studies on LiBF 4 salt concentration in propylene carbonate, carbon K-edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.

  6. Characterization of positive electrode/electrolyte interphase in lithium batteries

    Energy Technology Data Exchange (ETDEWEB)

    Dupre, N.; Martin, J.F.; Soudan, P.; Guyomard, D. [Inst.des Materiaux Jean Rouxel, Nantes (France)

    2008-07-01

    Lithium batteries appear to be the most viable energy source for portable electronic devices because of their energy density. The solid electrolyte interphase (SEI) between the negative electrode and the electrolyte of a Li-ion battery monitors the overall battery behaviour in terms of irreversible capacity loss, charge transfer kinetics and storage properties. This paper reported on a study that examined the influence of the storage atmosphere and the formation of a protective surface layer on the electrochemical performance. The objective was to better understand the interfacial problems controlling the long term life duration and cyclability. The positive/electrolyte interphase evolution was followed upon aging/cycling using 7Li MAS NMR, XPS and impedance spectroscopy. This very novel and uncommon technique was used to characterize the growth and evolution of the surface of some electrode materials for lithium batteries, due to contact with the ambient atmosphere or electrolyte or along electrochemical cycling. LiFePO4 and LiMn0.5Ni0.5O2 were chosen for the studies because they are among the most promising candidates for positive electrodes for future lithium batteries. The reaction of LiMn0.5Ni0.5O2 with the ambient atmosphere or LiPF6 electrolyte is extremely fast and leads to an important amount of lithium-containing diamagnetic species. The NMR spectra provided valuable structural information on the interaction between the interphase and the active material after contact with electrolyte or along electrochemical cycling. MAS NMR was shown to be a very promising tool to monitor phenomena taking place at the interface between electrode and electrolyte in lithium batteries. The study showed the affect of the potential on the strength of the interaction between the surface layer and the active material and the partial removal of this layer along the electrochemical cycling. 11 refs.

  7. A rocking chair type all-solid-state lithium ion battery adopting Li2O-ZrO2 coated LiNi0.8Co0.15Al0.05O2 and a sulfide based electrolyte

    Science.gov (United States)

    Ito, Seitaro; Fujiki, Satoshi; Yamada, Takanobu; Aihara, Yuichi; Park, Youngsin; Kim, Tae Young; Baek, Seung-Wook; Lee, Jae-Myung; Doo, Seokgwang; Machida, Nobuya

    2014-02-01

    An all-solid-state lithium-ion battery (ASSB) using non-flammable solid electrolytes is a candidate for a next-generation battery. Although the excellent cycle performance and its high energy density are suggested in the literature, a practical size battery has not been appeared yet. In this paper, we have adopted a sulfide based electrolyte, Li2S-P2S5 (80:20 mol%) to a rocking chair type lithium ion battery. The electrochemical cell consists of a Li2O-ZrO2 coated LiNi0.8Co0.15Al0.05O2 (NCA) cathode, an artificial graphite anode and the sulfide based electrolyte without any organic and inorganic liquids. The cathode charge transfer resistance is significantly reduced by the Li2O-ZrO2 coating. The total cell resistance of the Li2O-ZrO2 (LZO) coated NCA adopted cell is approximately one quarter of non-treated one. A standard type single cell with the nominal capacity of 100 mAh at 25 °C is fabricated by wet printing process, and its capacity retention is approximately 80% at 100 cycles. Also, a 1 Ah class battery was constructed by stacking the single cells, and demonstrated.

  8. Cross-Linked Solid Polymer Electrolyte for All-Solid-State Rechargeable Lithium Batteries

    International Nuclear Information System (INIS)

    Ben youcef, Hicham; Garcia-Calvo, Oihane; Lago, Nerea; Devaraj, Shanmukaraj; Armand, Michel

    2016-01-01

    Semi-interpenetrated network Solid Polymer Electrolytes (SPEs) were fabricated by UV-induced cross-linking of poly(ethyleneglycol) diacrylate (PEGDA) and divinylbenzene (DVB) within a poly(ethyleneoxide) (PEO) matrix (M v = 5 × 10 6 g mol −1 ), comprising lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI), at a molar ratio of EO:Li ∼ 30:1. The influence of the DVB content on the final SPE properties was investigated in detail. An increase of DVB concentration resulted in self-standing polymer electrolytes. The DVB cross-linker incorporation was found to decrease the crystallinity of the PEO matrix from 34% to 23%, with a decrease in the melting temperature (T m ) of the membrane from 50 °C to 34 °C. Moreover, the influence of the DVB concentration on the ionic conductivity was determined for polymer electrolytes with 0, 10, 20 and 45% DVB from room temperature (RT) to 80 °C. The resulting SPEs showed a high electrochemical stability of 4.3 V as well as practical conductivity values exceeding 10 −4 S cm −1 at 70 °C. Cycling performance of these semi-interpenetrated SPE’s have been shown with a Li metal polymer battery and all solid -state Li sulphur battery.

  9. Improved chemical stability and cyclability in Li2S–P2S5–P2O5–ZnO composite electrolytes for all-solid-state rechargeable lithium batteries

    International Nuclear Information System (INIS)

    Hayashi, Akitoshi; Muramatsu, Hiromasa; Ohtomo, Takamasa; Hama, Sigenori; Tatsumisago, Masahiro

    2014-01-01

    Highlights: • Chemical stability in air of Li 2 S–P 2 S 5 –P 2 O 5 –ZnO composite electrolytes was examined. • A partial substitution of P 2 O 5 for P 2 S 5 decreased the rate of H 2 S generation. • The addition of ZnO to the glasses reduced the amount of H 2 S. • All-solid-state lithium cells using the developed composite electrolytes exhibited good cyclability. -- Abstract: Sulfide glasses with high Li + ion conductivity are promising solid electrolytes for all-solid-state rechargeable lithium batteries. This study specifically examined the chemical stability of Li 2 S–P 2 S 5 -based glass electrolytes in air. Partial substitution of P 2 O 5 for P 2 S 5 decreased the rate of H 2 S generation from glass exposed to air. The addition of ZnO to the Li 2 S–P 2 S 5 –P 2 O 5 glasses as a H 2 S absorbent reduced the H 2 S gas release. A composite electrolyte prepared from 90 mol% of 75Li 2 S⋅21P 2 S 5 ⋅4P 2 O 5 (mol%) glass and 10 mol% ZnO was applied to all-solid-state cells. The all-solid-state In/LiCoO 2 cell with the composite electrolyte showed good cyclability as a lithium secondary battery

  10. Modeling of ionic transport in solid polymer electrolytes

    International Nuclear Information System (INIS)

    Cheang, P L; Teo, L L; Lim, T L

    2010-01-01

    A Monte Carlo model describing the ionic trans port in solid polyme relectrolyte is developed. Single cation simulation is carried out using hopping rate to study the transport mechanism of a thermally activated ion in solid polymer electrolyte. In our model, the ion is able to hop along a polymer chain and to jump between different chains, surmounting energy barriers that consist of polymer's activation energy and the externally applied electric field. The model is able to trace the motion of ion across polymer electrolyte. The mean hopping distance is calculated based on the available open bond in the next nearest side. Random numbers are used to determine the hopping distances, free flight times, final energy and direction of the cation after successful hop. Drift velocity and energy of cation are simulated in our work. The model is expected to be able to simulate the lithium-polymer battery in future.

  11. The Role of Sub- and Supercritical CO2 as “Processing Solvent” for the Recycling and Sample Preparation of Lithium Ion Battery Electrolytes

    Directory of Open Access Journals (Sweden)

    Sascha Nowak

    2017-03-01

    Full Text Available Quantitative electrolyte extraction from lithium ion batteries (LIB is of great interest for recycling processes. Following the generally valid EU legal guidelines for the recycling of batteries, 50 wt % of a LIB cell has to be recovered, which cannot be achieved without the electrolyte; hence, the electrolyte represents a target component for the recycling of LIBs. Additionally, fluoride or fluorinated compounds, as inevitably present in LIB electrolytes, can hamper or even damage recycling processes in industry and have to be removed from the solid LIB parts, as well. Finally, extraction is a necessary tool for LIB electrolyte aging analysis as well as for post-mortem investigations in general, because a qualitative overview can already be achieved after a few minutes of extraction for well-aged, apparently “dry” LIB cells, where the electrolyte is deeply penetrated or even gellified in the solid battery materials.

  12. Quantitative Visualization of Salt Concentration Distributions in Lithium-Ion Battery Electrolytes during Battery Operation Using X-ray Phase Imaging.

    Science.gov (United States)

    Takamatsu, Daiko; Yoneyama, Akio; Asari, Yusuke; Hirano, Tatsumi

    2018-02-07

    A fundamental understanding of concentrations of salts in lithium-ion battery electrolytes during battery operation is important for optimal operation and design of lithium-ion batteries. However, there are few techniques that can be used to quantitatively characterize salt concentration distributions in the electrolytes during battery operation. In this paper, we demonstrate that in operando X-ray phase imaging can quantitatively visualize the salt concentration distributions that arise in electrolytes during battery operation. From quantitative evaluation of the concentration distributions at steady states, we obtained the salt diffusivities in electrolytes with different initial salt concentrations. Because of no restriction on samples and high temporal and spatial resolutions, X-ray phase imaging will be a versatile technique for evaluating electrolytes, both aqueous and nonaqueous, of many electrochemical systems.

  13. Improved performance and safety of lithium ion cells with the use of fluorinated carbonate-based electrolytes

    Science.gov (United States)

    Smart, M. C.; Ratnakumar, B. V.; Ryan, V. S.; Surampudi, S.; Prakashi, G. K. S.; Hu, J.; Cheung, I.

    2002-01-01

    There has been increasing interest in developing lithium-ion electrolytes that possess enhanced safety characteristics, while still able to provide the desired stability and performance. Toward this end, our efforts have been focused on the development of lithium-ion electrolytes which contain partially and fully fluorinated carbonate solvents. The advantage of using such solvents is that they possess the requisite stability demonstrated by the hydrocarbon-based carbonates, while also possessing more desirable physical properties imparted by the presence of the fluorine substituents, such as lower melting points, increased stability toward oxidation, and favorable SEI film forming Characteristics on carbon. Specifically, we have demonstrated the beneficial effect of electrolytes which contain the following fluorinated carbonate-based solvents: methyl 2,2,2-trifluoroethyl carbonate (MTFEC), ethyl-2,2,2 trifluoroethyl carbonate (ETFEC), propyl 2,2,2-trifluoroethyl carbonate (PTFEC), methyl-2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (MHFPC), ethyl- 2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (EHFPC), and di-2,2,2-trifluoroethyl carbonate (DTFEC). These solvents have been incorporated into multi-component ternary and quaternary carbonate-based electrolytes and evaluated in lithium-carbon and carbon-LiNio.8Coo.202 cells (equipped with lithium reference electrodes). In addition to determining the charge/discharge behavior of these cells, a number of electrochemical techniques were employed (i.e., Tafel polarization measurements, linear polarization measurements, and electrochemical impedance spectroscopy (EIS)) to further characterize the performance of these electrolytes, including the SEI formation characteristics and lithium intercalatiodde-intercalation kinetics. In addition to their evaluation in experimental cells, cyclic voltammetry (CV) and conductivity measurements were performed on select electrolyte formulations to further our understanding of the trends

  14. New Ether-functionalized Morpholinium- and Piperidinium-based Ionic Liquids as Electrolyte Components in Lithium and Lithium-Ion Batteries.

    Science.gov (United States)

    Navarra, Maria Assunta; Fujimura, Kanae; Sgambetterra, Mirko; Tsurumaki, Akiko; Panero, Stefania; Nakamura, Nobuhumi; Ohno, Hiroyuki; Scrosati, Bruno

    2017-06-09

    Here, two ionic liquids, N-ethoxyethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide (M 1,2O2 TFSI) and N-ethoxyethyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide (P 1,2O2 TFSI) were synthesized and compared. Fundamental relevant properties, such as thermal and electrochemical stability, density, and ionic conductivity were analyzed to evaluate the effects caused by the presence of the ether bond in the side chain and/or in the organic cation ring. Upon lithium salt addition, two electrolytes suitable for lithium batteries applications were found. Higher conducting properties of the piperidinium-based electrolyte resulted in enhanced cycling performances when tested with LiFePO 4 (LFP) cathode in lithium cells. When mixing the P 1,2O2 TFSI/LiTFSI electrolyte with a tailored alkyl carbonate mixture, the cycling performance of both Li and Li-ion cells greatly improved, with prolonged cyclability delivering very stable capacity values, as high as the theoretical one in the case of Li/LFP cell configurations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Investigation of a nanoconfined, ceramic composite, solid polymer electrolyte

    International Nuclear Information System (INIS)

    Jayasekara, Indumini; Poyner, Mark; Teeters, Dale

    2017-01-01

    The challenges for further development of lithium rechargeable batteries are finding electrolyte materials that are safe, have mechanical and thermal stability and have sufficiently high ionic conduction. Polymer electrolytes have many of these advantages, but suffer with low ionic conduction. This study involves the use of anodic aluminum oxide (AAO) membranes having nanochannels filled with polymer electrolyte to make composite solid electrolytes having ionic conductivity several orders of magnitude higher (10 −4 Ω ‐1 cm −1 ) than non-confined polymer. SEM, ac impedance spectroscopy, temperature dependence studies, XRD, ATR- FTIR and DSC studies were done in order to characterize and understand the behavior of nanoconfined polymer electrolytes. The composite polymer electrolyte was found to be more amorphous with polymer chains aligned in the direction of the nanochannels, which is felt to promote ion conduction. The electrolyte systems, confined in nanoporous membranes, can be used as electrolytes for the fabrication of a room temperature all solid state battery.

  16. Symmetric lithium-ion cell based on lithium vanadium fluorophosphate with ionic liquid electrolyte

    International Nuclear Information System (INIS)

    Plashnitsa, Larisa S.; Kobayashi, Eiji; Okada, Shigeto; Yamaki, Jun-ichi

    2011-01-01

    Lithium vanadium fluorophosphate, LiVPO 4 F, was utilized as both cathode and anode for fabrication of a symmetric lithium-ion LiVPO 4 F//LiVPO 4 F cell. The electrochemical evolution of the LiVPO 4 F//LiVPO 4 F cell with the commonly used organic electrolyte LiPF 6 /EC-DMC has shown that this cell works as a secondary battery, but exhibits poor durability at room temperature and absolutely does not work at increased operating temperatures. To improve the performance and safety of this symmetric battery, we substituted a non-flammable ionic liquid (IL) LiBF 4 /EMIBF 4 electrolyte for the organic electrolyte. The symmetric battery using the IL electrolyte was examined galvanostatically at different rates and operating temperatures within the voltage range of 0.01-2.8 V. It was demonstrated that the IL-based symmetric cell worked as a secondary battery with a Coulombic efficiency of 77% at 0.1 mA cm -2 and 25 o C. It was also found that the use of the IL electrolyte instead of the organic one resulted in the general reduction of the first discharge capacity by about 20-25% but provided much more stable behavior and a longer cycle life. Moreover, an increase of the discharge capacity of the IL-based symmetric battery up to 120 mA h g -1 was observed when the operating temperature was increased up to 80 o C at 0.1 mA cm -2 . The obtained electrochemical behavior of both symmetric batteries was confirmed by complex-impedance measurements at different temperatures and cycling states. The thermal stability of LiVPO 4 F with both the IL and organic electrolytes was also examined.

  17. Compliant gel polymer electrolyte based on poly(methyl acrylate-co-acrylonitrile)/poly(vinyl alcohol) for flexible lithium-ion batteries

    International Nuclear Information System (INIS)

    Ma, Xianguo; Huang, Xinglan; Gao, Jiandong; Zhang, Shu; Deng, Zhenghua; Suo, Jishuan

    2014-01-01

    Highlights: •Compliant gel polymer electrolyte based on P(MA-co-AN)/PVA is facilely prepared for flexible lithium-ion batteries. •The compliant gel polymer electrolyte displays high ionic conductivity, self-standing and mechanical flexible. •The compliant gel polymer electrolyte exhibits excellent chemical and electrochemical performances. -- Abstract: In this report, mechanically compliant gel polymer electrolyte (GPE) for flexible lithium-ion batteries is facilely fabricated. The GPE that based on the poly(methyl acrylate-co-acrylonitrile)/poly(vinyl alcohol) (P(MA-co-AN)/PVA) was prepared via emulsion polymerization. Herein, the P(MA-co-AN) copolymer is anticipated to exert beneficial for the bendability of the GPE, as well as swollen with the liquid electrolyte to provide a facile pathway for ion movement. The PVA serves as a stabilizer during the emulsion polymerization and a mechanical framework for the compliant polymer membrane. Performance benefits of the mechanically compliant membrane are elucidated in terms of mechanical behavior, thermostability and ionic conductivity. The GPE is still self-standing and mechanical flexible after swollen with liquid electrolyte. The GPE displays a conductivity of 0.98 mS cm −1 with the uptake electrolyte up to 150% of its own weight at 30 °C, excellent electrochemical stability window (5.2 V vs. Li/Li + ) and favorable interfacial characteristics. When used in flexible lithium-ion batteries, such a GPE demonstrates satisfactory compatibility with LiCoO 2 and graphite electrodes

  18. In-situ preparation of poly(ethylene oxide)/Li3PS4 hybrid polymer electrolyte with good nanofiller distribution for rechargeable solid-state lithium batteries

    Science.gov (United States)

    Chen, Shaojie; Wang, Junye; Zhang, Zhihua; Wu, Linbin; Yao, Lili; Wei, Zhenyao; Deng, Yonghong; Xie, Dongjiu; Yao, Xiayin; Xu, Xiaoxiong

    2018-05-01

    Nano-sized fillers in a polymer matrix with good distribution can play a positive role in improving polymer electrolytes in the aspects of ionic conductivity, mechanical property and electrochemical performance of Li-ion cells. Herein, polyethylene oxide (PEO)/Li3PS4 hybrid polymer electrolyte is prepared via a new in-situ approach. The ionic conductivities of the novel hybrid electrolytes with variable proportions are measured, and the optimal electrolyte of PEO-2%vol Li3PS4 presents a considerable ionic conductivity of 8.01 × 10-4 S cm-1 at 60 °C and an electrochemical window up to 5.1 V. The tests of DSC and EDXS reveal that the Li3PS4 nanoparticles with better distribution, as active fillers scattering in the PEO, exhibit a positive effect on the transference of lithium ion and electrochemical interfacial stabilities. Finally, the assembled solid-state LiFePO4/Li battery presents a decent cycling performance (80.9% retention rate after 325 cycles at 60 °C) and excellent rate capacities with 153, 143, 139 and 127 mAh g-1 at the discharging rate of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C. It is fully proved that it is an advanced strategy to preparing the new organic/inorganic hybrid electrolytes for lithium-ion batteries applications.

  19. Lithium sulfide compositions for battery electrolyte and battery electrode coatings

    Science.gov (United States)

    Liang, Chengdu; Liu, Zengcai; Fu, Wunjun; Lin, Zhan; Dudney, Nancy J; Howe, Jane Y; Rondinone, Adam J

    2013-12-03

    Methods of forming lithium-containing electrolytes are provided using wet chemical synthesis. In some examples, the lithium containing electroytes are composed of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7. The solid electrolyte may be a core shell material. In one embodiment, the core shell material includes a core of lithium sulfide (Li.sub.2S), a first shell of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7, and a second shell including one or .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7 and carbon. The lithium containing electrolytes may be incorporated into wet cell batteries or solid state batteries.

  20. Temperature dependence of electrochemical properties of cross-linked poly(ethylene oxide)–lithium bis(trifluoromethanesulfonyl)imide–N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide solid polymer electrolytes for lithium batteries

    International Nuclear Information System (INIS)

    Wetjen, Morten; Kim, Guk-Tae; Joost, Mario; Winter, Martin; Passerini, Stefano

    2013-01-01

    Highlights: ► Solid-state electrolyte for lithium batteries. ► Polymer electrolyte with improved mechanical properties by cross-linking. ► Enhanced performance of polymer electrolytes using water- and air-stable ionic liquids as co-salts. ► Polymer electrolyte with high rate capability at moderate temperatures. - Abstract: An advanced electrochemical characterization of cross-linked ternary solid polymer electrolytes (SPEs), prepared by a solvent-free hot-pressing process, is reported. Ionic conductivity, electrochemical stability window and limiting current measurements were performed as a function of the temperature by using both potentiodynamic and galvanostatic techniques. Additionally, the lithium cycleability was evaluated with respect to its dependence on both the operating temperature and the current density by using a new multi-rate Li-stripping-plating procedure. The results clearly indicate the beneficial effect of higher operating temperatures on the rate-capability, without major degradation of the electrochemical stability of the SPE. All-solid-state lithium metal polymer batteries (LMPBs), comprising a lithium metal anode, the cross-linked ternary solid polymer electrolyte and a LiFePO 4 composite cathode, were manufactured and investigated in terms of the interdependencies of the delivered capacity, operating temperature and discharge rate. The results prove quite exceptional delivered capacities both at medium current densities at ambient temperatures and even more impressive capacities above 160 mAh g −1 at high discharge rates (1 C) and temperatures above 60 °C.

  1. Composite gel polymer electrolyte for lithium ion batteries

    Science.gov (United States)

    Naderi, Roya

    Composite gel polymer electrolyte (CGPE) films, consisting of poly (vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) as the membrane, DMF and PC as solvent and plasticizing agent, mixture of charge modified TiO2 and SiO 2 nano particles as ionic conductors, and LiClO4+LiPF 6 as lithium salts were fabricated. Following the work done by Li et al., CGPE was coated on an O2-plasma treated trilayer polypropylene-polyethylene-polypropylene membrane separator using solution casting technique in order to improve the adhesive properties of gel polymer electrolyte to the separator membrane and its respective ionic conductivity due to decreasing the bulk resistance. In acidic CGPE with, the mixture of acid treated TiO2 and neutral SiO2 nano particles played the role of the charge modified nano fillers with enhanced hydroxyl groups. Likely, the mixture of neutral TiO 2 nano particles with basic SiO2 prepared through the hydrolization of tetraethyl orthosilicate (TEOS) provided a more basic environment due to the residues of NH4OH (Ammonium hydroxide) catalyst. The O2 plasma treated separator was coated with the solution of PVDF-HFP: modified nano fillers: Organic solvents with the mixture ratio of 0.1:0.01:1. After the evaporation of the organic solvents, the dried coated separator was soaked in PC-LiClO4+LiPF6 in EC: DMC:DEC (4:2:4 in volume) solution (300% wt. of PVDF-HFP) to form the final CGPE. Lim et al. has reported the enhanced ionic conductivity of 9.78*10-5 Scm-1 in an acidic composite polystyrene-Al2O3 solid electrolyte system with compared to that of basic and neutral in which the ionic conductivity undergoes an ion hopping process in solid interface rather than a segmental movement of ions through the plasticized polymer chain . Half-cells with graphite anode and Li metal as reference electrode were then assembled and the electrochemical measurements and morphology examinations were successfully carried out. Half cells demonstrated a considerable change in their

  2. Single-ion conducting polymer-silicate nanocomposite electrolytes for lithium battery applications

    International Nuclear Information System (INIS)

    Kurian, Mary; Galvin, Mary E.; Trapa, Patrick E.; Sadoway, Donald R.; Mayes, Anne M.

    2005-01-01

    Solid-state polymer-silicate nanocomposite electrolytes based on an amorphous polymer poly[(oxyethylene) 8 methacrylate], POEM, and lithium montmorillonite clay were fabricated and characterized to investigate the feasibility of their use as 'salt-free' electrolytes in lithium polymer batteries. X-ray scattering and transmission electron microscopy studies indicate the formation of an intercalated morphology in the nanocomposites due to favorable interactions between the polymer matrix and the clay. The morphology of the nanocomposite is intricately linked to the amount of silicate in the system. At low clay contents, dynamic rheological testing verifies that silicate incorporation enhances the mechanical properties of POEM, while impedance spectroscopy shows an improvement in electrical properties. With clay content ≥15 wt.%, mechanical properties are further improved but the formation of an apparent superlattice structure correlates with a loss in the electrical properties of the nanocomposite. The use of suitably modified clays in nanocomposites with high clay contents eliminates this superstructure formation, yielding materials with enhanced performance

  3. The Evaluation of Triphenyl Phosphate as a Flame Retardant Additive to Improve the Safety of Lithium-Ion Battery Electrolytes

    Science.gov (United States)

    Smart, M. C.; Krause, F. C.; Hwang, C.; West, W. C.; Soler, J.; Prakash, G. K. S.; Ratnakumar, B. V.

    2011-01-01

    With the intent of improving the safety characteristics of lithium ion cells, electrolytes containing flame retardant additives have been investigated. A number of triphenyl phosphate-containing electrolytes were evaluated in both coin cells and experimental three electrode lithium-ion cells (containing reference electrodes). A number of chemistries were investigated, including MCMB carbon/LiNi(0.8)Co(0.2)O2 (NCO), graphite/LiNi(0.8)Co(0.15)Al(0.05)O2 (NCA), Li/Li(Li(0.17)Ni(0.25)Mn(0.58))O2, Li/LiNiMnCoO2 (NMC) and graphite/LiNiMnCoO2 (NMC), to study the effect that different electrolyte compositions have upon performance. A wide range of TPP-containing electrolytes were demonstrated to have good compatibility with the C/NCO, C/NCA, and Li/NMC systems, however, poor performance was initially observed with the high voltage C/NMC system. This necessitated the development of improved electrolytes with stabilizing additives, leading to formulations containing lithium bis(oxalato)borate (LiBOB) that displayed substantially improved performance.

  4. Gamma ray degradation of electrolytes containing alkylcarbonate solvents and a lithium salt

    Energy Technology Data Exchange (ETDEWEB)

    Caillon-Caravanier, Magaly; Jones, Jennifer; Anouti, Meriem; Lemordant, Daniel [Laboratoire CIME/PCMB (EA4244), Universite F. Rabelais, Faculte des Sciences et Techniques, Parc de Grandmont, 37200 Tours (France); Montigny, Frederic [Plateau d' Analyse Chimique, Universite F. Rabelais, Faculte de Pharmacie, 31 avenue Monge 37200 Tours (France); Willmann, Patrick [CNES, 18 avenue E. Belin, 31055 Toulouse (France); David, Jean-Pierre; Soonckindt, Sabine [Departement Environnement Spatial DSEP/ONERA, 2, avenue E. Belin, 31055 Toulouse (France)

    2010-01-15

    Lithium-ion batteries for space applications, such as satellites, are subjected to cosmic radiations, in particular, {gamma}-irradiation. In this study, the effects of this radiation on electrolytes and their components used in the lithium-ion batteries are investigated. The conductivity and viscosity of the samples have been measured before and after the irradiation. The modifications are evaluated by spectral analyses such as Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy ({sup 1}H and {sup 13}C NMR), solid phase microextraction-gas chromatography (SPME-GC) and gas chromatography-mass spectroscopy (GC-MS). The experimental results show that only the samples containing vinylene carbonate and/or the lithium salt LiPF{sub 6} are degraded by {gamma}-radiation. (author)

  5. Imidazolium-based Block Copolymers as Solid-State Separators for Alkaline Fuel Cells and Lithium Ion Batteries

    Science.gov (United States)

    Nykaza, Jacob Richard

    In this study, polymerized ionic liquid (PIL) diblock copolymers were explored as solid-state polymer separators as an anion exchange membrane (AEM) for alkaline fuel cells AFCs and as a solid polymer electrolyte (SPE) for lithium-ion batteries. Polymerized ionic liquid (PIL) block copolymers are a distinct set of block copolymers that combine the properties of both ionic liquids (e.g., high conductivity, high electrochemical stability) and block copolymers (e.g., self-assembly into various nanostructures), which provides the opportunity to design highly conductive robust solid-state electrolytes that can be tuned for various applications including AFCs and lithium-ion batteries via simple anion exchange. A series of bromide conducting PIL diblock copolymers with an undecyl alkyl side chain between the polymer backbone and the imidazolium moiety were first synthesized at various compositions comprising of a PIL component and a non-ionic component. Synthesis was achieved by post-functionalization from its non-ionic precursor PIL diblock copolymer, which was synthesized via the reverse addition fragmentation chain transfer (RAFT) technique. This PIL diblock copolymer with long alkyl side chains resulted in flexible, transparent films with high mechanical strength and high bromide ion conductivity. The conductivity of the PIL diblock copolymer was three times higher than its analogous PIL homopolymer and an order of magnitude higher than a similar PIL diblock copolymer with shorter alkyl side chain length, which was due to the microphase separated morphology, more specifically, water/ion clusters within the PIL microdomains in the hydrated state. Due to the high conductivity and mechanical robustness of this novel PIL block copolymer, its application as both the ionomer and AEM in an AFC was investigated via anion exchange to hydroxide (OH-), where a maximum power density of 29.3 mW cm-1 (60 °C with H2/O2 at 25 psig (172 kPa) backpressure) was achieved. Rotating disk

  6. Preparation and properties of new cross-linked polyurethane acrylate electrolytes for lithium batteries

    Energy Technology Data Exchange (ETDEWEB)

    Santhosh, P.; Vasudevan, T.; Gopalan, A. [Department of Industrial Chemistry, Alagappa University, Karaikudi-630 003 (India); Lee, Kwang-Pill [Department of Chemistry Education, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

    2006-09-29

    A cross-linked polyurethane acrylate (PUA) is synthesized by end-capping a hexamethylene diisocyanate, hexamethylene diisocyanate/poly(ethylene glycol)-based prepolymer with hydroxy butyl methacrylate (HBMA). Significant interactions of lithium ions with the soft and hard segments of the host polymer are observed for the PUA complexed with lithium perchlorate (LiClO{sub 4}) by means of differential scanning calorimetry (DSC), and Fourier transform infra-red (FT-IR) spectroscopy measurements. The DSC results indicate the formation of transient cross-links with the ether oxygen of the soft segment and mixing of soft and hard phases induced by the Li{sup +} ions. The results of FT-IR spectroscopy and thermogravimetric analysis measurements support the formation of different types of complexes by interaction of Li{sup +} ions with different coordination sites of PUA. No detectable interactions are found between Li{sup +} ions and groups in HBMA. In addition, PUA follows the Arrhenius relationship for ion transport. Predominant formation of contact ion-pairs of LiClO{sub 4} is observed through a.c. conductivity and DSC measurements. The lithium stripping-plating process is reversible and this implies better electrochemical stability over the working voltage range. Also, the PUA electrolyte shows better compatibility with lithium metal as inferred from impedance measurements and has a good cationic transference number that is suitable for the material to be used as a solid polymer electrolyte. Addition of HBMA into the PU matrix improves the tensile strength of the cross-linked PUA. Swelling measurements of PUA with plasticizer indicate better dimensional stability. A cell is constructed with PUA as the electrolyte and its performance is evaluated. (author)

  7. Electrospun PVdF-based fibrous polymer electrolytes for lithium ion polymer batteries

    International Nuclear Information System (INIS)

    Kim, Jeong Rae; Choi, Sung Won; Jo, Seong Mu; Lee, Wha Seop; Kim, Byung Chul

    2004-01-01

    This paper discusses the preparation of microporous fibrous membranes from PVdF solutions with different polymer contents, using the electrospinning technique. Electrospun PVdF-based fibrous membranes with average fiber diameters (AFD's) of 0.45-1.38 μm have an apparent porosity and a mean pore size (MPS) of 80-89% and 1.1-4.3 μm, respectively. They exhibited a high uptake of the electrolyte solution (320-350%) and a high ionic conductivity of above 1 x 10 -3 s/cm at room temperature. Their ionic conductivity increased with the decrease in the AFD of the fibrous membrane due to its high electrolyte uptake. The interaction between the electrolyte molecules and the PVdF with a high crystalline content may have had a minor effect on the lithium ion transfer in the fibrous polymer electrolyte, unlike in a nanoporous gel polymer electrolyte. The fibrous polymer electrolyte that contained a 1 M LiPF 6 -EC/DMC/DEC (1/1/1 by weight) solution showed a high electrochemical stability of above 5.0 V, which increased with the decrease in the AFD The interfacial resistance (R i ) between the polymer electrolyte and the lithium electrode slightly increased with the storage time, compared with the higher increase in the interfacial resistance of other gel polymer electrolytes. The prototype cell (MCMB/PVdF-based fibrous electrolyte/LiCoO 2 ) showed a very stable charge-discharge behavior with a slight capacity loss under constant current and voltage conditions at the C/2-rate of 20 and 60 deg. C

  8. Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

    Science.gov (United States)

    Wang, Aiping; Kadam, Sanket; Li, Hong; Shi, Siqi; Qi, Yue

    2018-03-01

    A passivation layer called the solid electrolyte interphase (SEI) is formed on electrode surfaces from decomposition products of electrolytes. The SEI allows Li+ transport and blocks electrons in order to prevent further electrolyte decomposition and ensure continued electrochemical reactions. The formation and growth mechanism of the nanometer thick SEI films are yet to be completely understood owing to their complex structure and lack of reliable in situ experimental techniques. Significant advances in computational methods have made it possible to predictively model the fundamentals of SEI. This review aims to give an overview of state-of-the-art modeling progress in the investigation of SEI films on the anodes, ranging from electronic structure calculations to mesoscale modeling, covering the thermodynamics and kinetics of electrolyte reduction reactions, SEI formation, modification through electrolyte design, correlation of SEI properties with battery performance, and the artificial SEI design. Multi-scale simulations have been summarized and compared with each other as well as with experiments. Computational details of the fundamental properties of SEI, such as electron tunneling, Li-ion transport, chemical/mechanical stability of the bulk SEI and electrode/(SEI/) electrolyte interfaces have been discussed. This review shows the potential of computational approaches in the deconvolution of SEI properties and design of artificial SEI. We believe that computational modeling can be integrated with experiments to complement each other and lead to a better understanding of the complex SEI for the development of a highly efficient battery in the future.

  9. Solid NMR study of lithium ions accommodated in various transition metal oxides

    International Nuclear Information System (INIS)

    Kanzaki, Yasushi; Suzuki, Noriko

    2008-01-01

    Solid NMR was used to elucidate the lithium accommodation/extraction reaction in various transition metal oxides. The first study was the lithium ion exchange reaction of titanium antimonic acid (TiSbA). The effect of hydration on the selectivity of lithium ion in the solid phase was examined using 7 Li NMR. The second study was the irreversible ion exchange behavior of HNbO 3 . The selectivity for the lithium ion and the irreversible behavior were examined using 1 H and 7 Li NMR. The third study was the isotope separation between 6 Li and 7 Li in various inorganic ion exchangers. The high isotope separation coefficient was ascribed to the degree of dehydration during the ion exchange reaction. The degree of dehydration was examined by 1 H and 7 Li NMR studies. The last study was determining the mechanism of the lithium accommodation/extraction reaction of λ-MnO 2 in an aqueous solution. The different paths between the accommodation and extraction and the formation of MnO 4- during the accommodation were determined by chemical analysis. The Knight shift in the 7 Li MAS-NMR spectra of Li 0.5 MnO 2 suggested the localization of the electron density on the lithium nuclei. An XPS study also suggested the presence of an electron density on the lithium nuclei. A pH-independent redox couple was assumed to account for the accommodation/extraction reaction of lithium ions, such as Li(I)/Li(0). (author)

  10. Development of Large-Format Lithium-Ion Cells with Silicon Anode and Low Flammable Electrolyte

    Science.gov (United States)

    Wu, James J.; Hernandez-Lugo, D. M.; Smart, M. C.; Ratnakumar, B. V.; Miller, T. B.; Lvovich, V. F.; Lytle, J. K.

    2014-01-01

    NASA is developing safe, high energy and high capacity lithium-ion cell designs and batteries for future missions under NASAs Advanced Space Power System (ASPS) project. Advanced cell components, such as high specific capacity silicon anodes and low-flammable electrolytes have been developed for improving the cell specific energy and enhancing safety. To advance the technology readiness level, we have developed large-format flight-type hermetically sealed battery cells by incorporating high capacity silicon anodes, commercially available lithium nickel, cobalt, aluminum oxide (NCA) cathodes, and low-flammable electrolytes. In this report, we will present the performance results of these various battery cells. In addition, we will also discuss the post-test cell analysis results as well.

  11. Simulation of electrochemical behavior in Lithium ion battery during discharge process.

    Science.gov (United States)

    Chen, Yong; Huo, Weiwei; Lin, Muyi; Zhao, Li

    2018-01-01

    An electrochemical Lithium ion battery model was built taking into account the electrochemical reactions. The polarization was divided into parts which were related to the solid phase and the electrolyte mass transport of species, and the electrochemical reactions. The influence factors on battery polarization were studied, including the active material particle radius and the electrolyte salt concentration. The results showed that diffusion polarization exist in the positive and negative electrodes, and diffusion polarization increase with the conducting of the discharge process. The physicochemical parameters of the Lithium ion battery had the huge effect on cell voltage via polarization. The simulation data show that the polarization voltage has close relationship with active material particle size, discharging rate and ambient temperature.

  12. Synthesis of rock-salt type lithium borohydride and its peculiar Li+ ion conduction properties

    Directory of Open Access Journals (Sweden)

    R. Miyazaki

    2014-05-01

    Full Text Available The high energy density and excellent cycle performance of lithium ion batteries makes them superior to all other secondary batteries and explains why they are widely used in portable devices. However, because organic liquid electrolytes have a higher operating voltage than aqueous solution, they are used in lithium ion batteries. This comes with the risk of fire due to their flammability. Solid electrolytes are being investigated to find an alternative to organic liquid. However, the nature of the solid-solid point contact at the interface between the electrolyte and electrode or between the electrolyte grains is such that high power density has proven difficult to attain. We develop a new method for the fabrication of a solid electrolyte using LiBH4, known for its super Li+ ion conduction without any grain boundary contribution. The modifications to the conduction pathway achieved by stabilizing the high pressure form of this material provided a new structure with some LiBH4, more suitable to the high rate condition. We synthesized the H.P. form of LiBH4 under ambient pressure by doping LiBH4 with the KI lattice by sintering. The formation of a KI - LiBH4 solid solution was confirmed both macroscopically and microscopically. The obtained sample was shown to be a pure Li+ conductor despite its small Li+ content. This conduction mechanism, where the light doping cation played a major role in ion conduction, was termed the “Parasitic Conduction Mechanism.” This mechanism made it possible to synthesize a new ion conductor and is expected to have enormous potential in the search for new battery materials.

  13. Towards a lattice-matching solid-state battery: synthesis of a new class of lithium-ion conductors with the spinel structure.

    Science.gov (United States)

    Rosciano, Fabio; Pescarmona, Paolo P; Houthoofd, Kristof; Persoons, Andre; Bottke, Patrick; Wilkening, Martin

    2013-04-28

    Lithium ion batteries have conquered most of the portable electronics market and are now on the verge of deployment in large scale applications. To be competitive in the automotive and stationary sectors, however, they must be improved in the fields of safety and energy density (W h L(-1)). Solid-state batteries with a ceramic electrolyte offer the necessary advantages to significantly improve the current state-of-the-art technology. The major limit towards realizing a practical solid-state lithium-ion battery lies in the lack of viable ceramic ionic conductors. Only a few candidate materials are available, each carrying a difficult balance between advantages and drawbacks. Here we introduce a new class of possible solid-state lithium-ion conductors with the spinel structure. Such compounds could be coupled with spinel-type electrode materials to obtain a "lattice matching" solid device where low interfacial resistance could be achieved. Powders were prepared by wet chemistry, their structure was studied by means of diffraction techniques and magic angle spinning NMR, and Li(+) self-diffusion was estimated by static NMR line shape measurements. Profound differences in the Li(+) diffusion properties were observed depending on the composition, lithium content and cationic distribution. Local Li(+) hopping in the spinel materials is accompanied by a low activation energy of circa 0.35 eV being comparable with that of, e.g., LLZO-type garnets, which represent the current benchmark in this field. We propose these novel materials as a building block for a lattice-matching all-spinel solid-state battery with low interfacial resistance.

  14. Conductivity through Polymer Electrolytes and Its Implications in Lithium-Ion Batteries: Real-World Application of Periodic Trends

    Science.gov (United States)

    Compton, Owen C.; Egan, Martin; Kanakaraj, Rupa; Higgins, Thomas B.; Nguyen, SonBinh T.

    2012-01-01

    Periodic conductivity trends are placed in the scope of lithium-ion batteries, where increases in the ionic radii of salt components affect the conductivity of a poly(ethyleneoxide)-based polymer electrolyte. Numerous electrolytes containing varying concentrations and types of metal salts are prepared and evaluated in either one or two laboratory…

  15. Developing New Electrolytes for Advanced Li-ion Batteries

    Science.gov (United States)

    McOwen, Dennis Wayne

    The use of renewable energy sources is on the rise, as new energy generating technologies continue to become more efficient and economical. Furthermore, the advantages of an energy infrastructure which relies more on sustainable and renewable energy sources are becoming increasingly apparent. The most readily available of these renewable energy sources, wind and solar energy in particular, are naturally intermittent. Thus, to enable the continued expansion and widespread adoption of renewable energy generating technology, a cost-effective energy storage system is essential. Additionally, the market for electric/hybrid electric vehicles, which both require efficient energy storage, continues to grow as more consumers seek to reduce their consumption of gasoline. These vehicles, however, remain quite expensive, due primarily to costs associated with storing the electrical energy. High-voltage and thermally stable Li-ion battery technology is a promising solution for both grid-level and electric vehicle energy storage. Current limitations in materials, however, limit the energy density and safe operating temperature window of the battery. Specifically, the state-of-the-art electrolyte used in Li-ion batteries is not compatible with recently developed high-voltage positive electrodes, which are one of the most effectual ways of increasing the energy density. The electrolyte is also thermally unstable above 50 °C, and prone to thermal runaway reaction if exposed to prolonged heating. The lithium salt used in such electrolytes, LiPF6, is a primary contributor to both of these issues. Unfortunately, an improved lithium salt which meets the myriad property requirements for Li-ion battery electrolytes has eluded researchers for decades. In this study, a renewed effort to find such a lithium salt was begun, using a recently developed methodology to rapidly screen for desirable properties. Four new lithium salts and one relatively new but uncharacterized lithium salt were

  16. Diffusion of Lithium Ions in Amorphous and Crystalline Poly(ethylene oxide)_3:LiCF_3SO_3 Polymer Electrolytes

    International Nuclear Information System (INIS)

    Xue, Sha; Liu, Yingdi; Li, Yaping; Teeters, Dale; Crunkleton, Daniel W.; Wang, Sanwu

    2017-01-01

    The PEO_3:LiCF_3SO_3 polymer electrolyte has attracted significant research due to high conductivity and enhanced stability in lithium polymer batteries. Most experimental studies have shown that amorphous PEO lithium salt electrolytes have higher conductivity than the crystalline ones. Other studies, however, have shown that crystalline PEO salt complexes can conduct ions. As a result, further theoretical investigations are warranted to help clarify the issue. In this work, we use density functional theory with the climbing image nudged elastic band method to investigate the atomic-scale mechanism of lithium ion transport in the polymer electrolytes. We also use density functional theory and ab initio molecular dynamics simulations to obtain the amorphous structure of PEO_3:LiCF_3SO_3. The diffusion pathways and activation energies of lithium ions in both crystalline and amorphous PEO_3:LiCF_3SO_3 are determined. In crystalline PEO_3:LiCF_3SO_3, the activation energy for the low-barrier diffusion pathway is approximately 1.0 eV. In the amorphous phase, the value is 0.6 eV. This result would support the experimental observation that amorphous PEO_3:LiCF_3SO_3 has higher ionic conductivity than the crystalline phase.

  17. Integrated Interface Strategy toward Room Temperature Solid-State Lithium Batteries.

    Science.gov (United States)

    Ju, Jiangwei; Wang, Yantao; Chen, Bingbing; Ma, Jun; Dong, Shanmu; Chai, Jingchao; Qu, Hongtao; Cui, Longfei; Wu, Xiuxiu; Cui, Guanglei

    2018-04-25

    Solid-state lithium batteries have drawn wide attention to address the safety issues of power batteries. However, the development of solid-state lithium batteries is substantially limited by the poor electrochemical performances originating from the rigid interface between solid electrodes and solid-state electrolytes. In this work, a composite of poly(vinyl carbonate) and Li 10 SnP 2 S 12 solid-state electrolyte is fabricated successfully via in situ polymerization to improve the rigid interface issues. The composite electrolyte presents a considerable room temperature conductivity of 0.2 mS cm -1 , an electrochemical window exceeding 4.5 V, and a Li + transport number of 0.6. It is demonstrated that solid-state lithium metal battery of LiFe 0.2 Mn 0.8 PO 4 (LFMP)/composite electrolyte/Li can deliver a high capacity of 130 mA h g -1 with considerable capacity retention of 88% and Coulombic efficiency of exceeding 99% after 140 cycles at the rate of 0.5 C at room temperature. The superior electrochemical performance can be ascribed to the good compatibility of the composite electrolyte with Li metal and the integrated compatible interface between solid electrodes and the composite electrolyte engineered by in situ polymerization, which leads to a significant interfacial impedance decrease from 1292 to 213 Ω cm 2 in solid-state Li-Li symmetrical cells. This work provides vital reference for improving the interface compatibility for room temperature solid-state lithium batteries.

  18. Hydrofluoroether electrolytes for lithium-ion batteries: Reduced gas decomposition and nonflammable

    Science.gov (United States)

    Nagasubramanian, Ganesan; Orendorff, Christopher J.

    2011-10-01

    The optimum combination of high energy density at the desired power sets lithium-ion battery technology apart from the other well known secondary battery chemistries. However, this is besieged by thermal instability of the electrolyte. This "Achilles heel" still remains a significant safety issue and unless this propensity is improved the promise of widespread adoption of Li-ion batteries for Transportation application may not be realized. With this in mind we launched a systematic study to evaluate fluoro solvents that are known to be nonflammable, for thermal and electrochemical performances. We investigated hydro-fluoro-ethers (HFE) (1) 2-trifluoromethyl-3-methoxyperfluoropentane {TMMP} and (2) 2-trifluoro-2-fluoro-3-difluoropropoxy-3-difluoro-4-fluoro-5-trifluoropentane {TPTP} in Sandia-built cells. Thermal properties under near abuse conditions that exist in thermal runaway environment and the electrochemical characteristics for these electrolytes were measured. In the thermal ramp (TR) measurement, EC:DEC:TPTP-1 M LiBETI (or TFSI or LiPF6) electrolytes exhibited no ignition/fire. Similar behavior was observed for the EC:DEC:TMMP-1 M LiBETI. Further, in ARC studies the HFE electrolytes generated less gas by 50% compared to the EC:EMC-1.2 M LiPF6 {CAR-1} electrolyte. Although in all cases the HFEs generated less gas, the onset of gas generation appears to depend on the salt. For the LiBETI and TFSI containing HFEs the onset is pushed out by ∼80 °C and for the LiPF6 the onset is comparable to that of the CAR-1. The solution ionic conductivity of these HFE electrolytes was lower (4-5 times) than that of the CAR-1 electrolyte however, the electrochemical performance was comparable. For example, full cells in 2032 type coin cells containing LiMN0.33Ni0.33Co0.33O2 cathode and carbon anode showed around 5 mA h capacity and the computed specific capacity was ∼154 mA h for all the electrolytes. In half-cells against lithium the cathode and anode gave specific

  19. Structural, thermal and ion transport properties of radiation grafted lithium conductive polymer electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Nasef, Mohamed Mahmoud [Business and Advanced Technology Centre (BATC), Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur (Malaysia)]. E-mail: mahmoudeithar@mailcity.com; Saidi, Hamdani [Business and Advanced Technology Centre (BATC), Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur (Malaysia)

    2006-10-10

    Structural, thermal and ion transport properties of lithium conductive polymer electrolytes prepared by radiation-induced grafting of styrene onto poly(vinylidene fluoride) (PVDF) films and subsequent activation with LiPH{sub 6}/EC/DEC liquid electrolyte were investigated in correlation with the content of the grafted polystyrene (Y%). The changes in the structure were studied using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Thermal gravimetric analysis (TGA) was used to evaluate the thermal stability. The ionic conductivity was measured by means of ac impedance spectroscopy at various temperatures. The polymer electrolytes were found to undergo considerable structural and morphological changes that resulted in a noticeable increase in their ionic conductivity with the increase in Y% at various temperatures (25-65 deg. C). The ionic conductivity achieved a value of 1.61 x 10{sup -3} S cm{sup -1} when Y of the polymer electrolyte reached 50% and at 25 deg. C. The polymer electrolytes also showed a multi-step degradation behaviour and thermal stability up to 120 deg. C, which suits normal lithium battery operation temperature range. The overall results of this work suggest that the structural changes took place in PVDF matrix during the preparation of these polymer electrolytes have a strong impact on their various properties.

  20. Ceramic solid electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Goodenough, John B. [Center for Materials Science and Engineering, University of Texas at Austin, Austin, TX (United States)

    1997-02-15

    Strategies for the design of ceramic solid electrolytes are reviewed. Problems associated with stoichiometric and doped compounds are compared. In the illustration of design principles, emphasis is given to oxide-ion electrolytes for use in solid-oxide fuel cells, oxygen pumps, and oxygen sensors

  1. Effect of lithium salt concentrations on blended 49% poly(methyl methacrylate) grafted natural rubber and poly(methyl methacrylate) based solid polymer electrolyte

    International Nuclear Information System (INIS)

    Su’ait, M.S.; Ahmad, A.; Hamzah, H.; Rahman, M.Y.A.

    2011-01-01

    The effect of lithium salts (lithium tetrafluoroborate, LiBF 4 and lithium perchlorate, LiClO 4 ) as doping salts in rubber-polymer blends, 49% poly(methyl methacrylate) grafted natural rubber (MG49) and poly(methyl methacrylate) (PMMA) in solid polymer electrolyte (SPE) film for electrochemical devices application was investigated. The electrolyte films were prepared via the solution casting technique using 0–25 wt.% lithium salt. The effect of the lithium salts on chemical interaction, ionic conductivity and structural and morphological studies of (70:30) MG49-PMMA films was analyzed using Fourier Transform Infrared (FT-IR) Spectroscopy, Electrochemical Impedance Spectroscopy (EIS), X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Infrared analysis showed that the interactions between lithium ions and oxygen atoms occur at the ether group (C–O–C) (1500–1100 cm −1 ) on the MMA structure in both MG49 and PMMA. The oxygen atoms in the structure of the polymer host act as electron donor atoms and form a coordinate bond with the lithium ions from the doping salt to form polymer–salt complexes. The ionic conductivity was investigated at room temperature as well as at a temperature range from 303 K to 373 K. The ionic conductivity without the addition of salt was 1.1 × 10 −12 S cm −1 . The highest conductivity at room temperature for (70:30) MG49-PMMA–LiBF 4 was 8.6 × 10 −6 S cm −1 at 25 wt.% of LiBF 4 . The ionic conductivity of (70:30) MG49-PMMA–LiClO 4 was 1.5 × 10 −8 S cm −1 at 25 wt.% of LiClO 4 . However, both electrolyte systems do not exhibit Arrhenius-like behavior. Systems with LiBF 4 salt have higher ionic conductivity than those with LiClO 4 salt because of the differences in anionic size and lattice energy of the appropriate salt. The observations from structural and morphology studies showed that complexation and re-crystallization occur in the system. The XRD studies showed a reduction of the MMA peak

  2. Electroless Formation of Hybrid Lithium Anodes for Fast Interfacial Ion Transport

    KAUST Repository

    Choudhury, Snehashis; Tu, Zhengyuan; Stalin, Sanjuna; Vu, Duylinh; Fawole, Kristen; Gunceler, Deniz; Sundararaman, Ravishankar; Archer, Lynden A.

    2017-01-01

    Rechargeable batteries based on metallic anodes are of interest for fundamental and application-focused studies of chemical and physical kinetics of liquids at solid interfaces. Approaches that allow facile creation of uniform coatings on these metals to prevent physical contact with liquid electrolytes, while enabling fast ion transport, are essential to address chemical instability of the anodes. Here, we report a simple electroless ion-exchange chemistry for creating coatings of indium on lithium. By means of joint density functional theory and interfacial characterization experiments, we show that In coatings stabilize Li by multiple processes, including exceptionally fast surface diffusion of lithium ions and high chemical resistance to liquid electrolytes. Indium coatings also undergo reversible alloying reactions with lithium ions, facilitating design of high-capacity hybrid In-Li anodes that use both alloying and plating approaches for charge storage. By means of direct visualization, we further show that the coatings enable remarkably compact and uniform electrodeposition. The resultant In-Li anodes are shown to exhibit minimal capacity fade in extended galvanostatic cycling when paired with commercial-grade cathodes.

  3. Electroless Formation of Hybrid Lithium Anodes for Fast Interfacial Ion Transport

    KAUST Repository

    Choudhury, Snehashis

    2017-08-17

    Rechargeable batteries based on metallic anodes are of interest for fundamental and application-focused studies of chemical and physical kinetics of liquids at solid interfaces. Approaches that allow facile creation of uniform coatings on these metals to prevent physical contact with liquid electrolytes, while enabling fast ion transport, are essential to address chemical instability of the anodes. Here, we report a simple electroless ion-exchange chemistry for creating coatings of indium on lithium. By means of joint density functional theory and interfacial characterization experiments, we show that In coatings stabilize Li by multiple processes, including exceptionally fast surface diffusion of lithium ions and high chemical resistance to liquid electrolytes. Indium coatings also undergo reversible alloying reactions with lithium ions, facilitating design of high-capacity hybrid In-Li anodes that use both alloying and plating approaches for charge storage. By means of direct visualization, we further show that the coatings enable remarkably compact and uniform electrodeposition. The resultant In-Li anodes are shown to exhibit minimal capacity fade in extended galvanostatic cycling when paired with commercial-grade cathodes.

  4. A Lithium-Ion Battery with Enhanced Safety Prepared using an Environmentally Friendly Process.

    Science.gov (United States)

    Mueller, Franziska; Loeffler, Nicholas; Kim, Guk-Tae; Diemant, Thomas; Behm, R Jürgen; Passerini, Stefano

    2016-06-08

    A new lithium-ion battery chemistry is presented based on a conversion-alloying anode material, a carbon-coated Fe-doped ZnO (TMO-C), and a LiNi1/3 Mn1/3 Co1/3 O2 (NMC) cathode. Both electrodes were fabricated using an environmentally friendly cellulose-based binding agent. The performance of the new lithium-ion battery was evaluated with a conventional, carbonate-based electrolyte (ethylene carbonate:diethyl carbonate-1 m lithium hexafluorophosphate, EC:DEC 1 m LiPF6 ) and an ionic liquid (IL)-based electrolyte (N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide-0.2 m lithium bis(trifluoromethanesulfonyl)imide, Pyr14 TFSI 0.2 m LiTFSI), respectively. Galvanostatic charge/discharge tests revealed a reduced rate capability of the TMO-C/Pyr14 TFSI 0.2 m LiTFSI/NMC full-cell compared to the organic electrolyte, but the coulombic efficiency was significantly enhanced. Moreover, the IL-based electrolyte substantially improves the safety of the system due to a higher thermal stability of the formed anodic solid electrolyte interphase and the IL electrolyte itself. While the carbonate-based electrolyte shows sudden degradation reactions, the IL exhibits a slowly increasing heat flow, which does not constitute a serious safety risk. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Iron titanium phosphates as high-specific-capacity electrode materials for lithium ion batteries

    Czech Academy of Sciences Publication Activity Database

    Essehli, R.; El Bali, B.; Faik, A.; Naji, M.; Benmokhtar, S.; Zhong, Y.R.; Su, L.W.; Zhou, Z.; Kim, J.; Kang, K.; Dušek, Michal

    2014-01-01

    Roč. 585, FEB (2014), s. 434-441 ISSN 0925-8388 Institutional support: RVO:68378271 Keywords : crystal structure * electrolyte * nasicon * oxyphosphate * lithium -ion batteries Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.999, year: 2014

  6. Preparation and performance of a novel gel polymer electrolyte based on poly(vinylidene fluoride)/graphene separator for lithium ion battery

    International Nuclear Information System (INIS)

    Liu, Jiuqing; Wu, Xiufeng; He, Junying; Li, Jie; Lai, Yanqing

    2017-01-01

    Poly(vinylidenefluoride)/graphene (PVDF/graphene) gel polymer electrolyte is prepared via non-solvent induced phase separation (NIPS) technique for lithium ion battery application. The effect of graphene on the ion conductivity is investigated by AC impedance measurement. The relationship among the chemical structure, PVDF crystallinity, the graphene on macroporous formation and the ion conductivity are investigated. The results indicate that the graphene disperses homogenously in PVDF, and it also increases the porosity and decreases the crystallinity of the PVDF. At the same time, the unique structure increases the liquid uptake capability of PVDF/graphene polymer electrolyte. The ionic conductivity of the PVDF/graphene polymer electrolyte increases significantly from 1.85 mS cm"−"1 in pristine PVDF to 3.61 mS cm"−"1 with 0.002 wt% graphene. It is found that graphene not only increases the ionic conductivity but also markedly enhances the rate capability and the cycling performances of coin cell. This study shows that PVDF/graphene gel polymer electrolyte is a very promising material for lithium ion batteries.

  7. Advanced High-Voltage Aqueous Lithium-Ion Battery Enabled by "Water-in-Bisalt" Electrolyte.

    Science.gov (United States)

    Suo, Liumin; Borodin, Oleg; Sun, Wei; Fan, Xiulin; Yang, Chongyin; Wang, Fei; Gao, Tao; Ma, Zhaohui; Schroeder, Marshall; von Cresce, Arthur; Russell, Selena M; Armand, Michel; Angell, Austen; Xu, Kang; Wang, Chunsheng

    2016-06-13

    A new super-concentrated aqueous electrolyte is proposed by introducing a second lithium salt. The resultant ultra-high concentration of 28 m led to more effective formation of a protective interphase on the anode along with further suppression of water activities at both anode and cathode surfaces. The improved electrochemical stability allows the use of TiO2 as the anode material, and a 2.5 V aqueous Li-ion cell based on LiMn2 O4 and carbon-coated TiO2 delivered the unprecedented energy density of 100 Wh kg(-1) for rechargeable aqueous Li-ion cells, along with excellent cycling stability and high coulombic efficiency. It has been demonstrated that the introduction of a second salts into the "water-in-salt" electrolyte further pushed the energy densities of aqueous Li-ion cells closer to those of the state-of-the-art Li-ion batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yanyan; Su, Mao; Yu, Xiaofei; Zhou, Yufan; Wang, Jungang; Cao, Ruiguo; Xu, Wu; Wang, Chongmin; Baer, Donald R.; Borodin, Oleg; Xu, Kang; Wang, Yanting; Wang, Xue-Lin; Xu, Zhijie; Wang, Fuyi; Zhu, Zihua

    2018-02-06

    Ion-solvent interactions in non-aqueous electrolytes are of fundamental interest and practical importance, yet debates regarding ion preferential solvation and coordination numbers persist. In this work, in situ liquid SIMS was used to examine ion-solvent interactions in three representative electrolytes, i.e., lithium hexafluorophosphate (LiPF6) at 1.0 M in ethylene carbonate (EC)-dimethyl carbonate (DMC), and lithium bis(fluorosulfonyl)imide (LiFSI) at both low (1.0 M) and high (4.0 M) concentrations in 1,2-dimethoxyethane (DME). In the positive ion mode, solid molecular evidence strongly supports the preferential solvation of Li+ by EC. Besides, from the negative spectra, we also found that PF6- forms association with EC, which has been neglected by previous studies due to the relatively weak interaction. While in both LiFSI in DME electrolytes, no evidence shows that FSI- is associated with DME. Furthermore, strong salt ion cluster signals were observed in the 1.0 M LiPF6 in EC-DMC electrolyte, suggesting that a significant amount of Li+ ions stay in vicinity of anions. In sharp comparison, weak ion cluster signals were detected in dilute LiFSI in DME electrolyte, suggesting most ions are well separated, in agreement with our molecular dynamics (MD) simulation results. These findings indicate that with virtues of little bias on detecting positive and negative ions and the capability of directly analyzing concentrated electrolytes, in situ liquid SIMS is a powerful tool that can provide key evidence for improved understanding on the ion-solvent interactions in non-aqueous electrolytes. Therefore, we anticipate wide applications of in situ liquid SIMS on investigations of various ion-solvent interactions in the near future.

  9. Aging Mechanisms of Electrode Materials in Lithium-Ion Batteries for Electric Vehicles

    Directory of Open Access Journals (Sweden)

    Cheng Lin

    2015-01-01

    Full Text Available Electrode material aging leads to a decrease in capacity and/or a rise in resistance of the whole cell and thus can dramatically affect the performance of lithium-ion batteries. Furthermore, the aging phenomena are extremely complicated to describe due to the coupling of various factors. In this review, we give an interpretation of capacity/power fading of electrode-oriented aging mechanisms under cycling and various storage conditions for metallic oxide-based cathodes and carbon-based anodes. For the cathode of lithium-ion batteries, the mechanical stress and strain resulting from the lithium ions insertion and extraction predominantly lead to structural disordering. Another important aging mechanism is the metal dissolution from the cathode and the subsequent deposition on the anode. For the anode, the main aging mechanisms are the loss of recyclable lithium ions caused by the formation and increasing growth of a solid electrolyte interphase (SEI and the mechanical fatigue caused by the diffusion-induced stress on the carbon anode particles. Additionally, electrode aging largely depends on the electrochemical behaviour under cycling and storage conditions and results from both structural/morphological changes and side reactions aggravated by decomposition products and protic impurities in the electrolyte.

  10. High Lithium Transference Number Electrolytes via Creation of 3-Dimensional, Charged, Nanoporous Networks from Dense Functionalized Nanoparticle Composites

    KAUST Repository

    Schaefer, Jennifer L.; Yanga, Dennis A.; Archer, Lynden A.

    2013-01-01

    High lithium transference number, tLi+, electrolytes are desired for use in both lithium-ion and lithium metal rechargeable battery technologies. Historically, low tLi+ electrolytes have hindered device performance by allowing ion concentration

  11. Solid electrolyte batteries and fast ion conducting glasses, factors affecting a proposed merger

    Energy Technology Data Exchange (ETDEWEB)

    Uhlmann, D R; Tuller, H L; Button, D P; Valez, M [Massachusetts Inst. of Tech., Cambridge (USA). Dept. of Materials Science and Engineering

    1983-01-01

    The present paper is concerned with advanced battery systems employing glass as a solid electrolyte. After an initial discussion of battery systems employing solid electrolytes, and of the attractive features offered by glass electrolytes, consideration is given to batteries fabricated with such electrolytes and to their performance characteristics. Subsequent discussion is directed to the two principal characteristics of glasses which are critical to their use as solid electrolytes - viz., their electrical conductivity and resistance to corrosive attack. The present state of knowledge in each of these areas is summarized, with particular focus on glasses with exceptionally high ionic conductivities - so-called fast ion conductors or FIC's.

  12. Comparative Study of Ether-Based Electrolytes for Application in Lithium-Sulfur Battery.

    Science.gov (United States)

    Carbone, Lorenzo; Gobet, Mallory; Peng, Jing; Devany, Matthew; Scrosati, Bruno; Greenbaum, Steve; Hassoun, Jusef

    2015-07-01

    Herein, we report the characteristics of electrolytes using various ether-solvents with molecular composition CH3O[CH2CH2O]nCH3, differing by chain length, and LiCF3SO3 as the lithium salt. The electrolytes, considered as suitable media for lithium-sulfur batteries, are characterized in terms of thermal properties (TGA, DSC), lithium ion conductivity, lithium interface stability, cyclic voltammetry, self-diffusion properties of the various components, and lithium transference number measured by NMR. Furthermore, the electrolytes are characterized in lithium cells using a sulfur-carbon composite cathode by galvanostatic charge-discharge tests. The results clearly evidence the influence of the solvent chain length on the species mobility within the electrolytes that directly affects the behavior in lithium sulfur cell. The results may effectively contribute to the progress of an efficient, high-energy lithium-sulfur battery.

  13. A Liquid Inorganic Electrolyte Showing an Unusually High Lithium Ion Transference Number: A Concentrated Solution of LiAlCl4 in Sulfur Dioxide

    Directory of Open Access Journals (Sweden)

    Martin Winter

    2013-08-01

    Full Text Available We report on studies of an inorganic electrolyte: LiAlCl4 in liquid sulfur dioxide. Concentrated solutions show a very high conductivity when compared with typical electrolytes for lithium ion batteries that are based on organic solvents. Our investigations include conductivity measurements and measurements of transference numbers via nuclear magnetic resonance (NMR and by a classical direct method, Hittorf’s method. For the use of Hittorf’s method, it is necessary to measure the concentration of the electrolyte in a selected cell compartment before and after electrochemical polarization very precisely. This task was finally performed by potentiometric titration after hydrolysis of the salt. The Haven ratio was determined to estimate the association behavior of this very concentrated electrolyte solution. The measured unusually high transference number of the lithium cation of the studied most concentrated solution, a molten solvate LiAlCl4 × 1.6SO2, makes this electrolyte a promising alternative for lithium ion cells with high power ability.

  14. In situ electron holography of electric potentials inside a solid-state electrolyte: Effect of electric-field leakage

    Energy Technology Data Exchange (ETDEWEB)

    Aizawa, Yuka; Yamamoto, Kazuo; Sato, Takeshi [Nanostructures Research Laboratory, Japan Fine Ceramics Center, 2-4-1 Mutsuno, Atsuta-ku, Nagoya, Aichi 456-8587 (Japan); Murata, Hidekazu [Faculty of Science and Technology, Meijo University, 1-501 Shiogamaguchi, Tempaku-ku, Nagoya, Aichi 468-8502 (Japan); Yoshida, Ryuji; Fisher, Craig A.J. [Nanostructures Research Laboratory, Japan Fine Ceramics Center, 2-4-1 Mutsuno, Atsuta-ku, Nagoya, Aichi 456-8587 (Japan); Kato, Takehisa; Iriyama, Yasutoshi [Department of Materials, Physics and Energy Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8601 (Japan); Hirayama, Tsukasa, E-mail: t-hirayama@jfcc.or.jp [Nanostructures Research Laboratory, Japan Fine Ceramics Center, 2-4-1 Mutsuno, Atsuta-ku, Nagoya, Aichi 456-8587 (Japan)

    2017-07-15

    In situ electron holography is used to observe changes of electric-potential distributions in an amorphous lithium phosphorus oxynitride (LiPON) solid-state electrolyte when different voltages are applied. 2D phase images are simulated by integrating the 3D potential distribution along the electron trajectory through a thin Cu/LiPON/Cu region. Good agreement between experimental and simulated phase distributions is obtained when the influence of the external electric field is taken into account using the 3D boundary-charge method. Based on the precise potential changes, the lithium-ion and lithium-vacancy distributions inside the LiPON layer and electric double layers (EDLs) are inferred. The gradients of the phase drops at the interfaces in relation to EDL widths are discussed. - Highlights: • Solid-state electrolyte LiPON has been observed by in situ electron holography. • Observed phase distributions are compared with those simulated numerically. • 3D electric fields around the specimen are taken into account in the simulation. • Electric-potential distributions inside LiPON have been obtained. • The lithium-ion and lithium-vacancy distributions inside the LiPON are inferred.

  15. To immobilize polyethylene glycol-borate ester/lithium fluoride in graphene oxide/poly(vinyl alcohol for synthesizing new polymer electrolyte membrane of lithium-ion batteries

    Directory of Open Access Journals (Sweden)

    Y. F. Huang

    2017-01-01

    Full Text Available Polymer electrolyte membranes (PEMs are potentially applicable in lithium-ion batteries with high safety, low cost and good performance. Here, to take advantages of ionic conductivity and selectivity of borate ester-functionalized small molecules as well as structural properties of polymer nanocomposite, a strategy of immobilizing as-synthesized polyethylene glycol-borate ester/lithium fluoride (B-PEG/LiF in graphene oxide/poly(vinyl alcohol (GO/PVA to prepare a PEM is put forward. Chemical structure of the PEM is firstly characterized by 1H-, 11B- and 19F-nuclear magnetic resonance spectra, and Fourier transform infrared spectroscopy spectra, respectively, and then is further investigated under consideration of the interactions among PVA, B-PEG and LiF components. The immobilization of B-PEG/LiF in PVA-based structure is confirmed. As the interactions within electrolyte components can be further tuned by GO, ionic conductivity (~10–3 S·cm–1, lithium-ion transfer number (~0.49, and thermal (~273 °C/electrochemical (>4 V stabilities of the PEM can be obtained, and the feasibility of PEMs applied in a lithium-ion battery is also confirmed. It is believed that such PEM is a promising candidate as a new battery separator.

  16. Ion transport property studies on PEO-PVP blended solid polymer electrolyte membranes

    International Nuclear Information System (INIS)

    Chandra, Angesh; Agrawal, R C; Mahipal, Y K

    2009-01-01

    The ion transport property studies on Ag + ion conducting PEO-PVP blended solid polymer electrolyte (SPE) membranes, (1 - x)[90PEO : 10AgNO 3 ] : xPVP, where x = 0, 1, 2, 3, 5, 7, 10 (wt%), are reported. SPE films were caste using a novel hot-press technique instead of the traditional solution cast method. The conventional solid polymeric electrolyte (SPE) film, (90PEO : 10AgNO 3 ), also prepared by the hot-press method and identified as the highest conducting composition at room temperature on the basis of PEO-AgNO 3 -salt concentration dependent conductivity studies, was used as the first-phase polymer electrolyte host into which PVP were dispersed as second-phase dispersoid. A two-fold conductivity enhancement from that of the PEO host could be achieved at room temperature for PVP blended SPE film composition: 98(90PEO : 10AgNO 3 ) : 2PVP. This has been referred to as optimum conducting composition (OCC). The formation of SPE membranes and material characterizations were done with the help of the XRD and DSC techniques. The ion transport mechanism in this SPE OCC has been characterized with the help of basic ionic parameters, namely ionic conductivity (σ), ionic mobility (μ), mobile ion concentration (n) and ionic transference number (t ion ). Solid-state polymeric batteries were fabricated using OCC as electrolyte and the cell-potential discharge characteristics were studied under different load conditions.

  17. Lanthanum Nitrate As Electrolyte Additive To Stabilize the Surface Morphology of Lithium Anode for Lithium-Sulfur Battery.

    Science.gov (United States)

    Liu, Sheng; Li, Guo-Ran; Gao, Xue-Ping

    2016-03-01

    Lithium-sulfur (Li-S) battery is regarded as one of the most promising candidates beyond conventional lithium ion batteries. However, the instability of the metallic lithium anode during lithium electrochemical dissolution/deposition is still a major barrier for the practical application of Li-S battery. In this work, lanthanum nitrate, as electrolyte additive, is introduced into Li-S battery to stabilize the surface of lithium anode. By introducing lanthanum nitrate into electrolyte, a composite passivation film of lanthanum/lithium sulfides can be formed on metallic lithium anode, which is beneficial to decrease the reducibility of metallic lithium and slow down the electrochemical dissolution/deposition reaction on lithium anode for stabilizing the surface morphology of metallic Li anode in lithium-sulfur battery. Meanwhile, the cycle stability of the fabricated Li-S cell is improved by introducing lanthanum nitrate into electrolyte. Apparently, lanthanum nitrate is an effective additive for the protection of lithium anode and the cycling stability of Li-S battery.

  18. Properties and structures of electrolyte solutions for lithium batteries

    Energy Technology Data Exchange (ETDEWEB)

    Blomgren, G. E.

    1985-01-15

    Rules which have been employed to explain and predict solvent properties of lithium battery electrolytes are described and results reviewed. The equilibrium behavior of moderate to high concentration electrolyte solutions is also reviewed. Recent theoretical approaches to explain the behavior are discussed, and a new theory incorporating contact ion pair concepts into an advanced statistical theory for free ions is proposed.

  19. Solid-state supercapacitors with ionic liquid based gel polymer electrolyte: Effect of lithium salt addition

    Science.gov (United States)

    Pandey, G. P.; Hashmi, S. A.

    2013-12-01

    Performance characteristics of the solid-state supercapacitors fabricated with ionic liquid (IL) incorporated gel polymer electrolyte and acid treated multiwalled carbon nanotube (MWCNT) electrodes have been studied. The effect of Li-salt (LiPF6) addition in the IL (1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate, EMImFAP) based gel electrolyte on the performance of supercapacitors has been specifically investigated. The LiPF6/IL/poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) gel electrolyte film possesses excellent electrochemical window of 4 V (from -2.0 to 2.0 V), high ionic conductivity ∼2.6 × 10-3 S cm-1 at 20 °C and high enough thermal stability. The comparative performance of supercapacitors employing electrolytes with and without lithium salt has been evaluated by impedance spectroscopy and cyclic voltammetric studies. The acid-treated MWCNT electrodes show specific capacitance of ∼127 F g-1 with IL/LiPF6 containing gel polymer electrolyte as compared to that with the gel polymer electrolyte without Li-salt, showing the value of ∼76 F g-1. The long cycling stability of the solid state supercapacitor based on the Li-salt containing gel polymer electrolyte confirms the electrochemical stability of the electrolyte.

  20. Modeling the Lithium Ion Battery

    Science.gov (United States)

    Summerfield, John

    2013-01-01

    The lithium ion battery will be a reliable electrical resource for many years to come. A simple model of the lithium ions motion due to changes in concentration and voltage is presented. The battery chosen has LiCoO[subscript 2] as the cathode, LiPF[subscript 6] as the electrolyte, and LiC[subscript 6] as the anode. The concentration gradient and…

  1. Ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multi-functional flame retardant electrolyte additive for lithium-ion batteries

    Science.gov (United States)

    Li, Xi; Li, Weikang; Chen, Lai; Lu, Yun; Su, Yuefeng; Bao, Liying; Wang, Jing; Chen, Renjie; Chen, Shi; Wu, Feng

    2018-02-01

    With the wide application of lithium-ion batteries (LiBs), safety performance is an important constraint on the commercialization of large-scale, high-capacity LIBs. The main reason for the safety problem is that the electrolyte of LiBs is highly flammable, especially under high temperature and high voltage. It is an effective method to improve the safety of cells by mixing flame retardant with conventional electrolyte comprising of LiPF6 and carbonates. Herein, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) is studied as a high efficiency flame retardant. Adding 5 vol% of PFPN results in a non-flammable electrolyte with self-extinguishing time (SET) of 12.38 s g-1 and critical oxygen index (COI) of 22.9, without compromising the capacity of cathode material. The initial discharge capacity of the LiCoO2 electrode with 5% PFPN is 150.7 mAh g-1, with a capacity retention of 99.14% after 30 cycles at 0.1 C. The results show that 5 vol% is the best adding amount of PFPN for electrolyte, which can modify the solid electrolyte interface (SEI). Moreover, PFPN reduces charge transfer resistance of the cells, resulting decreased electrode polarization and enhanced electrochemistry performances at low temperature. These results have confirmed that PFPN has the potential to be a multi-function additive for commercial LIBs production.

  2. Electroless formation of hybrid lithium anodes for fast interfacial ion transport

    Energy Technology Data Exchange (ETDEWEB)

    Choudhury, Snehashis; Stalin, Sanjuna; Vu, Duylinh; Fawole, Kristen; Archer, Lynden A. [School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, NY (United States); Tu, Zhengyuan [Department of Material Science and Engineering, Cornell University, Ithaca, NY (United States); Gunceler, Deniz [Department of Physics, Cornell University, Ithaca, NY (United States); Sundararaman, Ravishankar [Material Science and Engineering, Rensselaer Polytechnic Institute, Troy, NY (United States)

    2017-10-09

    Rechargeable batteries based on metallic anodes are of interest for fundamental and application-focused studies of chemical and physical kinetics of liquids at solid interfaces. Approaches that allow facile creation of uniform coatings on these metals to prevent physical contact with liquid electrolytes, while enabling fast ion transport, are essential to address chemical instability of the anodes. Here, we report a simple electroless ion-exchange chemistry for creating coatings of indium on lithium. By means of joint density functional theory and interfacial characterization experiments, we show that In coatings stabilize Li by multiple processes, including exceptionally fast surface diffusion of lithium ions and high chemical resistance to liquid electrolytes. Indium coatings also undergo reversible alloying reactions with lithium ions, facilitating design of high-capacity hybrid In-Li anodes that use both alloying and plating approaches for charge storage. By means of direct visualization, we further show that the coatings enable remarkably compact and uniform electrodeposition. The resultant In-Li anodes are shown to exhibit minimal capacity fade in extended galvanostatic cycling when paired with commercial-grade cathodes. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Using quasi-elastic neutron diffraction to study positive electrode for lithium and sodium-ion batteries

    International Nuclear Information System (INIS)

    Pramudita, James C.; Sharma, Neeraj

    2015-01-01

    Sodium-ion batteries has recently been proposed as the alternative for lithium-ion batteries to be the low cost energy storage system. However, challenges still remains for the development of sodium-ion batteries. Optimization of electrode materials and electrolyte capable of insertion/extraction of sodium-ion in a safe and economic way under high current density is needed in order to produce commercially viable sodium-ion batteries. While possible positive electrode material is more prevalent than negative electrode material, many of these material still need further understanding. Quasi-elastic Neutron Scatteringis a technique that utilize the inelastic Neutron Scatteringthat can be used to study solid-state diffusion in materials. This technique can be used to study the diffusion of sodium-ion under electric field through the electrolyte and positive electrode materials in order to further understand the mechanism of sodium insertion/extraction in a working battery. This technique can also be used to study available positive electrode material for lithium-ion batteries to further understand the mechanism of lithium-ion diffusion in current working lithiumion batteries.

  4. Synthesis and Electrochemical Performance of a Lithium Titanium Phosphate Anode for Aqueous Lithium-Ion Batteries

    KAUST Repository

    Wessells, Colin; La Mantia, Fabio; Deshazer, Heather; Huggins, Robert A.; Cui, Yi

    2011-01-01

    Lithium-ion batteries that use aqueous electrolytes offer safety and cost advantages when compared to today's commercial cells that use organic electrolytes. The equilibrium reaction potential of lithium titanium phosphate is -0.5 V with respect

  5. The Buried Carbon/Solid Electrolyte Interphase in Li-ion Batteries Studied by Hard X-ray Photoelectron Spectroscopy

    International Nuclear Information System (INIS)

    Ciosek Högström, Katarzyna; Malmgren, Sara; Hahlin, Maria; Gorgoi, Mihaela; Nyholm, Leif; Rensmo, Håkan; Edström, Kristina

    2014-01-01

    In cycled Li-ion batteries, the carbon negative electrode is buried under a thin passivating layer referred to as the solid electrolyte interphase (SEI). In the present study, the increased depth sensitivity of hard X-ray photoelectron spectroscopy (HAXPES) as compared to conventional X-ray photoelectron spectroscopy (XPS) is used to study electrochemical changes at such a buried carbon/SEI. Samples from graphite/LiFePO 4 cells cycled to specific potentials during the first four charge/discharge cycles were studied. The results show dynamic changes in the SEI during cycling. Reversible, state of charge (SOC) dependent changes in the SEI thickness as well as amounts of lithium oxide, lithium fluoride, lithium and carbon active material were discussed. Moreover, the results indicate lithium enrichment close to the carbon active material surface, which could not be explained by intercalation of lithium into carbon with LiC 6 structure or by SEI formation at the surface. Potential dependent shifts in the binding energy of the carbon active material C1s feature showed the importance of internal energy calibration with an SEI feature rather than carbon active material

  6. Sintered Cathodes for All-Solid-State Structural Lithium-Ion Batteries

    Science.gov (United States)

    Huddleston, William; Dynys, Frederick; Sehirlioglu, Alp

    2017-01-01

    All-solid-state structural lithium ion batteries serve as both structural load-bearing components and as electrical energy storage devices to achieve system level weight savings in aerospace and other transportation applications. This multifunctional design goal is critical for the realization of next generation hybrid or all-electric propulsion systems. Additionally, transitioning to solid state technology improves upon battery safety from previous volatile architectures. This research established baseline solid state processing conditions and performance benchmarks for intercalation-type layered oxide materials for multifunctional application. Under consideration were lithium cobalt oxide and lithium nickel manganese cobalt oxide. Pertinent characteristics such as electrical conductivity, strength, chemical stability, and microstructure were characterized for future application in all-solid-state structural battery cathodes. The study includes characterization by XRD, ICP, SEM, ring-on-ring mechanical testing, and electrical impedance spectroscopy to elucidate optimal processing parameters, material characteristics, and multifunctional performance benchmarks. These findings provide initial conditions for implementing existing cathode materials in load bearing applications.

  7. Novel, Solvent-Free, Single Ion Conductive Polymer Electrolytes

    National Research Council Canada - National Science Library

    Florjanczyk, Zbigniew

    2008-01-01

    This project report concerns studies on the synthesis of new polymer electrolytes for application in lithium and lithium-ion batteries characterized by limited participation of anions in the transport...

  8. Perfluoroalkyl-substituted ethylene carbonates: Novel electrolyte additives for high-voltage lithium-ion batteries

    Science.gov (United States)

    Zhu, Ye; Casselman, Matthew D.; Li, Yan; Wei, Alexander; Abraham, Daniel P.

    2014-01-01

    A new family of polyfluoroalkyl-substituted ethylene carbonates is synthesized and tested as additives in lithium-ion cells containing EC:EMC + LiPF6-based electrolyte. The influence of these compounds is investigated in Li1.2Ni0.15Mn0.55Co0.1O2//graphite cells via a combination of galvanostatic cycling and electrochemical impedance spectroscopy (EIS) tests. Among the four additives studied in this work (4-(trifluoromethyl)-1,3-dioxolan-2-one (TFM-EC), 4-(perfluorobutyl)-1,3-dioxolan-2-one (PFB-EC), 4-(perfluorohexyl)-1,3-dioxolan-2-one (PFH-EC), and 4-(perfluorooctyl)-1,3-dioxolan-2-one (PFO-EC)), small amounts (0.5 wt%) of PFO-EC is found to be most effective in lessening cell performance degradation during extended cycling. Linear sweep voltammetry (LSV), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy are used to further characterize the effects of PFO-EC on the positive and negative electrodes. LSV data from the electrolyte, and XPS analyses of electrodes harvested after cycling, suggest that PFO-EC is oxidized on the cathode forming surface films that slow electrode/cell impedance rise. Differential capacity (dQ/dV) plots from graphite//Li cells suggest that PFO-EC is involved in solid electrolyte interphase (SEI) formation. Raman data from anodes after cycling suggest that structural disordering of graphite is reduced by the addition of PFO-EC, which may explain the improved cell capacity retention.

  9. Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)

    DEFF Research Database (Denmark)

    Yu, Seungho; Schmidt, Robert D.; Garcia-Mendez, Regina

    2016-01-01

    The oxide known as LLZO, with nominal composition Li7La3Zr2O12, is a promising solid electrolyte for Li-based batteries due to its high Li ion conductivity and chemical stability with respect to lithium. Solid electrolytes may also enable the use of metallic Li anodes by serving as a physical bar...

  10. Experimental and Computational Approaches to Interfacial Resistance in Solid-State Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Takada, Kazunori, E-mail: takada.kazunori@nims.go.jp [Battery Materials Unit, National Institute for Materials Science, Tsukuba (Japan); Global Research Center for Environment and Energy Based on Nanomaterials Science, National Institute for Materials Science, Tsukuba (Japan); Ohno, Takahisa [Global Research Center for Environment and Energy Based on Nanomaterials Science, National Institute for Materials Science, Tsukuba (Japan); Computational Materials Science Unit, National Institute for Materials Science, Tsukuba (Japan)

    2016-03-30

    Solid-state batteries with inorganic solid electrolytes are expected to be an efficient solution to the issues of current lithium-ion batteries that are originated from their organic-solvent electrolytes. Although solid-state batteries had been suffering from low rate capability due to low ionic conductivities of solid electrolytes, some sulfide solid electrolytes exhibiting high ionic conductivity of the order of 10{sup −2} S cm{sup −1} have been recently developed. Since the conductivity is comparable to or even higher than that of liquid electrolytes, when taking the transport number of unity into account, ion transport in solid electrolytes has ceased from rate determination; however, it has been replaced by that across interfaces. The sulfide electrolytes show high interfacial resistance to the high-voltage cathodes. Our previous studies have demonstrated that oxide solid electrolytes interposed at the interface reduce the resistance, and they also suggest that the high resistance is attributable to a lithium-depleted layer formed at the interface. This study employs the first-principles calculation in order to gain insight into the interface. The interface structure between an oxide cathode/sulfide electrolyte simulated by the first-principles molecular dynamics has disclosed the presence of lithium-depleted layer at the interface, and the electronic structure calculated on the basis of density functional theory strongly suggests that the charge current preferentially removes lithium ions from the sulfide electrolyte side of the interface to deplete the lithium ion there. These calculation results are consistent with the transport mechanism proposed from the experimental results.

  11. Experimental and Computational Approaches to Interfacial Resistance in Solid-State Batteries

    International Nuclear Information System (INIS)

    Takada, Kazunori; Ohno, Takahisa

    2016-01-01

    Solid-state batteries with inorganic solid electrolytes are expected to be an efficient solution to the issues of current lithium-ion batteries that are originated from their organic-solvent electrolytes. Although solid-state batteries had been suffering from low rate capability due to low ionic conductivities of solid electrolytes, some sulfide solid electrolytes exhibiting high ionic conductivity of the order of 10 −2 S cm −1 have been recently developed. Since the conductivity is comparable to or even higher than that of liquid electrolytes, when taking the transport number of unity into account, ion transport in solid electrolytes has ceased from rate determination; however, it has been replaced by that across interfaces. The sulfide electrolytes show high interfacial resistance to the high-voltage cathodes. Our previous studies have demonstrated that oxide solid electrolytes interposed at the interface reduce the resistance, and they also suggest that the high resistance is attributable to a lithium-depleted layer formed at the interface. This study employs the first-principles calculation in order to gain insight into the interface. The interface structure between an oxide cathode/sulfide electrolyte simulated by the first-principles molecular dynamics has disclosed the presence of lithium-depleted layer at the interface, and the electronic structure calculated on the basis of density functional theory strongly suggests that the charge current preferentially removes lithium ions from the sulfide electrolyte side of the interface to deplete the lithium ion there. These calculation results are consistent with the transport mechanism proposed from the experimental results.

  12. Effects of Propylene Carbonate Content in CsPF6-Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo; Xiang, Hongfa; Engelhard, Mark H.; Polzin, Bryant; Wang, Chong M.; Zhang, Jiguang; Xu, Wu

    2016-02-10

    Cesium salt has been demonstrated as an efficient electrolyte additive in suppressing the lithium (Li) dendrite formation and directing the formation of an ultrathin and stable solid electrolyte interphase (SEI) even in propylene carbonate (PC)-ethylene carbonate (EC)-based electrolytes. Here, we further investigate the effect of PC content in the presence of CsPF6 additive (0.05 M) on the performances of graphite electrode in Li||graphite half cells and in graphite||LiNi0.80Co0.15Al0.05O2 (NCA) full cells. It is found that the performance of graphite electrode is also affected by PC content even though CsPF6 additive is present in the electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode is attributed to the synergistic effects of the Cs+ additive and the PC solvent. The formation of a robust, ultrathin and compact SEI layer containing lithium-enriched species on the graphite electrode, directed by Cs+, effectively suppresses the PC co-intercalation and thus prevents the graphite exfoliation. This SEI layer is only permeable for de-solvated Li+ ions and allows fast Li+ ion transport through it, which therefore largely alleviates the Li dendrite formation on graphite electrode during lithiation even at high current densities. The presence of low-melting-point PC solvent also enables the sustainable operation of the graphite||NCA full cells under a wide spectrum of temperatures. The fundamental findings of this work shed light on the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in a variety of energy storage devices.

  13. Investigation of the lithium ion mobility in cyclic model compounds and their ion conduction properties

    Energy Technology Data Exchange (ETDEWEB)

    Thielen, Joerg

    2011-07-27

    combination to changes in glass transition temperatures. Though the glass transition temperatures of the blends are low, their conductivities are only in the range of typical polymer electrolytes. The highest {sigma}{sub dc} obtained at ambient temperatures was 6.0 x 10{sup -6} S.cm{sup -1}, strongly suggesting a rather tight coordination of the lithium ions to the solvating 2-oxo-1,3-dioxolane moieties, supported by the increased {sigma}{sub dc} values for the oligo(ethylene oxide) based analogues. Further insights into the mechanism of lithium ion dynamics were derived from {sup 7}Li and {sup 13}C Solid-State NMR investigations. While localized ion motion was probed by i.e. {sup 7}Li spinlattice relaxation measurements with apparent activation energies E{sub a} of 20 to 40 kJ/mol, long-range macroscopic transport was monitored by Pulsed-Field Gradient (PFG) NMR, providing an E{sub a} of 61 kJ/mol. The latter is in good agreement with the values determined from bulk conductivity data, indicating the major contribution of ion transport was only detected by PFG NMR. However, the {mu}m-diffusion is rather slow, emphasizing the strong lithium coordination to the carbonyl oxygens, which hampers sufficient ion conductivities and suggests exploring 'softer' solvating moieties in future electrolytes.

  14. Neutron scattering study on cathode LiMn2O4 and solid electrolyte 5(Li2O)(P2O5)

    International Nuclear Information System (INIS)

    Kartini, E.; Putra, Teguh P.; Jahya, A. K.; Insani, A.; Adams, S.

    2014-01-01

    Neutron scattering is very important technique in order to investigate the energy storage materials such as lithium-ion battery. The unique advantages, neutron can see the light atoms such as Hydrogen, Lithium, and Oxygen, where those elements are negligible by other corresponding X-ray method. On the other hand, the energy storage materials, such as lithium ion battery is very important for the application in the electric vehicles, electronic devices or home appliances. The battery contains electrodes (anode and cathode), and the electrolyte materials. There are many challenging to improve the existing lithium ion battery materials, in order to increase their life time, cyclic ability and also its stability. One of the most scientific challenging is to investigate the crystal structure of both electrode and electrolyte, such as cathodes LiCoO 2 , LiMn 2 O 4 and LiFePO 4 , and solid electrolyte Li 3 PO 4 . Since all those battery materials contain Lithium ions and Oxygen, the used of neutron scattering techniques to study their structure and related properties are very important and indispensable. This article will review some works of investigating electrodes and electrolytes, LiMn 2 O 4 and 5(Li 2 O)(P 2 O 5 ), by using a high resolution powder diffraction (HRPD) at the multipurpose research reactor, RSG-Sywabessy of the National Nuclear Energy Agency (BATAN), Indonesia

  15. Interfaces and Materials in Lithium Ion Batteries: Challenges for Theoretical Electrochemistry.

    Science.gov (United States)

    Kasnatscheew, Johannes; Wagner, Ralf; Winter, Martin; Cekic-Laskovic, Isidora

    2018-04-18

    Energy storage is considered a key technology for successful realization of renewable energies and electrification of the powertrain. This review discusses the lithium ion battery as the leading electrochemical storage technology, focusing on its main components, namely electrode(s) as active and electrolyte as inactive materials. State-of-the-art (SOTA) cathode and anode materials are reviewed, emphasizing viable approaches towards advancement of the overall performance and reliability of lithium ion batteries; however, existing challenges are not neglected. Liquid aprotic electrolytes for lithium ion batteries comprise a lithium ion conducting salt, a mixture of solvents and various additives. Due to its complexity and its role in a given cell chemistry, electrolyte, besides the cathode materials, is identified as most susceptible, as well as the most promising, component for further improvement of lithium ion batteries. The working principle of the most important commercial electrolyte additives is also discussed. With regard to new applications and new cell chemistries, e.g., operation at high temperature and high voltage, further improvements of both active and inactive materials are inevitable. In this regard, theoretical support by means of modeling, calculation and simulation approaches can be very helpful to ex ante pre-select and identify the aforementioned components suitable for a given cell chemistry as well as to understand degradation phenomena at the electrolyte/electrode interface. This overview highlights the advantages and limitations of SOTA lithium battery systems, aiming to encourage researchers to carry forward and strengthen the research towards advanced lithium ion batteries, tailored for specific applications.

  16. Towards Safer Lithium-Ion Batteries

    OpenAIRE

    Herstedt, Marie

    2003-01-01

    Surface film formation at the electrode/electrolyte interface in lithium-ion batteries has a crucial impact on battery performance and safety. This thesis describes the characterisation and treatment of electrode interfaces in lithium-ion batteries. The focus is on interface modification to improve battery safety, in particular to enhance the onset temperature for thermally activated reactions, which also can have a negative influence on battery performance. Photoelectron Spectroscopy (PES) ...

  17. Development of Lithium Stuffed Garnet-Type Oxide Solid Electrolytes with High Ionic Conductivity for Application to All-Solid-State Batteries

    Directory of Open Access Journals (Sweden)

    Ryoji Inada

    2016-07-01

    Full Text Available All-solid-state lithium-ion battery (LiB is expected as one of the next generation energy storage devices because of their high energy density, high safety and excellent cycle stability. Although oxide-based solid electrolyte materials have rather lower conductivity and poor deformability than sulfide-based one, they have other advantages such as their chemical stability and easiness for handling. Among the various oxide-based SEs, lithium stuffed garnet-type oxide with the formula of Li7La3Zr2O12 (LLZ have been widely studied because of their high conductivity above 10-4 Scm-1 at room temperature, excellent thermal performance and stability against Li metal anode.Here, we present our recent progress for the development of garnet-type solid electrolytes with high conductivity by simultaneous substitution of Ta5+ into Zr4+ site and Ba2+ into La3+ site in LLZ. Li+ concentration was fixed to 6.5 per chemical formulae, so that the formulae of our Li garnet-type oxide is expressed as Li6.5La3-xBaxZr1.5-xTa0.5+xO12 (LLBZT and Ba contents x are changed from 0 to 0.3. As results, all LLBZT samples have cubic garnet structure without containing any secondary phases. The lattice parameters of LLBZT decrease with increasing Ba2+ contents x < 0.10 while increase with x from 0.10 to 0.30, possibly due to the simultaneous change of Ba2+ and Ta5+ substitution levels. Relative densities of LLBZT are in the range between 89% and 93% and not influenced so much by the compositions. From AC impedance spectroscopy measurements, the total (bulk + grain conductivity at 27ºC of LLBZT shows its maximum value of 8.34 x 10-4 S cm-1 at x = 0.10, which is slightly higher than the conductivity (= 7.94 x 10-4 S cm-1 of LLZT without substituting Ba (x = 0. Activation energy of the conductivity tends to become lower by Ba substation, while excess Ba substitution degrades the conductivity in LLBZT. LLBZT has wide electrochemical potential window of 0-6 V vs. Li+/Li and

  18. Emerging applications of spark plasma sintering in all solid-state lithium-ion batteries and beyond

    Science.gov (United States)

    Zhu, Hongzheng; Liu, Jian

    2018-07-01

    Solid-state batteries have received increasing attention due to their high safety aspect and high energy and power densities. However, the development of solid-state batteries is hindered by inferior solid-solid interfaces between the solid-state electrolyte and electrode, which cause high interfacial resistance, reduced Li-ion and electron transfer rate, and limited battery performance. Recently, spark plasma sintering (SPS) is emerging as a promising technique for fabricating solid-state electrolyte and electrode pellets with clean and intimate solid-solid interfaces. During the SPS process, the unique reaction mechanism through the combination of current, pressure and high heating rate allow the formation of desirable solid-solid interfaces between active material particles. Herein, this work focuses on the overview of the application of SPS for fabricating solid-state electrolyte and electrode in all solid-state Li-ion batteries, and beyond, such as solid-state Li-S and Na-ion batteries. The correlations among SPS parameters, interfacial resistance, and electrochemical properties of solid-state electrolytes and electrodes are discussed for different material systems. In the end, we point out future opportunities and challenges associated with SPS application in the hot area of solid-state batteries. It is expected that this timely review will stimulate more fundamental and applied research in the development of solid-state batteries by SPS.

  19. High Lithium Transference Number Electrolytes via Creation of 3-Dimensional, Charged, Nanoporous Networks from Dense Functionalized Nanoparticle Composites

    KAUST Repository

    Schaefer, Jennifer L.

    2013-03-26

    High lithium transference number, tLi+, electrolytes are desired for use in both lithium-ion and lithium metal rechargeable battery technologies. Historically, low tLi+ electrolytes have hindered device performance by allowing ion concentration gradients within the cell, leading to high internal resistances that ultimately limit cell lifetime, charging rates, and energy density. Herein, we report on the synthesis and electrochemical features of electrolytes based on nanoparticle salts designed to provide high tLi+. The salts are created by cofunctionalization of metal oxide nanoparticles with neutral organic ligands and tethered lithium salts. When dispersed in a conducting fluid such as tetraglyme, they spontaneously form a charged, nanoporous network of particles at moderate nanoparticle loadings. Modification of the tethered anion chemistry from -SO3 - to -SO3BF3 - is shown to enhance ionic conductivity of the electrolytes by facilitating ion pair dissociation. At a particle volume fraction of 0.15, the electrolyte exists as a self-supported, nanoporous gel with an optimum ionic conductivity of 10 -4 S/cm at room temperature. Galvanostatic polarization measurements on symmetric lithium metal cells containing the electrolyte show that the cell short circuit time, tSC, is inversely proportional to the square of the applied current density tSC ∼ J-2, consistent with previously predicted results for traditional polymer-in-salt electrolytes with low tLi+. Our findings suggest that electrolytes with tLi+ ≈ 1 and good ion-pair dissociation delay lithium dendrite nucleation and may lead to improved lithium plating in rechargeable batteries with metallic lithium anodes. © 2013 American Chemical Society.

  20. Recent Advances in Fast Ion Conducting Materials and Devices - Proceedings of the 2nd Asian Conference on Solid State Ionics

    Science.gov (United States)

    Chowdari, B. V. R.; Liu, Qingguo; Chen, Liquan

    The Table of Contents for the book is as follows: * Preface * Invited Papers * Recent Trends in Solid State Ionics * Theoretical Aspects of Fast Ion Conduction in Solids * Chemical Bonding and Intercalation Processes in Framework Structures * Extra-Large Near-Electrode Regions and Diffusion Length on the Solid Electrolyte-Electrode Interface as Studied by Photo-EMF Method * Frequency Response of Glasses * XPS Studies on Ion Conducting Glasses * Characterization of New Ambient Temperature Lithium Polymer-Electrolyte * Recent Development of Polymer Electrolytes: Solid State Voltammetry in Polymer Electrolytes * Secondary Solid State Batteries: From Material Properties to Commercial Development * Silver Vanadium Oxide Bronze and its Applications for Electrochemical Devices * Study on β''-Alumina Solid Electrolyte and β Battery in SIC * Materials for Solid Oxide Fuel Cells * Processing for Super Superionic Ceramics * Hydrogen Production Using Oxide Ionic or Protonic Conductor * Ionically Conductive Sulfide-Based Lithium Glasses * Relation of Conductivity to Structure and Structural Relaxation in Ion-Conducting Glasses * The Mechanism of Ionic Conductivity in Glass * The Role of Synthesis and Structure in Solid State Ionics - Electrodes to Superconductors * Electrochromism in Spin-Coated Thin Films from Peroxo-Poly tungstate Solutions * Electrochemical Studies on High Tc Superconductors * Multivalence Fast Ionic Conductors - Montmorillonites * Contributed Papers * Volt-Ampere Characteristics and Interface Charge Transport in Solid Electrolytes * Internal Friction of Silver Chalcogenides * Thermal Expansion of Ionic and Superionic Solids * Improvement of PEO-LiCF3SO3 Complex Electrolytes Using Additives * Ionic Conductivity of Modified Poly (Methoxy Polyethylene Glycol Methacrylate) s-Lithium Salt Complexes * Solid Polymer Electrolytes of Crosslinked Polyethylene Glycol and Lithium Salts * Single Ionic Conductors Prepared by in Situ Polymerization of Methacrylic Acid

  1. Lithium bis(fluorosulfonyl)imide-PYR14TFSI ionic liquid electrolyte compatible with graphite

    Czech Academy of Sciences Publication Activity Database

    Nádherná, Martina; Reiter, Jakub; Moškon, J.; Dominko, R.

    2011-01-01

    Roč. 196, č. 18 (2011), s. 7700-7706 ISSN 0378-7753 R&D Projects: GA AV ČR(CZ) KJB200320801; GA AV ČR KJB200320901; GA MŠk(CZ) LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : Graphite * Ionic liquid * Bis(fluorosulfonyl)imide * Lithium -ion battery * Solid electrolyte interface Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 4.951, year: 2011

  2. Two-dimensional ion chromatography for the separation of ionic organophosphates generated in thermally decomposed lithium hexafluorophosphate-based lithium ion battery electrolytes.

    Science.gov (United States)

    Kraft, Vadim; Grützke, Martin; Weber, Waldemar; Menzel, Jennifer; Wiemers-Meyer, Simon; Winter, Martin; Nowak, Sascha

    2015-08-28

    A two-dimensional ion chromatography (IC/IC) technique with heart-cutting mode for the separation of ionic organophosphates was developed. These analytes are generated during thermal degradation of three different commercially available Selectilyte™ lithium ion battery electrolytes. The composition of the investigated electrolytes is based on 1M lithium hexafluorophosphate (LiPF6) dissolved in ethylene carbonate/dimethyl carbonate (50:50wt%, LP30), ethylene carbonate/diethyl carbonate (50:50wt%, LP40) and ethylene carbonate/ethyl methyl carbonate (50:50wt%, LP50). The organophosphates were pre-separated from PF6(-) anion on the low capacity A Supp 4 column, which was eluted with a gradient step containing acetonitrile. The fraction containing analytes was retarded on a pre-concentration column and after that transferred to the high capacity columns, where the separation was performed isocratically. Different stationary phases and eluents were applied on the 2nd dimension for the investigation of retention times, whereas the highly promising results were obtained with a high capacitive A Supp 10 column. The organophosphates generated in LP30 and LP40 electrolytes could be separated by application of an aqueous NaOH eluent providing fast analysis time within 35min. For the separation of the organophosphates of LP50 electrolyte due to its complexity a NaOH eluent containing a mixture of methanol/H2O was necessary. In addition, the developed two dimensional IC method was hyphenated to an inductively coupled plasma mass spectrometer (ICP-MS) using aqueous NaOH without organic modifiers. This proof of principle measurement was carried out for future quantitative investigation regarding the concentration of the ionic organophosphates. Furthermore, the chemical stability of several ionic organophosphates in water and acetonitrile at room temperature over a period of 10h was investigated. In both solvents no decomposition of the investigated analytes was observed and

  3. Benchmarking of electrolyte mass transport in next generation lithium batteries

    Directory of Open Access Journals (Sweden)

    Jonas Lindberg

    2017-12-01

    Full Text Available Beyond conductivity and viscosity, little is often known about the mass transport properties of next generation lithium battery electrolytes, thus, making performance estimation uncertain when concentration gradients are present, as conductivity only describes performance in the absence of these gradients. This study experimentally measured the diffusion resistivity, originating from voltage loss due to a concentration gradient, together with the ohmic resistivity, obtained from ionic conductivity measurements, hence, evaluating electrolytes both with and without the presence of concentration gradients. Under galvanostatic conditions, the concentration gradients, of all electrolytes examined, developed quickly and the diffusion resistivity rapidly dominated the ohmic resistivity. The electrolytes investigated consisted of lithium salt in: room temperature ionic liquids (RTIL, RTIL mixed organic carbonates, dimethyl sulfoxide (DMSO, and a conventional Li-ion battery electrolyte. At steady state the RTIL electrolytes displayed a diffusion resistivity ~ 20 times greater than the ohmic resistivity. The DMSO-based electrolyte showed mass transport properties similar to the conventional Li-ion battery electrolyte. In conclusion, the results presented in this study show that the diffusion polarization must be considered in applications where high energy and power density are desired.

  4. Epoxy-silica hybrid organic–inorganic electrolytes with a high Li-ion conductivity

    International Nuclear Information System (INIS)

    Vélez, J.F.; Procaccini, R.A.; Aparicio, M.; Mosa, J.

    2013-01-01

    Organic–inorganic hybrid electrolytes were prepared by co-hydrolysis and co-condensation of 3-glycidoxipropyltrimethoxysilane (GPTMS) and tetraethyl orthosilicate (TEOS) doped with lithium acetate as self-supported materials and thin-films. The effects of the relative molar content of LiAc on the physicochemical properties of electrolytes, such as morphology, thermal, chemical and electrochemical properties were investigated. Two and four probes test cells were designed for comparative studies of ionic conductivity of hybrid electrolytes using electrochemical impedance spectroscopy (EIS). Similar ionic conductivities were obtained using both measurement methods, reaching a maximum ionic conductivity value of around 10 −6 S/cm at 25 °C. The conductivity mechanism presents Arrehenius behavior with the increase of the temperature from 25 °C to 120 °C. The electrochemical stability window is found to be in the range of 0–5 V, which ensures that hybrid organic–inorganic materials are potential electrolytes for solid-state rechargeable lithium ion batteries

  5. Electrochemical studies of ferrocene in a lithium ion conducting organic carbonate electrolyte

    International Nuclear Information System (INIS)

    Laoire, Cormac O.; Plichta, Edward; Hendrickson, Mary; Mukerjee, Sanjeev; Abraham, K.M.

    2009-01-01

    We carried out a detailed study of the kinetics of oxidation of ferrocene (Fc) to ferrocenium ion (Fc + ) in the non-aqueous lithium ion conducting electrolyte composed of a solution of 1 M LiPF 6 in 1:1 EC:EMC solvent mixture. This study using cyclic (CV) and rotating disk electrode (RDE) voltammetry showed that the Fc 0 /Fc + redox couple is reversible in this highly concentrated electrolyte. The ferrocene and ferrocenium ion diffusion coefficients (D) were calculated from these results. In addition, the electron transfer rate constant (k 0 ) and the exchange current density for the oxidation of ferrocene were determined. A comparison of the kinetic data obtained from the two electrochemical techniques appears to show that the data from the RDE experiments are more reliable because they are collected under strict mass transport control. A Tafel slope of c.a. 79 mV/decade and a transfer coefficient α of 0.3 obtained from analysis of the RDE data for ferrocene oxidation suggest that the structure of the activated complex is closer to that of the oxidized specie due to strong interactions with the carbonate solvents. The experiments reported here are relevant to the study of redox reagents for the chemical overcharge protection of Li-ion batteries.

  6. Synthesis and Electrochemical Performance of a Lithium Titanium Phosphate Anode for Aqueous Lithium-Ion Batteries

    KAUST Repository

    Wessells, Colin

    2011-01-01

    Lithium-ion batteries that use aqueous electrolytes offer safety and cost advantages when compared to today\\'s commercial cells that use organic electrolytes. The equilibrium reaction potential of lithium titanium phosphate is -0.5 V with respect to the standard hydrogen electrode, which makes this material attractive for use as a negative electrode in aqueous electrolytes. This material was synthesized using a Pechini type method. Galvanostatic cycling of the resulting lithium titanium phosphate showed an initial discharge capacity of 115 mAh/g and quite good capacity retention during cycling, 84% after 100 cycles, and 70% after 160 cycles at a 1 C cycling rate in an organic electrolyte. An initial discharge capacity of 113 mAh/g and capacity retention of 89% after 100 cycles with a coulombic efficiency above 98% was observed at a C/5 rate in pH -neutral 2 M Li2 S O4. The good cycle life and high efficiency in an aqueous electrolyte demonstrate that lithium titanium phosphate is an excellent candidate negative electrode material for use in aqueous lithium-ion batteries. © 2011 The Electrochemical Society.

  7. Advances of aqueous rechargeable lithium-ion battery: A review

    Science.gov (United States)

    Alias, Nurhaswani; Mohamad, Ahmad Azmin

    2015-01-01

    The electrochemical characteristic of the aqueous rechargeable lithium-ion battery has been widely investigated in efforts to design a green and safe technology that can provide a highly specific capacity, high efficiency and long life for high power applications such as the smart grid and electric vehicle. It is believed that the advantages of this battery will overcome the limitations of the rechargeable lithium-ion battery with organic electrolytes that comprise safety and create high fabrication cost issues. This review focuses on the opportunities of the aqueous rechargeable lithium-ion battery compared to the conventional rechargeable lithium-ion battery with organic-based electrolytes. Previously reported studies are briefly summarised, together with the presentation of new findings based on the conductivity, morphology, electrochemical performance and cycling stability results. The factors that influence the electrochemical performance, the challenges and potential of the aqueous rechargeable lithium-ion battery are highlighted in order to understand and maintained the excellent battery performance.

  8. Restricted lithium ion dynamics in PEO-based block copolymer electrolytes measured by high-field nuclear magnetic resonance relaxation

    Science.gov (United States)

    Huynh, Tan Vu; Messinger, Robert J.; Sarou-Kanian, Vincent; Fayon, Franck; Bouchet, Renaud; Deschamps, Michaël

    2017-10-01

    The intrinsic ionic conductivity of polyethylene oxide (PEO)-based block copolymer electrolytes is often assumed to be identical to the conductivity of the PEO homopolymer. Here, we use high-field 7Li nuclear magnetic resonance (NMR) relaxation and pulsed-field-gradient (PFG) NMR diffusion measurements to probe lithium ion dynamics over nanosecond and millisecond time scales in PEO and polystyrene (PS)-b-PEO-b-PS electrolytes containing the lithium salt LiTFSI. Variable-temperature longitudinal (T1) and transverse (T2) 7Li NMR relaxation rates were acquired at three magnetic field strengths and quantitatively analyzed for the first time at such fields, enabling us to distinguish two characteristic time scales that describe fluctuations of the 7Li nuclear electric quadrupolar interaction. Fast lithium motions [up to O (ns)] are essentially identical between the two polymer electrolytes, including sub-nanosecond vibrations and local fluctuations of the coordination polyhedra between lithium and nearby oxygen atoms. However, lithium dynamics over longer time scales [O (10 ns) and greater] are slower in the block copolymer compared to the homopolymer, as manifested experimentally by their different transverse 7Li NMR relaxation rates. Restricted dynamics and altered thermodynamic behavior of PEO chains anchored near PS domains likely explain these results.

  9. Solid electrolytes

    Science.gov (United States)

    Abraham, Kuzhikalail M.; Alamgir, Mohamed

    1993-06-15

    This invention pertains to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized (encapsulated) in a solid organic polymer matrix. In particular, this invention relates to solid polymer electrolytes derived by immobilizing complexes (solvates) formed between a Li salt such as LiAsF.sub.6, LiCF.sub.3 SO.sub.3 or LiClO.sub.4 and a mixture of aprotic organic solvents having high dielectric constants such as ethylene carbonate (EC) (dielectric constant=89.6) and propylene carbonate (PC) (dielectric constant=64.4) in a polymer matrix such as polyacrylonitrile, poly(tetraethylene glycol diacrylate), or poly(vinyl pyrrolidinone).

  10. New Polymer and Liquid Electrolytes for Lithium Batteries

    International Nuclear Information System (INIS)

    McBreen, J.; Lee, H. S.; Yang, X. Q.; Sun, X.

    1999-01-01

    All non-aqueous lithium battery electrolytes are Lewis bases that interact with cations. Unlike water, they don't interact with anions. The result is a high degree of ion pairing and the formation of triplets and higher aggregates. This decreases the conductivity and the lithium ion transference and results in polarization losses in batteries. Approaches that have been used to increase ion dissociation in PEO based electrolytes are the use of salts with low lattice energy, the addition of polar plasticizers to the polymer, and the addition of cation completing agents such as crown ethers or cryptands. Complexing of the anions is a more promising approach since it should increase both ion dissociation and the lithium transference. At Brookhaven National Laboratory (BNL) we have synthesized two new families of neutral anion completing agents, each based on Lewis acid centers. One is based on electron deficient nitrogen sites on substituted aza-ethers, wherein the hydrogen on the nitrogen is replaced by electron withdrawing groups such as CF 3 SO 3- . The other is based on electron deficient boron sites on borane or borate compounds with various fluorinated aryl or alkyl groups. Some of the borane based anion receptors can promote the dissolution of LiF in several solvents. Several of these compounds, when added in equivalent amounts, produce 1.2M LiF solutions in DME, an increase in volubility of LiF by six orders of magnitude. Some of these LiF electrolytes have conductivities as high as 6 x 10 -3 Scm -1 . The LiF electrolytes with borane anion acceptors in PC:EC:DEC solvents have excellent electrochemical stability. This has been demonstrated in small Li/LiMn 2 O 4 cells

  11. Tracking Lithium Ions via Widefield Fluorescence Microscopy for Battery Diagnostics.

    Science.gov (United States)

    Padilla, Nicolas A; Rea, Morgan T; Foy, Michael; Upadhyay, Sunil P; Desrochers, Kyle A; Derus, Tyler; Knapper, Kassandra A; Hunter, Nathanael H; Wood, Sharla; Hinton, Daniel A; Cavell, Andrew C; Masias, Alvaro G; Goldsmith, Randall H

    2017-07-28

    Direct tracking of lithium ions with time and spatial resolution can provide an important diagnostic tool for understanding mechanisms in lithium ion batteries. A fluorescent indicator of lithium ions, 2-(2-hydroxyphenyl)naphthoxazole, was synthesized and used for real-time tracking of lithium ions via widefield fluorescence microscopy. The fluorophore can be excited with visible light and was shown to enable quantitative determination of the lithium ion diffusion constant in a microfluidic model system for a plasticized polymer electrolyte lithium battery. The use of widefield fluorescence microscopy for in situ tracking of lithium ions in batteries is discussed.

  12. Interphase Evolution of a Lithium-Ion/Oxygen Battery.

    Science.gov (United States)

    Elia, Giuseppe Antonio; Bresser, Dominic; Reiter, Jakub; Oberhumer, Philipp; Sun, Yang-Kook; Scrosati, Bruno; Passerini, Stefano; Hassoun, Jusef

    2015-10-14

    A novel lithium-ion/oxygen battery employing Pyr14TFSI-LiTFSI as the electrolyte and nanostructured LixSn-C as the anode is reported. The remarkable energy content of the oxygen cathode, the replacement of the lithium metal anode by a nanostructured stable lithium-alloying composite, and the concomitant use of nonflammable ionic liquid-based electrolyte result in a new and intrinsically safer energy storage system. The lithium-ion/oxygen battery delivers a stable capacity of 500 mAh g(-1) at a working voltage of 2.4 V with a low charge-discharge polarization. However, further characterization of this new system by electrochemical impedance spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy reveals the progressive decrease of the battery working voltage, because of the crossover of oxygen through the electrolyte and its direct reaction with the LixSn-C anode.

  13. High ion conductive Sb2O5-doped β-Li3PS4 with excellent stability against Li for all-solid-state lithium batteries

    Science.gov (United States)

    Xie, Dongjiu; Chen, Shaojie; Zhang, Zhihua; Ren, Jie; Yao, Lili; Wu, Linbin; Yao, Xiayin; Xu, Xiaoxiong

    2018-06-01

    The combination of high conductivity and good stability against Li is not easy to achieve for solid electrolytes, hindering the development of high energy solid-state batteries. In this study, doped electrolytes of Li3P1-xSbxS4-2.5xO2.5x are successfully prepared via the high energy ball milling and subsequent heat treatment. Plenty of techniques like XRD, Raman, SEM, EDS and TEM are utilized to characterize the crystal structures, particle sizes, and morphologies of the glass-ceramic electrolytes. Among them, the Li3P0.98Sb0.02S3.95O0.05 (x = 0.02) exhibits the highest ionic conductivity (∼1.08 mS cm-1) at room temperature with an excellent stability against lithium. In addition, all-solid-state lithium batteries are assembled with LiCoO2 as cathode, Li10GeP2S12/Li3P0.98Sb0.02S3.95O0.05 as the bi-layer electrolyte, and lithium as anode. The constructed solid-state batteries delivers a high initial discharge capacity of 133 mAh g-1 at 0.1C in the range of 3.0-4.3 V vs. Li/Li+ at room temperature, and shows a capacity retention of 78.6% after 50 cycles. Most importantly, the all-solid-state lithium batteries with the Li10GeP2S12/Li3P0.98Sb0.02S3.95O0.05 electrolyte can be workable even at -10 °C. This study provides a promising electrolyte with the improved conductivity and stability against Li for the application of all-solid-state lithium batteries.

  14. Lithium-conducting ionic melt electrolytes from polyether-functionalized fluorosulfonimide anions

    International Nuclear Information System (INIS)

    Hallac, B.B.; Geiculescu, O.E.; Rajagopal, R.V.; Creager, S.E.; DesMarteau, D.D.

    2008-01-01

    Solvent-free lithium-conducting ionic melt (IM) electrolytes were synthesized and characterized with respect to chemical structure, purity, and ion transport properties. The melts consist of lithium (perfluorovinylether)sulfonimide salts attached covalently to a lithium-solvating polyether chain. Ionic conductivities are relatively high which is a consequence of the favorable combination of the low lattice energy of the lithium fluorosulfonimide salt (low basicity of the fluorosulfonimide anion), the relatively low viscosity of the polyether matrix, and the relatively high salt content of the melts. Galvanostatic dc polarization experiments, using cells with non-blocking Li electrodes, indicate that salt concentration polarization does not occur in these electrolytes as dc current is passed through them

  15. High-capacity nanocarbon anodes for lithium-ion batteries

    International Nuclear Information System (INIS)

    Zhang, Haitao; Sun, Xianzhong; Zhang, Xiong; Lin, He; Wang, Kai; Ma, Yanwei

    2015-01-01

    Highlights: • The nanocarbon anodes in lithium-ion batteries deliver a high capacity of ∼1100 mA h g −1 . • The nanocarbon anodes exhibit excellent cyclic stability. • A novel structure of carbon materials, hollow carbon nanoboxes, has potential application in lithium-ion batteries. - Abstract: High energy and power density of secondary cells like lithium-ion batteries become much more important in today’s society. However, lithium-ion battery anodes based on graphite material have theoretical capacity of 372 mA h g −1 and low charging-discharging rate. Here, we report that nanocarbons including mesoporous graphene (MPG), carbon tubular nanostructures (CTN), and hollow carbon nanoboxes (HCB) are good candidate for lithium-ion battery anodes. The nanocarbon anodes have high capacity of ∼1100, ∼600, and ∼500 mA h g −1 at 0.1 A g −1 for MPG, CTN, and HCB, respectively. The capacity of 181, 141, and 139 mA h g −1 at 4 A g −1 for MPG, CTN, and HCB anodes is retained. Besides, nanocarbon anodes show high cycling stability during 1000 cycles, indicating formation of a passivating layer—solid electrolyte interphase, which support long-term cycling. Nanocarbons, constructed with graphene layers which fulfill lithiation/delithiation process, high ratio of graphite edge structure, and high surface area which facilitates capacitive behavior, deliver high capacity and improved rate-capability

  16. Structural and electrical properties of NASICON type solid electrolyte nanoscaled glass-ceramic powder by mechanical milling for thin film batteries.

    Science.gov (United States)

    Patil, Vaishali; Patil, Arun; Yoon, Seok-Jin; Choi, Ji-Won

    2013-05-01

    During last two decades, lithium-based glasses have been studied extensively as electrolytes for solid-state secondary batteries. For practical use, solid electrolyte must have high ionic conductivity as well as chemical, thermal and electrochemical stability. Recent progresses have focused on glass electrolytes due to advantages over crystalline solid. Glass electrolytes are generally classified into two types oxide glass and sulfide glass. Oxide glasses do not react with electrode materials and this chemical inertness is advantageous for cycle performances of battery. In this study, major effort has been focused on the improvement of the ion conductivity of nanosized LiAlTi(PO4)3 oxide electrolyte prepared by mechanical milling (MM) method. After heating at 1000 degrees C the material shows good crystallinity and ionic conductivity with low electronic conductivity. In LiTi2(PO4)3, Ti4+ ions are partially substituted by Al3+ ions by heat-treatment of Li20-Al2O3-TiO2-P2O5 glasses at 1000 degrees C for 10 h. The conductivity of this material is 1.09 x 10(-3) S/cm at room temp. The glass-ceramics show fast ion conduction and low E(a) value. It is suggested that high conductivity, easy fabrication and low cost make this glass-ceramics promising to be used as inorganic solid electrolyte for all-solid-state Li rechargeable batteries.

  17. Minimization of Ion-Solvent Clusters in Gel Electrolytes Containing Graphene Oxide Quantum Dots for Lithium-Ion Batteries.

    Science.gov (United States)

    Chen, Yen-Ming; Hsu, Shih-Ting; Tseng, Yu-Hsien; Yeh, Te-Fu; Hou, Sheng-Shu; Jan, Jeng-Shiung; Lee, Yuh-Lang; Teng, Hsisheng

    2018-03-01

    This study uses graphene oxide quantum dots (GOQDs) to enhance the Li + -ion mobility of a gel polymer electrolyte (GPE) for lithium-ion batteries (LIBs). The GPE comprises a framework of poly(acrylonitrile-co-vinylacetate) blended with poly(methyl methacrylate) and a salt LiPF 6 solvated in carbonate solvents. The GOQDs, which function as acceptors, are small (3-11 nm) and well dispersed in the polymer framework. The GOQDs suppress the formation of ion-solvent clusters and immobilize PF6- anions, affording the GPE a high ionic conductivity and a high Li + -ion transference number (0.77). When assembled into Li|electrolyte|LiFePO 4 batteries, the GPEs containing GOQDs preserve the battery capacity at high rates (up to 20 C) and exhibit 100% capacity retention after 500 charge-discharge cycles. Smaller GOQDs are more effective in GPE performance enhancement because of the higher dispersion of QDs. The minimization of both the ion-solvent clusters and degree of Li + -ion solvation in the GPEs with GOQDs results in even plating and stripping of the Li-metal anode; therefore, Li dendrite formation is suppressed during battery operation. This study demonstrates a strategy of using small GOQDs with tunable properties to effectively modulate ion-solvent coordination in GPEs and thus improve the performance and lifespan of LIBs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. The LiBH4-LiI Solid Solution as an Electrolyte in an All-Solid-State Battery

    DEFF Research Database (Denmark)

    Sveinbjörnsson, Dadi Þorsteinn; Christiansen, Ane Sælland; Viskinde, Rasmus

    2014-01-01

    The charge and discharge performance of an all-solid-state lithium battery with the LiBH4-LiI solid solution as an electrolyte is reported. Lithium titanate (Li4Ti5O12) was used as the positive electrode and lithium metal as the negative electrode. The performance of the all-solid-state cell...

  19. A novel perspective on the formation of the solid electrolyte interphase on the graphite electrode for lithium-ion batteries

    International Nuclear Information System (INIS)

    Yan Jian; Zhang Jian; Su Yuchang; Zhang Xigui; Xia Baojia

    2010-01-01

    In this paper, we describe how the mechanism of formation of a protective film [the solid electrolyte interphase (or interface) (SEI)] on a graphite electrode for Li-ion batteries was investigated from the novel perspective of precipitation of the final decomposition products that arise from the reduction of a nonaqueous electrolyte solution in contact with the graphite electrode. Within the framework of this new perspective, we can elegantly account for the compositional and structural differences between the basal-plane and edge-plane SEIs and for the origins of the multi-layer structure and the parabolic growth law of the SEIs on both the edge-plane and basal-plane surfaces of the graphite electrode.

  20. Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

    Science.gov (United States)

    Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

    2016-01-11

    The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Synthesis of polymer electrolyte membranes from cellulose acetate/poly(ethylene oxide)/LiClO{sub 4} for lithium ion battery application

    Energy Technology Data Exchange (ETDEWEB)

    Nurhadini,, E-mail: nur-chem@yahoo.co.id; Arcana, I Made, E-mail: arcana@chem.itb.ac.id [Inorganic and Physical Chemistry Research Division, Faculty of Mathematics and Natural Sciences, Institiut Teknologi Bandung, Jalan Ganesha 10, Bandung 40132 (Indonesia)

    2015-09-30

    This study was conducted to determine the effect of cellulose acetate on poly(ethylene oxide)-LiClO{sub 4} membranes as the polymer electrolyte. Cellulose acetate is used as an additive to increase ionic conductivity and mechanical property of polymer electrolyte membranes. The increase the percentage of cellulose acetate in membranes do not directly effect on the ionic conductivity, and the highest ionic conductivity of membranes about 5,7 × 10{sup −4} S/cm was observed in SA/PEO/LiClO{sub 4} membrane with cellulose ratio of 10-25% (w/w). Cellulose acetate in membranes increases mechanical strength of polymer electrolyte membranes. Based on TGA analysis, this polymer electrolyte thermally is stable until 270 °C. The polymer electrolyte membrane prepared by blending the cellulose acetate, poly(ethylene oxide), and lithium chlorate could be potentially used as a polymer electrolyte for lithium ion battery application.

  2. Lithium ion batteries based on nanoporous silicon

    Science.gov (United States)

    Tolbert, Sarah H.; Nemanick, Eric J.; Kang, Chris Byung-Hwa

    2015-09-22

    A lithium ion battery that incorporates an anode formed from a Group IV semiconductor material such as porous silicon is disclosed. The battery includes a cathode, and an anode comprising porous silicon. In some embodiments, the anode is present in the form of a nanowire, a film, or a powder, the porous silicon having a pore diameters within the range between 2 nm and 100 nm and an average wall thickness of within the range between 1 nm and 100 nm. The lithium ion battery further includes, in some embodiments, a non-aqueous lithium containing electrolyte. Lithium ion batteries incorporating a porous silicon anode demonstrate have high, stable lithium alloying capacity over many cycles.

  3. Recovery of cobalt and lithium fromspent Li-ion batteries

    OpenAIRE

    Busnardo, Natália Giovanini; Paulino, Jéssica Frontino; Afonso, Julio Carlos

    2007-01-01

    The "active mass" (cathode + anode + electrolyte) of spent Li-ion batteries was submitted to one of the following procedures: (a) it was calcined (500 ºC) and submitted to extraction with water to recover lithium salts. The residual solid was treated with sulfuric acid containing hydrogen peroxide. Cobalt was recovered as sulfate; (b) the "active mass" was treated with potassium hydrogen sulfate (500 ºC) and dissolved in water. Cobalt was precipitated together with copper after addition of so...

  4. Ion conducting polymers and polymer blends for alkali metal ion batteries

    Science.gov (United States)

    DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

    2017-08-29

    Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

  5. Polymer electrolytes: an investigation of some poly (N-propylaziridine)/lithium salt compositions

    Energy Technology Data Exchange (ETDEWEB)

    Baldwin, K R; Golder, A J; Knight, J

    1984-04-01

    Poly (N-propylaziridine)/lithium salt compositions were synthesized and their electrical conductivities were measured to assess their suitability as electrolytes in safe, leakproof, high energy-density lithium batteries operating at ambient temperature. The effects on conductivity of temperature, and the nature and concentration of the salt were studied. The salts markedly improve conductivity of the compositions over that of the undoped polymer but they are insufficiently conducting to be considered as battery electrolytes, due possibly to ion pairing. Their creep resistance is also low. Less fluid compositions containing higher molecular weight polymers better able to promote ion separation are more suitable. (ESA)

  6. Numerical Study of Electrolyte Wetting Phenomena in the Electrode of Lithium Ion Battery Using Lattice Boltzmann Method

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sang Gun [Seoul Nat' l Univ., Seoul (Korea, Republic of); Jeon, Dong Hyup [Dongguk Univ., Seoul (Korea, Republic of)

    2014-04-15

    The electrolyte wetting phenomena in the electrode of lithium ion battery is studied numerically using a multiphase lattice Boltzmann method (LBM). When a porous electrode is compressed during roll-pressing process, the porosity and thickness of the compressed electrode are changed, which can affect its wettability. In this study, the change in electrolyte distribution and degree of saturation as a result of varying the compression ratio are investigated with two-dimensional LBM approach. We found that changes in the electrolyte transport path are caused by a reduction in through-plane pore size and result in a decrease in the wettability of the compressed electrode.

  7. Sparingly Solvating Electrolytes for High Energy Density Lithium-Sulfur Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Lei; Curtiss, Larry A.; Zavadil, Kevin R.; Gewirth, Andrew A.; Shao, Yuyan; Gallagher, Kevin

    2016-07-11

    Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systems that fundamentally decouple electrolyte volume from reaction mechanism. This perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.

  8. Investigation of Novel Electrolytes for Use in Lithium-Ion Batteries and Direct Methanol Fuel Cells

    Science.gov (United States)

    Pilar, Kartik

    Energy storage and conversion plays a critical role in the efficient use of available energy and is crucial for the utilization of renewable energy sources. To achieve maximum efficiency of renewable energy sources, improvements to energy storage materials must be developed. In this work, novel electrolytes for secondary batteries and fuel cells have been studied using nuclear magnetic resonance and high pressure x-ray scattering techniques to form a better understanding of dynamic and structural properties of these materials. Ionic liquids have been studied due to their potential as a safer alternative to organic solvent-based electrolytes in lithium-ion batteries and composite sulfonated polyetheretherketone (sPEEK) membranes have been investigated for their potential use as a proton exchange membrane electrolyte in direct methanol fuel cells. The characterization of these novel electrolytes is a step towards the development of the next generation of improved energy storage and energy conversion devices.

  9. Dielectric and impedance analysis of Li0.5La0.5Ti1-xZrxO3(x = 0.05 and 0.1 ceramics as improved electrolyte material for lithium-ion batteries

    Directory of Open Access Journals (Sweden)

    Babu K. Vijaya

    2016-09-01

    Full Text Available The most attractive property of Li0.5La0.5TiO3 (LLTO electrolytes is their high ionic conductivity. Studies have shown that LLTO is capable of existing in a state with an ionic conductivity of 10-3 S/cm, which is comparable to liquid electrolytes. In addition to the high ionic conductivity of the material, LLTO is electrochemically stable and able to withstand hundreds of cycles. So, the studies of the solid electrolyte material are very important for the development of lithium-ion batteries. In the present paper, Li0.5La0.5Ti1-xZrxO3 (x = 0.05 and 0.1 have been prepared by a solid-state reaction method at 1300 °C for 6 hours to improve electrolyte materials for lithium-ion batteries. The phase identified by X-ray diffractometry and crystal structure corresponds to pm3m (2 2 1 space group (Z = 1. The frequency and temperature dependence of impedance, dielectric permittivity, dielectric loss and electric modulus of the Li0.5La0.5Ti1-xZrxO3 (x = 0.05 and 0.1 have been investigated. The dielectric and impedance properties have been studied over a range of frequency (42 Hz to 5 MHz and temperatures (30 °C to 100 °C. The frequency dependent plot of modulus shows that the conductivity relaxation is of non-Debye type.

  10. Gel polymer electrolyte lithium-ion cells with improved low temperature performance

    Energy Technology Data Exchange (ETDEWEB)

    Smart, M.C.; Ratnakumar, B.V.; Behar, A.; Whitcanack, L.D. [Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109 (United States); Yu, J.-S. [LG Chem/Research Park, P.O. Box 61Yu Song, Science Town, Daejon (Korea); Alamgir, M. [Compact Power, Inc., 1857 Technology Drive, Troy, MI 48083 (United States)

    2007-03-20

    For a number of NASA's future planetary and terrestrial applications, high energy density rechargeable lithium batteries that can operate at very low temperature are desired. In the pursuit of developing Li-ion batteries with improved low temperature performance, we have also focused on assessing the viability of using gel polymer systems, due to their desirable form factor and enhanced safety characteristics. In the present study we have evaluated three classes of promising liquid low-temperature electrolytes that have been impregnated into gel polymer electrolyte carbon-LiMn{sub 2}O{sub 4}-based Li-ion cells (manufactured by LG Chem. Inc.), consisting of: (a) binary EC + EMC mixtures with very low EC-content (10%), (b) quaternary carbonate mixtures with low EC-content (16-20%), and (c) ternary electrolytes with very low EC-content (10%) and high proportions of ester co-solvents (i.e., 80%). These electrolytes have been compared with a baseline formulation (i.e., 1.0 M LiPF{sub 6} in EC + DEC + DMC (1:1:1%, v/v/v), where EC, ethylene carbonate, DEC, diethyl carbonate, and DMC, dimethyl carbonate). We have performed a number of characterization tests on these cells, including: determining the rate capacity as a function of temperature (with preceding charge at room temperature and also at low temperature), the cycle life performance (both 100% DOD and 30% DOD low earth orbit cycling), the pulse capability, and the impedance characteristics at different temperatures. We have obtained excellent performance at low temperatures with ester-based electrolytes, including the demonstration of >80% of the room temperature capacity at -60 C using a C/20 discharge rate with cells containing 1.0 M LiPF{sub 6} in EC + EMC + MB (1:1:8%, v/v/v) (MB, methyl butyrate) and 1.0 M LiPF{sub 6} in EC + EMC + EB (1:1:8%, v/v/v) (EB, ethyl butyrate) electrolytes. In addition, cells containing the ester-based electrolytes were observed to support 5C pulses at -40 C, while still

  11. Designed synergetic effect of electrolyte additives to improve interfacial chemistry of MCMB electrode in propylene carbonate-based electrolyte for enhanced low and room temperature performance.

    Science.gov (United States)

    Wotango, Aselefech Sorsa; Su, Wei-Nien; Haregewoin, Atetegeb Meazah; Chen, Hung-Ming; Cheng, Ju-Hsiang; Lin, Ming-Hsien; Wang, Chia-Hsin; Hwang, Bing-Joe

    2018-05-09

    The performance of lithium ion batteries rapidly falls at lower temperatures due to decreasing conductivity of electrolytes and Solid Electrolyte Interphase (SEI) on graphite anode. Hence, it limits the practical use of lithium ion batteries at sub-zero temperatures and also affects the development of lithium ion batteries for widespread applications. The SEI formed on the graphite surface is very influential in determining the performance of the battery. Herein, a new electrolyte additive, 4-Chloromethyl-1,3,2-dioxathiolane-2-oxide (CMDO), is prepared to improve the properties of commonly used electrolyte constituents - ethylene carbonate (EC), and fluoroethylene carbonate (FEC). The formation of an efficient passivation layer in propylene carbonate (PC) -based electrolyte for MCMB electrode was investigated. The addition of CMDO resulted in a much less irreversible capacity loss and induces thin SEI formation. However, the combination of the three additives played a key role to enhance reversible capacity of MCMB electrode at lower or ambient temperature. The electrochemical measurement analysis showed that the SEI formed from a mixture of the three additives gave better intercalation-deintercalation of lithium ions.

  12. Recovery of cobalt and lithium from spent Li-ion batteries

    International Nuclear Information System (INIS)

    Busnardo, Natalia Giovanini; Paulino, Jessica Frontino; Afonso, Julio Carlos

    2007-01-01

    The 'active mass' (cathode + anode + electrolyte) of spent Li-ion batteries was submitted to one of the following procedures: (a) it was calcined (500 deg C) and submitted to extraction with water to recover lithium salts. The residual solid was treated with sulfuric acid containing hydrogen peroxide. Cobalt was recovered as sulfate; (b) the 'active mass' was treated with potassium hydrogen sulfate (500 deg C) and dissolved in water. Cobalt was precipitated together with copper after addition of sodium hydroxide. Lithium was partially recovered as lithium fluoride. Co-processing of other battery components (aluminum and copper foils) affected negatively the behavior of the recovery procedures. Previous segregation of battery components is essential for an efficient and economical processing of the 'active mass'. (author)

  13. Room-Temperature-Cured Copolymers for Lithium Battery Gel Electrolytes

    Science.gov (United States)

    Meador, Mary Ann B.; Tigelaar, Dean M.

    2009-01-01

    Polyimide-PEO copolymers (PEO signifies polyethylene oxide) that have branched rod-coil molecular structures and that can be cured into film form at room temperature have been invented for use as gel electrolytes for lithium-ion electric-power cells. These copolymers offer an alternative to previously patented branched rod-coil polyimides that have been considered for use as polymer electrolytes and that must be cured at a temperature of 200 C. In order to obtain sufficient conductivity for lithium ions in practical applications at and below room temperature, it is necessary to imbibe such a polymer with a suitable carbonate solvent or ionic liquid, but the high-temperature cure makes it impossible to incorporate and retain such a liquid within the polymer molecular framework. By eliminating the high-temperature cure, the present invention makes it possible to incorporate the required liquid.

  14. A Catalytic Path for Electrolyte Reduction in Lithium-Ion Cells Revealed by in Situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy

    KAUST Repository

    Shi, Feifei; Ross, Philip N.; Zhao, Hui; Liu, Gao; Somorjai, Gabor A.; Komvopoulos, Kyriakos

    2015-01-01

    © 2015 American Chemical Society. Although controlling the interfacial chemistry of electrodes in Li-ion batteries (LIBs) is crucial for maintaining the reversibility, electrolyte decomposition has not been fully understood. In this study, electrolyte decomposition on model electrode surfaces (Au and Sn) was investigated by in situ attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Simultaneously obtained ATR-FTIR spectra and cyclic voltammetry measurements show that lithium ethylene dicarbonate and lithium propionate form on the Au electrode at 0.6 V, whereas diethyl 2,5-dioxahexane dicarboxylate and lithium propionate form on the Sn electrode surface at 1.25 V. A noncatalytic reduction path on the Au surface and a catalytic reduction path on the Sn surface are introduced to explain the surface dependence of the overpotential and product selectivity. This represents a new concept for explaining electrolyte reactions on the anode of LIBs. The present investigation shows that catalysis plays a dominant role in the electrolyte decomposition process and has important implications in electrode surface modification and electrolyte recipe selection, which are critical factors for enhancing the efficiency, durability, and reliability of LIBs.

  15. A Catalytic Path for Electrolyte Reduction in Lithium-Ion Cells Revealed by in Situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy

    KAUST Repository

    Shi, Feifei

    2015-03-11

    © 2015 American Chemical Society. Although controlling the interfacial chemistry of electrodes in Li-ion batteries (LIBs) is crucial for maintaining the reversibility, electrolyte decomposition has not been fully understood. In this study, electrolyte decomposition on model electrode surfaces (Au and Sn) was investigated by in situ attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Simultaneously obtained ATR-FTIR spectra and cyclic voltammetry measurements show that lithium ethylene dicarbonate and lithium propionate form on the Au electrode at 0.6 V, whereas diethyl 2,5-dioxahexane dicarboxylate and lithium propionate form on the Sn electrode surface at 1.25 V. A noncatalytic reduction path on the Au surface and a catalytic reduction path on the Sn surface are introduced to explain the surface dependence of the overpotential and product selectivity. This represents a new concept for explaining electrolyte reactions on the anode of LIBs. The present investigation shows that catalysis plays a dominant role in the electrolyte decomposition process and has important implications in electrode surface modification and electrolyte recipe selection, which are critical factors for enhancing the efficiency, durability, and reliability of LIBs.

  16. Size effects in lithium ion batteries

    International Nuclear Information System (INIS)

    Yao Hu-Rong; Yin Ya-Xia; Guo Yu-Gao

    2016-01-01

    Size-related properties of novel lithium battery materials, arising from kinetics, thermodynamics, and newly discovered lithium storage mechanisms, are reviewed. Complementary experimental and computational investigations of the use of the size effects to modify electrodes and electrolytes for lithium ion batteries are enumerated and discussed together. Size differences in the materials in lithium ion batteries lead to a variety of exciting phenomena. Smaller-particle materials with highly connective interfaces and reduced diffusion paths exhibit higher rate performance than the corresponding bulk materials. The thermodynamics is also changed by the higher surface energy of smaller particles, affecting, for example, secondary surface reactions, lattice parameter, voltage, and the phase transformation mechanism. Newly discovered lithium storage mechanisms that result in superior storage capacity are also briefly highlighted. (topical review)

  17. Effect of iron ions on corrosion of lithium in a thionyl chloride electrolytes

    International Nuclear Information System (INIS)

    Shirokov, A.V.; Churikov, A.V.

    1999-01-01

    The effect of the iron electrolyte addition on the growth rate of the passivating layer on lithium in the LiAlCl 4 1 M solution in thionyl chloride is experimentally studied. It is established, that kinetic curved in the first 10 hours of the Li-electrode contact with electrolyte are described by the equation, assuming mixed diffusion kinetic control over the corrosion process. It is shown that introduction of Fe 3+ into electrolyte causes increase in both ionic and electron conductivity constituents. Increase in the electron carrier concentration is the cause of lithium corrosion in the iron-containing thionyl chloride solutions [ru

  18. Electrochemical performance of high specific capacity of lithium-ion cell LiV3O8//LiMn2O4 with LiNO3 aqueous solution electrolyte

    International Nuclear Information System (INIS)

    Zhao Mingshu; Zheng Qingyang; Wang Fei; Dai Weimin; Song Xiaoping

    2011-01-01

    Research highlights: → In this paper, the electrochemical performance of aqueous rechargeable lithium battery with LiV 3 O 8 and LiMn 2 O 4 in saturated LiNO 3 electrolyte is studied. → The electrochemical performance tests show that the specific capacity of LiMn 2 O 4 using as the cathode of ARLB is similar to that of ordinary lithium-ion battery with organic electrolyte, which works much better than the formerly reported. → In addition, the cell systems exhibit good cycling performance. Therefore, it has great potential comparing with other batteries such as lead acid batteries and alkaline manganese batteries. - Abstract: The electrochemical performance of aqueous rechargeable lithium battery (ARLB) with LiV 3 O 8 and LiMn 2 O 4 in saturated LiNO 3 electrolyte is studied. The results indicate that these two electrode materials are stable in the aqueous solution and no hydrogen or oxygen produced, moreover, intercalation/de-intercalation of lithium ions occurred within the range of electrochemical stability of water. The electrochemical performance tests show that the specific capacity of LiMn 2 O 4 using as the cathode of ARLB is similar to that of ordinary lithium-ion battery with organic electrolyte, which works much better than the formerly reported. In addition, the cell systems exhibit good cycling performance. Therefore, it has great potential comparing with other batteries such as lead acid batteries and alkaline manganese batteries.

  19. Enhanced lithium battery with polyethylene oxide-based electrolyte containing silane-Al2 O3 ceramic filler.

    Science.gov (United States)

    Zewde, Berhanu W; Admassie, Shimelis; Zimmermann, Jutta; Isfort, Christian Schulze; Scrosati, Bruno; Hassoun, Jusef

    2013-08-01

    A solid polymer electrolyte prepared by using a solvent-free, scalable technique is reported. The membrane is formed by low-energy ball milling followed by hot-pressing of dry powdered polyethylene oxide polymer, LiCF3 SO3 salt, and silane-treated Al2 O3 (Al2 O3 -ST) ceramic filler. The effects of the ceramic fillers on the properties of the ionically conducting solid electrolyte membrane are characterized by using electrochemical impedance spectroscopy, XRD, differential scanning calorimeter, SEM, and galvanostatic cycling in lithium cells with a LiFePO4 cathode. We demonstrate that the membrane containing Al2 O3 -ST ceramic filler performs well in terms of ionic conductivity, thermal properties, and lithium transference number. Furthermore, we show that the lithium cells, which use the new electrolyte together with the LiFePO4 electrode, operate within 65 and 90 °C with high efficiency and long cycle life. Hence, the Al2 O3 -ST ceramic can be efficiently used as a ceramic filler to enhance the performance of solid polymer electrolytes in lithium batteries. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Poly(oxyethylene) electrolytes based on lithium pentafluorobenzene sulfonate

    International Nuclear Information System (INIS)

    Paillard, E.; Iojoiu, C.; Alloin, F.; Guindet, J.; Sanchez, J.-Y.

    2007-01-01

    Lithium pentafluorobenzene sulfonate was synthesized by a protocol whereby pollution by aromatic nucleophilic substitutions on the perfluorinated ring was avoided. Its poly(oxyethylene) complexes, although less conductive than lithium imide complexes, provided cationic transference numbers higher than 0.5. Surprisingly, even at fairly low concentrations, this salt markedly increased the mechanical properties of the polymer electrolyte. This effect was attributed to telechelic interactions of the ion pairs with distinct polyether chains and is in agreement with the high cationic transference numbers

  1. Electrochemical performance of a hybrid lithium-ion capacitor with a graphite anode preloaded from lithium bis(trifluoromethane)sulfonimide-based electrolyte

    International Nuclear Information System (INIS)

    Decaux, C.; Lota, G.; Raymundo-Piñero, E.; Frackowiak, E.; Béguin, F.

    2012-01-01

    A hybrid LiC capacitor combining a lithium-ion battery type (graphite) electrode and an electrical double-layer (activated carbon) one has been developed by preloading graphite from 2 mol L −1 lithium bis(trifluoromethane)sulfonimide (LiTFSI) organic electrolyte. The graphite intercalation compound was formed by applying ca. 10 successive charge/self-discharge pulses. The optimized hybrid device operates in the voltage range from 1.5 to 4.2 V and displays 60% higher gravimetric capacitance than an electric double-layer (EDL) capacitor using the same activated carbon for both electrodes. As a result, the energy density reaches 80 Wh kg −1 , which is four times higher than the value for the EDL capacitor with the same total mass of carbon.

  2. Redox-assisted Li+-storage in lithium-ion batteries

    International Nuclear Information System (INIS)

    Huang Qizhao; Wang Qing

    2016-01-01

    Interfacial charge transfer is the key kinetic process dictating the operation of lithium-ion battery. Redox-mediated charge propagations of the electronic (e − and h + ) and ionic species (Li + ) at the electrode–electrolyte interface have recently gained increasing attention for better exploitation of battery materials. This article briefly summarises the energetic and kinetic aspects of lithium-ion batteries, and reviews the recent progress on various redox-assisted Li + storage approaches. From molecular wiring to polymer wiring and from redox targeting to redox flow lithium battery, the role of redox mediators and the way of the redox species functioning in lithium-ion batteries are discussed. (topical review)

  3. Robust Pinhole-free Li3N Solid Electrolyte Grown from Molten Lithium

    Directory of Open Access Journals (Sweden)

    Yanbin Li

    2017-12-01

    Full Text Available Lithium metal is the ultimate anode choice for high energy density rechargeable lithium batteries. However, it suffers from inferior electrochemical performance and safety issues due to its high reactivity and the growth of lithium dendrites. It has long been desired to develop a materials coating on Li metal, which is pinhole-free, mechanically robust without fracture during Li metal deposition and stripping, and chemically stable against Li metal and liquid electrolytes, all while maintaining adequate ionic conductivity. However, such an ideal material coating has yet to be found. Here we report a novel synthesis method by reacting clean molten lithium foil directly with pure nitrogen gas to generate instantaneously a pinhole-free and ionically conductive α-Li3N film directly bonded onto Li metal foil. The film consists of highly textured large Li3N grains (tens of μm with (001 crystalline planes parallel to the Li metal surface. The bonding between textured grains is strong, resulting in a mechanically robust film which does not crack even when bent to a 0.8 cm curvature radius and is found to maintain pinhole-free coverage during Li metal deposition and stripping. The measured ionic conductivity is up to 5.2 × 10–4 S cm–1, sufficient for maintaining regular current densities for controllable film thicknesses ranging from 2 to 30 μm. This Li3N coating is chemically stable, isolating the reactive metallic lithium from liquid electrolyte, prevents continuous electrolyte consumption during battery cycling, and promotes dendrite-free uniform lithium plating/stripping underneath. We demonstrated Li|Li4Ti5O12 cells with stable and flat potential profiles for 500 cycles without capacity decay or an increase in potential hysteresis.

  4. Electrolytic method for the production of lithium using a lithium-amalgam electrode

    Science.gov (United States)

    Cooper, John F.; Krikorian, Oscar H.; Homsy, Robert V.

    1979-01-01

    A method for recovering lithium from its molten amalgam by electrolysis of the amalgam in an electrolytic cell containing as a molten electrolyte a fused-salt consisting essentially of a mixture of two or more alkali metal halides, preferably alkali metal halides selected from lithium iodide, lithium chloride, potassium iodide and potassium chloride. A particularly suitable molten electrolyte is a fused-salt consisting essentially of a mixture of at least three components obtained by modifying an eutectic mixture of LiI-KI by the addition of a minor amount of one or more alkali metal halides. The lithium-amalgam fused-salt cell may be used in an electrolytic system for recovering lithium from an aqueous solution of a lithium compound, wherein electrolysis of the aqueous solution in an aqueous cell in the presence of a mercury cathode produces a lithium amalgam. The present method is particularly useful for the regeneration of lithium from the aqueous reaction products of a lithium-water-air battery.

  5. Carbon Nanotube-CoF2 Multifunctional Cathode for Lithium Ion Batteries: Effect of Electrolyte on Cycle Stability.

    Science.gov (United States)

    Wang, Xinran; Gu, Wentian; Lee, Jung Tae; Nitta, Naoki; Benson, Jim; Magasinski, Alexandre; Schauer, Mark W; Yushin, Gleb

    2015-10-01

    Transition metal fluorides (MFx ) offer remarkably high theoretical energy density. However, the low cycling stability, low electrical and ionic conductivity of metal fluorides have severely limited their applications as conversion-type cathode materials for lithium ion batteries. Here, a scalable and low-cost strategy is reported on the fabrication of multifunctional cobalt fluoride/carbon nanotube nonwoven fabric nanocomposite, which demonstrates a combination of high capacity (near-theoretical, 550mAhgCoF2-1) and excellent mechanical properties. Its strength and modulus of toughness exceed that of many aluminum alloys, cast iron, and other structural materials, fulfilling the use of MFx -based materials in batteries with load-bearing capabilities. In the course of this study, cathode dissolution in conventional electrolytes has been discovered as the main reason that leads to the rapid growth of the solid electrolyte interphase layer and attributes to rapid cell degradation. And such largely overlooked degradation mechanism is overcome by utilizing electrolyte comprising a fluorinated solvent, which forms a protective ionically conductive layer on the cathode and anode surfaces. With this approach, 93% capacity retention is achieved after 200 cycles at the current density of 100 mA g(-1) and over 50% after 10 000 cycles at the current density of 1000 mA g(-1) . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The effects of functional ionic liquid on properties of solid polymer electrolyte

    International Nuclear Information System (INIS)

    An Yongxin; Cheng Xinqun; Zuo Pengjian; Liao Lixia; Yin Geping

    2011-01-01

    Highlights: → The functional ionic liquid(IL)-polymer electrolytes were successfully prepared. → The ionic conductivity of PEO electrolytes was raised to above 10-4 S.cm-1 at room temperature by functional IL. → The cells using functional IL-PEO electrolyte show higher reversible capacity and long cycle life. - Abstract: Polyethylene oxide (PEO) based solid state electrolytes have been thought as promising electrolytes to replace the organic liquid electrolyte for lithium ion batteries. But the lower ionic conductivities at room temperature restrict their application. In this paper, functional ionic liquid and polymer mixed electrolytes are prepared from N-methyoxymethyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide (PP1.1O1TFSI) and polyethylene oxide. The PP1.1O1TFSI, a kind of room-temperature molten salt, was added to the conventional P(EO) 20 LiTFSI polymer electrolyte and resulted in a significant improvement of the ionic conductivity at room temperature. LiFePO 4 /Li and Li 4 Ti 5 O 12 /Li cells using this kind of electrolyte show high reversible capacity and stable cycle performance.

  7. Redox shuttles for safer lithium-ion batteries

    International Nuclear Information System (INIS)

    Chen, Zonghai; Qin, Yan; Amine, Khalil

    2009-01-01

    Overcharge protection is not only critical for preventing the thermal runaway of lithium-ion batteries during operation, but also important for automatic capacity balancing during battery manufacturing and repair. A redox shuttle is an electrolyte additive that can be used as intrinsic overcharge protection mechanism to enhance the safety characteristics of lithium-ion batteries. The advances on stable redox shuttles are briefly reviewed. Fundamental studies for designing stable redox shuttles are also discussed.

  8. Effect of Heat Treatment on the Lithium Ion Conduction of the LiBH4–LiI Solid Solution

    DEFF Research Database (Denmark)

    Sveinbjörnsson, Dadi Þorsteinn; Mýrdal, Jón Steinar Garðarsson; Blanchard, Didier

    2013-01-01

    The LiBH4–LiI solid solution is a good Li+ conductor and a promising crystalline electrolyte for all-solid-state lithium based batteries. The focus of the present work is on the effect of heat treatment on the Li+ conduction. Solid solutions with a LiI content of 6.25–50% were synthesized by high...

  9. Physical properties of a new Deep Eutectic Solvent based on lithium bis[(trifluoromethyl)sulfonyl]imide and N-methylacetamide as superionic suitable electrolyte for lithium ion batteries and electric double layer capacitors

    International Nuclear Information System (INIS)

    Boisset, Aurélien; Jacquemin, Johan; Anouti, Mérièm

    2013-01-01

    Highlights: • Preparation of new Deep Eutectic Solvent (DES) based on N-methylacetamide and TFSI. • Characterization of conductivity, viscosity and thermal properties of DES. • DES presents a superionic character in Walden classification. • DES is suitable electrolyte for lithium ion batteries and electric double layer capacitors. -- Abstract: Herein we present a study on the physical/chemical properties of a new Deep Eutectic Solvent (DES) based on N-methylacetamide (MAc) and lithium bis[(trifluoromethyl)sulfonyl]imide (LiTFSI). Due to its interesting properties, such as wide liquid-phase range from −60 °C to 280 °C, low vapor pressure, and high ionic conductivity up to 28.4 mS cm −1 at 150 °C and at x LiTFSI = 1/4, this solution can be practically used as electrolyte for electrochemical storage systems such as electric double-layer capacitors (EDLCs) and/or lithium ion batteries (LiBs). Firstly, relationships between its transport properties (conductivity and viscosity) as a function of composition and temperature were discussed through Arrhenius’ Law and Vogel–Tamman–Fulcher (VTF) equations, as well as by using the Walden classification. From this investigation, it appears that this complex electrolyte possesses a number of excellent transport properties, like a superionic character for example. Based on which, we then evaluated its electrochemical performances as electrolyte for EDLCs and LiBs applications by using activated carbon (AC) and lithium iron phosphate (LiFePO 4 ) electrodes, respectively. These results demonstrate that this electrolyte has a good compatibility with both electrodes (AC and LiFePO 4 ) in each testing cell driven also by excellent electrochemical properties in specific capacitance, rate and cycling performances, indicating that the LiTFSI/MAc DES can be a promising electrolyte for EDLCs and LiBs applications especially for those requiring high safety and stability

  10. Lithium isotope effect accompanying electrochemical intercalation of lithium into graphite

    CERN Document Server

    Yanase, S; Oi, T

    2003-01-01

    Lithium has been electrochemically intercalated from a 1:2 (v/v) mixed solution of ethylene carbonate (EC) and methylethyl carbonate (MEC) containing 1 M LiClO sub 4 into graphite, and the lithium isotope fractionation accompanying the intercalation was observed. The lighter isotope was preferentially fractionated into graphite. The single-stage lithium isotope separation factor ranged from 1.007 to 1.025 at 25 C and depended little on the mole ratio of lithium to carbon of the lithium-graphite intercalation compounds (Li-GIC) formed. The separation factor increased with the relative content of lithium. This dependence seems consistent with the existence of an equilibrium isotope effect between the solvated lithium ion in the EC/MEC electrolyte solution and the lithium in graphite, and with the formation of a solid electrolyte interfaces on graphite at the early stage of intercalation. (orig.)

  11. Tuning the Solid Electrolyte Interphase for Selective Li- and Na-Ion Storage in Hard Carbon

    Energy Technology Data Exchange (ETDEWEB)

    Soto, Fernando A. [Department of Chemical Engineering, Texas A& M University, College Station TX 77843-3122 USA; Yan, Pengfei [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Engelhard, Mark H. [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Marzouk, Asma [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 5825 Doha Qatar; Wang, Chongmin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Xu, Guiliang [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Chen, Zonghai [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Amine, Khalil [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Liu, Jun [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Sprenkle, Vincent L. [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; El-Mellouhi, Fedwa [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 5825 Doha Qatar; Balbuena, Perla B. [Department of Chemical Engineering, Texas A& M University, College Station TX 77843-3122 USA; Li, Xiaolin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA

    2017-03-07

    Solid-electrolyte interphase (SEI) with controllable properties are highly desirable to improve battery performance. In this paper, we use a combined experimental and simulation approach to study the SEI formation on hard carbon in Li and Na-ion batteries. We show that with proper additives, stable SEI can be formed on hard carbon by pre-cycling the electrode materials in Li or Na-ion electrolyte. Detailed mechanistic studies suggest that the ion transport in the SEI layer is kinetically controlled and can be tuned by the applied voltage. Selective Na and Li-ion SEI membranes are produced using the Na or Li-ion based electrolytes respectively. The large Na ion SEI allows easy transport of Li ions, while the small Li ion SEI shuts off the Na-ion transport. Na-ion storage can be manipulated by tuning the SEI with film-forming electrolyte additives or preforming a SEI on the electrodes’ surface. The Na specific capacity can be controlled to <25 mAh/g, ~1/10 of the normal capacity (250 mAh/g). Unusual selective/preferential transport of Li-ion is demonstrated by preforming a SEI on the electrode’s surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion selective conductors using electrochemical approaches in the future.

  12. Improving the performance of soft carbon for lithium-ion batteries

    International Nuclear Information System (INIS)

    Chen Zonghai; Wang Qingzheng; Amine, K.

    2006-01-01

    A novel technique for designing a robust solid electrolyte interface (SEI) on the negative electrodes of lithium-ion batteries has been developed using a silane coating. Two silane compounds, 3,3,3-trifluoropropyltrimethoxysilane (TFPTMS) and dimethoxybis(2-(2-(2-mothoxyethoxy)ethoxy)ethoxy)silane (1ND3(MeO)), have been investigated with respect to improving the capacity retention of lithium manganese oxide spinel/soft carbon cells. The impact of the silane coating on the soft carbon electrode will be attributed to (1) changes in surface functional groups (2) compositional change of the SEI, and (3) changes in the kinetics of manganese deposition. The impact of the upper cutoff voltage on the capacity retention of the cell was also discussed

  13. Tuning the Solid Electrolyte Interphase for Selective Li- and Na-Ion Storage in Hard Carbon

    Energy Technology Data Exchange (ETDEWEB)

    Soto, Fernando A. [Department of Chemical Engineering, Texas A& M University, College Station TX 77843-3122 USA; Yan, Pengfei [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Engelhard, Mark H. [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Marzouk, Asma [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 5825 Doha Qatar; Wang, Chongmin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Xu, Guiliang [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Chen, Zonghai [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Amine, Khalil [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Liu, Jun [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Sprenkle, Vincent L. [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; El-Mellouhi, Fedwa [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 5825 Doha Qatar; Balbuena, Perla B. [Department of Chemical Engineering, Texas A& M University, College Station TX 77843-3122 USA; Li, Xiaolin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA

    2017-03-07

    Solid-electrolyte interphase (SEI) films with controllable properties are highly desirable for improving battery performance. In this paper, a combined experimental and theoretical approach is used to study SEI films formed on hard carbon in Li- and Na-ion batteries. It is shown that a stable SEI layer can be designed by precycling an electrode in a desired Li- or Na-based electrolyte, and that ionic transport can be kinetically controlled. Selective Li- and Na-based SEI membranes are produced using Li- or Na-based electrolytes, respectively. The Na-based SEI allows easy transport of Li ions, while the Li-based SEI shuts off Na-ion transport. Na-ion storage can be manipulated by tuning the SEI layer with film-forming electrolyte additives, or by preforming an SEI layer on the electrode surface. The Na specific capacity can be controlled to < 25 mAh g(-1); approximate to 1/10 of the normal capacity (250 mAh g(-1)). Unusual selective/ preferential transport of Li ions is demonstrated by preforming an SEI layer on the electrode surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion-selective conductors using electrochemical approaches.

  14. Neutron scattering study on cathode LiMn{sub 2}O{sub 4} and solid electrolyte 5(Li{sub 2}O)(P{sub 2}O{sub 5})

    Energy Technology Data Exchange (ETDEWEB)

    Kartini, E., E-mail: kartini@batan.go.id; Putra, Teguh P., E-mail: kartini@batan.go.id; Jahya, A. K., E-mail: kartini@batan.go.id; Insani, A., E-mail: kartini@batan.go.id [Technology Center for Nuclear Industry Materials, National Nuclear Energy Agency, Serpong 15314 (Indonesia); Adams, S. [Department of Materials Science and Engineering, National University of Singapore, Singapore-117576 (Singapore)

    2014-09-30

    Neutron scattering is very important technique in order to investigate the energy storage materials such as lithium-ion battery. The unique advantages, neutron can see the light atoms such as Hydrogen, Lithium, and Oxygen, where those elements are negligible by other corresponding X-ray method. On the other hand, the energy storage materials, such as lithium ion battery is very important for the application in the electric vehicles, electronic devices or home appliances. The battery contains electrodes (anode and cathode), and the electrolyte materials. There are many challenging to improve the existing lithium ion battery materials, in order to increase their life time, cyclic ability and also its stability. One of the most scientific challenging is to investigate the crystal structure of both electrode and electrolyte, such as cathodes LiCoO{sub 2}, LiMn{sub 2}O{sub 4} and LiFePO{sub 4}, and solid electrolyte Li{sub 3}PO{sub 4}. Since all those battery materials contain Lithium ions and Oxygen, the used of neutron scattering techniques to study their structure and related properties are very important and indispensable. This article will review some works of investigating electrodes and electrolytes, LiMn{sub 2}O{sub 4} and 5(Li{sub 2}O)(P{sub 2}O{sub 5}), by using a high resolution powder diffraction (HRPD) at the multipurpose research reactor, RSG-Sywabessy of the National Nuclear Energy Agency (BATAN), Indonesia.

  15. Challenge in manufacturing electrolyte solutions for lithium and lithium ion batteries quality control and minimizing contamination level

    Science.gov (United States)

    Heider, U.; Oesten, R.; Jungnitz, M.

    The quality of electrolytes for lithium batteries are a major topic in science and battery industries. The solvents and lithium salts should be of highest purity. Therefore, during preparation and handling of electrolyte solutions, the contamination level has to be minimized and the quality during packaging, storage and transportation has to be guaranteed. Especially, protic impurities are found to be very critical for LiPF 6-based electrolytes. The influence of water is reported to be tremendous. But also other protic impurities like alcohols are considered to play an important role in the electrolyte quality. The reaction of the protic impurities with LiPF 6 leads to the formation of HF which further reacts with cathode active materials (e.g., spinel) and the passivating films of the cathode and anode. For a better understanding of the protic impurities and their role in the electrolyte quality a systematic investigation of different impurities was carried out. Electrolytes were doped with different protic compounds. Then the electrolyte was analyzed for protic impurities and HF in dependence of time. First results showing the relation between protic impurities and HF are presented and discussed. In addition, different packaging materials for the electrolyte solutions were investigated. Storage tests were carried out at different temperatures and in different atmospheres. Results on contamination levels, influence of packaging, high temperature storage and handling are addressed.

  16. Block copolymer with simultaneous electric and ionic conduction for use in lithium ion batteries

    Science.gov (United States)

    Javier, Anna Esmeralda K; Balsara, Nitash Pervez; Patel, Shrayesh Naran; Hallinan, Jr., Daniel T

    2013-10-08

    Redox reactions that occur at the electrodes of batteries require transport of both ions and electrons to the active centers. Reported is the synthesis of a block copolymer that exhibits simultaneous electronic and ionic conduction. A combination of Grignard metathesis polymerization and click reaction was used successively to synthesize the block copolymer containing regioregular poly(3-hexylthiophene) (P3HT) and poly(ethylene oxide) (PEO) segments. The P3HT-PEO/LiTFSI mixture was then used to make a lithium battery cathode with LiFePO.sub.4 as the only other component. All-solid lithium batteries of the cathode described above, a solid electrolyte and a lithium foil as the anode showed capacities within experimental error of the theoretical capacity of the battery. The ability of P3HT-PEO to serve all of the transport and binding functions required in a lithium battery electrode is thus demonstrated.

  17. Improving cyclic stability of lithium nickel manganese oxide cathode for high voltage lithium ion battery by modifying electrode/electrolyte interface with electrolyte additive

    International Nuclear Information System (INIS)

    Li, Bin; Wang, Yaqiong; Tu, Wenqiang; Wang, Zaisheng; Xu, Mengqing; Xing, Lidan; Li, Weishan

    2014-01-01

    Highlights: • Cyclic stability of LiNi 0.5 Mn 1.5 O 4 is improved significantly by using PES as additive. • A protective SEI is formed on LiNi 0.5 Mn 1.5 O 4 due to the preferential oxidation of PES. • The SEI suppresses electrolyte decomposition and structure destruction of LiNi 0.5 Mn 1.5 O 4 . - Abstract: We report a new approach to improve the cyclic stability of lithium nickel manganese oxide (LiNi 0.5 Mn 1.5 O 4 ) cathode, in which the cathode/electrolyte interface is modified by using prop-1-ene-1, 3-sultone (PES) as an electrolyte additive. The interfacial properties of LiNi 0.5 Mn 1.5 O 4 cathode in PES-containing electrolyte have been investigated by scanning electron spectroscopy (SEM), transmission electron microscopy (TEM), thermal gravimetry (TG), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), cyclic voltammometry (CV), chronoamperometry (CA), and constant current charge/discharge test. It is found that the application of PES improves significantly the cyclic stability of LiNi 0.5 Mn 1.5 O 4 . After 400 cycles at 1C rate (1C=147 mA g −1 ), the capacity retention of LiNi 0.5 Mn 1.5 O 4 is 90% for the cell using 1.0 wt% PES, while only 49% for the cell without the additive. The characterizations from SEM, TEM, TG, XRD, and XPS confirm that the LiNi 0.5 Mn 1.5 O 4 /electrolyte interface is modified and a protective solid electrolyte interface film is formed on LiNi 0.5 Mn 1.5 O 4 particles, which prevents LiNi 0.5 Mn 1.5 O 4 from destruction and suppresses the electrolyte decomposition

  18. Comparative Study on the Solid Electrolyte Interface Formation by the Reduction of Alkyl Carbonates in Lithium ion Battery

    International Nuclear Information System (INIS)

    Haregewoin, Atetegeb Meazah; Leggesse, Ermias Girma; Jiang, Jyh-Chiang; Wang, Fu-Ming; Hwang, Bing-Joe; Lin, Shawn D.

    2014-01-01

    Mixed alkyl carbonates are widely used as solvent for a various lithium-ion battery applications. Understanding the behavior of each solvent in the mixed system is crucial for controlling the electrolyte composition. In this paper, we report a systematic electrochemical and spectroscopic comparison of the reduction of propylene carbonate (PC), ethylene carbonate (EC), and diethyl carbonate (DEC) when used as single (PC), binary (EC/PC, EC/DEC), and ternary (EC/PC/DEC) solvent systems. The reduction products are identified based on Fourier transform infrared spectroscopy (FTIR) after employing linear sweep voltammetry to certain potential regions and their possible formation mechanisms are discussed. FTIR analyses revealed that the reduction of EC and PC was not considerably influenced by the presence of other alkyl carbonates. However, DEC exhibited a different reduction product when used in EC/DEC and EC/PC/DEC solvent systems. The reduction of EC occurred before that of PC and DEC and produced a passivating surface film that prevented carbon exfoliation caused by PC. Battery performance test, cyclic voltammetry, electrochemical impedance spectroscopy, and scanning electron microscope is employed to study the surface films formed. The binary EC/DEC solvent system demonstrated more favorable performance, smaller impedance, and higher Li + ion diffusivity than did the other solvent systems used in this study

  19. Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires

    Science.gov (United States)

    Liu, Wei; Lee, Seok Woo; Lin, Dingchang; Shi, Feifei; Wang, Shuang; Sendek, Austin D.; Cui, Yi

    2017-04-01

    In contrast to conventional organic liquid electrolytes that have leakage, flammability and chemical stability issues, solid electrolytes are widely considered as a promising candidate for the development of next-generation safe lithium-ion batteries. In solid polymer electrolytes that contain polymers and lithium salts, inorganic nanoparticles are often used as fillers to improve electrochemical performance, structure stability, and mechanical strength. However, such composite polymer electrolytes generally have low ionic conductivity. Here we report that a composite polymer electrolyte with well-aligned inorganic Li+-conductive nanowires exhibits an ionic conductivity of 6.05 × 10-5 S cm-1 at 30 ∘C, which is one order of magnitude higher than previous polymer electrolytes with randomly aligned nanowires. The large conductivity enhancement is ascribed to a fast ion-conducting pathway without crossing junctions on the surfaces of the aligned nanowires. Moreover, the long-term structural stability of the polymer electrolyte is also improved by the use of nanowires.

  20. A zwitterionic gel electrolyte for efficient solid-state supercapacitors

    Science.gov (United States)

    Peng, Xu; Liu, Huili; Yin, Qin; Wu, Junchi; Chen, Pengzuo; Zhang, Guangzhao; Liu, Guangming; Wu, Changzheng; Xie, Yi

    2016-01-01

    Gel electrolytes have attracted increasing attention for solid-state supercapacitors. An ideal gel electrolyte usually requires a combination of advantages of high ion migration rate, reasonable mechanical strength and robust water retention ability at the solid state for ensuring excellent work durability. Here we report a zwitterionic gel electrolyte that successfully brings the synergic advantages of robust water retention ability and ion migration channels, manifesting in superior electrochemical performance. When applying the zwitterionic gel electrolyte, our graphene-based solid-state supercapacitor reaches a volume capacitance of 300.8 F cm−3 at 0.8 A cm−3 with a rate capacity of only 14.9% capacitance loss as the current density increases from 0.8 to 20 A cm−3, representing the best value among the previously reported graphene-based solid-state supercapacitors, to the best of our knowledge. We anticipate that zwitterionic gel electrolyte may be developed as a gel electrolyte in solid-state supercapacitors. PMID:27225484

  1. Effects of Propylene Carbonate Content in CsPF 6 -Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo; Xiang, Hongfa [School of; Engelhard, Mark H.; Polzin, Bryant J. [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States; Wang, Chongmin; Zhang, Ji-Guang; Xu, Wu

    2016-02-15

    The effects Of propylene carbonate (PC) content in CsPF6-containing electrolytes on the performances of graphite electrode in lithium half cells and in graphite parallel to LiNi0.80Co0.15Al0.05O2 (NCA) full cells are investigated. It is found that the performance of graphite electrode is significantly-affected by PC content in the CsPF6-containing electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode can be attributed to the synergistic effects of the PC solvent and the Cs+ additive. The synergistic effects of Cs+ additive and appropriate amount of PC enable the formation of a robust, ultrathin, and compact solid electrolyte interphase (SEI) layer on the surface of graphite electrode, which is only permeable for desolvated Li+ ions and allows fast Li+ ion transport through it. Therefore, this SEI layer effectively suppresses the PC cointercalation and largely alleviates the Li dendrite formation on graphite electrode during lithiation even at relatively high current densities. The presence of low-melting-point PC solvent improves the sustainable operation of graphite parallel to NCA full cells under a wide temperature range. The fundamental findings also shed light On the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in various energy-storage devices.

  2. Poly(vinylpyridine-co-styrene) based in situ cross-linked gel polymer electrolyte for lithium-ion polymer batteries

    International Nuclear Information System (INIS)

    Oh, Sijin; Kim, Dong Wook; Lee, Changjin; Lee, Myong-Hoon; Kang, Yongku

    2011-01-01

    A gel polymer electrolyte (GPE) was successfully prepared by means of an in situ cross-linking reaction of poly(2-vinylpyridine-co-styrene) and oligo(ethylene oxide) with epoxide functional groups at 65 °C without using a polymerization initiator. A stable gel polymer electrolyte could be obtained by adding only 1% of a polymer gelator. The ionic conductivity of the GPE containing 99 wt% of liquid electrolyte was measured to be ca. 10 −2 S/cm at the ambient temperature. The ionic conductivity of the resulting GPE was comparable to that of a pure liquid electrolyte. The electrochemical stability window of the prepared gel polymer electrolytes was measured to be 5.2 V. The test cell carried a discharge capacity of 133.2 mAh/g at 0.1 C and showed good cycling performance with negligible capacity fading after the 200th cycle, maintaining 99.5% coulombic efficiency throughout 200 cycles. The resulting gel polymer electrolyte prepared by in situ thermal cross-linking without a polymerization initiator holds promise for application to on the high power lithium-ion polymer batteries.

  3. NREL's Advanced Atomic Layer Deposition Enables Lithium-Ion Battery

    Science.gov (United States)

    Battery Technology News Release: NREL's Advanced Atomic Layer Deposition Enables Lithium-Ion Battery increasingly demanding needs of any battery application. These lithium-ion batteries feature a hybrid solid further customized lithium-ion battery materials for high performance devices by utilizing our patented

  4. New polymer lithium secondary batteries based on ORMOCER (R) electrolytes-inorganic-organic polymers

    DEFF Research Database (Denmark)

    Popall, M.; Buestrich, R.; Semrau, G.

    2001-01-01

    Based on new plasticized inorganic-organic polymer electrolytes CM. Popall, M. Andrei, J. Kappel, J. Kron, K. Olma, B. Olsowski,'ORMOCERs as Inorganic-organic Electrolytes for New Solid State Lithium Batteries and Supercapacitors', Electrochim. Acta 43 (1998) 1155] new flexible foil-batteries...... electrolyte, typical for polymer electrolytes. Cycling tests (more than 900 cycles) proved that the unplasticized electrolyte can act as binder in composite cathodes of lithium secondary batteries [2]. Charge/discharge cycles of complete batteries like (Cu/active carbon/ORMOCER(R)/LiCoO2/Al) with an ORMOCER......(R) as separator electrolyte were measured. The voltage drop of these batteries is very similar to cells with standard liquid electrolytes and the efficiency is close to 100%. Cycling the batteries with a current density of 0.25 mA cm(-2) between the voltage limits of 3.1 and 4.1 V results in a charge...

  5. Polymerizable Ionic Liquid Crystals Comprising Polyoxometalate Clusters toward Inorganic-Organic Hybrid Solid Electrolytes

    Directory of Open Access Journals (Sweden)

    Takeru Ito

    2017-07-01

    Full Text Available Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is employing a thermally-stable inorganic component and a structurally-flexible organic moiety to construct inorganic-organic hybrid materials. Ionic liquids as the organic component will be advantageous for the emergence of high conductivity, and polyoxometalate, such as heteropolyacids, are well-known as inorganic proton conductors. Here, newly-designed ionic liquid imidazolium cations, having a polymerizable methacryl group (denoted as MAImC1, were successfully hybridized with heteropolyanions of [PW12O40]3− (PW12 to form inorganic-organic hybrid monomers of MAImC1-PW12. The synthetic procedure of MAImC1-PW12 was a simple ion-exchange reaction, being generally applicable to several polyoxometalates, in principle. MAImC1-PW12 was obtained as single crystals, and its molecular and crystal structures were clearly revealed. Additionally, the hybrid monomer of MAImC1-PW12 was polymerized by a radical polymerization using AIBN as an initiator. Some of the resulting inorganic-organic hybrid polymers exhibited conductivity of 10−4 S·cm−1 order under humidified conditions at 313 K.

  6. Mechanism of ion exchange in zirconium phosphates. 17. Dehydration behavior of lithium ion exchanged phases

    Energy Technology Data Exchange (ETDEWEB)

    Clearfield, A; Pack, S P; Troup, J M [Ohio Univ., Athens (USA). Dept. of Chemistry

    1977-01-01

    The phases formed by the dehydration of lithium exchanged ..cap alpha..-zirconium phosphate, Zr(HP0/sub 4/).H/sub 2/0, were determined by a combination of X-ray, TGA and DTA studies. Samples containing 10, 20, 30 ..... 100% of theoretical lithium ion capacity were examined. The data are summarized in a phase diagram which however is not an equilibrium diagram because of the slowness of approach to equilibrium. The numerous phases obtained and the ease with which they rearrange indicates a high mobility for the incorporated cations. This suggested that ..cap alpha..-zirconium phosphate may behave as a solid electrolyte and indeed this was demonstrated by having it serve in that capacity in a small sodium sulfur battery.

  7. Study on property-gradient polymer electrolyte for rechargeable lithium batteries; Lithium niji denchi no tame no keisha tokusei kobunshi denkaishitsu no sosei ni kansuru kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    Kokumi, Z; Kanemura, S; Inaba, M; Takehara, Z; Yao, K; Uchimoto, Y [Kyoto University, Kyoto (Japan)

    1997-02-01

    This paper describes the fundamental experiments for creating property-gradient polymer electrolyte for rechargeable lithium batteries. The rechargeable lithium battery is composed of an anodic composite agent section with high ion conductivity, a separator equivalent section with high mechanical strength (high bridging degree), and a section surpressing the precipitation of metal lithium by contacting with it. The continuous property-gradient polymer electrolyte was tried to be synthesized by means of the plasma polymerization method. As a result, plasma polymerization electrolyte with high ion conductivity could be prepared from the liquid phase by using a monomer with low vapor pressure. Porous material simulating the anodic composite agent was impregnated by the monomer, which was plasma-polymerized. As a result, it was found that the bridging degree decreased from the surface towards the inside of the plasma-polymerized porous material. In addition, polymer was prepared using fluorine-base monomer. Thus, LiF thin film could be prepared through the reaction between the polymer and metal lithium. 3 figs.

  8. In-Situ Observation of Solid Electrolyte Interphase Formation in Ordered Mesoporous Hard Carbon by Small-Angle Neutron Scattering

    International Nuclear Information System (INIS)

    Bridges, Craig A.; Paranthaman, Mariappan Parans; Sun, Xiao-Guang; Zhao, Jinkui; Dai, Sheng

    2012-01-01

    The aim of this work was to better understand the electrochemical processes occurring during the cycling of a lithium-ion half-cell containing ordered mesoporous hard carbon using time-resolved in situ small-angle neutron scattering (SANS). Utilizing electrolytes containing mixtures of deuterated (2H) and non-deuterated (1H) carbonates, we have addressed the challenging task of monitoring the formation and evolution of the solid-electrolyte interphase (SEI) layer. An evolution occurs in the SEI layer during discharge from a composition dominated by a higher scattering length density (SLD) lithium salt, to a lower SLD lithium salt for the ethylene carbonate/dimethyl carbonate (EC/DMC) mixture employed. By comparing half-cells containing different solvent deuteration levels, we show that it is possible to observe both SEI formation and lithium intercalation occurring concurrently at the low voltage region in which lithium intercalates into the hard carbon. These results demonstrate that SANS can be employed to monitor complicated electrochemical processes occurring in rechargeable batteries, in a manner that simultaneously provides information on the composition and microstructure of the electrode.

  9. An approach to beneficiation of spent lithium-ion batteries for recovery of materials

    Science.gov (United States)

    Marinos, Danai

    Lithium ion batteries are one of the most commonly used batteries. A large amount of these have been used over the past 25 years and the use is expected to rise more due to their use in automotive batteries. Lithium ion batteries cannot be disposed into landfill due to safety reasons and cost. Thus, over the last years, there has been a lot of effort to find ways to recycle lithium ion batteries. A lot of valuable materials are present in a lithium ion battery making their recycling favorable. Many attempts, including pyrometallurgical and hydrometallurgical methods, have been researched and some of them are already used by the industry. However, further improvements are needed to the already existing processes, to win more valuable materials, use less energy and be more environmentally benign. The goal of this thesis is to find a low-temperature, low-energy method of recovering lithium from the electrolyte and to develop pathways for complete recycling of the battery. The research consists of the following parts: Pure LiPF6 powder, which is the electrolyte material, was characterized using x- ray diffraction analysis and DSC/TGA analysis. The LiPF6 powder was titrated using acid (HCl, HNO3, H2SO4), bases (NH4 OH) and distilled water. It was concluded that distilled water was the best solvent to selectively leach lithium from lithium-ion batteries. Leaching conditions were optimized including time, temperature, solid/liquid ratio and stirring velocity. All the samples were tested using ICP for chemical composition. Because leaching could be performed at room temperature, leaching was conducted in a flotation machine that was able to separate plastics by creating bubbles with no excess reagents use. The solution that contained lithium had to be concentrated more in order for lithium to be able to precipitate and it was shown that the solution could be concentrated by using the same solution over and over again. The next set of experiments was composed of battery

  10. The Effects of Lithium Triflate (LiCF3SO3) on the PMMA-based Solid Polymer Electrolytes

    International Nuclear Information System (INIS)

    Chew, K. W.; Chen, S. S.; Pang, W. L.; Tan, C. G.; Osman, Z.

    2010-01-01

    The effects of Lithium triflate salt (LiCF 3 SO 3 ), on the poly (methyl methacrylate)(PMMA)-based solid polymer electrolytes plasticized with propylene carbonate (PC) solvated in Tetrahydrofuran (THF) have been studied through a.c impedance spectroscopy and infrared spectroscopy. Lithium triflate was incorporated into the predetermined PMMA/PC system that has the highest value of ionic conductivity. In current investigations, four combination systems: Pure PMMA, (PMMA+PC) systems, (PMMA+LiCF 3 SO 3 ) and (PMMA+PC+LiCF 3 SO 3 ) systems were prepared using the solution cast method. Solutions were stirred for numerous hours to obtain a homogenous solution before it is poured into the petri dishes under ambient temperature to form the solid electrolyte thin film. The films were then removed from petri discs and transferred into the dessicator for further drying prior to the different tests. From the characterization done through the a.c impedance spectroscopy, the highest room temperature ionic conductivity in the pure PMMA sample, (PMMA+PC) system and (PMMA+LiCF 3 SO 3 ) system is 2.83x10 -12 Scm -1 , 4.39x10 -11 Scm -1 and 3.93x10 -6 Scm -1 respectively. The conductivity for (PMMA+PC+LiCF 3 SO 3 ) system was obtained with the 30 wt% of lithium triflate, which is 2.48x10 -5 Scm -1 . Infrared spectroscopy shows that complexation occurred between the polymer and the plasticizer, and the polymer and plasticizer and salt. The interactions have been studied in the C=O band, C-O-C band and the O-CH 3 band.

  11. Impedance Analysis of Silicon Nanowire Lithium Ion Battery Anodes

    KAUST Repository

    Ruffo, Riccardo

    2009-07-02

    The impedance behavior of silicon nanowire electrodes has been investigated to understand the electrochemical process kinetics that influences the performance when used as a high-capacity anode in a lithium ion battery. The ac response was measured by using impedance spectroscopy in equilibrium conditions at different lithium compositions and during several cycles of charge and discharge in a half cell vs. metallic lithium. The impedance analysis shows the contribution of both surface resistance and solid state diffusion through the bulk of the nanowires. The surface process is dominated by a solid electrolyte layer (SEI) consisting of an inner, inorganic insoluble part and several organic compounds at the outer interface, as seen by XPS analysis. The surface resistivity, which seems to be correlated with the Coulombic efficiency of the electrode, grows at very high lithium contents due to an increase in the inorganic SEI thickness. We estimate the diffusion coefficient of about 2 × 10 -10 cm 2/s for lithium diffusion in silicon. A large increase in the electrode impedance was observed at very low lithium compositions, probably due to a different mechanism for lithium diffusion inside the wires. Restricting the discharge voltage to 0.7 V prevents this large impedance and improves the electrode lifetime. Cells cycled between 0.07 and 0.70 V vs. metallic lithium at a current density of 0.84 A/g (C/5) showed good Coulombic efficiency (about 99%) and maintained a capacity of about 2000 mAh/g after 80 cycles. © 2009 American Chemical Society.

  12. Novel configuration of polyimide matrix-enhanced cross-linked gel separator for high performance lithium ion batteries

    International Nuclear Information System (INIS)

    Zhang, Hong; Zhang, Yin; Yao, Zhikan; John, Angelin Ebanezar; Li, Yang; Li, Weishan; Zhu, Baoku

    2016-01-01

    Highlights: • For the first time, a cross-linked gel polymer electrolyte with additional lithium ions, was introduced into a nonwoven separator. • The PI nonwoven is employed to ensure enhanced thermal stability and mechanical strength of the IACS. • With the introduction of PAMPS(Li"+), the migration and mobility rate of anions could be hindered by the -SO_3"− group, giving rise to a high lithium ion transference number. • This IACS is recommended as a promising candidate for the high-power and high-safety lithium ion batteries. - Abstract: A novel composite nonwoven separator exhibiting high heat resistance, high ionic conductivity and high lithium ion transference number is fabricated by a simple dip-coating and heat treatment method. The thermal stable polyimide (PI) nonwoven matrix is chosen as a mechanical support and contributes to improving the thermal shrinkage of the composite nonwoven separator (abbreviated as IACS). The cross-linked poly(2-acrylamido-2-methylpropanesulfonic acid) PAMPS(Li"+) gel polymer electrolyte (GPE), lithium ion sources of a single ion conductor, is introduced into the PI nonwoven matrix and acts as a functional filler. This PAMPS (Li"+) GPE is proved to be able to provide internal short circuit protection, to alleviate liquid electrolyte leakage effectively, to supply more lithium ions dissociating from PAMPS (Li"+) by liquid electrolyte solvent, to contribute a more stable interfacial resistance, and thus resulting in an excellent cyclability. More notably, the migration and mobility rate of anions could be hindered by the −SO_3"− group in the PAMPS (Li"+) polymer based on electrostatic interaction, giving rise to a very high lithium ion transference number. These fascinating characteristics endow the IACS a great promise for the application in the high power and high safety lithium ion batteries.

  13. Ion transport properties of lithium ionic liquids and their ion gels

    International Nuclear Information System (INIS)

    Shobukawa, Hitoshi; Tokuda, Hiroyuki; Susan, Md. Abu Bin Hasan; Watanabe, Masayoshi

    2005-01-01

    A new series of lithium ionic liquids were prepared by introducing of two electron-withdrawing trifluoroacetyl groups in borate salts containing two methoxy-oligo(ethylene oxide) groups in the structures. Successive substitution reactions of oligo-ethylene glycol monomethyl ether and trifluroacetic acid from LiBH 4 yielded the lithium salts, which were clear and colorless liquids at room temperature. The fundamental physicochemical properties, such as density, thermal property, viscosity, ionic conductivity, self-diffusion coefficients, and electrochemical stability, were measured. The lithium ionic liquids had self-dissociation ability and conducted ions even in the absence of organic solvents. New polymer electrolytes, named 'ion gels', were prepared by radical cross-linking reactions of a poly(ethylene oxide-co-propylene oxide)tri-acrylate macromonomer in the presence the lithium ionic liquid. An increase in the glass transition temperatures (T g ) of the ion gels was very small even with increasing lithium ionic liquid concentration, and the T g 's were lower than that of the ionic liquid itself. The ionic conductivity of the ion gels surpassed that of the lithium ionic liquid in the bulk at certain compositions

  14. Multivalent ion conducting solids

    Energy Technology Data Exchange (ETDEWEB)

    Imanaka, N. [Osaka Univ., Suita, Osaka (Japan). Dept. of Applied Chemistry

    2008-07-01

    Solid electrolytes possess important characteristics for industrial applications. Only a single ionic species can macroscopically migrate in these solids. This paper described a the new NASICON (M-Zr-Nb-P-O) type system, exhibiting an exceptionally high level of trivalent M3+ ion conductivity on polycrystalline solids. The partial substitution of the smaller higher valent Nb5+ ion for Zr4+ stabilized the NASICON phase and realized the M3+ ion conduction in the NASICON structure. It was concluded that the conductivities of the series are comparable to those of the practically applied solid electrolytes of oxide anion conductors of YSZ and CSZ. 3 refs., 2 figs.

  15. A molecular dynamics study of lithium-containing aprotic heterocyclic ionic liquid electrolytes

    Science.gov (United States)

    Lourenço, Tuanan C.; Zhang, Yong; Costa, Luciano T.; Maginn, Edward J.

    2018-05-01

    Classical molecular dynamics simulations were performed on twelve different ionic liquids containing aprotic heterocyclic anions doped with Li+. These ionic liquids have been shown to be promising electrolytes for lithium ion batteries. Self-diffusivities, lithium transference numbers, densities, and free volumes were computed as a function of lithium concentration. The dynamics and free volume decreased with increasing lithium concentration, and the trends were rationalized by examining the changes to the liquid structure. Of those examined in the present work, it was found that (methyloxymethyl)triethylphosphonium triazolide ionic liquids have the overall best performance.

  16. Development of novel strategies for enhancing the cycle life of lithium solid polymer electrolyte batteries. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Macdonald, Digby D.; Urquidi-Macdonald, Mirna; Allcock, Harry; Engelhard, George; Bomberger, N.; Gao, L.; Olmeijer, D.

    2001-04-30

    Lithium/solid polymer electrolyte (Li/SPE) secondary batteries are under intense development as power sources for portable electronic devices as well as electric vehicles. These batteries offer high specific energy, high energy density, very low self-discharge rates, and flexibility in packaging; however, problems have inhibited their introduction into the marketplace. This report summarizes findings to examine processes that occur with Li/SPE secondary batteries upon cyclic charging/discharging. The report includes a detailed analysis of the impedance measured on the Li/SPE/IC and IC/SPE/IC systems. The SPE was a derivative of methoxyethoxyethoxyphosphazene (MEEP) with lithium triflate salt as the electrolyte, while the intercalated cathodes (IC) comprised mixtures of manganese dioxide, carbon powder, and MEEP as a binder. Studies on symmetrical Li/SPE/Li laminates show that cycling results in a significant expansion of the structure over the first few tens of cycles; however, no corresponding increase in the impedance was noted. The cycle life of the intercalation cathode was found to be very sensitive to the method of fabrication. Results indicate that the cycle life is due to the failure of the IC, not to the failure of the lithium/SPE interface. A pattern recognition neural network was developed to predict the cycle life of a battery from the charge/discharge characteristics.

  17. Interfacial reactions in lithium batteries

    International Nuclear Information System (INIS)

    Chen, Zonghai; Amine, Khalil; Amine, Rachid; Ma, Zi-Feng

    2017-01-01

    The lithium-ion battery was first commercially introduced by Sony Corporation in 1991 using LiCoO 2 as the cathode material and mesocarbon microbeads (MCMBs) as the anode material. After continuous research and development for 25 years, lithium-ion batteries have been the dominant energy storage device for modern portable electronics, as well as for emerging applications for electric vehicles and smart grids. It is clear that the success of lithium-ion technologies is rooted to the existence of a solid electrolyte interphase (SEI) that kinetically suppresses parasitic reactions between the lithiated graphitic anodes and the carbonate-based non-aqueous electrolytes. Recently, major attention has been paid to the importance of a similar passivation/protection layer on the surface of cathode materials, aiming for a rational design of high-energy-density lithium-ion batteries with extended cycle/calendar life. In this article, the physical model of the SEI, as well as recent research efforts to understand the nature and role of the SEI are summarized, and future perspectives on this important research field will also be presented. (topical review)

  18. Interfacial reactions in lithium batteries

    Science.gov (United States)

    Chen, Zonghai; Amine, Rachid; Ma, Zi-Feng; Amine, Khalil

    2017-08-01

    The lithium-ion battery was first commercially introduced by Sony Corporation in 1991 using LiCoO2 as the cathode material and mesocarbon microbeads (MCMBs) as the anode material. After continuous research and development for 25 years, lithium-ion batteries have been the dominant energy storage device for modern portable electronics, as well as for emerging applications for electric vehicles and smart grids. It is clear that the success of lithium-ion technologies is rooted to the existence of a solid electrolyte interphase (SEI) that kinetically suppresses parasitic reactions between the lithiated graphitic anodes and the carbonate-based non-aqueous electrolytes. Recently, major attention has been paid to the importance of a similar passivation/protection layer on the surface of cathode materials, aiming for a rational design of high-energy-density lithium-ion batteries with extended cycle/calendar life. In this article, the physical model of the SEI, as well as recent research efforts to understand the nature and role of the SEI are summarized, and future perspectives on this important research field will also be presented.

  19. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries.

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-12-23

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn 4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g -1 based on solid-state redox reaction of oxide ions.

  20. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-01-01

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

  1. Preparation of hydroxide ion conductive KOH–layered double hydroxide electrolytes for an all-solid-state iron–air secondary battery

    Directory of Open Access Journals (Sweden)

    Taku Tsuneishi

    2014-06-01

    Full Text Available Anion conductive solid electrolytes based on Mg–Al layered double hydroxide (LDH were prepared for application in an all-solid-state Fe–air battery. The ionic conductivity and the conducting ion species were evaluated from impedance and electromotive force measurements. The ion conductivity of LDH was markedly enhanced upon addition of KOH. The electromotive force in a water vapor concentration cell was similar to that of an anion-conducting polymer membrane. The KOH–LDH obtained was used as a hydroxide ion conductive electrolyte for all-solid-state Fe–air batteries. The cell performance of the Fe–air batteries was examined using a mixture of KOH–LDH and iron-oxide-supported carbon as the negative electrode.

  2. Stable lithium electrodeposition in salt-reinforced electrolytes

    KAUST Repository

    Lu, Yingying

    2015-04-01

    © 2015 Elsevier B.V. Development of high-energy lithium-based batteries that are safe remains a challenge due to the non-uniform lithium electrodeposition during repeated charge and discharge cycles. We report on the effectiveness of lithium bromide (LiBr) salt additives in a common liquid electrolyte (i.e. propylene carbonate (PC)) on the stability of lithium electrodeposition. From galvanostatic cycling measurements, we find that the presence of LiBr in PC provides more than 20-fold enhancement in cell lifetime over the control LiTFSI/PC electrolyte. Batteries containing 30 mol% LiBr additive in the electrolytes are able to cycle stably for at least 1.8 months with no observations of cell failure. From galvanostatic polarization measurements, an electrolyte containing 30 mol% LiBr shows a maximum improvement in lifetime. The formation of uneven lithium electrodeposits is significantly suppressed by the Br-containing SEI layers, evidenced by impedance spectra, post-mortem SEM and XPS analyses. The study also concludes that good solubility of halogenated salts is not necessary for achieving the observed improvements in cell lifetime.

  3. Relevant Features of a Triethylene Glycol Dimethyl Ether-Based Electrolyte for Application in Lithium Battery.

    Science.gov (United States)

    Carbone, Lorenzo; Di Lecce, Daniele; Gobet, Mallory; Munoz, Stephen; Devany, Matthew; Greenbaum, Steve; Hassoun, Jusef

    2017-05-24

    Triethylene glycol dimethyl ether (TREGDME) dissolving lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) is studied as a suitable electrolyte medium for lithium battery. Thermal and rheological characteristics, transport properties of the dissolved species, and the electrochemical behavior in lithium cell represent the most relevant investigated properties of the new electrolyte. The self-diffusion coefficients, the lithium transference numbers, the ionic conductivity, and the ion association degree of the solution are determined by pulse field gradient nuclear magnetic resonance and electrochemical impedance spectroscopy. The study sheds light on the determinant role of the lithium nitrate (LiNO 3 ) addition for allowing cell operation by improving the electrode/electrolyte interfaces and widening the voltage stability window. Accordingly, an electrochemical activation procedure of the Li/LiFePO 4 cell using the upgraded electrolyte leads to the formation of stable interfaces at the electrodes surface as clearly evidenced by cyclic voltammetry, impedance spectroscopy, and ex situ scanning electron microscopy. Therefore, the lithium battery employing the TREGDME-LiCF 3 SO 3 -LiNO 3 solution shows a stable galvanostatic cycling, a high efficiency, and a notable rate capability upon the electrochemical conditions adopted herein.

  4. Concept of polymer alloy electrolytes: towards room temperature operation of lithium-polymer batteries

    International Nuclear Information System (INIS)

    Noda, Kazuhiro; Yasuda, Toshikazu; Nishi, Yoshio

    2004-01-01

    Polymer alloy technique is very powerful tool to tune the ionic conductivity and mechanical strength of polymer electrolyte. A semi-interpenetrating polymer network (semi-IPN) polymer alloy electrolyte, composed of non-cross-linkable siloxane-based polymer and cross-linked 3D network polymer, was prepared. Such polymer alloy electrolyte has quite high ionic conductivity (more than 10 -4 Scm -1 at 25 o C and 10 -5 Scm -1 at -10 o C) and mechanical strength as a separator film with a wide electrochemical stability window. A lithium metal/semi-IPN polymer alloy solid state electrolyte/LiCoO 2 cell demonstrated promising cycle performance with room temperature operation of the energy density of 300Wh/L and better rate performance than conventional PEO based lithium polymer battery ever reported

  5. Polymer electrolytes: an investigation of some poly (n-propylaziridine)/lithium salt compositions. Technical report

    Energy Technology Data Exchange (ETDEWEB)

    Baldwin, K R; Golder, A J; Knight, J

    1984-04-01

    Some poly(N-propylaziridine)/lithium salt compositions have been synthesized and their electrical conductivities have been measured in order to assess their suitability as electrolytes in safe, leakproof, high energy-density lithium batteries operating at ambient temperature. The effects on conductivity of temperature, and the nature and concentration of the salt have also been studied. The presence of the salts markedly improved the conductivity of the compositions over that of the undoped polymer but they were insufficiently conducting to be considered as battery electrolytes, due possibly to ion-pairing. Their creep resistance was also low. It was concluded that less fluid compositions containing higher molecular weight polymers better able to promote ion separation would be more suitable.

  6. Aggressive electrolyte poisons and multifunctional fluids comprised of diols and diamines for emergency shutdown of lithium-ion batteries

    Science.gov (United States)

    Noelle, Daniel J.; Shi, Yang; Wang, Meng; Le, Anh V.; Qiao, Yu

    2018-04-01

    Electrolyte poisons comprised of diols and diamines are investigated for the intended function of exacerbating internal resistance in lithium-ion batteries upon short circuit failure, to quickly arrest uncontrolled joule heat generation in the earliest stages. The competing dynamics of powerful short circuit currents and electrolyte poisoning interactions are evaluated via simultaneous nail penetration and poison injection of LIR2450 format LiCoO2/graphite 120 mAh coin cells. To forcibly increase electrolyte impedance, diols serve to hinder charge-carrying ion mobility by raising solution viscosity, while diamines disrupt solvent permittivity by rapidly polymerizing the ethylene carbonate solvent. Diamines demonstrate great potency, and are suitable for integration into battery cells within chemically-inert, breakable containers, rigged for release upon mechanical activation. Mixtures of 1,2-ethanediol and 1,2-ethanediamine show synergistic poisoning effects, decreasing peak temperature accrued by 70% when introduced simultaneously upon nail penetration. With the innate presence and abundance of diols and diamines in electric vehicle heat exchangers, they may be employed for multifunctional applications.

  7. Negative electrode materials for lithium-ion solid-state microbatteries

    NARCIS (Netherlands)

    Baggetto, L.

    2010-01-01

    Electronic portable devices are becoming more and more important in our daily life. Many portable types of electronic equipment rely on rechargeable lithium-ion batteries as they can reversibly deliver the highest gravimetric and volumetric energy densities. Lithium-ion batteries are currently

  8. Lithium ion conduction in sol-gel synthesized LiZr2(PO4)3 polymorphs

    Science.gov (United States)

    Kumar, Milind; Yadav, Arun Kumar; Anita, Sen, Somaditya; Kumar, Sunil

    2018-04-01

    Safety issue associated with the high flammability and volatility of organic electrolytes used in commercial rechargeable lithium ion batteries has led to significant attention to ceramic-based solid electrolytes. In the present study, lithium ion conduction in two polymorphs of LiZr2(PO4)3 synthesized via the sol-gel route has been investigated. Rietveld refinement of room temperature X-ray diffraction data of LiZr2(PO4)3 powders calcined at 900 °C and 1300 °C confirmed these to be the monoclinic phase with P21/n structure and rhombohedral phase with R3¯c structure, respectively. Increase in calcination temperature and resultant phase transformation improved the room temperature conductivity from 2.27×10-6 ohm-1m-1 for the monoclinic phase to 1.41×10-4 ohm-1m-1 for rhombohedral phase. Temperature dependence of conductivity was modeled using Arrhenius law and activation energy of ˜ 0.59 eV (for monoclinic phase) and ˜0.50 eV (for rhombohedral phase) were obtained.

  9. New insights into the structure-property relationship of high-voltage electrolyte components for lithium-ion batteries using the pKa value

    International Nuclear Information System (INIS)

    Gallus, Dennis Roman; Wagner, Ralf; Wiemers-Meyer, Simon; Winter, Martin; Cekic-Laskovic, Isidora

    2015-01-01

    In pursuit of higher energy density in lithium-ion batteries (LIBs), a most promising approach focuses on cathode materials that operate at higher potentials and exhibit even higher specific charges than present LIB cathodes charged up to only 3.8 to 4.3 V vs. Li/Li + . To enable a high-voltage (HV) application of the cathode, the “by-materials”, in particular the electrolyte components have to be either thermodynamically or kinetically stable. For this reason, the stability of the electrolyte components towards oxidation, in particular, depending on their HOMO energy levels, is crucial. The theoretical calculation of molecular orbital energies is a helpful and commonly used tool to predict electrochemical stability. Earlier studies demonstrated strong correlation between the HOMO energy and the pK a value, as both depend on electron affinity. Here we report on the first study referring to a pK a value based selection procedure on development of new electrolyte components for the application in lithium-ion batteries. The identified trimethylsilyl(TMS)-based additives, which are known to scavenge HF and show sufficient oxidation stability, enable the application of LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM) at an increased upper cut-off potential of 4.6 V vs. Li/Li + without severe degradation, leading to a 50% higher energy density. The use of pK a values is a simple, but highly effective methodology to select appropriate electrolyte components and thus helps to identify functional electrolytes beyond the typical trial and error approach or time-consuming theoretical calculations.

  10. Lithium ion conducting biopolymer electrolyte based on pectin doped with Lithium nitrate

    Science.gov (United States)

    Manjuladevi, R.; Selvin, P. Christopher; Selvasekarapandian, S.; Shilpa, R.; Moniha, V.

    2018-04-01

    The Biopolymer electrolyte based on pectin doped with lithium nitrate of different concentrations have been prepared by solution casting technique. The decrease in crystalline nature of the biopolymer has been identified by XRD analyses. The complex formation between the polymer and the salt has been revealed using FTIR analysis. The ionic conductivity has been explored using A.C. impedance spectroscopy which reveals that the biopolymer containing 30 wt% Pectin: 70wt%LiNO3 has highest ionic conductivity of 3.97 × 10-3 Scm-1.

  11. Surface-Modified Membrane as A Separator for Lithium-Ion Polymer Battery

    Directory of Open Access Journals (Sweden)

    Jun Young Kim

    2010-04-01

    Full Text Available This paper describes the fabrication of novel modified polyethylene (PE membranes using plasma technology to create high-performance and cost-effective separator membranes for practical applications in lithium-ion polymer batteries. The modified PE membrane via plasma modification process plays a critical role in improving wettability and electrolyte retention, interfacial adhesion between separators and electrodes, and cycle performance of lithium-ion polymer batteries. This paper suggests that the performance of lithium-ion polymer batteries can be greatly enhanced by the plasma modification of commercial separators with proper functional materials for targeted application.

  12. Cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    Science.gov (United States)

    Jacobson, Allan J; Wang, Shuangyan; Kim, Gun Tae

    2014-01-28

    Novel cathode, electrolyte and oxygen separation materials are disclosed that operate at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes based on oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  13. Influence of Electrolyte Modulus on the Local Current Density at a Dendrite Tip on a Lithium Metal Electrode

    Energy Technology Data Exchange (ETDEWEB)

    Harry, KJ; Higa, K; Srinivasan, V; Balsara, NP

    2016-08-10

    Understanding and controlling the electrochemical deposition of lithium is imperative for the safe use of rechargeable batteries with a lithium metal anode. Solid block copolymer electrolyte membranes are known to enhance the stability of lithium metal anodes by mechanically suppressing the formation of lithium protrusions during battery charging. Time-resolved hard X-ray microtomography was used to monitor the internal structure of a symmetric lithium-polymer cell during galvanostatic polarization. The microtomography images were used to determine the local rate of lithium deposition, i.e. local current density, in the vicinity of a lithium globule growing through the electrolyte. Measurements of electrolyte displacement enabled estimation of local stresses in the electrolyte. At early times, the current density was maximized at the globule tip, as expected from simple current distribution arguments. At later times, the current density was maximized at the globule perimeter. We show that this phenomenon is related to the local stress fields that arise as the electrolyte is deformed. The local current density, normalized for the radius of curvature, decreases with increasing compressive stresses at the lithium-polymer interface. To our knowledge, our study provides the first direct measurement showing the influence of local mechanical stresses on the deposition kinetics at lithium metal electrodes.

  14. Conjugated polymer energy level shifts in lithium-ion battery electrolytes.

    Science.gov (United States)

    Song, Charles Kiseok; Eckstein, Brian J; Tam, Teck Lip Dexter; Trahey, Lynn; Marks, Tobin J

    2014-11-12

    The ionization potentials (IPs) and electron affinities (EAs) of widely used conjugated polymers are evaluated by cyclic voltammetry (CV) in conventional electrochemical and lithium-ion battery media, and also by ultraviolet photoelectron spectroscopy (UPS) in vacuo. By comparing the data obtained in the different systems, it is found that the IPs of the conjugated polymer films determined by conventional CV (IPC) can be correlated with UPS-measured HOMO energy levels (EH,UPS) by the relationship EH,UPS = (1.14 ± 0.23) × qIPC + (4.62 ± 0.10) eV, where q is the electron charge. It is also found that the EAs of the conjugated polymer films measured via CV in conventional (EAC) and Li(+) battery (EAB) media can be linearly correlated by the relationship EAB = (1.07 ± 0.13) × EAC + (2.84 ± 0.22) V. The slopes and intercepts of these equations can be correlated with the dielectric constants of the polymer film environments and the redox potentials of the reference electrodes, as modified by the surrounding electrolyte, respectively.

  15. Infrared thermography non-destructive evaluation of lithium-ion battery

    Science.gov (United States)

    Wang, Zi-jun; Li, Zhi-qiang; Liu, Qiang

    2011-08-01

    The power lithium-ion battery with its high specific energy, high theoretical capacity and good cycle-life is a prime candidate as a power source for electric vehicles (EVs) and hybrid electric vehicles (HEVs). Safety is especially important for large-scale lithium-ion batteries, especially the thermal analysis is essential for their development and design. Thermal modeling is an effective way to understand the thermal behavior of the lithium-ion battery during charging and discharging. With the charging and discharging, the internal heat generation of the lithium-ion battery becomes large, and the temperature rises leading to an uneven temperature distribution induces partial degradation. Infrared (IR) Non-destructive Evaluation (NDE) has been well developed for decades years in materials, structures, and aircraft. Most thermographic methods need thermal excitation to the measurement structures. In NDE of battery, the thermal excitation is the heat generated from carbon and cobalt electrodes in electrolyte. A technique named "power function" has been developed to determine the heat by chemical reactions. In this paper, the simulations of the transient response of the temperature distribution in the lithium-ion battery are developed. The key to resolving the security problem lies in the thermal controlling, including the heat generation and the internal and external heat transfer. Therefore, three-dimensional modelling for capturing geometrical thermal effects on battery thermal abuse behaviour is required. The simulation model contains the heat generation during electrolyte decomposition and electrical resistance component. Oven tests are simulated by three-dimensional model and the discharge test preformed by test system. Infrared thermography of discharge is recorded in order to analyze the security of the lithium-ion power battery. Nondestructive detection is performed for thermal abuse analysis and discharge analysis.

  16. A Nanophase-Separated, Quasi-Solid-State Polymeric Single-Ion Conductor: Polysulfide Exclusion for Lithium–Sulfur Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jinhong; Song, Jongchan; Lee, Hongkyung; Noh, Hyungjun; Kim, Yun-Jung; Kwon, Sung Hyun; Lee, Seung Geol; Kim, Hee-Tak

    2017-04-19

    Formation of soluble polysulfide (PS), which is a key feature of lithium sulfur (Li–S) batteries, provides a fast redox kinetic based on a liquid–solid mechanism; however, it imposes the critical problem of PS shuttle. Here, we address the dilemma by exploiting a solvent-swollen polymeric single-ion conductor (SPSIC) as the electrolyte medium of the Li–S battery. The SPSIC consisting of a polymeric single-ion conductor and lithium salt-free organic solvents provides Li ion hopping by forming a nanoscale conducting channel and suppresses PS shuttle according to the Donnan exclusion principle when being employed for Li–S batteries. The organic solvents at the interface of the sulfur/carbon composite and SPSIC eliminate the poor interfacial contact and function as a soluble PS reservoir for maintaining the liquid–solid mechanism. Furthermore, the quasi-solid-state SPSIC allows the fabrication of a bipolar-type stack, which promises the realization of a high-voltage and energy-dense Li–S battery.

  17. Elucidating the Performance Limitations of Lithium-ion Batteries due to Species and Charge Transport through Five Characteristic Parameters

    Science.gov (United States)

    Jiang, Fangming; Peng, Peng

    2016-01-01

    Underutilization due to performance limitations imposed by species and charge transports is one of the key issues that persist with various lithium-ion batteries. To elucidate the relevant mechanisms, two groups of characteristic parameters were proposed. The first group contains three characteristic time parameters, namely: (1) te, which characterizes the Li-ion transport rate in the electrolyte phase, (2) ts, characterizing the lithium diffusion rate in the solid active materials, and (3) tc, describing the local Li-ion depletion rate in electrolyte phase at the electrolyte/electrode interface due to electrochemical reactions. The second group contains two electric resistance parameters: Re and Rs, which represent respectively, the equivalent ionic transport resistance and the effective electronic transport resistance in the electrode. Electrochemical modeling and simulations to the discharge process of LiCoO2 cells reveal that: (1) if te, ts and tc are on the same order of magnitude, the species transports may not cause any performance limitations to the battery; (2) the underlying mechanisms of performance limitations due to thick electrode, high-rate operation, and large-sized active material particles as well as effects of charge transports are revealed. The findings may be used as quantitative guidelines in the development and design of more advanced Li-ion batteries. PMID:27599870

  18. Ionic conduction in polyether-based lithium arylfluorosulfonimide ionic melt electrolytes

    International Nuclear Information System (INIS)

    Herath, Mahesha B.; Creager, Stephen E.; Rajagopal, Rama V.; Geiculescu, Olt E.; DesMarteau, Darryl D.

    2009-01-01

    We report synthesis, characterization and ion transport in polyether-based ionic melt electrolytes consisting of Li salts of low-basicity anions covalently attached to polyether oligomers. Purity of the materials was investigated by HPLC analysis and electrospray ionization mass spectrometry. The highest ionic conductivity of 7.1 x 10 -6 S/cm at 30 deg. C was obtained for the sample consisting of a lithium salt of an arylfluorosulfonimide anion attached to a polyether oligomer with an ethyleneoxide (EO) to lithium ratio of 12. The conductivity order of various ionic melts having different polyether chain lengths suggests that at higher EO:Li ratios the conductivity of the electrolytes at room temperature is determined in part by the amount of crystallization of the polyether portion of the ionic melt.

  19. Cycle life performance of rechargeable lithium ion batteries and mathematical modeling

    Science.gov (United States)

    Ning, Gang

    Capacity fade of commercial Sony US 18650 Li-ion batteries cycled at high discharge rates was studied at ambient temperature. Battery cycled at the highest discharge rate (3 C) shows the largest internal resistance increase of 27.7% relative to the resistance of fresh battery. It's been observed anode carbon loses 10.6% of its capability to intercalate or deintercalate Li+ after it was subjected to 300 cycles at discharge rate of 3 C. This loss dominates capacity fade of full battery. A mechanism considering continuous parasitic reaction at anode/electrolyte interface and film thickening has been proposed. First principles based charge-discharge models to simulate cycle life behavior of rechargeable Li-ion batteries have been developed. In the generalized model, transport in both electrolyte phase and solid phase were simultaneously taken into account. Under mild charge-discharge condition, transport of lithium in the electrolyte phase has been neglected in the simplified model. Both models are based on loss of the active lithium ions due to the electrochemical parasitic reaction at anode/electrolyte interface and on rise of the anode film resistance. The effect of parameters such as depth of discharge (DOD), end of charge voltage (EOCV) and overvoltage of the parasitic reaction on the cycle life behavior of a battery has been analyzed. The experimental results obtained at a charge rate of 1 C, discharge rate of 0.5 C, EOCV of 4.0 V and DOD of 0.4 have been used to validate cycle life models. Good agreement between the simulations and the experiments has been achieved up to 1968 cycles with both models. Simulation of cycle life of battery under multiple cycling regimes has also been demonstrated.

  20. Synthesis and Characterization of Lithium-Doped Lanthanum ...

    African Journals Online (AJOL)

    Vostro 2520

    made of the above materials showed very promising features for future development of microbatteries. Solid electrolytes with ... promising option to meet such demands because of their inherent .... derivatives, show the highest bulk lithium ion.

  1. Challenges and issues facing lithium metal for solid-state rechargeable batteries

    Science.gov (United States)

    Mauger, A.; Armand, M.; Julien, C. M.; Zaghib, K.

    2017-06-01

    The commercial use of lithium metal batteries was delayed because of dendrite formation on the surface of the lithium electrode, and the difficulty finding a suitable electrolyte that has both the mechanical strength and ionic conductivity required for solid electrolytes. Recently, strategies have developed to overcome these difficulties, so that these batteries are currently an option for different applications, including electric cars. In this work, we review these strategies, and discuss the different routes that are promising for progress in the near future.

  2. Lithium ion batteries with titania/graphene anodes

    Science.gov (United States)

    Liu, Jun; Choi, Daiwon; Yang, Zhenguo; Wang, Donghai; Graff, Gordon L; Nie, Zimin; Viswanathan, Vilayanur V; Zhang, Jason; Xu, Wu; Kim, Jin Yong

    2013-05-28

    Lithium ion batteries having an anode comprising at least one graphene layer in electrical communication with titania to form a nanocomposite material, a cathode comprising a lithium olivine structure, and an electrolyte. The graphene layer has a carbon to oxygen ratio of between 15 to 1 and 500 to 1 and a surface area of between 400 and 2630 m.sup.2/g. The nanocomposite material has a specific capacity at least twice that of a titania material without graphene material at a charge/discharge rate greater than about 10 C. The olivine structure of the cathode of the lithium ion battery of the present invention is LiMPO.sub.4 where M is selected from the group consisting of Fe, Mn, Co, Ni and combinations thereof.

  3. A New Class of Ternary Compound for Lithium-Ion Battery: from Composite to Solid Solution.

    Science.gov (United States)

    Wang, Jiali; Wu, Hailong; Cui, Yanhua; Liu, Shengzhou; Tian, Xiaoqing; Cui, Yixiu; Liu, Xiaojiang; Yang, Yin

    2018-02-14

    Searching for high-performance cathode materials is a crucial task to develop advanced lithium-ion batteries (LIBs) with high-energy densities for electrical vehicles (EVs). As a promising lithium-rich material, Li 2 MnO 3 delivers high capacity over 200 mAh g -1 but suffers from poor structural stability and electronic conductivity. Replacing Mn 4+ ions by relatively larger Sn 4+ ions is regarded as a possible strategy to improve structural stability and thus cycling performance of Li 2 MnO 3 material. However, large difference in ionic radii of Mn 4+ and Sn 4+ ions leads to phase separation of Li 2 MnO 3 and Li 2 SnO 3 during high-temperature synthesis. To prepare solid-solution phase of Li 2 MnO 3 -Li 2 SnO 3 , a buffer agent of Ru 4+ , whose ionic radius is in between that of Mn 4+ and Sn 4+ ions, is introduced to assist the formation of a single solid-solution phase. The results show that the Li 2 RuO 3 -Li 2 MnO 3 -Li 2 SnO 3 ternary system evolves from mixed composite phases into a single solid-solution phase with increasing Ru content. Meanwhile, discharge capacity of this ternary system shows significantly increase at the transformation point which is ascribed to the improvement of Li + /e - transportation kinetics and anionic redox chemistry for solid-solution phase. The role of Mn/Sn molar ratio of Li 2 RuO 3 -Li 2 MnO 3 -Li 2 SnO 3 ternary system has also been studied. It is revealed that higher Sn content benefits cycling stability of the system because Sn 4+ ions with larger sizes could partially block the migration of Mn 4+ and Ru 4+ from transition metal layer to Li layer, thus suppressing structural transformation of the system from layered-to-spinel phase. These findings may enable a new route for exploring ternary or even quaternary lithium-rich cathode materials for LIBs.

  4. Thermal aging of electrolytes used in lithium-ion batteries - An investigation of the impact of protic impurities and different housing materials

    Science.gov (United States)

    Handel, Patricia; Fauler, Gisela; Kapper, Katja; Schmuck, Martin; Stangl, Christoph; Fischer, Roland; Uhlig, Frank; Koller, Stefan

    2014-12-01

    Thermal degradation products in lithium-ion batteries result mainly from hydrolysis sensitivity of lithium hexafluorophosphate (LiPF6). As organic carbonate solvents contain traces of protic impurities, the thermal decomposition of electrolytes is enhanced. Therefore, resulting degradation products are studied with nuclear magnetic resonance spectroscopy (NMR) and gas chromatography mass spectrometry (GC-MS). The electrolyte contains 1 M LiPF6 in a binary mixture of ethylene carbonate (EC) and diethylene carbonate (DEC) in a ratio of 1:2 (v/v) and is aged at ambient and elevated temperature. The impact of protic impurities, either added as deionized water or incorporated in positive electrode material, upon aging is investigated. Further, the influence of different housing materials on the electrolyte degradation is shown. Difluorophosphoric acid is identified as main decomposition product by NMR-spectroscopy. Traces of other decomposition products are determined by headspace GC-MS. Acid-base and coulometric titration are used to determine the total amount of acid and water content upon aging, respectively. The aim of this investigation is to achieve profound understanding about the thermal decomposition of one most common used electrolyte in a battery-like housing material.

  5. Vacuum pyrolysis and hydrometallurgical process for the recovery of valuable metals from spent lithium-ion batteries

    International Nuclear Information System (INIS)

    Sun, Liang; Qiu, Keqiang

    2011-01-01

    Highlights: → The cathode active materials LiCoO 2 from spent lithium-ion batteries peeled completely from aluminum foils by vacuum pyrolysis and hydrometallurgical process. → The aluminum foils were excellent without damage after vacuum pyrolysis. → The pyrolysis products organic fluorine compounds from organic electrolyte and binder were collected and enriched. → High leaching efficiencies of cobalt and lithium were obtained with H 2 SO 4 and H 2 O 2 . - Abstract: Spent lithium-ion batteries contain lots of strategic resources such as cobalt and lithium together with other hazardous materials, which are considered as an attractive secondary resource and environmental contaminant. In this work, a novel process involving vacuum pyrolysis and hydrometallurgical technique was developed for the combined recovery of cobalt and lithium from spent lithium-ion batteries. The results of vacuum pyrolysis of cathode material showed that the cathode powder composing of LiCoO 2 and CoO peeled completely from aluminum foils under the following experimental conditions: temperature of 600 o C, vacuum evaporation time of 30 min, and residual gas pressure of 1.0 kPa. Over 99% of cobalt and lithium could be recovered from peeled cobalt lithium oxides with 2 M sulfuric acid leaching solution at 80 o C and solid/liquid ratio of 50 g L -1 for 60 min. This technology offers an efficient way to recycle valuable materials from spent lithium-ion batteries, and it is feasible to scale up and help to reduce the environmental pollution of spent lithium-ion batteries.

  6. Vacuum pyrolysis and hydrometallurgical process for the recovery of valuable metals from spent lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Liang [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Key Laboratory of Resources Chemistry of Nonferrous Metals, Central South University, Ministry of Education of the People' s Republic of China (China); Qiu, Keqiang, E-mail: qiuwhs@sohu.com [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Key Laboratory of Resources Chemistry of Nonferrous Metals, Central South University, Ministry of Education of the People' s Republic of China (China)

    2011-10-30

    Highlights: {yields} The cathode active materials LiCoO{sub 2} from spent lithium-ion batteries peeled completely from aluminum foils by vacuum pyrolysis and hydrometallurgical process. {yields} The aluminum foils were excellent without damage after vacuum pyrolysis. {yields} The pyrolysis products organic fluorine compounds from organic electrolyte and binder were collected and enriched. {yields} High leaching efficiencies of cobalt and lithium were obtained with H{sub 2}SO{sub 4} and H{sub 2}O{sub 2}. - Abstract: Spent lithium-ion batteries contain lots of strategic resources such as cobalt and lithium together with other hazardous materials, which are considered as an attractive secondary resource and environmental contaminant. In this work, a novel process involving vacuum pyrolysis and hydrometallurgical technique was developed for the combined recovery of cobalt and lithium from spent lithium-ion batteries. The results of vacuum pyrolysis of cathode material showed that the cathode powder composing of LiCoO{sub 2} and CoO peeled completely from aluminum foils under the following experimental conditions: temperature of 600 {sup o}C, vacuum evaporation time of 30 min, and residual gas pressure of 1.0 kPa. Over 99% of cobalt and lithium could be recovered from peeled cobalt lithium oxides with 2 M sulfuric acid leaching solution at 80 {sup o}C and solid/liquid ratio of 50 g L{sup -1} for 60 min. This technology offers an efficient way to recycle valuable materials from spent lithium-ion batteries, and it is feasible to scale up and help to reduce the environmental pollution of spent lithium-ion batteries.

  7. New approaches to the design of polymer and liquid electrolytes for lithium batteries

    Science.gov (United States)

    McBreen, J.; Lee, H. S.; Yang, X. Q.; Sun, X.

    All non-aqueous lithium battery electrolytes are Lewis bases that interact with cations. Unlike water, they do not interact with anions. The result is a high degree of ion pairing and the formation of triplets and higher aggregates. This decreases the conductivity and the lithium ion transference, and results in polarization losses in batteries. Approaches that have been used to increase ion dissociation in poly(ethylene oxide) (PEO)-based electrolytes are the use of salts with low lattice energy, the addition of polar plasticizers to the polymer, and the addition of cation complexing agents such as crown ethers or cryptands. Complexing of the anions is a more promising approach, since it should increase both ion dissociation and the lithium transference. At Brookhaven National Laboratory (BNL) we have synthesized two new families of neutral anion complexing agents, each based on Lewis acid centers. One is based on electron deficient nitrogen sites on substituted aza-ethers, wherein the hydrogen on the nitrogen is replaced by electron withdrawing groups such as CF 3SO 3-. The other is based on electron deficient boron sites on borane or borate compounds with various fluorinated aryl or alkyl groups. Some of the borane-based anion receptors can promote the dissolution of LiF in several solvents. Several of these compounds, when added in equivalent amounts, produce 1.2 M LiF solutions in DME, an increase in solubility of LiF by six orders of magnitude. Some of these LiF electrolytes have conductivities as high as 6×10 -3 S cm -1. The LiF electrolytes with borane anion acceptors in PC:EC:DEC solvents have excellent electrochemical stability. This has been demonstrated in small Li/LiMn 2O 4 cells.

  8. Enhanced performance of P(VDF-HFP)-based composite polymer electrolytes doped with organic-inorganic hybrid particles PMMA-ZrO2 for lithium ion batteries

    Science.gov (United States)

    Xiao, Wei; Wang, Zhiyan; Zhang, Yan; Fang, Rui; Yuan, Zun; Miao, Chang; Yan, Xuemin; Jiang, Yu

    2018-04-01

    To improve the ionic conductivity as well as enhance the mechanical strength of the gel polymer electrolyte, poly(vinylidene fluoride-hexafluoroprolene) (P(VDF-HFP))-based composite polymer electrolyte (CPE) membranes doped with the organic-inorganic hybrid particles poly(methyl methacrylate) -ZrO2 (PMMA-ZrO2) are prepared by phase inversion method, in which PMMA is successfully grafted onto the surface of the homemade nano-ZrO2 particles via in situ polymerization confirmed by FT-IR. XRD and DSC patterns show adding PMMA-ZrO2 particles into P(VDF-HFP) can significantly decrease the crystallinity of the CPE membrane. The CPE membrane doped with 5 wt % PMMA-ZrO2 particles can not only present a homogeneous surface with abundant interconnected micro-pores, but maintain its initial shape after thermal exposure at 160 °C for 1 h, in which the ionic conductivity and lithium ion transference number at room temperature can reach to 3.59 × 10-3 S cm-1 and 0.41, respectively. The fitting results of the EIS plots indicate the doped PMMA-ZrO2 particles can significantly lower the interface resistance and promote lithium ions diffusion rate. The Li/CPE-sPZ/LiCoO2 and Li/CPE-sPZ/Graphite coin cells can deliver excellent rate and cycling performance. Those results suggest the P(VDF-HFP)-based CPE doped with 5 wt % PMMA-ZrO2 particles can become an exciting potential candidate as polymer electrolyte for the lithium ion battery.

  9. New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xuefeng; Zhang, Minghao; Alvarado, Judith; Wang, Shen; Sina, Mahsa; Lu, Bingyu; Bouwer, James; Xu, Wu [Energy; Xiao, Jie [Energy; Zhang, Ji-Guang [Energy; Liu, Jun [Energy; Meng, Ying Shirley

    2017-11-02

    Lithium metal has been considered as the “holy grail” anode material for rechargeable batteries though the dendritic growth and low Coulombic efficiency (CE) have crippled its practical use for decades. Its high chemical reactivity and low stability make it difficult to explore the intrinsic chemical and physical properties of the electrochemically deposited lithium (EDLi) and its accompanied solid electrolyte interphase (SEI). To prevent the dendritic growth and enhance the electrochemical reversibility, it is crucial to understand the nano- and meso- structures of EDLi. However, Li metal is very sensitive to beam damage and has low contrast for commonly used characterization techniques such as electron microscopy. Inspired by biological imaging techniques, this work demonstrates the power of cryogenic (cryo)- electron microscopy to reveal the detailed structure of EDLi and the SEI composition at the nano scale while minimizing beam damage during imaging. Surprisingly, the results show that the nucleation dominated EDLi (five minutes at 0.5 mA cm-2) is amorphous while there is some crystalline LiF present in the SEI. The EDLi grown from various electrolytes with different additives exhibits distinctive surface properties. Consequently, these results highlight the importance of the SEI and its relationship with the CE. Our findings not only illustrate the capabilities of cryogenic microscopy for beam (thermal)-sensitive materials, but it yields crucial structural information of the EDLi evolution with and without electrolyte additives.

  10. Facile synthesis of Li2S-P2S5 glass-ceramics electrolyte with micron range particles for all-solid-state batteries via a low-temperature solution technique (LTST)

    Science.gov (United States)

    Choi, Sunho; Lee, Sewook; Park, Jongyeop; Nichols, William T.; Shin, Dongwook

    2018-06-01

    A lithium ion conductive 75Li2Sṡ25P2S5 glass-ceramics electrolyte is, for the first time, successfully synthesized via a new low-temperature solution technique (LTST) and compared to the conventional mechanical-milling technique. Both samples are composed of the highly lithium ion conductive thio-LISICON III analog phase. Due to the uniform dispersion of reactants in an organic liquid, the use of LTST produced significantly smaller and more uniform particle sizes (2.2 ± 1.68 μm) resulting in a 6.5 times higher specific surface area compared to the mechanically-milled sample. A pronounced enhancement of both the rate capability and cyclability is demonstrated for the LTST solid electrolyte sample due to the more intimate contact with the LiCoO2 active material. Furthermore, the LTST sample shows excellent electrochemical stability throughout the potential range of -1 to 5 V. These results suggest that the proposed technique using the optimized LTST process is promising for the preparation of 75Li2Sṡ25P2S5 solid electrolytes for use in advanced Li-ion batteries.

  11. Physicochemical properties of the electrolyte system lithium tetrachloraluminate(III)-thionyl chloride

    Energy Technology Data Exchange (ETDEWEB)

    Demakhin, A.G.; Kuznetsov, N.N.

    1992-07-20

    The solubility of lithium chloroaluminate in thionyl chloride has been determined over the temperature range 233-323 K. The composition of solid phases in equilibrium with saturated solution was found. The density, viscosity, and electrical conductance of lithium chloroaluminate solutions in thionyl chloride were determined over the temperature range 263-333 K and pseudomolar volumes of the solution and apparent molar volumes of the electrolyte calculated. Activation energies for viscous flow and conductance have been calculated. 12 refs., 5 figs., 1 tab.

  12. Properties of solid electrolyte interphase formed by prop-1-ene-1,3-sultone on graphite anode of Li-ion batteries

    International Nuclear Information System (INIS)

    Li, Bin; Xu, Mengqing; Li, Benzhen; Liu, Yanlin; Yang, Liang; Li, Weishan; Hu, Shejun

    2013-01-01

    Highlights: • SEI formed by PES on NG was characterized with charge/discharge test, SEM, FTIR, and XPS. • NG in PC-based electrolyte can be well protected using PES. • Sulfur-containing species is the main component of the SEI formed by PES. • Preferable reduction of PES results in the formation of protective SEI on NG. -- Abstract: The physical and chemical properties of the solid electrolyte interphase (SEI) formed by prop-1-ene-1,3-sultone (PES) on graphite anode in propylene carbonate (PC) based electrolyte for lithium ion battery were investigated by charge–discharge test, scanning electron spectroscopy with energy dispersive X-ray spectroscopy (SEM–EDS), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). It is found that the charge–discharge performance of the cell LiCoO 2 /natural graphite (NG) using PC-based electrolyte containing 3 wt% PES is superior to that containing 6 wt% propane sultone (PS), an SEI formation additive that has the similar molecular structure to PES but is reduced not as easily as PES. The results from SEM–EDS, FTIR and XPS show that the structure of graphite has been protected and some S-containing species are proven to be components of the SEI, suggesting that the preferable reduction of PES plays an important role in the formation of a protective SEI on NG

  13. Lithium Ion Transport Across and Between Phase Boundaries in Heterogeneous Polymer Electrolytes, Based on PVdF

    National Research Council Canada - National Science Library

    Greenbaum, Steven

    1998-01-01

    .... In the first reported attempt to exploit 17O NMR to study lithium battery electrolytes, we have prepared 17O-enriched Li triflate and several electrolytes containing the isotopically enriched salt...

  14. Electrolyte additive enabled fast charging and stable cycling lithium metal batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jianming; Engelhard, Mark H.; Mei, Donghai; Jiao, Shuhong; Polzin, Bryant J.; Zhang, Ji-Guang; Xu, Wu

    2017-03-01

    Batteries using lithium (Li) metal as anodes are considered promising energy storage systems because of their high energy densities. However, safety concerns associated with dendrite growth along with limited cycle life, especially at high charge current densities, hinder their practical uses. Here we report that an optimal amount (0.05 M) of LiPF6 as an additive in LiTFSI-LiBOB dual-salt/carbonate-solvent-based electrolytes significantly enhances the charging capability and cycling stability of Li metal batteries. In a Li metal battery using a 4-V Li-ion cathode at a moderately high loading of 1.75mAh cm(-2), a cyclability of 97.1% capacity retention after 500 cycles along with very limited increase in electrode overpotential is accomplished at a charge/discharge current density up to 1.75 mA cm(-2). The fast charging and stable cycling performances are ascribed to the generation of a robust and conductive solid electrolyte interphase at the Li metal surface and stabilization of the Al cathode current collector.

  15. Bubble-Sheet-Like Interface Design with an Ultrastable Solid Electrolyte Layer for High-Performance Dual-Ion Batteries.

    Science.gov (United States)

    Qin, Panpan; Wang, Meng; Li, Na; Zhu, Haili; Ding, Xuan; Tang, Yongbing

    2017-05-01

    In this work, a bubble-sheet-like hollow interface design on Al foil anode to improve the cycling stability and rate performance of aluminum anode based dual-ion battery is reported, in which, a carbon-coated hollow aluminum anode is used as both anode materials and current collector. This anode structure can guide the alloying position inside the hollow nanospheres, and also confine the alloy sizes within the hollow nanospheres, resulting in significantly restricted volumetric expansion and ultrastable solid electrolyte interface (SEI). As a result, the battery demonstrates an excellent long-term cycling stability within 1500 cycles with ≈99% capacity retention at 2 C. Moreover, this cell displays an energy density of 169 Wh kg -1 even at high power density of 2113 W kg -1 (10 C, charge and discharge within 6 min), which is much higher than most of conventional lithium ion batteries. The interfacial engineering strategy shown in this work to stabilize SEI layer and control the alloy forming position could be generalized to promote the research development of metal anodes based battery systems. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. A Flexible Solid Electrolyte Interphase Layer for Long-Life Lithium Metal Anodes.

    Science.gov (United States)

    Li, Nian-Wu; Shi, Yang; Yin, Ya-Xia; Zeng, Xian-Xiang; Li, Jin-Yi; Li, Cong-Ju; Wan, Li-Jun; Wen, Rui; Guo, Yu-Guo

    2018-02-05

    Lithium (Li) metal is a promising anode material for high-energy density batteries. However, the unstable and static solid electrolyte interphase (SEI) can be destroyed by the dynamic Li plating/stripping behavior on the Li anode surface, leading to side reactions and Li dendrites growth. Herein, we design a smart Li polyacrylic acid (LiPAA) SEI layer high elasticity to address the dynamic Li plating/stripping processes by self-adapting interface regulation, which is demonstrated by in situ AFM. With the high binding ability and excellent stability of the LiPAA polymer, the smart SEI can significantly reduce the side reactions and improve battery safety markedly. Stable cycling of 700 h is achieved in the LiPAA-Li/LiPAA-Li symmetrical cell. The innovative strategy of self-adapting SEI design is broadly applicable, providing opportunities for use in Li metal anodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Polymer electrolytes based on aromatic lithium sulfonyl-imide compounds; Electrolytes polymeres a base de sulfonylimidures de lithium aromatiques

    Energy Technology Data Exchange (ETDEWEB)

    Reibel, L.; Bayoudh, S. [Centre National de la Recherche Scientifique (CNRS), 67 - Strasbourg (France). Institut Charles Sadron; Baudry, P. [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches; Majastre, H. [Bollore Technologies, 29 - Quimper (France); Herlem, G. [UFR de Sciences et Techniques, L.E.S., 25 - Besancon (France)

    1996-12-31

    This paper presents ionic conductivity results obtained with polymer electrolytes and also with propylene carbonate solutions. The domain of electrochemical activity of this salt has been determined using cycle volt-amperometry in propylene carbonate. Preliminary experiments on the stability of the polymer electrolyte with respect to the lithium electrode have been carried out for a possible subsequent use in lithium batteries. (J.S.) 4 refs.

  18. Polymer electrolytes based on aromatic lithium sulfonyl-imide compounds; Electrolytes polymeres a base de sulfonylimidures de lithium aromatiques

    Energy Technology Data Exchange (ETDEWEB)

    Reibel, L; Bayoudh, S [Centre National de la Recherche Scientifique (CNRS), 67 - Strasbourg (France). Institut Charles Sadron; Baudry, P [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches; Majastre, H [Bollore Technologies, 29 - Quimper (France); Herlem, G [UFR de Sciences et Techniques, L.E.S., 25 - Besancon (France)

    1997-12-31

    This paper presents ionic conductivity results obtained with polymer electrolytes and also with propylene carbonate solutions. The domain of electrochemical activity of this salt has been determined using cycle volt-amperometry in propylene carbonate. Preliminary experiments on the stability of the polymer electrolyte with respect to the lithium electrode have been carried out for a possible subsequent use in lithium batteries. (J.S.) 4 refs.

  19. How a gel polymer electrolyte affects performance of lithium/sulfur batteries

    International Nuclear Information System (INIS)

    Zhang, Sheng S.; Tran, Dat T.

    2013-01-01

    Highlights: •Conventional separator is coated with a 50PEO-50SiO 2 (wt.%) composite layer. •Composite coating increases tensile strength and electrolyte wettability. •Coated separator offers an alternative approach for making gel polymer Li/S battery. •Li/S battery takes benefits of gel polymer electrolyte at the expense of capacity. -- Abstract: Gel polymer electrolyte (GPE) and composite gel polymer electrolyte (CGPE) have been widely employed to improve the safety and cycling performance of rechargeable lithium and lithium-ion batteries. In order to determine whether this approach is applicable to lithium/sulfur (Li/S) battery, we examine the effect of CGPE on the cycling and storage performances of Li/S cells by comparing a 50PEO-50SiO 2 (wt.%) composite coated separator (C-separator) with a pristine separator (P-separator). Results show that the composite coating significantly enhances the wettability of liquid electrolyte on the separator and that resulting CGPE can tightly glue the separator and electrode together. In comparison with the P-separator, the C-separator offers Li/S cells similar capacity retention and rate capability; however it greatly affects the specific capacity of sulfur. The analysis on the impedance spectrum of a lithium polysulfide (PS) solution reveal that the reduction of sulfur specific capacity is due to the high viscosity of the CGPE and the strong adsorption of SiO 2 filler to the PS species, which trap PS species in the separator and hence reduce the utilization of sulfur active material. Therefore, the benefits of the GPE and CGPE to the Li/S batteries can be taken only at the expense of sulfur specific capacity

  20. Sodium-ion transfer at the interface between ceramic and organic electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Sagane, Fumihiro; Abe, Takeshi; Ogumi, Zempachi [Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)

    2010-11-01

    Sodium-ion transfer through the interface between ceramic and organic electrolytes was studied by AC impedance spectroscopy. Na{sub 3}Zr{sub 1.88}Y{sub 0.12}Si{sub 2}PO{sub 12} (NASICON) and Na-{beta}''-alumina were used as ceramic electrolytes, and propylene carbonate (PC) and dimethyl sulfoxide (DMSO) containing 0.05 mol dm{sup -3} NaCF{sub 3}SO{sub 3} were used as organic electrolytes. The semi-circle ascribed to interfacial charge transfer resistance (R{sub ct}) was observed. The activation energies for sodium-ion transfer at the interface between ceramic and organic electrolytes were evaluated by the temperature dependency of R{sub ct}. As a result, the activation energies depended on the ceramic electrolytes but not on the solvents. These results suggest that sodium-ion transfer from ceramic to organic electrolytes should be responsible for the activation energies, which is contrary to the case in a lithium-ion transfer system. Based on these results, the mechanism of interfacial sodium-ion transfer was discussed. (author)

  1. Ionic diffusion and salt dissociation conditions of lithium liquid crystal electrolytes.

    Science.gov (United States)

    Saito, Yuria; Hirai, Kenichi; Murata, Shuuhei; Kishii, Yutaka; Kii, Keisuke; Yoshio, Masafumi; Kato, Takashi

    2005-06-16

    Salt dissociation conditions and dynamic properties of ionic species in liquid crystal electrolytes of lithium were investigated by a combination of NMR spectra and diffusion coefficient estimations using the pulsed gradient spin-echo NMR techniques. Activation energies of diffusion (Ea) of ionic species changed with the phase transition of the electrolyte. That is, Ea of the nematic phase was lower than that of the isotropic phase. This indicates that the aligned liquid crystal molecules prepared efficient conduction pathways for migration of ionic species. The dissociation degree of the salt was lower compared with those of the conventional electrolyte solutions and polymer gel electrolytes. This is attributed to the low concentration of polar sites, which attract the dissolved salt and promote salt dissociation, on the liquid crystal molecules. Furthermore, motional restriction of the molecules due to high viscosity and molecular oriented configuration in the nematic phase caused inefficient attraction of the sites for the salt. With a decreased dissolved salt concentration of the liquid crystal electrolyte, salt dissociation proceeded, and two diffusion components attributed to the ion and ion pair were detected independently. This means that the exchange rate between the ion and the ion pair is fairly slow once the salt is dissociated in the liquid crystal electrolytes due to the low motility of the medium molecules that initiate salt dissociation.

  2. Critical evaluation of the stability of highly concentrated LiTFSI - Acetonitrile electrolytes vs. graphite, lithium metal and LiFePO4 electrodes

    Science.gov (United States)

    Nilsson, Viktor; Younesi, Reza; Brandell, Daniel; Edström, Kristina; Johansson, Patrik

    2018-04-01

    Highly concentrated LiTFSI - acetonitrile electrolytes have recently been shown to stabilize graphite electrodes in lithium-ion batteries (LIBs) much better than comparable more dilute systems. Here we revisit this system in order to optimise the salt concentration vs. both graphite and lithium metal electrodes with respect to electrochemical stability. However, we observe an instability regardless of concentration, making lithium metal unsuitable as a counter electrode, and this also affects evaluation of e.g. graphite electrodes. While the highly concentrated electrolytes have much improved electrochemical stabilities, their reductive decomposition below ca. 1.2 V vs. Li+/Li° still makes them less practical vs. graphite electrodes, and the oxidative reaction with Al at ca. 4.1 V vs. Li+/Li° makes them problematic for high voltage LIB cells. The former originates in an insufficiently stable solid electrolyte interphase (SEI) dissolving and continuously reforming - causing self-discharge, as observed by paused galvanostatic cycling, while the latter is likely caused by aluminium current collector corrosion. Yet, we show that medium voltage LiFePO4 positive electrodes can successfully be used as counter and reference electrodes.

  3. Recovery of cobalt and lithium from spent Li-ion batteries; Recuperacao de cobalto e de litio de baterias ion-litio usadas

    Energy Technology Data Exchange (ETDEWEB)

    Busnardo, Natalia Giovanini; Paulino, Jessica Frontino; Afonso, Julio Carlos [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Quimica. Dept. de Quimica Analitica]. E-mail: julio@iq.ufrj.br

    2007-07-15

    The 'active mass' (cathode + anode + electrolyte) of spent Li-ion batteries was submitted to one of the following procedures: (a) it was calcined (500 deg C) and submitted to extraction with water to recover lithium salts. The residual solid was treated with sulfuric acid containing hydrogen peroxide. Cobalt was recovered as sulfate; (b) the 'active mass' was treated with potassium hydrogen sulfate (500 deg C) and dissolved in water. Cobalt was precipitated together with copper after addition of sodium hydroxide. Lithium was partially recovered as lithium fluoride. Co-processing of other battery components (aluminum and copper foils) affected negatively the behavior of the recovery procedures. Previous segregation of battery components is essential for an efficient and economical processing of the 'active mass'. (author)

  4. Chemical overcharge protection of lithium and lithium-ion secondary batteries

    Science.gov (United States)

    Abraham, Kuzhikalail M.; Rohan, James F.; Foo, Conrad C.; Pasquariello, David M.

    1999-01-01

    This invention features the use of redox reagents, dissolved in non-aqueous electrolytes, to provide overcharge protection for cells having lithium metal or lithium-ion negative electrodes (anodes). In particular, the invention features the use of a class of compounds consisting of thianthrene and its derivatives as redox shuttle reagents to provide overcharge protection. Specific examples of this invention are thianthrene and 2,7-diacetyl thianthrene. One example of a rechargeable battery in which 2,7-diacetyl thianthrene is used has carbon negative electrode (anode) and spinet LiMn.sub.2 O.sub.4 positive electrode (cathode).

  5. Organosilicon-Based Electrolytes for Long-Life Lithium Primary Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Fenton, Kyle R. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Nagasubramanian, Ganesan [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Staiger, Chad L. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Pratt, III, Harry D. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Rempe, Susan B. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Leung, Kevin [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Chaudhari, Mangesh I. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Anderson, Travis Mark [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

    2015-09-01

    This report describes advances in electrolytes for lithium primary battery systems. Electrolytes were synthesized that utilize organosilane materials that include anion binding agent functionality. Numerous materials were synthesized and tested in lithium carbon monofluoride battery systems for conductivity, impedance, and capacity. Resulting electrolytes were shown to be completely non-flammable and showed promise as co-solvents for electrolyte systems, due to low dielectric strength.

  6. The influence of the carbonate species on LiNi0.8Co0.15Al0.05O2 surfaces for all-solid-state lithium ion battery performance

    Science.gov (United States)

    Visbal, Heidy; Fujiki, Satoshi; Aihara, Yuichi; Watanabe, Taku; Park, Youngsin; Doo, Seokgwang

    2014-12-01

    The influence of selected carbonate species on LiNi0.8Co0.15Al0.05O2 (NCA) surface for all-solid-state lithium-ion battery (ASSB) with a sulfide based solid electrolyte was studied for its electrochemical properties, structural stabilities, and surface characteristics. The rated discharge performance improved with the reduction of the carbonate concentration on the NCA surface due to the decrease of the interface resistance. The species and coordination of the adsorbed carbonates on the NCA surface were analyzed by diffuse reflectance Fourier transformed infrared (DRIFT) spectroscopy. The coordination of the adsorbed carbonate anion was determined based on the degree of splitting of the ν3(CO) stretching vibrations. It is found that the surface carbonate species exists in an unidentate coordination on the surface. They react with the sulfide electrolyte to form an irreversible passivation layer. This layer obstructs the charge transfer process at the cathode/electrolyte interface, and results in the rise of the interface resistance and drop of the rated discharge capability.

  7. The Role of Cations on the Performance of Lithium Ion Batteries: A Quantitative Analytical Approach.

    Science.gov (United States)

    Nowak, Sascha; Winter, Martin

    2018-02-20

    Lithium ion batteries are nowadays the state-of-the-art power sources for portable electronic devices and the most promising candidate for energy storage in large-size batteries, e.g., pure and hybrid vehicles. However, the degradation of the cell components minimizes both storage and operation lifetime (calendar and cycle life), which is called aging. Due to the numerous different aging effects, in either the single constituents or their interactions with each other, many reports about methodologies and techniques, both electrochemical and analytical, can be found in the literature. However, quantitative data about the degradation effects were seldom stated. One important effect is the cation distribution and migration during operation. Metal dissolution and metal migration of the cathode and the corresponding deposition of these metals on the graphitic anode are known harmful degradation effects, especially for the formed solid electrolyte interphase on the surface of the anode. Depending on the applied cell chemistries and therefore the cathode material, different mechanisms were reported so far. For lithium manganese oxide based cells, the acidification of the electrolyte due to composition of the conduction salt is attributed as the main source of metal migration. Due to subsequent loss of manganese from the cathode, the overall performance of the cell is seriously impaired. Based on the obtained observations, this degradation mechanism was adapted to lithium nickel cobalt manganese based cells as main cause of the capacity fading. However, with the help a developed total X-ray fluorescence method and additional surface and electrolyte investigations, the proposed HF based mechanism was disproven. Instead, the migration was directly associated with material defects or mechanical spalling of the particles. Furthermore, with the obtained quantitative data of the migrated transition metals on the anode and separator, the contribution on the capacity fade was

  8. Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

    Science.gov (United States)

    Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

    2014-01-01

    Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses. PMID:25168309

  9. Cycling of lithium/metal oxide cells using composite electrolytes containing fumed silicas

    International Nuclear Information System (INIS)

    Zhou Jian; Fedkiw, Peter S.

    2003-01-01

    The effect on cycle capacity is reported of cathode material (metal oxide, carbon, and current collector) in lithium/metal oxide cells cycled with fumed silica-based composite electrolytes. Three types of electrolytes are compared: filler-free electrolyte consisting of methyl-terminated poly(ethylene glycol) oligomer (PEGdm, M w =250)+lithium bis(trifluromethylsufonyl)imide (LiTFSI) (Li:O=1:20), and two composite systems of the above baseline liquid electrolyte containing 10-wt% A200 (hydrophilic fumed silica) or R805 (hydrophobic fumed silica with octyl surface group). The composite electrolytes are solid-like gels. Three cathode active materials (LiCoO 2 , V 6 O 13 , and Li x MnO 2 ), four conducting carbons (graphite Timrex [reg] SFG 15, SFG 44, carbon black Vulcan XC72R, and Ketjenblack EC-600JD), and three current collector materials (Al, Ni, and carbon fiber) were studied. Cells with composite electrolytes show higher capacity, reduced capacity fade, and less cell polarization than those with filler-free electrolyte. Among the three active materials studied, V 6 O 13 cathodes deliver the highest capacity and Li x MnO 2 cathodes render the best capacity retention. Discharge capacity of Li/LiCoO 2 cells is affected greatly by cathode carbon type, and the capacity decreases in the order of Ketjenblack>SFG 15>SFG 44>Vulcan. Current collector material also plays a significant role in cell cycling performance. Lithium/vanadium oxide (V 6 O 13 ) cells deliver increased capacity using Ni foil and carbon fiber current collectors in comparison to an Al foil current collector

  10. Optimizing areal capacities through understanding the limitations of lithium-ion electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Gallagher, Kevin G.; Trask, Stephen E.; Bauer, Christoph; Woehrle, Thomas; Lux, Simon; Tschech, Matthias; Polzin, Bryant J.; Ha, Seungbum; Long, Brandon R.; Wu, Qingliu; Lu, Wenquan; Dees, Dennis W.; Jansen, Andrew N.

    2016-01-01

    Increasing the areal capacity or electrode thickness in lithium ion batteries is one possible means to increase pack level energy density while simultaneously lowering cost. The physics that limit use of high areal capacity as a function of battery power to energy ratio are poorly understood and thus most currently produced automotive lithium ion cells utilize modest loadings to ensure long life over the vehicle battery operation. Here we show electrolyte transport limits the utilization of the positive electrode at critical C-rates during discharge; whereas, a combination of electrolyte transport and polarization lead to lithium plating in the graphite electrode during charge. Experimental measurements are compared with theoretical predictions based on concentrated solution and porous electrode theories. An analytical expression is derived to provide design criteria for long lived operation based on the physical properties of the electrode and electrolyte. Finally, a guideline is proposed that graphite cells should avoid charge current densities near or above 4 mA/cm2 unless additional precautions have been made to avoid deleterious side reaction.

  11. Raman spectral and electrochemical studies of lithium/electrolyte interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Odziemkowski, M

    1922-01-01

    Cyclic voltammetry, corrosion potential-time transients and Normal Raman spectroscopy have been employed to characterize the lithium-lithium salt, organic solvent, interfacial region. An in-situ cutting technique was developed to expose lithium metal. In-situ optical and ex-situ scanning electron microscopy (SEM) have been used to examine the morphology of the lithium electrode surface during exposure at open circuit and after anodic polarization. The main reaction product detected by in-situ Raman spectroscopy in the system/lithium/LiAsF[sub 6], tetrahydrofuran (THF) electrolyte was polytetrahydrofuran (PTHF). The conditions for the polymerization reaction in the presence of lithium metal have been determined. Tetrahydrofuran (THF) decomposition reaction mechanisms are discussed. Decomposition reaction products have been determined as arsenic (II) oxide, As[sub 2]O[sub 3] (arsenolite) and arsenious oxyfluoride AsF[sub 2]-O-AsF[sub 2]. Potentiodynamic polarization measurements revealed a substantial shift of the corrosion potential towards positive values and only a moderate increase of anodic dissolution current for in-situ cut lithium metal. Corrosion potential-time merits have been measured. The following electrolytes have been investigated: LiAsF[sub 6], LiPF[sub 6], LiClO[sub 4], and Li(CF[sub 3]SO[sub 2])[sub 2]N in THF, 2Me-THF, and propylene carbonate (PC). The transients permit the ranking of the reactivity of the electrolytes. These measurements have shed light on understanding the stability of various stability and and solvents in contact with lithium. Compared to purified electrolytes, small amounts of water shift the corrosion potential towards even more positive values. Intensive anodic cycling of a Li electrode in unpurified LiAsF[sub 6]/THF electrolyte leads to the breakdown of a surface film/films. While at the open circuit potential (OCP), water in this same electrolyte leads to crack formation in the bulk lithium electrode.

  12. Thermal characteristics of Lithium-ion batteries

    Science.gov (United States)

    Hauser, Dan

    2004-01-01

    Lithium-ion batteries have a very promising future for space applications. Currently they are being used on a few GEO satellites, and were used on the two recent Mars rovers Spirit and Opportunity. There are still problem that exist that need to be addressed before these batteries can fully take flight. One of the problems is that the cycle life of these batteries needs to be increased. battery. Research is being focused on the chemistry of the materials inside the battery. This includes the anode, cathode, and the cell electrolyte solution. These components can undergo unwanted chemical reactions inside the cell that deteriorate the materials of the battery. During discharge/ charge cycles there is heat dissipated in the cell, and the battery heats up and its temperature increases. An increase in temperature can speed up any unwanted reactions in the cell. Exothermic reactions cause the temperature to increase; therefore increasing the reaction rate will cause the increase of the temperature inside the cell to occur at a faster rate. If the temperature gets too high thermal runaway will occur, and the cell can explode. The material that separates the electrode from the electrolyte is a non-conducting polymer. At high temperatures the separator will melt and the battery will be destroyed. The separator also contains small pores that allow lithium ions to diffuse through during charge and discharge. High temperatures can cause these pores to close up, permanently damaging the cell. My job at NASA Glenn research center this summer will be to perform thermal characterization tests on an 18650 type lithium-ion battery. High temperatures cause the chemicals inside lithium ion batteries to spontaneously react with each other. My task is to conduct experiments to determine the temperature that the reaction takes place at, what components in the cell are reacting and the mechanism of the reaction. The experiments will be conducted using an accelerating rate calorimeter

  13. Solid state electrolyte systems

    Energy Technology Data Exchange (ETDEWEB)

    Pederson, L.R.; Armstrong, B.L.; Armstrong, T.R. [Pacific Northwest Lab., Richland, WA (United States)] [and others

    1997-12-01

    Lanthanum gallates are a new family of solid electrolytes that exhibit high ionic conductivity and are stable to high temperatures. Compositions have been developed that are as much as a factor of two more conductive than yttria-stabilized zirconia at a given temperature, through partial replacement of lanthanum by calcium, strontium, and/or barium and through partial replacement of gallium by magnesium. Oxide powders were prepared using combustion synthesis techniques developed in this laboratory; these were sintered to >95% of theoretical density and consisted of a single crystalline phase. Electrical conductivities, electron and ion transference numbers, thermal expansion, and phase behavior were evaluated as a function of temperature and oxygen partial pressure. A key advantage of the use of lanthanum gallate electrolytes in solid oxide fuel cells is that the temperature of operation may be lowered to perhaps 800 C, yet provide approximately the same power density as zirconia-based cells operating at 1000 C. Ceramic electrolytes that conduct both oxygen ions and electrons are potentially useful to passively separate pure oxygen from an air source at low cost. In such materials, an oxygen ion flux in one direction is charge-compensated by an opposing electron flux. The authors have examined a wide range of mixed ion and electron conducting perovskite ceramics in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, where M = Sr, Ca, and Ba, and N = Pr, Mn, Ni, Cu, Ti, and Al, as well as mixed conducting brownmillerite ceramics, and have characterized oxygen permeation behavior, defect chemistry, structural and phase stability, and performance as cathodes.

  14. Ion Transport in Organic Electrolyte Solution through the Pore Channels of Anodic Nanoporous Alumina Membranes

    International Nuclear Information System (INIS)

    Fukutsuka, Tomokazu; Koyamada, Kohei; Maruyama, Shohei; Miyazaki, Kohei; Abe, Takeshi

    2016-01-01

    Highlights: • Ion transport in organic electrolyte solution in macro- and meso-pores was focused. • Anodic nanoporous alumina membrane was used as a porous material. • The specific ion conductivities drastically decreased in macro- and meso-pores. - Abstract: For the development of high energy density lithium-ion batteries with the high rate performance, the enhancement of the ion transport in the electrolyte solutions impregnated in the porous electrodes is a key. To study the ion transport in porous electrodes, anodic nanoporous alumina (APA) self-standing membranes with macro- or meso-pores were used as model porous materials. These membranes had nearly spherical pore channels of discrete 20–68 nm in diameters. By using the geometric shape of the pores, we attempted to evaluate the specific ion conductivities of the organic electrolyte solution dissolving lithium salt simply. AC impedance spectroscopy measurement of a four-electrode cell with membranes showed one depressed semi-circle in the Nyquist plots and this semi-circle can be assigned as the ion transport resistance in the pores. The specific ion conductivities evaluated from the ion transport resistances and the geometric parameters showed very small values, even in the macro-pores, as compared with that of the bulk electrolyte solution.

  15. Pyrrolidinium FSI and TFSI-Based Polymerized Ionic Liquids as Electrolytes for High-Temperature Lithium-Ion Batteries

    Directory of Open Access Journals (Sweden)

    Manfred Kerner

    2018-02-01

    Full Text Available Promising electrochemical and dynamical properties, as well as high thermal stability, have been the driving forces behind application of ionic liquids (ILs and polymerized ionic liquids (PILs as electrolytes for high-temperature lithium-ion batteries (HT-LIBs. Here, several ternary lithium-salt/IL/PIL electrolytes (PILel have been investigated for synergies of having both FSI and TFSI anions present, primarily in terms of physico-chemical properties, for unique application in HT-LIBs operating at 80 °C. All of the electrolytes tested have low Tg and are thermally stable ≥100 °C, and with TFSI as the exclusive anion the electrolytes (set A have higher thermal stabilities ≥125 °C. Ionic conductivities are in the range of 1 mS/cm at 100 °C and slightly higher for set A PILel, which, however, have lower oxidation stabilities than set B PILel with both FSI and TFSI anions present: 3.4–3.7 V vs. 4.2 V. The evolution of the interfacial resistance increases for all PILel during the first 40 h, but are much lower for set B PILel and generally decrease with increasing Li-salt content. The higher interfacial resistances only influence the cycling performance at high C-rates (1 C, where set B PILel with high Li-salt content performs better, while the discharge capacities at the 0.1 C rate are comparable. Long-term cycling at 0.5 C, however, shows stable discharge capacities for 100 cycles, with the exception of the set B PILel with high Li-salt content. Altogether, the presence of both FSI and TFSI anions in the PILel results in lower ionic conductivities and decreased thermal stabilities, but also higher oxidation stabilities and reduced interfacial resistances and, in total, result in an improved rate capability, but compromised long-term capacity retention. Overall, these electrolytes open for novel designs of HT-LIBs.

  16. Electrochemical performance of lithium-ion capacitors evaluated under high temperature and high voltage stress using redox stable electrolytes and additives

    Science.gov (United States)

    Boltersdorf, Jonathan; Delp, Samuel A.; Yan, Jin; Cao, Ben; Zheng, Jim P.; Jow, T. Richard; Read, Jeffrey A.

    2018-01-01

    Lithium-ion capacitors (LICs) were investigated for high power, moderate energy density applications for operation in extreme environments with prolonged cycle-life performance. The LICs were assembled as three-layered pouch cells in an asymmetric configuration employing Faradaic pre-lithiated hard carbon anodes and non-Faradaic ion adsorption-desorption activated carbon (AC) cathodes. The capacity retention was measured under high stress conditions, while the design factor explored was electrolyte formulation using a set of carbonates and electrolyte additives, with a focus on their stability. The LIC cells were evaluated using critical performance tests under the following high stress conditions: long-term voltage floating-cycling stability at room temperature (2.2-3.8 V), high temperature storage at 3.8 V, and charge voltages up to 4.4 V. The rate performance of different electrolytes and additives was measured after the initial LIC cell formation for a 1C-10C rate. The presence of vinylene carbonate (VC) and tris (trimethylsilyl) phosphate (TMSP) were found to be essential to the improved electrochemical performance of the LIC cells under all testing conditions.

  17. Highly stable bilayer of LiPON and B2O3 added Li1.5Al0.5Ge1.5(PO4) solid electrolytes for non-aqueous rechargeable Li-O2 batteries

    International Nuclear Information System (INIS)

    Jadhav, Harsharaj S.; Kalubarme, Ramchandra S.; Jadhav, Arvind H.; Seo, Jeong Gil

    2016-01-01

    Highlights: • LiPON thin film deposited by RF-sputtering technique. • The effect of deposition temperature on ionic conductivity was investigated. • The LiPON/B-LAGP composite was successfully employed in Li-O 2 battery. • LiPON interlayer enhances stability of B-LAGP in contact with Li-metal. - Abstract: Lithium ion conducting membranes are barely studied, although they are essentially indispensable for building Li-air batteries composed of aqueous and non-aqueous electrolytes for long-term operation. Lithium phosphorous oxynitride (LiPON) thin films were deposited by RF-sputtering technique on B 2 O 3 -added lithium aluminum germanium phosphate (B-LAGP). Compact thin amorphous LiPON layer could act as a protective interlayer for B-LAGP by separating it from Li metal electrode and mitigate the reaction between them. Large electrochemical stability window (0–5 V) of LiPON/B-LAGP solid electrolyte shows promising feasibility for applications in all lithium based batteries. The aprotic Li-O 2 cell with protected lithium electrode configuration employing LiPON/B-LAGP solid electrolyte has exhibited reasonable cycling stability with long-life of 52 cycles at a limited capacity of 1000 mA h g −1 .

  18. Understanding the thermal instability of fluoroethylene carbonate in LiPF6-based electrolytes for lithium ion batteries

    International Nuclear Information System (INIS)

    Kim, Koeun; Park, Inbok; Ha, Se-Young; Kim, Yeonkyoung; Woo, Myung-Heuio; Jeong, Myung-Hwan; Shin, Woo Cheol; Ue, Makoto; Hong, Sung You; Choi, Nam-Soon

    2017-01-01

    Highlights: • The FEC in LiPF 6 -based electrolytes thermally decomposes at elevated temperatures. • Lewis acids in the electrolyte promote de-fluorination of the FEC to form HF. • The HF causes the SEI destruction and severe metal ion dissolution from the cathode. - Abstract: The cycling and storage performances of LiCoO 2 (LCO)-LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM)/pitch-coated silicon alloy-graphite (Si-C) full cells with ethylene carbonate (EC)–based and fluoroethylene carbonate (FEC)–based electrolytes are investigated at elevated temperatures. Excess FEC (used as a co-solvent in LiPF 6 -based electrolytes), which is not completely consumed during the formation of the solid electrolyte interphase (SEI) layer on the electrodes, is prone to defluorination in the presence of Lewis acids such as PF 5 ; this reaction can generate unwanted HF and various acids (H 3 OPF 6 , HPO 2 F 2 , H 2 PO 3 F, H 3 PO 4 ) at elevated temperatures. Our investigation reveals that the HF and acid compounds that are formed by FEC decomposition causes significant dissolution of transition metal ions (from the LCO-NCM cathode) into the electrolyte at elevated temperatures; as a result, the reversible capacity of the full cells reduces because of the deposition of the dissolved metal ions onto the anode. Moreover, we demonstrate possible mechanisms that account for the thermal instability of FEC in LiPF 6 -based electrolytes at elevated temperatures using model experiments.

  19. Modified carbon black materials for lithium-ion batteries

    Science.gov (United States)

    Kostecki, Robert; Richardson, Thomas; Boesenberg, Ulrike; Pollak, Elad; Lux, Simon

    2016-06-14

    A lithium (Li) ion battery comprising a cathode, a separator, an organic electrolyte, an anode, and a carbon black conductive additive, wherein the carbon black has been heated treated in a CO.sub.2 gas environment at a temperature range of between 875-925 degrees Celsius for a time range of between 50 to 70 minutes to oxidize the carbon black and reduce an electrochemical reactivity of the carbon black towards the organic electrolyte.

  20. Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

    Science.gov (United States)

    Joshi, Ashok V [Salt Lake City, UT; Balagopal, Shekar [Sandy, UT; Pendelton, Justin [Salt Lake City, UT

    2011-12-13

    Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

  1. BFR Electrolyte Additive Safety and Flammability Characterization

    Energy Technology Data Exchange (ETDEWEB)

    Allcorn, Eric [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2017-10-13

    Lithium-ion battery safety is a critical issue in the adoption of the chemistry to larger scale applications such as transportation and stationary storage. One of the critical components impacting the safety of lithium-ion batteries is their use of highly flammable organic electrolytes. In this work, brominated flame retardants (BFR’s) – an existing class of flame retardant materials – are incorporated as additives to lithium-ion battery electrolytes with the intention to reduce the electrolyte flammability and thereby improve safety. There are a few critical needs for a successful electrolyte additive: solubility in the electrolyte, electrochemical stability over the range of battery operation, and minimal detrimental effects on battery performance. Those detrimental effects can take the form of electrolyte specific impacts, such as a reduction in conductivity, or electrode impacts, such as SEI-layer modification or chemical instability to the active material. In addition to these needs, the electrolyte additive also needs to achieve its intended purpose, which in this case is to reduce the flammability of the electrolyte. For the work conducted as part of this SPP agreement three separate BFR materials were provided by Albemarle to be tested by Sandia as additives in a traditional lithium-ion battery electrolyte. The provided BFR materials were tribromo-neopentyl alcohol, tetrabromo bisphenol A, and tribromoethylene. These materials were incorporated as separate 4 wt.% additives into a traditional lithium-ion battery electrolyte and compared to said traditional electrolyte, designated Gen2.

  2. Solid-state ionics: Studies of lithium-conducting sulfide glasses and a superconducting oxide compound

    International Nuclear Information System (INIS)

    Ahn, Byung Tae.

    1989-01-01

    The first part of this work studies lithium-conducting sulfide glasses for battery applications, while the second part studies the thermodynamic properties of a superconducting oxide compound by using an oxide electrolyte. Lithium conducting glasses based on the SiS 2 -Li 2 S system are possible solid electrolytes for high-energy-density lithium batteries. The foremost requirement for solid electrolytes is that they should have high ionic conductivities. Unfortunately, most crystalline lithium conductors have low ionic conductivities at room temperature. However, glass ionic conductors show higher ionic conductivities than do crystalline forms of the same material. In addition to higher ionic conductivities, glasses appear to have several advantages over crystalline materials. These advantages include isotropic conductivity, absence of grain boundary effects, ease of glass forming, and the potential for a wide range of stability to oxidizing and reducing conditions. Using pyrolitic graphite-coated quartz ampoules, new ternary compounds and glasses in the SiS 2 -Li 2 S system were prepared. Several techniques were used to characterize the materials: powder x-ray diffraction, differential thermal analysis, differential scanning calorimetry, and AC impedance spectroscopy. The measured lithium conductivity of the sulfide glasses was one of the highest among the known solid lithium conductors. Measuring the equilibrium open circuit voltages assisted in determining the electrochemical stabilities of the ternary compounds and glasses with respect to pure Li. A solid-state ionic technique called oxygen coulometric titration was used to measure the thermodynamic stability, the oxygen stoichiometry, and the effects of the oxygen stoichiometry, and the effects of the oxygen stoichiometry and the cooling rate on superconductivity of the YBa 2 Cu 3 O 7-x compound were investigated

  3. Designable ultra-smooth ultra-thin solid-electrolyte interphases of three alkali metal anodes.

    Science.gov (United States)

    Gu, Yu; Wang, Wei-Wei; Li, Yi-Juan; Wu, Qi-Hui; Tang, Shuai; Yan, Jia-Wei; Zheng, Ming-Sen; Wu, De-Yin; Fan, Chun-Hai; Hu, Wei-Qiang; Chen, Zhao-Bin; Fang, Yuan; Zhang, Qing-Hong; Dong, Quan-Feng; Mao, Bing-Wei

    2018-04-09

    Dendrite growth of alkali metal anodes limited their lifetime for charge/discharge cycling. Here, we report near-perfect anodes of lithium, sodium, and potassium metals achieved by electrochemical polishing, which removes microscopic defects and creates ultra-smooth ultra-thin solid-electrolyte interphase layers at metal surfaces for providing a homogeneous environment. Precise characterizations by AFM force probing with corroborative in-depth XPS profile analysis reveal that the ultra-smooth ultra-thin solid-electrolyte interphase can be designed to have alternating inorganic-rich and organic-rich/mixed multi-layered structure, which offers mechanical property of coupled rigidity and elasticity. The polished metal anodes exhibit significantly enhanced cycling stability, specifically the lithium anodes can cycle for over 200 times at a real current density of 2 mA cm -2 with 100% depth of discharge. Our work illustrates that an ultra-smooth ultra-thin solid-electrolyte interphase may be robust enough to suppress dendrite growth and thus serve as an initial layer for further improved protection of alkali metal anodes.

  4. Solid ion-conducting material, its use, and method for its manufacture. Festes Ionenleitermaterial, seine Verwendung und Verfahren zu dessen Herstellung

    Energy Technology Data Exchange (ETDEWEB)

    Wichelhaus, W; Weppner, W; Hartwig, P

    1984-04-19

    The invention concerns a solid ion conducting material for a battery. Lithium nitride and lithium halogen compounds are mixed in the required mol ratio under an inert gas, compressed and the compressed substance is quickly heated in a nitrogen atmosphere to 460 to 550 deg C, and then tempered at 350 to 450 deg C until the reaction is finished. The lithium halogen compound and lithium metal can also be mixed in the required mol ratio and heated under nitrogen. Here the required temperature is 150 to 500 deg C. The lithium nitride halogen compouhnds exist as crystals. They are suitable for use as the electrolyte in batteries.

  5. Thermal stability and modeling of lithium ion batteries

    Science.gov (United States)

    Botte, Gerardine Gabriela

    2000-10-01

    First-principles mathematical models were developed to examine the effect of the lithium-lithium ion interactions inside the anode particles on the performance of a lithium foil cell. Two different models were developed: the chemical potential model (CPM) that includes the lithium-lithium ion interactions inside the anode particles and the diffusion model (DIM) that does not include the interactions. Significant differences in the thermal and electrochemical performance of the cell were observed between the two approaches. The temperature of the cell predicted by the DFM is higher than the one predicted by the CPM at a given capacity. The discharge time of the cell predicted by the DFM is shorter than the one predicted by the CPM. The results indicate that the cell needs to be modeled using the CPM approach especially at high discharge rates. An evaluation of the numerical techniques, control volume formulation (CVF) and finite difference method (FDM), used for the models was performed. It is shown that the truncation error is the same for both methods when the boundary conditions are of the Dirichlet type, the system of equations are linear and represented in Cartesian coordinates. A new technique to analyze the accuracy of the methods is presented. The only disadvantage of the FDM is that it failed to conserve mass for a small number of nodes when both boundary conditions include a derivative term whereas the CVF did conserve mass for these cases. However, for a large number of nodes the FDM provides mass conservation. It is important to note that the CVF has only (DeltaX) order of accuracy for a Neumann type boundary condition whereas the FDM has (DeltaX) 2 order. The second topic of this dissertation presents a study of the thermal stability of LiPF6 EC:EMC electrolyte for lithium ion batteries. A differential scanning calorimeter (DSC) was used to perform the study of the electrolyte. For first time, the effect of different variables on its thermal stability

  6. Functional Polymer Electrolytes for Multidimensional All-Solid-State Lithium Batteries

    OpenAIRE

    Sun, Bing

    2015-01-01

    Pressing demands for high power and high energy densities in novel electrical energy storage units have caused reconsiderations regarding both the choice of battery chemistry and design. Practical concerns originating in the conventional use of flammable liquid electrolytes have renewed the interests of using solvent-free polymer electrolytes (SPEs) as solid ionic conductors for safer batteries. In this thesis work, SPEs developed from two polymer host structures, polyethers and polycarbonate...

  7. Chemical Shuttle Additives in Lithium Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Patterson, Mary

    2013-03-31

    than NMC) and the DDB is useful for lithium ion cells with LFP cathodes (potential that is lower than NMC). A 4.5 V class redox shuttle provided by Argonne National Laboratory was evaluated which provides a few cycles of overcharge protection for lithium ion cells containing NMC cathodes but it is not stable enough for consideration. Thus, a redox shuttle with an appropriate redox potential and sufficient chemical and electrochemical stability for commercial use in larger format lithium ion cells with NMC cathodes was not found. Molecular imprinting of the redox shuttle molecule during solid electrolyte interphase (SEI) layer formation likely contributes to the successful reduction of oxidized redox shuttle species at carbon anodes. This helps to understand how a carbon anode covered with an SEI layer, that is supposed to be electrically insulating, can reduce the oxidized form of a redox shuttle.

  8. Tri-(4-methoxythphenyl) phosphate: A new electrolyte additive with both fire-retardancy and overcharge protection for Li-ion batteries

    International Nuclear Information System (INIS)

    Feng, J.K.; Cao, Y.L.; Ai, X.P.; Yang, H.X.

    2008-01-01

    A novel compound, tri-(4-methoxythphenyl) phosphate, was synthesized and investigated as a safety electrolyte additive for lithium-ion batteries. It was found that this additive could lower the flammability of the electrolyte, and thereby enhance the thermal stability of the Li-ion battery. Moreover, this molecule can also be polymerized at 4.35 V (vs. Li/Li + ) to form a conducting polymer, which can protect the batteries from voltage runaway at overcharge by internal bypassing the overcharging current in the batteries. Thus, it is possible to use this electrolyte additive to provide both overcharge protection and flame retardancy for lithium-ion batteries without much influence on the battery performance

  9. Electrolytes for Use in High Energy Lithium-ion Batteries with Wide Operating Temperature Range

    Science.gov (United States)

    Smart, Marshall C.; Ratnakumar, B. V.; West, W. C.; Whitcanack, L. D.; Huang, C.; Soler, J.; Krause, F. C.

    2012-01-01

    Met programmatic milestones for program. Demonstrated improved performance with wide operating temperature electrolytes containing ester co-solvents (i.e., methyl butyrate) containing electrolyte additives in A123 prototype cells: Previously demonstrated excellent low temperature performance, including 11C rates at -30 C and the ability to perform well down to -60 C. Excellent cycle life at room temperature has been displayed, with over 5,000 cycles being demonstrated. Good high temperature cycle life performance has also been achieved. Demonstrated improved performance with methyl propionate-containing electrolytes in large capacity prototype cells: Demonstrated the wide operating temperature range capability in large cells (12 Ah), successfully scaling up technology from 0.25 Ah size cells. Demonstrated improved performance at low temperature and good cycle life at 40 C with methyl propionate-based electrolyte containing increasing FEC content and the use of LiBOB as an additive. Utilized three-electrode cells to investigate the electrochemical characteristics of high voltage systems coupled with wide operating temperature range electrolytes: From Tafel polarization measurements on each electrode, it is evident the NMC-based cathode displays poor lithium kinetics (being the limiting electrode). The MB-based formulations containing LiBOB delivered the best rate capability at low temperature, which is attributed to improved cathode kinetics. Whereas, the use of lithium oxalate as an additive lead to the highest reversible capacity and lower irreversible losses.

  10. Analysis of influence of heat exchange conditions on the outer surface of the lithium-ion battery to electrolyte temperature under the conditions of high current loads

    Directory of Open Access Journals (Sweden)

    Krasnoshlykov Alexander

    2017-01-01

    Full Text Available Numerical analysis of thermal conditions of a lithium-ion battery using the software package ANSYS Electric and ANSYS Fluent has been carried out. Time dependence of the electrolyte temperature on the various heat exchange conditions on the outer surface has been obtained.

  11. Polymer Electrolytes

    Science.gov (United States)

    Hallinan, Daniel T.; Balsara, Nitash P.

    2013-07-01

    This review article covers applications in which polymer electrolytes are used: lithium batteries, fuel cells, and water desalination. The ideas of electrochemical potential, salt activity, and ion transport are presented in the context of these applications. Potential is defined, and we show how a cell potential measurement can be used to ascertain salt activity. The transport parameters needed to fully specify a binary electrolyte (salt + solvent) are presented. We define five fundamentally different types of homogeneous electrolytes: type I (classical liquid electrolytes), type II (gel electrolytes), type III (dry polymer electrolytes), type IV (dry single-ion-conducting polymer electrolytes), and type V (solvated single-ion-conducting polymer electrolytes). Typical values of transport parameters are provided for all types of electrolytes. Comparison among the values provides insight into the transport mechanisms occurring in polymer electrolytes. It is desirable to decouple the mechanical properties of polymer electrolyte membranes from the ionic conductivity. One way to accomplish this is through the development of microphase-separated polymers, wherein one of the microphases conducts ions while the other enhances the mechanical rigidity of the heterogeneous polymer electrolyte. We cover all three types of conducting polymer electrolyte phases (types III, IV, and V). We present a simple framework that relates the transport parameters of heterogeneous electrolytes to homogeneous analogs. We conclude by discussing electrochemical stability of electrolytes and the effects of water contamination because of their relevance to applications such as lithium ion batteries.

  12. Solid-solution-like ZnO/C composites as excellent anode materials for lithium ion batteries

    International Nuclear Information System (INIS)

    Zhang, Guanhua; Zhang, Hang; Zhang, Xiang; Zeng, Wei; Su, Qingmei; Du, Gaohui; Duan, Huigao

    2015-01-01

    Exploring advanced anode materials to maximize the capacity of lithium ion batteries has been an active research area for decades. Constructing composites materials has been proved to be one of the most effective methods to achieve higher capacity due to the synergistic effect. In this work, we proposed and demonstrated a concept of solid-solution-like ZnO/C composites to approach the largest possible synergistic effect by introducing the most interfaces and minimizing the pulverization. The solid-solution-like ZnO/C electrode could achieve a high reversible capacity of 813.3 mAh g −1 at a current density of 100 mA g −1 after 100 cycles with a decrease rate of only 0.4% per cycle. Moreover, the discharge capacity still maintained 53.5% of the original value even when the current density increased to 40 times as much as the original, showing a distinguished rate performance. In addition, such solid-solution-like nanofibers can be easily prepared because of their compatibility with the existing industrial PAN-based spinning process. This may pave the way to mass produce lithium ion batteries with significantly enhanced performance using existing low-cost commercial facilities and recipes.

  13. Superior lithium adsorption and required magnetic separation behavior of iron-doped lithium ion-sieves

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Shulei; Zheng, Shili; Wang, Zheming; Cui, Wenwen; Zhang, Hailin; Yang, Liangrong; Zhang, Yi; Li, Ping

    2018-01-01

    The recent research on adsorption-based lithium recovery from lithium-containing solutions has been centred on adsorption capacity and separation of lithium ion-sieves powder from solutions. Herein, an effective iron-doped lithium titanium oxide (Fe-doped Li2TiO3) was synthesized by Fe-doping via solid state reactions followed by acid treatment to form iron-doped lithium ion-sieves (Fe/Ti-x(H)). The resulting solid powder displays both superior adsorption capacity of lithium and high separation efficiency of the adsorbent from the solutions. SEM imaging and BET surface area measurement results showed that at Fe doping levels x0.15, Fe-doping led to grain shrinkage as compared to Li2TiO3 and at the same time the BET surface area increased. The Fe/Ti-0.15(H) exhibited saturated magnetization values of 13.76 emu g-1, allowing effective separation of the material from solid suspensions through the use of a magnet. Consecutive magnetic separation results suggested that the Fe/Ti-0.15(H) powders could be applied at large-scale and continuously removed from LiOH solutions with separation efficiency of 96% or better. Lithium adsorption studies indicated that the equilibrium adsorption capacity of Fe/Ti-0.15(H) in LiOH 2 solutions (1.8 g L-1 Li, pH 12) reached 53.3 mg g-1 within 24 h, which was higher than that of pristine Li2TiO3 (50.5 mg g-1) without Fe doping. Competitive adsorption and regeneration results indicated that the Fe/Ti-0.15(H) possessed a high selectivity for Li with facile regeneration. Therefore, it could be expected that the iron-doped lithium ion-sieves have practical applicability potential for large scale lithium extraction and recovery from lithium-bearing solutions.

  14. Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries

    Science.gov (United States)

    Li, Wangda; Dolocan, Andrei; Oh, Pilgun; Celio, Hugo; Park, Suhyeon; Cho, Jaephil; Manthiram, Arumugam

    2017-01-01

    Undesired electrode–electrolyte interactions prevent the use of many high-energy-density cathode materials in practical lithium-ion batteries. Efforts to address their limited service life have predominantly focused on the active electrode materials and electrolytes. Here an advanced three-dimensional chemical and imaging analysis on a model material, the nickel-rich layered lithium transition-metal oxide, reveals the dynamic behaviour of cathode interphases driven by conductive carbon additives (carbon black) in a common nonaqueous electrolyte. Region-of-interest sensitive secondary-ion mass spectrometry shows that a cathode-electrolyte interphase, initially formed on carbon black with no electrochemical bias applied, readily passivates the cathode particles through mutual exchange of surface species. By tuning the interphase thickness, we demonstrate its robustness in suppressing the deterioration of the electrode/electrolyte interface during high-voltage cell operation. Our results provide insights on the formation and evolution of cathode interphases, facilitating development of in situ surface protection on high-energy-density cathode materials in lithium-based batteries. PMID:28443608

  15. Carboxymethyl Carrageenan Based Biopolymer Electrolytes

    International Nuclear Information System (INIS)

    Mobarak, N.N.; Jumaah, F.N.; Ghani, M.A.; Abdullah, M.P.; Ahmad, A.

    2015-01-01

    Highlights: • The paper highlights the potential of carboxymethyl carrageenan based on iota and kappa to be utilized as host polymer. • The highest conductivity were achieved up to ∼10 −3 S cm −1 by carboxymethyl carrageenan without the addition of plasticizer. • The electrochemical stability windows of the films were electrochemically stable up to 3.0 V. - Abstract: A series of biodegradable carboxymethyl carrageenan based polymer electrolytes, which are carboxymethyl kappa carrageenan (sulphate per disaccharide) and carboxymethyl iota carrageenan (two sulphates per disaccharide), have been prepared by a solution casting technique with different ratios of lithium nitrate (LiNO 3 ) salts. Interestingly, the lithium ions tended to interact with the carbonyl group in the different modes of symmetry, as observed from reflection Fourier transform infrared (ATR-FTIR) spectroscopy analysis. In the carboxymethyl kappa carrageenan electrolytes, as the concentration of LiNO 3 increased, the asymmetric stretching peak of the carbonyl bond became dominant because it can be observed clearly with the shifting of the peak from 1592 to 1602 cm −1 due to the interaction between the lithium ion and the carbonyl group, while the broad O-H stretching peak became sharp and intense. However, for the carboxymethyl iota carrageenan, the asymmetry stretching mode of the carbonyl group shifted from 1567 to 1599 cm −1 , as the salt concentration increased. The shifting of the C-O-C peak also occurred in the iota-based electrolytes. However, the changes in the peak that represented SO 4 2− symmetric stretching were only detected when the ion pair formation was observed. It was proposed that the peak shifting was due to the presence of the lithium ion pathway, forming a dative bond between the lithium and oxygen in the carbonyl group. Accordingly, as more peak shifting was observed, the number of the ion pathways also increased. This hypothesis was supported by the impedance

  16. A Quasi-Solid-State Li-Ion Capacitor Based on Porous TiO2 Hollow Microspheres Wrapped with Graphene Nanosheets.

    Science.gov (United States)

    Wang, Faxing; Wang, Chun; Zhao, Yujuan; Liu, Zaichun; Chang, Zheng; Fu, Lijun; Zhu, Yusong; Wu, Yuping; Zhao, Dongyuan

    2016-12-01

    The quasi-solid-state Li-ion capacitor is demonstrated with graphene nanosheets prepared by an electrochemical exfoliation as the positive electrode and the porous TiO 2 hollow microspheres wrapped with the same graphene nanosheets as the negative electrode, using a Li-ion conducting gel polymer electrolyte. This device may be the key to bridging the gap between conventional lithium-ion batteries and supercapacitors, meanwhile meeting the safety demands of electronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Electrochemical behavior of lithium imide/cyclic ether electrolytes for 4 V lithium metal rechargeable batteries

    Energy Technology Data Exchange (ETDEWEB)

    Wang, X.; Yasukawa, Eiki; Mori, Shoichiro

    1999-11-01

    To develop organic electrolytes for 4 V lithium metal rechargeable batteries, LiN(SO{sub 2}CF{sub 3}){sub 2} electrolytes with five-, six-, and seven-membered cyclic ether solvents were characterized. Among these examined electrolytes, LiN(SO{sub 2}CF{sub 3}){sub 2}/tetrahydropyran (THP) electrolyte was found to possess the most advantages, such as high cycling efficiency, good oxidation stability, and high boiling point. Furthermore, lithium cycling efficiency and conductivity were improved by mixing 50% ethylene carbonate (EC) in 1 mol/dm{sup 3} LiN(SO{sub 2}CF{sub 3}){sub 2}/THP electrolyte. By using LiN(SO{sub 2}C{sub 2}F{sub 5}){sub 2} solute as an alternative to LiN(SO{sub 2}CF{sub 3}){sub 2} in EC + THP (1:1) electrolyte, corrosion of the aluminum current collector was inhibited and therefore, excellent cycling performance of a Li/LiMn{sub 2}O{sub 4} coin cell was realized. It was also found that lithium cycling efficiency increased with decreasing deposition current density or increasing dissolution current density. Especially at deposition/dissolution current densities of 0.2/0.6 mA/cm{sup 2}, the observed lithium cycling efficiency in 1 mol/dm{sup 3} LiN(SO{sub 2}C{sub 2}F{sub 5}){sub 2}/EC + THP (1:1) electrolyte was above 99%. Thermal tests further disclosed that this mixed electrolyte has good thermal stability even in the presence of lithium metal or cathode materials.

  18. Battery of circular cell shape with central lithium anode and non-aqueous electrolytes. Galvanisches Element in Rundzellenform mit zentrisch angeordneter Lithium-Anode und nichtwaessrigem Elektrolyten

    Energy Technology Data Exchange (ETDEWEB)

    Kretzschmar, R

    1987-06-11

    The separation of such a cell situated between the negative and positive electrode is formed by a loose plastic vliess cut into a strip, which during assembly of the cells, is laid with central orientation on the open cell cup already provided with a circular cathode and filled with electrolyte and is pressed directly through the bar-shaped lithium electrode into the hollow space of the annular cathode, where it surrounds the lithium electrode as a compressed, closed sheath. Excess electrolyte flows into the sheath from the uncompressed top part of the separator vliess over the electrodes, to the extent that the lithium electrode is electrochemically dissolved and the expanding vliess maintaining contact with the lithium takes up liquid so that there is no interruption of ion conduction between the electrodes.

  19. Solidification of liquid electrolyte with imidazole polymers for quasi-solid-state dye-sensitized solar cells

    International Nuclear Information System (INIS)

    Wang Miao; Lin Yuan; Zhou Xiaowen; Xiao Xurui; Yang Lei; Feng Shujing; Li Xueping

    2008-01-01

    Quasi-solid-state electrolytes were prepared by employing the imidazole polymers to solidify the liquid electrolyte containing lithium iodide, iodine and ethylene carbonate (EC)/propylene carbonate (PC) mixed solvent. The ionic conductivity and diffusion behavior of triiodide in the quasi-solid-state electrolytes were examined in terms of the polymer content. Application of the quasi-solid-state electrolytes to the dye-sensitized solar cells, the maximum energy conversion efficiency of 7.6% (AM 1.5, 100 mW cm -2 ) was achieved. The dependence of the photovoltaic performance on the polymer content and on the different anions of the imidazole polymers was studied by electrochemical impedance spectroscopy and cyclic voltammetry. The results indicate the charge transfer behaviors occurred at nanocrystalline TiO 2 /electrolyte and Pt/electrolyte interface play an important role in influencing the photovoltaic performance of quasi-solid-state dye-sensitized solar cells

  20. Investigating the low-temperature impedance increase of lithium-ion cells

    International Nuclear Information System (INIS)

    Abraham, D. P.; Heaton, J. R.; Kang, S.-H.; Dees, D. W.; Jansen, A. N.; Chemical Engineering

    2008-01-01

    Low-temperature performance loss is a significant barrier to commercialization of lithium-ion cells in hybrid electric vehicles. Increased impedance, especially at temperatures below 0 C, reduces the cell pulse power performance required for cold engine starts, quick acceleration, or regenerative braking. Here we detail electrochemical impedance spectroscopy data on binder- and carbon-free layered-oxide and spinel-oxide electrodes, obtained over the +30 to ?30 C temperature range, in coin cells containing a lithium-preloaded Li 4/3 Ti 5/3 O 4 composite (LTOc) counter electrode and a LiPF 6 -bearing ethylene carbonate/ethyl methyl carbonate electrolyte. For all electrodes studied, the impedance increased with decreasing cell temperature; the increases observed in the midfrequency arc dwarfed the increases in ohmic resistance and diffusional impedance. Our data suggest that the movement of lithium ions across the electrochemical interface on the active material may have been increasingly hindered at lower temperatures, especially below 0 C. Low-temperature performance may be improved by modifying the electrolyte-active material interface (for example, through electrolyte composition changes). Increasing surface area of active particles (for example, through nanoparticle use) can lower the initial electrode impedance and lead to lower cell impedances at -30 C

  1. Oxidation processes on conducting carbon additives for lithium-ion batteries

    KAUST Repository

    La Mantia, Fabio; Huggins, Robert A.; Cui, Yi

    2012-01-01

    The oxidation processes at the interface between different types of typical carbon additives for lithium-ion batteries and carbonates electrolyte above 5 V versus Li/Li+ were investigated. Depending on the nature and surface area of the carbon

  2. Electrolyte for a lithium/thionyl chloride electric cell, a method of preparing said electrolyte and an electric cell which includes said electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Gabano, J.

    1983-03-01

    An electrolyte for an electric cell whose negative active material is constituted by lithium and whose positive active material is constituted by thionyl chloride. The electrolyte contains at least one solvent and at least one solute, said solvent being thionyl chloride and said solute being chosen from the group which includes lithium tetrachloroaluminate and lithium hexachloroantimonate. According to the invention said electrolyte further includes a complex chosen from the group which includes AlCl/sub 3/,SO/sub 2/ and SbCl/sub 5/,SO/sub 2/. The voltage rise of electric cells which include such an electrolyte takes negligible time.

  3. Current Progress of Si/Graphene Nanocomposites for Lithium-Ion Batteries

    Directory of Open Access Journals (Sweden)

    Yinjie Cen

    2018-03-01

    Full Text Available The demand for high performance lithium-ion batteries (LIBs is increasing due to widespread use of portable devices and electric vehicles. Silicon (Si is one of the most attractive candidate anode materials for next generation LIBs. However, the high-volume change (>300% during lithium ion alloying/de-alloying leads to poor cycle life. When Si is used as the anode, conductive carbon is needed to provide the necessary conductivity. However, the traditional carbon coating method could not overcome the challenges of pulverization and unstable Solid Electrolyte Interphase (SEI layer during long-term cycling. Since 2010, Si/Graphene composites have been vigorously studied in hopes of providing a material with better cycling performance. This paper reviews current progress of Si/Graphene nanocomposites in LIBs. Different fabrication methods have been studied to synthesize Si/Graphene nanocomposites with promising electrochemical performances. Graphene plays a key enabling role in Si/Graphene anodes. However, the desired properties of graphene for this application have not been systematically studied and understood. Further systematic investigation of the desired graphene properties is suggested to better control the Si/Graphene anode performance.

  4. Reliable reference electrodes for lithium-ion batteries

    KAUST Repository

    La Mantia, F.

    2013-06-01

    Despite the high attention drawn to the lithium-ion batteries by the scientific and industrial community, most of the electrochemical characterization is carried out using poor reference electrodes or even no reference electrode. In this case, the performances of the active material are inaccurate, especially at high current densities. In this work we show the error committed in neglecting the polarizability of lithium counter electrodes, and we propose two reference electrodes to use in organic electrolytes based on lithium salts, namely Li4Ti5O12 and LiFePO 4. In particular, it was observed that, the polarizability of the metallic lithium counter electrode has a relevant stochastic component, which renders measurements at high current densities (above 1 mA·cm - 2) in two electrode cells non reproducible.

  5. Role of Amines in Thermal-Runaway-Mitigating Lithium-Ion Battery.

    Science.gov (United States)

    Shi, Yang; Noelle, Daniel J; Wang, Meng; Le, Anh V; Yoon, Hyojung; Zhang, Minghao; Meng, Ying Shirley; Qiao, Yu

    2016-11-16

    Benzylamine (BA), dibenzylamine (DBA), and trihexylamine (THA) are investigated as thermal-runaway retardants (TRR) for lithium-ion batteries (LIBs). In a LIB, TRR is packaged separately and released when internal shorting happens, so as to suppress exothermic reactions and slow down temperature increase. THA is identified as the most efficient TRR. Upon nail penetration, 4 wt % THA can reduce the peak temperature by nearly 50%. The working mechanisms of the three amines are different: THA is highly wettable to the separator and immiscible with the electrolyte, and therefore, it blocks lithium-ion (Li + ) transport. BA and DBA decrease the ionic conductivity of electrolyte and increase the charge transfer resistance. All three amines react with charged electrodes; the reactions of DBA and THA do not have much influence on the overall heat generation, while the reaction of BA cannot be ignored.

  6. Novel Energy Sources -Material Architecture and Charge Transport in Solid State Ionic Materials for Rechargeable Li ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Katiyar, Ram S; Gómez, M; Majumder, S B; Morell, G; Tomar, M S; Smotkin, E; Bhattacharya, P; Ishikawa, Y

    2009-01-19

    Since its introduction in the consumer market at the beginning of 1990s by Sony Corporation ‘Li-ion rechargeable battery’ and ‘LiCoO2 cathode’ is an inseparable couple for highly reliable practical applications. However, a separation is inevitable as Li-ion rechargeable battery industry demand more and more from this well serving cathode. Spinel-type lithium manganate (e.g., LiMn2O4), lithium-based layered oxide materials (e.g., LiNiO2) and lithium-based olivine-type compounds (e.g., LiFePO4) are nowadays being extensively studied for application as alternate cathode materials in Li-ion rechargeable batteries. Primary goal of this project was the advancement of Li-ion rechargeable battery to meet the future demands of the energy sector. Major part of the research emphasized on the investigation of electrodes and solid electrolyte materials for improving the charge transport properties in Li-ion rechargeable batteries. Theoretical computational methods were used to select electrodes and electrolyte material with enhanced structural and physical properties. The effect of nano-particles on enhancing the battery performance was also examined. Satisfactory progress has been made in the bulk form and our efforts on realizing micro-battery based on thin films is close to give dividend and work is progressing well in this direction.

  7. Carbon-Based Materials for Lithium-Ion Batteries, Electrochemical Capacitors, and Their Hybrid Devices.

    Science.gov (United States)

    Yao, Fei; Pham, Duy Tho; Lee, Young Hee

    2015-07-20

    A rapidly developing market for portable electronic devices and hybrid electrical vehicles requires an urgent supply of mature energy-storage systems. As a result, lithium-ion batteries and electrochemical capacitors have lately attracted broad attention. Nevertheless, it is well known that both devices have their own drawbacks. With the fast development of nanoscience and nanotechnology, various structures and materials have been proposed to overcome the deficiencies of both devices to improve their electrochemical performance further. In this Review, electrochemical storage mechanisms based on carbon materials for both lithium-ion batteries and electrochemical capacitors are introduced. Non-faradic processes (electric double-layer capacitance) and faradic reactions (pseudocapacitance and intercalation) are generally explained. Electrochemical performance based on different types of electrolytes is briefly reviewed. Furthermore, impedance behavior based on Nyquist plots is discussed. We demonstrate the influence of cell conductivity, electrode/electrolyte interface, and ion diffusion on impedance performance. We illustrate that relaxation time, which is closely related to ion diffusion, can be extracted from Nyquist plots and compared between lithium-ion batteries and electrochemical capacitors. Finally, recent progress in the design of anodes for lithium-ion batteries, electrochemical capacitors, and their hybrid devices based on carbonaceous materials are reviewed. Challenges and future perspectives are further discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Mechanism of Formation of Li 7 P 3 S 11 Solid Electrolytes through Liquid Phase Synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yuxing [Energy; Lu, Dongping [Energy; Bowden, Mark [Environmental; El Khoury, Patrick Z. [Environmental; Han, Kee Sung [Environmental; Deng, Zhiqun Daniel [Energy; Xiao, Jie [Energy; Zhang, Ji-Guang [Energy; Liu, Jun [Energy

    2018-01-22

    Crystalline Li7P3S11 is a promising solid electrolyte for all solid state lithium/lithium ion batteries. A controllable liquid phase synthesis of Li7P3S11 is more desirable compared to conventional mechanochemical synthesis, but recent attempts suffer from reduced ionic conductivities. Here we elucidate the formation mechanism of crystalline Li7P3S11 synthesized in the liquid phase (acetonitrile, or ACN). We conclude that the crystalline Li7P3S11 forms through a two-step reaction: 1) formation of solid Li3PS4∙ACN and amorphous Li2S∙P2S5 phases in the liquid phase; 2) solid-state conversion of the two phases. The implication of this two-step reaction mechanism to the morphology control and the transport properties of liquid phase synthesized Li7P3S11 is identified and discussed.

  9. Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode

    Science.gov (United States)

    Gao, Jing; Sun, Chunshui; Xu, Lei; Chen, Jian; Wang, Chong; Guo, Decai; Chen, Hao

    2018-04-01

    Due to flexible property and light weight, the lithiated Nafion membrane swollen with PC (PC-Li-Nafion) has been employed as both solid-state electrolyte and separator to fabricate solid-state Li-S cells. The electrochemical measurements of PC-Li-Nafion membrane show that its Li-ion transference number is 0.928, ionic conductivity of 2.1 × 10-4 S cm-1 can be achieved at 70 °C and its electrochemical window is 0 ∼ +4.1 V vs. Li+/Li. It is observed that the Li dendrites are suppressed by using PC-Li-Nafion membrane due to its single-ion conducting property. The amounts of Li-Nafion resin binder and conductive carbon in the cathode are optimized as 40% and 10% respectively to make a balance of ionic and electronic conductivities. A thin-layer Li-Nafion resin with a thickness of around 2 μm is fabricated between the cathode and PC-Li-Nafion membrane to improve the interfacial contact and further enhance the specific capacity of the cell. When measured at 70 °C, the Li-S cell delivers a reversible specific capacity of 1072.8 mAh g-1 (S) at 0.05 C and 895 mAh g-1 (S) at 1 C. The capacity retention at 1 C is 89% after 100 cycles. These results suggest that high-performance solid-state Li-S cells can be fabricated with the Li-Nafion polymer electrolyte.

  10. Protected Lithium-Metal Anodes in Batteries: From Liquid to Solid.

    Science.gov (United States)

    Yang, Chunpeng; Fu, Kun; Zhang, Ying; Hitz, Emily; Hu, Liangbing

    2017-09-01

    High-energy lithium-metal batteries are among the most promising candidates for next-generation energy storage systems. With a high specific capacity and a low reduction potential, the Li-metal anode has attracted extensive interest for decades. Dendritic Li formation, uncontrolled interfacial reactions, and huge volume effect are major hurdles to the commercial application of Li-metal anodes. Recent studies have shown that the performance and safety of Li-metal anodes can be significantly improved via organic electrolyte modification, Li-metal interface protection, Li-electrode framework design, separator coating, and so on. Superior to the liquid electrolytes, solid-state electrolytes are considered able to inhibit problematic Li dendrites and build safe solid Li-metal batteries. Inspired by the bright prospects of solid Li-metal batteries, increasing efforts have been devoted to overcoming the obstacles of solid Li-metal batteries, such as low ionic conductivity of the electrolyte and Li-electrolyte interfacial problems. Here, the approaches to protect Li-metal anodes from liquid batteries to solid-state batteries are outlined and analyzed in detail. Perspectives regarding the strategies for developing Li-metal anodes are discussed to facilitate the practical application of Li-metal batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Effects of crown ethers in nanocomposite silica-gel electrolytes on the performance of quasi-solid-state dye-sensitized solar cells

    KAUST Repository

    Huang, Kuan-Chieh

    2010-04-01

    The effects of crown ethers (CEs) on the performance of quasi-solid-state dye-sensitized solar cells (DSSCs) have been investigated. Nanocomposite silica was used to form gel matrices in the electrolytes, which contained lithium iodide (LiI) and iodine (I2) in 3-methoxypropionitrile (MPN) solvent. Three types of CEs, 12-crown-4 (12-C-4), 15-crown-5 (15-C-5), and 18-crown-6 (18-C-6) were used as additives to the gel electrolytes. DSSCs containing CEs showed enhancements in solar-to-electricity conversion efficiencies (η), with reference to the one without them. The crown ether, 15-C-5, with a size of cavity matching with the size of Li+ in the electrolyte rendered for its DSSC the best performance with an η of 3.60%, under 100 mW/cm2 illumination, as compared to 2.44% for the cell without any CE. Enhancements in the photovoltaic parameters of the cells with the CEs were explained based on the binding abilities of the CEs with lithium ions (Li+) in the electrolyte. Linear sweep voltammetry (LSV) measurements and electrochemical impedance spectra were used to substantiate the explanations. © 2009 Elsevier B.V. All rights reserved.

  12. Piperidinium tethered nanoparticle-hybrid electrolyte for lithium metal batteries

    KAUST Repository

    Korf, Kevin S.

    2014-06-23

    We report on the synthesis of novel piperidinium-based ionic liquid tethered nanoparticle hybrid electrolytes and investigate their physical and electrochemical properties. Hybrid electrolytes based on the ionic liquid 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfone) imide covalently tethered to silica nanoparticles (SiO2-PP-TFSI) were blended with propylene carbonate-1 M lithium bis(trifluoromethanesulfone) imide (LiTFSI). We employed NMR analysis to confirm the successful creation of the hybrid material. Dielectric and rheological measurements show that these electrolytes exhibit exceptional room-temperature DC ionic conductivity (10-2 to 10 -3 S cm-1) as well as high shear mechanical moduli (105 to 106 Pa). Lithium transference numbers were found to increase with particle loading and to reach values as high as 0.22 at high particle loadings where the particle jam to form a soft glassy elastic medium. Analysis of lithium electrodeposits obtained in the hybrid electrolytes using SEM and EDX spectra show that the SiO2-PP-TFSI nanoparticles are able to smooth lithium deposition and inhibit lithium dendrite proliferation in Li metal batteries. LTOSiO2-PP-TFSI/PC in 1 M LiTFSILi half-cells based on the SiO2-PP-TFSI hybrid electrolytes exhibit attractive voltage profiles and trouble-free extended cycling behavior over more than 1000 cycles of charge and discharge. This journal is © the Partner Organisations 2014.

  13. A novel class of halogen-free, super-conductive lithium argyrodites: Synthesis and characterization

    Science.gov (United States)

    Schneider, Holger; Du, Hui; Kelley, Tracy; Leitner, Klaus; ter Maat, Johan; Scordilis-Kelley, Chariclea; Sanchez-Carrera, Roel; Kovalev, Igor; Mudalige, Anoma; Kulisch, Jörn; Safont-Sempere, Marina M.; Hartmann, Pascal; Weiβ, Thomas; Schneider, Ling; Hinrichsen, Bernd

    2017-10-01

    Solid electrolytes are the core components for many next generation lithium battery concepts such as all-solid-state batteries (ASSB) or batteries based on metallic lithium anodes protected by a ceramic or composite passivation layer. Therefore, the search for new solid state Li-ion conductors with superior properties and improved electrochemical stabilities remains of high interest. In this work, the synthesis of a new class of silicon-containing, sulfide-based lithium-ion conductors is reported. Very good conductivities of up to ∼2.0-3.0·10-3 S/cm could be achieved for compositions such as Li22SiP2S18, among the highest for silicon sulfide containing materials. Based on the recorded powder XRD diffraction patterns and simulations it could be confirmed that they constitute novel members of the argyrodite family of sulfide lithium-ion conductors. The cubic high-temperature modification of such argyrodites with high lithium-ion conductivity can therefore be stabilized by implementation of silicon into the lattice, while additional doping with halogen atoms is not necessary.

  14. Kinetics Tuning the Electrochemistry of Lithium Dendrites Formation in Lithium Batteries through Electrolytes

    International Nuclear Information System (INIS)

    Tao, Ran; Bi, Xuanxuan; The Ohio State University, Columbus, OH; Li, Shu; Yao, Ying

    2017-01-01

    Lithium batteries are one of the most advance energy storage devices in the world and have attracted extensive research interests. However, lithium dendrite growth was a safety issue which handicapped the application of pure lithium metal in the negative electrode. In this paper, two solvents, propylene carbonate (PC) and 2-methyl-tetrahydrofuran (2MeTHF), and four Li"+ salts, LiPF_6, LiAsF_6, LiBF_4 and LiClO_4 were investigated in terms of their effects on the kinetics of lithium dendrite formation in eight electrolyte solutions. The kinetic parameters of charge transfer step (exchange current density, j_0, transfer coefficient, α) of Li"+/Li redox system, the mass transfer parameters of Li"+ (transfer number of Li"+, t_L_i_+, diffusion coefficient of Li"+, D_L_i_+), and the conductivity (κ) of each electrolyte were studied separately. The results demonstrate that the solvents play a critical role in the measured j_0, t_L_i_+, D_L_i_+, and κ of the electrolyte, while the choice of Li"+ salts only slightly affect the measured parameters. Finally, the understanding of the kinetics will gain insight into the mechanism of lithium dendrite formation and provide guidelines to the future application of lithium metal.

  15. Redox Species-Based Electrolytes for Advanced Rechargeable Lithium Ion Batteries

    KAUST Repository

    Ming, Jun; Li, Mengliu; Kumar, Pushpendra; Lu, Ang-Yu; Wahyudi, Wandi; Li, Lain-Jong

    2016-01-01

    Seeking high-capacity cathodes has become an intensive effort in lithium ion battery research; however, the low energy density still remains a major issue for sustainable handheld devices and vehicles. Herein, we present a new strategy

  16. Impedance spectroscopy of ceramic solid electrolytes

    International Nuclear Information System (INIS)

    Muccillo, R.; Cosentino, I.C.; Florio, D.Z. de; Franca, Y.V.

    1996-01-01

    The Impedance Spectroscopy (IS) technique has been used to the study of Th O 2 :Y 2 O 3 , Zr O 2 :La 2 O 3 and Zr O 2 :Y 2 O 3 solid electrolytes. The results show that solid solution has been attained, grain boundaries act as oxygen-ion blockers, and the importance of the IS technique to study phase transformation in ceramics. (author)

  17. Solid State Ionic Materials - Proceedings of the 4th Asian Conference on Solid State Ionics

    Science.gov (United States)

    Chowdari, B. V. R.; Yahaya, M.; Talib, I. A.; Salleh, M. M.

    1994-07-01

    The Table of Contents for the full book PDF is as follows: * Preface * I. INVITED PAPERS * Diffusion of Cations and Anions in Solid Electrolytes * Silver Ion Conductors in the Crystalline State * NMR Studies of Superionic Conductors * Hall Effect and Thermoelectric Power in High Tc Hg-Ba-Ca-Cu-O Ceramics * Solid Electrolyte Materials Prepared by Sol-Gel Chemistry * Preparation of Proton-Conducting Gel Films and their Application to Electrochromic Devices * Thin Film Fuel Cells * Zirconia based Solid Oxide Ion Conductors in Solid Oxide Fuel Cells * The Influence of Anion Substitution on Some Phosphate-based Ion Conducting Glasses * Lithium Intercalation in Carbon Electrodes and its Relevance in Rocking Chair Batteries * Chemical Sensors using Proton Conducting Ceramics * NMR/NQR Studies of Y-Ba-Cu-O Superconductors * Silver Molybdate Glasses and Battery Systems * New Highly Conducting Polymer Ionics and their Application in Electrochemical Devices * Study of Li Electrokinetics on Oligomeric Electrolytes using Microelectrodes * Calculation of Conductivity for Mixed-Phase Electrolytes PEO-MX-Immiscible Additive by Means of Effective Medium Theory * II. CONTRIBUTED PAPERS * Phase Relationship and Electrical Conductivity of Sr-V-O System with Vanadium Suboxide * Amorphous Li+ Ionic Conductors in Li2SO4-Li2O-P2O5 System * Fast Ion Transport in KCl-Al2O3 Composites * The Effect of the Second Phase Precipitation on the Ionic Conductivity of Zr0.85Mg0.15O1.85 * Conductivity Measurements and Phase Relationships in CaCl2-CaHCl Solid Electrolyte * Relationships Between Crystal Structure and Sodium Ion Conductivity in Na7Fe4(AsO4)6 and Na3Al2(AsO4)3 * Electrical Conductivity and Solubility Limit of Ti4+ Ion in Na1+x TiyZr2-ySixP3-xO12 System * Study on Sodium Fast Ion Conductors of Na1+3xAlxTi2-xSi2xP3-2xO12 System * Influences of Zirconia on the Properties of β''-Alumina Ceramics * Decay of Luminescence from Cr3+ Ions in β-Alumina * Lithium Ion Conductivity in the Li4XO4-Li2

  18. Development of Sulfide Solid Electrolytes and Interface Formation Processes for Bulk-Type All-Solid-State Li and Na Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Hayashi, Akitoshi, E-mail: hayashi@chem.osakafu-u.ac.jp [Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka (Japan); Sakuda, Atsushi [Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka (Japan); Department of Energy and Environment, Research Institute of Electrochemical Energy, National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka (Japan); Tatsumisago, Masahiro [Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka (Japan)

    2016-07-15

    All-solid-state batteries with inorganic solid electrolytes (SEs) are recognized as an ultimate goal of rechargeable batteries because of their high safety, versatile geometry, and good cycle life. Compared with thin-film batteries, increasing the reversible capacity of bulk-type all-solid-state batteries using electrode active material particles is difficult because contact areas at solid–solid interfaces between the electrode and electrolyte particles are limited. Sulfide SEs have several advantages of high conductivity, wide electrochemical window, and appropriate mechanical properties, such as formability, processability, and elastic modulus. Sulfide electrolyte with Li{sub 7}P{sub 3}S{sub 11} crystal has a high Li{sup +} ion conductivity of 1.7 × 10{sup −2} S cm{sup −1} at 25°C. It is far beyond the Li{sup +} ion conductivity of conventional organic liquid electrolytes. The Na{sup +} ion conductivity of 7.4 × 10{sup −4} S cm{sup −1} is achieved for Na{sub 3.06}P{sub 0.94}Si{sub 0.06}S{sub 4} with cubic structure. Moreover, formation of favorable solid–solid interfaces between electrode and electrolyte is important for realizing solid-state batteries. Sulfide electrolytes have better formability than oxide electrolytes. Consequently, a dense electrolyte separator and closely attached interfaces with active material particles are achieved via “room-temperature sintering” of sulfides merely by cold pressing without heat treatment. Elastic moduli for sulfide electrolytes are smaller than that of oxide electrolytes, and Na{sub 2}S–P{sub 2}S{sub 5} glass electrolytes have smaller Young’s modulus than Li{sub 2}S–P{sub 2}S{sub 5} electrolytes. Cross-sectional SEM observations for a positive electrode layer reveal that sulfide electrolyte coating on active material particles increases interface areas even with a minimum volume of electrolyte, indicating that the energy density of bulk-type solid-state batteries is enhanced. Both surface coating

  19. Lithium and sodium batteries with polysulfide electrolyte

    KAUST Repository

    Li, Mengliu; Ming, Jun; Li, Lain-Jong

    2017-01-01

    A battery comprising: at least one cathode, at least one anode, at least one battery separator, and at least one electrolyte disposed in the separator, wherein the anode is a lithium metal or lithium alloy anode or an anode adapted for intercalation

  20. NREL/NASA Internal Short-Circuit Instigator in Lithium Ion Cells

    Energy Technology Data Exchange (ETDEWEB)

    Keyser, Matthew; Long, Dirk; Pesaran, Ahmad; Darcy, Eric; Shoesmith, Mark; McCarthy, Ben

    2015-10-11

    Lithium-ion cells provide the highest specific energy (>280 Wh/kg) and energy density (>600 Wh/L) rechargeable battery building block to date with the longest life. Electrode/electrolyte thermal instability and flammability of the electrolyte of Li-ion cells make them prone to catastrophic thermal runaway under some rare internal short circuit conditions. Despite extensive QC/QA, standardized industry safety testing, and over 18 years of manufacturing experience, major recalls have taken place and incidents still occur. Many safety incidents that take place in the field originate due to an internal short that was not detectable or predictable at the point of manufacture. The Internal Short-Circuit Instigator can be used to study types of separators, non-flammable electrolytes, electrolyte additives, fusible tabs, propagation studies, and gas generation within a cell.

  1. Confined SnO2 quantum-dot clusters in graphene sheets as high-performance anodes for lithium-ion batteries

    OpenAIRE

    Zhu, Chengling; Zhu, Shenmin; Zhang, Kai; Hui, Zeyu; Pan, Hui; Chen, Zhixin; Li, Yao; Zhang, Di; Wang, Da-Wei

    2016-01-01

    Construction of metal oxide nanoparticles as anodes is of special interest for next-generation lithium-ion batteries. The main challenge lies in their rapid capacity fading caused by the structural degradation and instability of solid-electrolyte interphase (SEI) layer during charge/discharge process. Herein, we address these problems by constructing a novel-structured SnO2-based anode. The novel structure consists of mesoporous clusters of SnO2 quantum dots (SnO2 QDs), which are wrapped with...

  2. Micro-sized organometallic compound of ferrocene as high-performance anode material for advanced lithium-ion batteries

    Science.gov (United States)

    Liu, Zhen; Feng, Li; Su, Xiaoru; Qin, Chenyang; Zhao, Kun; Hu, Fang; Zhou, Mingjiong; Xia, Yongyao

    2018-01-01

    An organometallic compound of ferrocene is first investigated as a promising anode for lithium-ion batteries. The electrochemical properties of ferrocene are conducted by galvanostatic charge and discharge. The ferrocene anode exhibits a high reversible capacity and great cycling stability, as well as superior rate capability. The electrochemical reaction of ferrocene is semi-reversible and some metallic Fe remains in the electrode even after delithiation. The metallic Fe formed in electrode and the stable solid electrolyte interphase should be responsible for its excellent electrochemical performance.

  3. Thermally-responsive, nonflammable phosphonium ionic liquid electrolytes for lithium metal batteries: operating at 100 degrees celsius.

    Science.gov (United States)

    Lin, X; Kavian, R; Lu, Y; Hu, Q; Shao-Horn, Y; Grinstaff, M W

    2015-11-13

    Rechargeable batteries such as Li ion/Li metal batteries are widely used in the electronics market but the chemical instability of the electrolyte limits their use in more demanding environmental conditions such as in automotive, oil exploration, or mining applications. In this study, a series of alkyl phosphonium ionic liquid electrolyte are described with high thermal stability and solubility for LiTFSI. A lithium metal battery (LMB) containing a tailored phosphonium ionic liquid/LiTFSI electrolyte operates at 100 °C with good specific capacities and cycling stability. Substantial capacity is maintained during 70 cycles or 30 days. Instant on-off battery operation is realized via the significant temperature dependence of the electrolyte material, demonstrating the robustness and potential for use at high temperature.

  4. In-situ measurement of the lithium distribution in Li-ion batteries using micro-IBA techniques

    International Nuclear Information System (INIS)

    Yamazaki, A.; Orikasa, Y.; Chen, K.; Uchimoto, Y.; Kamiya, T.; Koka, M.; Satoh, T.; Mima, K.; Kato, Y.; Fujita, K.

    2016-01-01

    Direct observation of lithium concentration distribution in lithium-ion battery composite electrodes has been performed for the first time. Lithium-ion battery model cells for particle induced X-ray emission (PIXE) and particle induced gamma ray emission (PIGE) measurements were designed and fabricated. Two dimensional images of lithium concentration in LiFePO_4 composite electrodes were obtained with PIXE and PIGE by scanning the proton microbeam for various charged states of the electrodes. Lithium concentration in LiFePO_4 composite electrodes was decreased from the contact interface between LiFePO_4 electrode and liquid electrolyte during the charge reaction.

  5. Electrochemical behavior of LiCoO2 as aqueous lithium-ion battery electrodes

    KAUST Repository

    Ruffo, Riccardo

    2009-02-01

    Despite the large number of studies on the behavior of LiCoO2 in organic electrolytes and its recent application as a positive electrode in rechargeable water battery prototypes, a little information is available about the lithium intercalation reaction in this layered compound in aqueous electrolytes. This work shows that LiCoO2 electrodes can be reversibly cycled in LiNO3 aqueous electrolytes for tens of cycles at remarkably high rates with impressive values specific capacity higher than 100 mAh/g, and with a coulomb efficiency greater than 99.7%. Stable and reproducible cycling measurements have been made using a simple cell design that can be easily applied to the study of other intercalation materials, assuming that they are stable in water and that their intercalation potential range matches the electrochemical stability window of the aqueous electrolyte. The experimental arrangement uses a three-electrode flooded cell in which another insertion compound acts as a reversible source and sink of lithium ions, i.e., as the counter electrode. A commercial reference electrode is also present. Both the working and the counter electrodes have been prepared as thin layers on a metallic substrate using the procedures typical for the study of electrodes for lithium-ion batteries in organic solvent electrolytes. © 2008 Elsevier B.V. All rights reserved.

  6. The Incorporation of Lithium Alloying Metals into Carbon Matrices for Lithium Ion Battery Anodes

    Science.gov (United States)

    Hays, Kevin A.

    An increased interest in renewable energies and alternative fuels has led to recognition of the necessity of wide scale adoption of the electric vehicle. Automotive manufacturers have striven to produce an electric vehicle that can match the range of their petroleum-fueled counterparts. However, the state-of-the-art lithium ion batteries used to power the current offerings still do not come close to the necessary energy density. The energy and power densities of the lithium ion batteries must be increased significantly if they are going to make electric vehicles a viable option. The chemistry of the lithium ion battery, based on lithium cobalt oxide cathodes and graphite anodes, is limited by the amount of lithium the cathode can provide and the anode will accept. While these materials have proven themselves in portable electronics over the past two decades, plausible higher energy alternatives do exist. The focus is of this study is on anode materials that could achieve a capacity of more than 3 times greater than that of graphite anodes. The lithium alloying anode materials investigated and reported herein include tin, arsenic, and gallium arsenide. These metals were synthesized with nanoscale dimensions, improving their electrochemical and mechanical properties. Each exhibits their own benefits and challenges, but all display opportunities for incorporation in lithium ion batteries. Tin is incorporated in multilayer graphene nanoshells by introducing small amounts of metal in the core and, separately, on the outside of these spheres. Electrolyte decomposition on the anode limits cycle life of the tin cores, however, tin vii oxides introduced outside of the multilayer graphene nanoshells have greatly improved long term battery performance. Arsenic is a lithium alloying metal that has largely been ignored by the research community to date. One of the first long term battery performance tests of arsenic is reported in this thesis. Anodes were made from nanoscale

  7. Ion and solvent diffusion and ion conduction of PC-DEC and PC-DME binary solvent electrolytes of LiN(SO2CF3)2

    International Nuclear Information System (INIS)

    Hayamizu, Kikuko; Aihara, Yuichi

    2004-01-01

    Two binary mixed solvent systems typically used for lithium batteries were studied by measuring the self-diffusion coefficients of the solvent, lithium ion and anion, independently by using the multi-nuclear pulsed field-gradient spin-echo (PGSE) 1 H, 7 Li and 19 F NMR method. One system was propylene carbonate (PC) and diethyl carbonate (DEC) system and the other binary system was PC and 1,2-dimethoxyethane (DME), and the lithium salt used was LiN(SO 2 CF 3 ) 2 (LiTFSI). The relative ratio of the PC was changed from zero (pure DME and DEC) to 100% (pure PC) in the DME-PC and the DEC-PC systems, respectively. The self-diffusion coefficients of the solvents were measured with and without the lithium salt, and the two solvents had almost the same diffusion coefficient in the DEC-PC system, while DME diffused faster than PC in the DME-PC system. In the electrolytes the solvents diffused the fastest, followed by the anion with the lithium ion diffusing the slowest. The degree of ion dissociation was estimated for each electrolyte by comparing the ionic conductivities estimated from the ion diffusion and those measured directly by the electrochemical method

  8. An insight into intrinsic interfacial properties between Li metals and Li10GeP2S12 solid electrolytes.

    Science.gov (United States)

    Chen, Bingbing; Ju, Jiangwei; Ma, Jun; Zhang, Jianjun; Xiao, Ruijuan; Cui, Guanglei; Chen, Liquan

    2017-11-29

    Density functional theory simulations and experimental studies were performed to investigate the interfacial properties, including lithium ion migration kinetics, between lithium metal anode and solid electrolyte Li 10 GeP 2 S 12 (LGPS). The LGPS[001] plane was chosen as the studied surface because the easiest Li + migration pathway is along this direction. The electronic structure of the surface states indicated that the electrochemical stability was reduced at both the PS 4 - and GeS 4 -teminated surfaces. For the interface cases, the equilibrium interfacial structures of lithium metal against the PS 4 -terminated LGPS[001] surface (Li/PS 4 -LGPS) and the GeS 4 -terminated LGPS[001] surface (Li/GeS 4 -LGPS) were revealed based on the structural relaxation and adhesion energy analysis. Solid electrolyte interphases were expected to be formed at both Li/PS 4 -LGPS and Li/GeS 4 -LGPS interfaces, resulting in an unstable state of interface and large interfacial resistance, which was verified by the EIS results of the Li/LGPS/Li cell. In addition, the simulations of the migration kinetics show that the energy barriers for Li + crossing the Li/GeS 4 -LGPS interface were relatively low compared with the Li/PS 4 -LGPS interface. This may contribute to the formation of Ge-rich phases at the Li/LGPS interface, which can tune the interfacial structures to improve the ionic conductivity for future all-solid-state batteries. This work will offer a thorough understanding of the Li/LGPS interface, including local structures, electronic states and Li + diffusion behaviors in all-solid-state batteries.

  9. Advanced Surface and Microstructural Characterization of Natural Graphite Anodes for Lithium Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Gallego, Nidia C [ORNL; Contescu, Cristian I [ORNL; Meyer III, Harry M [ORNL; Howe, Jane Y [ORNL; Meisner, Roberta Ann [ORNL; Payzant, E Andrew [ORNL; Lance, Michael J [ORNL; Yoon, Steve [A123 Systems, Inc.; Denlinger, Matthew [A123 Systems, Inc.; Wood III, David L [ORNL

    2014-01-01

    Natural graphite powders were subjected to a series of thermal treatments in order to improve the anode irreversible capacity loss (ICL) and capacity retention during long-term cycling of lithium ion batteries. A baseline thermal treatment in inert Ar or N2 atmosphere was compared to cases with a proprietary additive to the furnace gas environment. This additive substantially altered the surface chemistry of the natural graphite powders and resulted in significantly improved long-term cycling performance of the lithium ion batteries over the commercial natural graphite baseline. Different heat-treatment temperatures were investigated ranging from 950-2900 C with the intent of achieving the desired long-term cycling performance with as low of a maximum temperature and thermal budget as possible. A detailed summary of the characterization data is also presented, which includes X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and temperature-programed desorption mass spectroscopy (TPD-MS). This characterization data was correlated to the observed capacity fade improvements over the course of long-term cycling at high charge-discharge rates in full lithium-ion coin cells. It is believed that the long-term performance improvements are a result of forming a more stable solid electrolyte interface (SEI) layer on the anode graphite surfaces, which is directly related to the surface chemistry modifications imparted by the proprietary gas environment during thermal treatment.

  10. Lithium-ion battery electrolyte emissions analyzed by coupled thermogravimetric/Fourier-transform infrared spectroscopy

    Science.gov (United States)

    Bertilsson, Simon; Larsson, Fredrik; Furlani, Maurizio; Albinsson, Ingvar; Mellander, Bengt-Erik

    2017-10-01

    In the last few years the use of Li-ion batteries has increased rapidly, powering small as well as large applications, from electronic devices to power storage facilities. The Li-ion battery has, however, several safety issues regarding occasional overheating and subsequent thermal runaway. During such episodes, gas emissions from the electrolyte are of special concern because of their toxicity, flammability and the risk for gas explosion. In this work, the emissions from heated typical electrolyte components as well as from commonly used electrolytes are characterized using FT-IR spectroscopy and FT-IR coupled with thermogravimetric (TG) analysis, when heating up to 650 °C. The study includes the solvents EC, PC, DEC, DMC and EA in various single, binary and ternary mixtures with and without the LiPF6 salt, a commercially available electrolyte, (LP71), containing EC, DEC, DMC and LiPF6 as well as extracted electrolyte from a commercial 6.8 Ah Li-ion cell. Upon thermal heating, emissions of organic compounds and of the toxic decomposition products hydrogen fluoride (HF) and phosphoryl fluoride (POF3) were detected. The electrolyte and its components have also been extensively analyzed by means of infrared spectroscopy for identification purposes.

  11. An Insoluble Benzoquinone-Based Organic Cathode for Use in Rechargeable Lithium-Ion Batteries.

    Science.gov (United States)

    Luo, Zhiqiang; Liu, Luojia; Zhao, Qing; Li, Fujun; Chen, Jun

    2017-10-02

    Application of organic electrode materials in rechargeable batteries has attracted great interest because such materials contain abundant carbon, hydrogen, and oxygen elements. However, organic electrodes are highly soluble in organic electrolytes. An organic electrode of 2,3,5,6-tetraphthalimido-1,4-benzoquinone (TPB) is reported in which rigid groups coordinate to a molecular benzoquinone skeleton. The material is insoluble in aprotic electrolyte, and demonstrates a high capacity retention of 91.4 % (204 mA h g -1 ) over 100 cycles at 0.2 C. The extended π-conjugation of the material contributes to enhancement of the electrochemical performance (155 mA h g -1 at 10 C). Moreover, density functional theory calculations suggest that favorable synergistic reactions between multiple carbonyl groups and lithium ions can enhance the initial lithium ion intercalation potential. The described approach may provide a novel entry to next-generation organic electrode materials with relevance to lithium-ion batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Conductivity of liquid lithium electrolytes with dispersed mesoporous silica particles

    International Nuclear Information System (INIS)

    Sann, K.; Roggenbuck, J.; Krawczyk, N.; Buschmann, H.; Luerßen, B.; Fröba, M.; Janek, J.

    2012-01-01

    Highlights: ► The conductivity of disperse lithium electrolytes with mesoporous fillers is studied. ► In contrast to other investigations in literature, no conductivity enhancement could be observed for standard battery electrolytes and typical mesoporous fillers in various combinations. ► Disperse electrolytes can become relevant in terms of battery safety. ► Dispersions of silicas and electrolyte with LiPF 6 as conducting salt are not stable, although the silicas were dried prior to preparation and the electrolyte water content was controlled. Surface modification of the fillers improved the stability. ► The observed conductivity decrease varied considerably for various fillers. - Abstract: The electrical conductivity of disperse electrolytes was systematically measured as a function of temperature (0 °C to 60 °C) and filler content for different types of fillers with a range of pore geometry, pore structure and specific surface area. As fillers mesoporous silicas SBA-15, MCM-41 and KIT-6 with pore ranges between 3 nm and 15 nm were dispersed in commercially available liquid lithium electrolytes. As electrolytes 1 M of lithium hexafluorophosphate (LiPF 6 ) in a mixture of ethylene carbonate (EC) and diethylene carbonate (DEC) at the ratio 3:7 (wt/wt) and the same solvent mixture with 0.96 M lithium bis(trifluoromethanesulfon)imide (LiTFSI) were used. No conductivity enhancement could be observed, but with respect to safety aspects the highly viscous disperse pastes might be useful. The conductivity decrease varied considerably for the different fillers.

  13. Energy landscapes for mobile ions in ion conducting solids

    Indian Academy of Sciences (India)

    molecular dynamics (MD) simulations yields quantitative predictions of the ion transport characteristics. As ... Solid electrolytes; bond valence analysis; ion transport in glasses. 1. .... clusters are considered to contribute only to a.c. conduc-.

  14. AC impedance electrochemical modeling of lithium-ion positive electrodes

    International Nuclear Information System (INIS)

    Dees, D.; Gunen, E.; Abraham, D.; Jansen, A.; Prakash, J.

    2004-01-01

    Under Department of Energy's Advanced Technology Development Program,various analytical diagnostic studies are being carried out to examine the lithium-ion battery technology for hybrid electric vehicle applications, and a series of electrochemical studies are being conducted to examine the performance of these batteries. An electrochemical model was developed to associate changes that were observed in the post-test analytical diagnostic studies with the electrochemical performance loss during testing of lithium ion batteries. While both electrodes in the lithium-ion cell have been studied using a similar electrochemical model, the discussion here is limited to modeling of the positive electrode. The positive electrode under study has a composite structure made of a layered nickel oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) active material, a carbon black and graphite additive for distributing current, and a PVDF binder all on an aluminum current collector. The electrolyte is 1.2M LiPF 6 dissolved in a mixture of EC and EMC and a Celgard micro-porous membrane is used as the separator. Planar test cells (positive/separator/negative) were constructed with a special fixture and two separator membranes that allowed the placement of a micro-reference electrode between the separator membranes (1). Electrochemical studies including AC impedance spectroscopy were then conducted on the individual electrodes to examine the performance and ageing effects in the cell. The model was developed by following the work of Professor Newman at Berkeley (2). The solid electrolyte interface (SEI) region, based on post-test analytical results, was assumed to be a film on the oxide and an oxide layer at the surface of the oxide. A double layer capacity was added in parallel with the Butler-Volmer kinetic expression. The pertinent reaction, thermodynamic, and transport equations were linearized for a small sinusoidal perturbation (3). The resulting system of differential equations was solved

  15. Electrode Materials for Lithium/Sodium-Ion Batteries

    DEFF Research Database (Denmark)

    Shen, Yanbin

    2014-01-01

    The synthesis of electrode materials for lithium/sodium ion batteries and their structural stability during lithium/sodium insertion/extraction are the two essential issues that have limited battery application in the fields requiring long cycle life and high safety. During her PhD studies, Yanbin...... Shen systematically investigated the controlled synthesis of electrode materials for lithium/sodium ion batteries. She also investigated their formation mechanisms and structural evolution during the operation of batteries using in situ/operando X-ray diffraction techniques. The research findings...... provide insights into formation mechanisms of Li4Ti5O12 anode material from both hydrothermal and solid-state reaction. The results also contribute to a thorough understanding of the intercalation and decay mechanisms of O3/P2 layered sodium cathode materials in sodium ion batteries....

  16. Mathematical modeling of the lithium deposition overcharge reaction in lithium-ion batteries using carbon-based negative electrodes

    International Nuclear Information System (INIS)

    Arora, P.; Doyle, M.; White, R.E.

    1999-01-01

    Two major issues facing lithium-ion battery technology are safety and capacity grade during cycling. A significant amount of work has been done to improve the cycle life and to reduce the safety problems associated with these cells. This includes newer and better electrode materials, lower-temperature shutdown separators, nonflammable or self-extinguishing electrolytes, and improved cell designs. The goal of this work is to predict the conditions for the lithium deposition overcharge reaction on the negative electrode (graphite and coke) and to investigate the effect of various operating conditions, cell designs and charging protocols on the lithium deposition side reaction. The processes that lead to capacity fading affect severely the cycle life and rate behavior of lithium-ion cells. One such process is the overcharge of the negative electrode causing lithium deposition, which can lead to capacity losses including a loss of active lithium and electrolyte and represents a potential safety hazard. A mathematical model is presented to predict lithium deposition on the negative electrode under a variety of operating conditions. The Li x C 6 vertical bar 1 M LiPF 6 , 2:1 ethylene carbonate/dimethyl carbonate, poly(vinylidene fluoride-hexafluoropropylene) vert b ar LiMn 2 O 4 cell is simulated to investigate the influence of lithium deposition on the charging behavior of intercalation electrodes. The model is used to study the effect of key design parameters (particle size, electrode thickness, and mass ratio) on the lithium deposition overcharge reaction. The model predictions are compared for coke and graphite-based negative electrodes. The cycling behavior of these cells is simulated before and after overcharge to understand the hazards and capacity fade problems, inherent in these cells, can be minimized

  17. Organic-inorganic hybrid polymer electrolytes based on polyether diamine, alkoxysilane, and trichlorotriazine: Synthesis, characterization, and electrochemical applications

    Science.gov (United States)

    Saikia, Diganta; Wu, Cheng-Gang; Fang, Jason; Tsai, Li-Duan; Kao, Hsien-Ming

    2014-12-01

    A new type of highly conductive organic-inorganic hybrid polymer electrolytes has been synthesized by the reaction of poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether), 2,4,6-trichloro-1,3,5-triazine and alkoxysilane precursor 3-(glycidyloxypropyl)trimethoxysilane, followed by doping of LiClO4. The 13C and 29Si solid-sate NMR results confirm the successful synthesis of the organic-inorganic hybrid structure. The solid hybrid electrolyte thus obtained exhibits a maximum ionic conductivity of 1.6 × 10-4 S cm-1 at 30 °C, which is the highest among the organic-inorganic hybrid electrolytes. The hybrid electrolytes are electrochemically stable up to 4.2 V. The prototype electrochromic device with such a solid hybrid electrolyte demonstrates a good coloration efficiency value of 183 cm2 C-1 with a cycle life over 200 cycles. For the lithium-ion battery test, the salt free solid hybrid membrane is swelled with a LiPF6-containing electrolyte solution to reach an acceptable ionic conductivity value of 6.5 × 10-3 S cm-1 at 30 °C. The battery cell carries an initial discharge capacity of 100 mAh g-1 at 0.2C-rate and a coulombic efficiency of about 95% up to 30 cycles without the sign of cell failure. The present organic-inorganic hybrid electrolytes hold promise for applications in electrochromic devices and lithium ion batteries.

  18. A lattice-gas model of the ion current across the solid interface: fast-ion conductor - intercalate

    International Nuclear Information System (INIS)

    Nachev, I.; Balkanski, M.

    1994-12-01

    The transport of Lithium ions across the material interface: fast-ion conducting glass - intercalate is simulated by a non-trivial lattice-gas model. The model takes explicitly into account the influence of the Coulomb correlations, the site-blocking effect and the boundary conditions on the ion kinetics. Potential device applications of the model are pointed out by computing the current density of Lithium ions for material parameters of the real interface: doped ternary borate glass - Indium Selenide, which constitute the electrolyte and the cathode, respectively, of a thin-film microbattery with improved performance. (author). 10 refs, 4 figs

  19. Predicting electrical and thermal abuse behaviours of practical lithium-ion cells from accelerating rate calorimeter studies on small samples in electrolyte

    Science.gov (United States)

    Richard, M. N.; Dahn, J. R.

    An accelerating rate calorimeter (ARC) is used to measure the thermal stability of de-intercalated Li 1+ xMn 2- xO 4 in LiPF 6 EC:DEC (33:67) electrolyte. Self-heating is detected well after the 80°C onset of self-heating measured for lithium intercalated mesocarbon microbead (MCMB) electrodes in LiPF 6 EC:DEC (33:67) electrolyte. As a result, the initial self-heating measured in a practical carbon/Li 1+ xMn 2- xO 4 lithium-ion cell is caused by reactions at the anode. In previous work, we have proposed a model for the reactions that cause self-heating in MCMB electrodes in electrolyte. By assuming that a cell self-heats only because reactions occur at the anode, the model can be used to predict the power generated by the amount of MCMB in practical cells with an inert cathode. The calculated chemically generated power can be combined with power loss measurements, due to the transfer of heat to the environment, to predict the short-circuit behaviour and the oven exposure behaviour for a cell containing an MCMB anode and an inert cathode. The results agree qualitatively with short-circuit and oven exposure results measured on NEC Moli energy 18650 cells containing an Li 1+ xMn 2- xO 4 cathode.

  20. In-situ measurement of the lithium distribution in Li-ion batteries using micro-IBA techniques

    Energy Technology Data Exchange (ETDEWEB)

    Yamazaki, A., E-mail: yamazaki@tac.tsukuba.ac.jp [Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 (Japan); Orikasa, Y.; Chen, K.; Uchimoto, Y. [Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-nihonmatsucho, Sakyo-ku, Kyoto 606-8501 (Japan); Kamiya, T.; Koka, M.; Satoh, T. [Takasaki Advanced Radiation Research Institute, Japan Atomic Energy Agency (JAEA), 1233, Watanuki-machi, Takasaki, Gunma 370-1292 (Japan); Mima, K.; Kato, Y.; Fujita, K. [The Graduate School for the Creation of New Photonics Industries, 1955-1, Kurematsu, NIshi-ku, Hamamatsu, Shizuoka 431-1202 (Japan)

    2016-03-15

    Direct observation of lithium concentration distribution in lithium-ion battery composite electrodes has been performed for the first time. Lithium-ion battery model cells for particle induced X-ray emission (PIXE) and particle induced gamma ray emission (PIGE) measurements were designed and fabricated. Two dimensional images of lithium concentration in LiFePO{sub 4} composite electrodes were obtained with PIXE and PIGE by scanning the proton microbeam for various charged states of the electrodes. Lithium concentration in LiFePO{sub 4} composite electrodes was decreased from the contact interface between LiFePO{sub 4} electrode and liquid electrolyte during the charge reaction.

  1. Methods for using novel cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    Science.gov (United States)

    Jacobson, Allan J.; Wang, Shuangyan; Kim, Gun Tae

    2016-01-12

    Methods using novel cathode, electrolyte and oxygen separation materials operating at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes include oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  2. Nitrogen dissociation during RF sputtering of Lipon electrolyte for all-solid-states batteries

    DEFF Research Database (Denmark)

    Stamate, Eugen; Christiansen, Ane Sælland; Holtappels, Peter

    2013-01-01

    Small size and high power density secondary batteries are desired for a large number of applications based on miniature wireless devices and sensors that need to be compatible with the microelectronic fabrication technology. This fact resulted in the development of solid electrolytes, like lithium...

  3. Simultaneous Extraction of Lithium and Hydrogen from Seawater

    Science.gov (United States)

    2011-01-26

    P2S5 glass ceramic membrane . The potential was scanned to 4V at the rate of 50mV/sec. Operating Conditions: Anode: carbon felt (0.5mm) Anolyte...significantly. Further, the ceramic membrane only allows diffusion of ions but prevents transport of bulk solution. Figure 8 shows the IC chromatogram...electrochemical process employing solid electrolytes. Li ion conducting ceramic membrane produces high selectivity to lithium ion in the catholyte. Cell

  4. Lithium Polymer Electrolytes Based On PMMA / PEG And Penetrant Diffusion In Kraton Penta-Block Ionomer

    Science.gov (United States)

    Meng, Yan

    The study of diffusion in polymeric material is critical to many research fields and applications, such as polymer morphology, protective coatings (paints and varnishes), separation membranes, transport phenomena, polymer electrolytes, polymer melt, and controlled release of drugs from polymer carriers [1-9]. However, it is still a challenge to understand, predict and control the diffusion of molecules and ions of different sizes in polymers [2]. This work studied the medium to long range diffusion of species (i.e., ions and molecules) in solid polymer electrolytes based on poly(ethylene glycol)/poly(methyl methacrylate) (PEG/PMMA) for Li-based batteries, and polymeric permselective membranes via pulsed-field gradient NMR and a.c. impedance. Over the past decades polymer electrolytes have attracted much attention because of their promising technological application as an ion-conducting medium in solid-state batteries, fuel cells, electrochromic displays, and chemical sensors [10, 11]. However, despite numerous studies related to ionic transport in these electrolytes the understanding of the migration mechanism is still far from being complete, and progress in the field remains largely empirical [10, 12-15]. Among various candidates for solid polymer electrolyte (SPE) material, the miscible polymer pair, poly(ethylene oxide)/poly(methyl methacrylate) (PEO/PMMA), is an attractive one, because there is a huge difference in mobility between PEO and PMMA in their blends, and PEO chains remain exceptionally mobile in the blend even at temperature below the glass transition temperature of the blend [ 16]. Thus the mechanical strength and dimensional stability is maintained by PMMA component, while the chain motions or rearrangements of the PEO component virtually contribute to the ion transport [17]. The current work prepared two types of SPE based on poly(ethylene glycol) (PEG) /PMMA (40/60 by weight) for Li-based batteries: lithium bis(trifluoromethylsulfonylimide) (Li

  5. Molecular simulations of electrolyte structure and dynamics in lithium-sulfur battery solvents

    Science.gov (United States)

    Park, Chanbum; Kanduč, Matej; Chudoba, Richard; Ronneburg, Arne; Risse, Sebastian; Ballauff, Matthias; Dzubiella, Joachim

    2018-01-01

    The performance of modern lithium-sulfur (Li/S) battery systems critically depends on the electrolyte and solvent compositions. For fundamental molecular insights and rational guidance of experimental developments, efficient and sufficiently accurate molecular simulations are thus in urgent need. Here, we construct a molecular dynamics (MD) computer simulation model of representative state-of-the art electrolyte-solvent systems for Li/S batteries constituted by lithium-bis(trifluoromethane)sulfonimide (LiTFSI) and LiNO3 electrolytes in mixtures of the organic solvents 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOL). We benchmark and verify our simulations by comparing structural and dynamic features with various available experimental reference systems and demonstrate their applicability for a wide range of electrolyte-solvent compositions. For the state-of-the-art battery solvent, we finally calculate and discuss the detailed composition of the first lithium solvation shell, the temperature dependence of lithium diffusion, as well as the electrolyte conductivities and lithium transference numbers. Our model will serve as a basis for efficient future predictions of electrolyte structure and transport in complex electrode confinements for the optimization of modern Li/S batteries (and related devices).

  6. Towards high-energy and durable lithium-ion batteries via atomic layer deposition: elegantly atomic-scale material design and surface modification

    International Nuclear Information System (INIS)

    Meng, Xiangbo

    2015-01-01

    Targeted at fueling future transportation and sustaining smart grids, lithium-ion batteries (LIBs) are undergoing intensive investigation for improved durability and energy density. Atomic layer deposition (ALD), enabling uniform and conformal nanofilms, has recently made possible many new advances for superior LIBs. The progress was summarized by Liu and Sun in their latest review [1], offering many insightful views, covering the design of nanostructured battery components (i.e., electrodes and solid electrolytes), and nanoscale modification of electrode/electrolyte interfaces. This work well informs peers of interesting research conducted and it will also further help boost the applications of ALD in next-generation LIBs and other advanced battery technologies. (viewpoint)

  7. Pseudo-solid-solution CuCo2O4/C nanofibers as excellent anodes for lithium ion batteries

    International Nuclear Information System (INIS)

    Zhang, Hang; Tang, Zhiyong; Zhang, Kang; Wang, Lei; Shi, Huimin; Zhang, Guanhua; Duan, Huigao

    2017-01-01

    Ternary transition metal oxides have received intense research interest as electrode materials for lithium ion batteries, due to their high specific capacity originating from the synergic effects of multiple metal active sites. Reducing the size of metal oxides nanoparticles and dispersing these nanoparticles in carbon matrix are considering effective strategies to improve the electrochemical performance of transition metal oxides. Ternary CuCo 2 O 4 nanoclusters ultra-uniformly dispersed in carbon nanofiber matrix forming a pseudo-solid-solution structure are successfully synthesized by a facile electrospinning method followed by an appropriate annealing process. As the anodic electrode for lithium ion batteries, the pseudo-solid-solution CuCo 2 O 4 /C electrode exhibits a high reversible specific capacity, improved rate capacity and excellent cycling stability. A discharge capacity of 865 mAh g −1 is obtained at the current density of 200 mA g −1 after 400 cycles. Surprisingly, the electrode still retains about 610 mAh g −1 after 800 cycles even at the current density of 600 mA g −1 . The superior lithium storage performance of the pseudo-solid-solution CuCo 2 O 4 /C composites is mainly attributed to the unique amorphous structure. The ultrafine CuCo 2 O 4 nanoclusters uniformly dispersed in carbon matrix can buffer the volume change and improve the conductivity of the metal oxide based electrode, guaranteeing the structure stability and fast electron transfer.

  8. Lithium current sources with an electrolyte based on aprotonic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Shembel, Ye.M.; Ksenzhek, O.S.; Litvinova, V.I.; Martynenko, T.L.; Raykhelson, L.B.; Sokolov, L.A.; Strizhko, A.S.

    1984-01-01

    Lithium current sources with an electrolyte based on aprotonic solvents are examined. The effect of the composition of the electrolyte solution on the solubility of SO2 and the excess pressure of the gas above the electrolyte solution is established. The temperature characteristics of the electrolyte are studied from the standpoint of salt solubility, the association between the discharge conditions, the macrostructure of the porous inert cathode and the degree of usage of the active cathode substance of the SO2 as the necessary aspects for solving the problems of optimizing a lithium and SO2 system.

  9. Tuning thin-film electrolyte for lithium battery by grafting cyclic carbonate and combed poly(ethylene oxide) on polysiloxane.

    Science.gov (United States)

    Li, Jie; Lin, Yue; Yao, Hehua; Yuan, Changfu; Liu, Jin

    2014-07-01

    A tunable polysiloxane thin-film electrolyte for all-solid-state lithium-ion batteries was developed. The polysiloxane was synthesized by hydrosilylation of polymethylhydrosiloxane with cyclic [(allyloxy)methyl]ethylene ester carbonic acid and vinyl tris(2-methoxyethoxy)silane. (1) H NMR spectroscopy and gel-permeation chromatography demonstrated that the bifunctional groups of the cyclic propylene carbonate (PC) and combed poly(ethylene oxide) (PEO) were well grafted on the polysiloxane. At PC/PEO=6:4, the polysiloxane-based electrolyte had an ionic conductivity of 1.55 × 10(-4) and 1.50 × 10(-3)  S cm(-1) at 25 and 100 °C, respectively. The LiFePO4 /Li batteries fabricated with the thin-film electrolyte presented excellent cycling performance in the temperature range from 25 to 100 °C with an initial discharge capacity at a rate of 1 C of 88.2 and 140 mA h g(-1) at 25 and 100 °C, respectively. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Investigating the stability of cathode materials for rechargeable lithium ion batteries

    Science.gov (United States)

    Huang, Yiqing

    Lithium ion batteries are widely used in portable electronic devices and electric vehicles. However, safety is one of the most important issues for the Li-ion batteries' use. Some cathode materials, such as LiCoO 2, are thermally unstable in the charged state. Upon decomposition these cathode materials release O2, which could react with organic electrolyte, leading to a thermal runaway. Thus understanding the stability of the cathode materials is critical to the safety of lithium ion batteries. Olivine-type LiMnPO4 is a promising cathode material for lithium ion batteries because of its high energy density. We have revealed the critical role of carbon in the stability and thermal behaviour of olivine MnPO 4 obtained by chemical delithiation of LiMnPO4. (Li)MnPO 4 samples with various particle sizes and carbon contents were studied. Carbon-free LiMnPO4 obtained by solid state synthesis in O 2 becomes amorphous upon delithiation. Small amounts of carbon (0.3 wt.%) help to stabilize the olivine structure, so that completely delithiated crystalline olivine MnPO4 can be obtained. Larger amount of carbon (2 wt.%) prevents full delithiation. Heating in air, O2, or N 2 results in structural disorder (cathode materials and the electrolyte. The thermal stability of electrochemically delithiated Li0.1N 0.8C0.15Al0.05O2 (NCA), FePO4 (FP), Mn0.8Fe0.2PO4 (MFP), hydrothermally synthesized VOPO4, LiVOPO4 and electrochemically lithiated Li2VOPO4 is investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis, coupled with mass spectrometry (TGA-MS). The thermal stability is found in the order: NCA< VOPO4< MFP< FP=LiVOPO4=Li2VOPO4. Sealed capsule high pressure experiments show a phase transformation of VOPO4 → HVOPO4 → H2VOPO4 when VOPO4 reacts with electrolyte (1 M LiPF6 in EC: DMC=1:1) between 200 and 300 °C. Finally, we characterize the lithium storage and release mechanism of V2O5 aerogels by x-ray photoelectron spectroscopy (XPS). We study the

  11. Optimising the concentration of LiNO3 additive in C4mpyr-TFSI electrolyte-based Li-S battery

    International Nuclear Information System (INIS)

    Barghamadi, Marzieh; Best, Adam S.; Hollenkamp, Anthony F.; Mahon, Peter; Musameh, Mustafa; Rüther, Thomas

    2016-01-01

    In the context of lithium-sulfur (Li-S) battery technology, LiNO 3 is known to improve performance by protecting the lithium anode via the formation of an optimized solid electrolyte interphase (SEI) as well as suppressing the associated lithium polysulfides shuttle effect during cycling. Herein, the concentration of added LiNO 3 (0.05–0.4 mol kg −1 ) in a C 4 mpyr-TFSI- organic mixed electrolyte has been varied, with any changes in cell performance monitored against the physical (viscosity) and ion-transport (NMR-based ion diffusion and conductivity) properties of each variant. We find that an electrolyte with 0.1 mol kg −1 LiNO 3 shows the best performance and that this is because this electrolyte has the highest conductivity, lowest viscosity and shows the lowest glass transition temperature (T g ), measured with differential scanning calorimetry (DSC). While the long-term benefits of adding lithium nitrate to the electrolyte of Li-S cells are known to be related to effects centred on the lithium anode, the short-term influence of this additive on capacity performance is clearly related to promoting better access to the porous cathode. The range of concentration over which this effect is operative (0.05–0.20 mol kg −1 ) overlaps with the range recommended for optimum performance of the lithium anode.

  12. Multifunctional structural lithium ion batteries for electrical energy storage applications

    Science.gov (United States)

    Javaid, Atif; Zeshan Ali, Muhammad

    2018-05-01

    Multifunctional structural batteries based on carbon fiber-reinforced polymer composites are fabricated that can bear mechanical loads and act as electrochemical energy storage devices simultaneously. Structural batteries, containing woven carbon fabric anode; lithium cobalt oxide/graphene nanoplatelets coated aluminum cathode; filter paper separator and cross-linked polymer electrolyte, were fabricated through resin infusion under flexible tooling (RIFT) technique. Compression tests, dynamic mechanical thermal analysis, thermogravimetric analysis and impedance spectroscopy were done on the cross-linked polymer electrolytes while cyclic voltammetry, impedance spectroscopy, dynamic mechanical thermal analysis and in-plane shear tests were conducted on the fabricated structural batteries. A range of solid polymer electrolytes with increasing concentrations of lithium perchlorate salt in crosslinked polymer epoxies were formulated. Increased concentrations of electrolyte salt in cross-linked epoxy increased the ionic conductivity, although the compressive properties were compromised. A structural battery, exhibiting simultaneously a capacity of 0.16 mAh L‑1, an energy density of 0.32 Wh L‑1 and a shear modulus of 0.75 GPa have been reported.

  13. Performance of titanium dioxide-based cathodes in a lithium polymer electrolyte cell

    Energy Technology Data Exchange (ETDEWEB)

    Macklin, W.J. (Applied Electrochemistry Dept., AEA Industry Technology, Harwell (United Kingdom)); Neat, R.J. (Applied Electrochemistry Dept., AEA Industry Technology, Harwell (United Kingdom))

    Performance data on two polymorphs of titanium dioxide (anatase and rutile) operating in a lithium polymer electrolyte cell at 120 C are presented. On the first discharge lithium ions can be electrochemically inserted into both forms to an approximate composition LiTiO[sub 2]. However, only the rutile material cycles with a significant capacity ([proportional to] 0.5 Li/TiO[sub 2]) with an average cell voltage of 1.73 V corresponding to a theoretical energy density of [proportional to] 290 W h kg[sup -1]. Our results are in contrast to earlier work reported on the intercalation of lithium into these phases at room temperature, where only the anatase form was found to intercalate lithium. X-ray diffraction data indicate that the rutile form undergoes a structural change during the first discharge resulting in the formation of a hexagonal form of LiTiO[sub 2].

  14. The effect of Li2CO3 substitution on synthesis of LiBOB compounds as salt of electrolyte battery lithium ion

    Science.gov (United States)

    Lestariningsih, Titik; Wigayati, Etty Marty; Sabrina, Qolby; Prihandoko, Bambang; Priyono, Slamet

    2018-04-01

    Development of the synthesis of LiB(C2O4)2 compounds continues to evolve along with the need for electrolyte salts to support the research of the manufacture of lithium ion batteries. A study had been conducted on the effect of Li2CO3 substitution on the synthesis of LiB(C2O4)2 or LiBOB compounds. LiBOB was a major candidate to replace LiPF6 as a highly toxic lithium battery electrolyte and harmful to human health. Synthesis of Lithium bis(oxalato) borate used powder metallurgy method. The raw materials used are H2C2O4.2H2O, Li2CO3 or LiOH and H2BO3 from Merck Germany products. The materials are mixed with 2: 1: 1 mol ratio until homogeneous. The synthesis of LiBOB refers to previous research, where the heating process was done gradually. The first stage heating is carried out at 120°C for 4 hours, then the next stage heating is carried out at 240°C for 7 hours. The sample variation in this study was to distinguish the lithium source from Li2CO3 and LiOH. Characterization was done by XRD to know the phase formed, FTIR to confirm that functional group of LiB(C2O4)2 compound, SEM to know the morphological structure, and TG/DTA to know the thermal properties. The results of the analysis shows that LiBOB synthesis using Lithium source from Li2CO3 has succeeded to form LiBOB compound with more LiBOB phase composition is 59.1% and 40.9% LiBOB hydrate phase, SEM morphology shows powder consist of elongated round particle porous and similar to LiBOB commercial and show higher thermal stability.

  15. High-Performance Lithium-Oxygen Battery Electrolyte Derived from Optimum Combination of Solvent and Lithium Salt.

    Science.gov (United States)

    Ahn, Su Mi; Suk, Jungdon; Kim, Do Youb; Kang, Yongku; Kim, Hwan Kyu; Kim, Dong Wook

    2017-10-01

    To fabricate a sustainable lithium-oxygen (Li-O 2 ) battery, it is crucial to identify an optimum electrolyte. Herein, it is found that tetramethylene sulfone (TMS) and lithium nitrate (LiNO 3 ) form the optimum electrolyte, which greatly reduces the overpotential at charge, exhibits superior oxygen efficiency, and allows stable cycling for 100 cycles. Linear sweep voltammetry (LSV) and differential electrochemical mass spectrometry (DEMS) analyses reveal that neat TMS is stable to oxidative decomposition and exhibit good compatibility with a lithium metal. But, when TMS is combined with typical lithium salts, its performance is far from satisfactory. However, the TMS electrolyte containing LiNO 3 exhibits a very low overpotential, which minimizes the side reactions and shows high oxygen efficiency. LSV-DEMS study confirms that the TMS-LiNO 3 electrolyte efficiently produces NO 2 - , which initiates a redox shuttle reaction. Interestingly, this NO 2 - /NO 2 redox reaction derived from the LiNO 3 salt is not very effective in solvents other than TMS. Compared with other common Li-O 2 solvents, TMS seems optimum solvent for the efficient use of LiNO 3 salt. Good compatibility with lithium metal, high dielectric constant, and low donicity of TMS are considered to be highly favorable to an efficient NO 2 - /NO 2 redox reaction, which results in a high-performance Li-O 2 battery.

  16. Li-Ion Electrolytes with Improved Safety and Tolerance to High-Voltage Systems

    Science.gov (United States)

    Smart, Marshall C.; Bugga, Ratnakumar V.; Prakash, Surya; Krause, Frederick C.

    2013-01-01

    Given that lithium-ion (Li-ion) technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. Therefore, extensive effort has been devoted to developing nonflammable electrolytes to reduce the flammability of the cells/battery. A number of promising electrolytes have been developed incorporating flame-retardant additives, and have been shown to have good performance in a number of systems. However, these electrolyte formulations did not perform well when utilizing carbonaceous anodes with the high-voltage materials. Thus, further development was required to improve the compatibility. A number of Li-ion battery electrolyte formulations containing a flame-retardant additive [i.e., triphenyl phosphate (TPP)] were developed and demonstrated in high-voltage systems. These electrolytes include: (1) formulations that incorporate varying concentrations of the flame-retardant additive (from 5 to 15%), (2) the use of mono-fluoroethylene carbonate (FEC) as a co-solvent, and (3) the use of LiBOB as an electrolyte additive intended to improve the compatibility with high-voltage systems. Thus, improved safety has been provided without loss of performance in the high-voltage, high-energy system.

  17. A Consistent Derivation of the Impedance of a Lithium-Ion Battery Electrode and its Dependency on the State-of-Charge

    International Nuclear Information System (INIS)

    Schönleber, M.; Uhlmann, C.; Braun, P.; Weber, A.; Ivers-Tiffée, E.

    2017-01-01

    Highlights: •A derivation of the impedance model of a Lithium-Ion battery electrode is given. •The dependency of all partial impedances on the State-of-Charge is revealed. •The lasting disagreement in how to model solid-state diffusion is settled. •A solid starting point to derive models of any complexity is provided. •The connection between differential capacity and solid-state diffusion is revealed. -- Abstract: A derivation of the fundamental impedance of a Lithium-Ion battery electrode is given, exemplarily conducted for a solid thin-film electrode. The focus of this derivation is not on developing a model which is able to reproduce the exact behaviour of a given electrode, but rather on deriving its fundamental characteristics from few and intuitive assumptions in a simple and transparent way. It is thus shown, that the fundamental impedance of a solid thin-film electrode consists of an RC-element for charge-transfer, a Finite-Length Warburg element for diffusion in the electrolyte and a Finite-Space Warburg element for diffusion in the solid-state. The use of a Finite-Length Warburg element with a serially connected capacitor for modelling diffusion in the solid-state is thus indicated to be physically questionable. In addition, the theoretically expected behaviour of charge-transfer and solid-state diffusion on the degree of lithiation (State-of-Charge) is derived and discussed.

  18. Novel lithium titanate-graphene hybrid containing two graphene conductive frameworks for lithium-ion battery with excellent electrochemical performance

    Energy Technology Data Exchange (ETDEWEB)

    Ruiyi, Li; Tengyuan, Chen; Beibei, Sun [School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China); Zaijun, Li [School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China); Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, Wuxi 214122 (China); Zhiquo, Gu; Guangli, Wang; Junkang, Liu [School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China)

    2015-10-15

    Graphical abstract: We developed a new Novel lithium titanate-graphene nanohybrid containing two graphene conductive frameworks. The unique architecture creates fast electron transfer and rapid mass transport of electrolyte. The hybrid electrode provides excellent electrochemical performances for lithium-ion batteries, including high specific capacity, outstanding rate capability and intriguing cycling stability. - Highlights: • We reported a new LTO-graphene nanohybrid containing two graphene conductive frameworks. • One graphene framework greatly improves the electrical conductivity of LTO crystal. • Another graphene framework enhances electrical conductivity of between LTO crystals and electrolyte transport. • The unique architecture creates big tap density, ultrafast electron transfer and rapid mass transport. • The hybrid electrode provides excellent electrochemical performance for lithium-ion batteries. - ABSTRACT: The paper reported the synthesis of lithium titanate(LTO)-graphene hybrid containing two graphene conductive frameworks (G@LTO@G). Tetrabutyl titanate and graphene were dispersed in tertbutanol and heated to reflux state by microwave irradiation. Followed by adding lithium acetate to produce LTO precursor/graphene (p-LTO/G). The resulting p-LTO/G offers homogeneous morphology and ultra small size. All graphene sheets were buried in the spherical agglomerates composed of primitive particles through the second agglomeration. The p-LTO/G was calcined to LTO@graphene (LTO@G). To obtain G@LTO@G, the LTO@G was further hybridized with graphene. The as-prepared G@LTO@G shows well-defined three-dimensional structure and hierarchical porous distribution. Its unique architecture creates big tap density, fast electron transfer and rapid electrolyte transport. As a result, the G@LTO@G provides high specific capacity (175.2 mA h g{sup −1} and 293.5 mA cm{sup −3}), outstanding rate capability (155.7 mAh g{sup −1} at 10C) and intriguing cycling

  19. Printable Solid-State Lithium-Ion Batteries: A New Route toward Shape-Conformable Power Sources with Aesthetic Versatility for Flexible Electronics.

    Science.gov (United States)

    Kim, Se-Hee; Choi, Keun-Ho; Cho, Sung-Ju; Choi, Sinho; Park, Soojin; Lee, Sang-Young

    2015-08-12

    Forthcoming flexible/wearable electronic devices with shape diversity and mobile usability garner a great deal of attention as an innovative technology to bring unprecedented changes in our daily lives. From the power source point of view, conventional rechargeable batteries (one representative example is a lithium-ion battery) with fixed shapes and sizes have intrinsic limitations in fulfilling design/performance requirements for the flexible/wearable electronics. Here, as a facile and efficient strategy to address this formidable challenge, we demonstrate a new class of printable solid-state batteries (referred to as "PRISS batteries"). Through simple stencil printing process (followed by ultraviolet (UV) cross-linking), solid-state composite electrolyte (SCE) layer and SCE matrix-embedded electrodes are consecutively printed on arbitrary objects of complex geometries, eventually leading to fully integrated, multilayer-structured PRISS batteries with various form factors far beyond those achievable by conventional battery technologies. Tuning rheological properties of SCE paste and electrode slurry toward thixotropic fluid characteristics, along with well-tailored core elements including UV-cured triacrylate polymer and high boiling point electrolyte, is a key-enabling technology for the realization of PRISS batteries. This process/material uniqueness allows us to remove extra processing steps (related to solvent drying and liquid-electrolyte injection) and also conventional microporous separator membranes, thereupon enabling the seamless integration of shape-conformable PRISS batteries (including letters-shaped ones) into complex-shaped objects. Electrochemical behavior of PRISS batteries is elucidated via an in-depth analysis of cell impedance, which provides a theoretical basis to enable sustainable improvement of cell performance. We envision that PRISS batteries hold great promise as a reliable and scalable platform technology to open a new concept of cell

  20. Effect of a novel amphipathic ionic liquid on lithium deposition in gel polymer electrolytes

    International Nuclear Information System (INIS)

    Choi, Nam-Soon; Koo, Bonjae; Yeon, Jin-Tak; Lee, Kyu Tae; Kim, Dong-Won

    2011-01-01

    Highlights: · Synthesis of a dimeric ionic liquid. · Gel polymer electrolytes providing uniform lithium deposit pathway. · An amphipathic ionic liquid locates at the interface between an electrolyte-rich phase and a polymer matrix in a gel polymer electrolyte. · The presence of PDMITFSI ionic liquid leads to the suppression of dendritic lithium formation on a lithium metal electrode. - Abstract: A novel dimeric ionic liquid based on imidazolium cation and bis(trifluoromethanesulfonyl) imide (TFSI) anion has been synthesized through a metathesis reaction. Its chemical shift values and thermal properties are identified via 1 H nuclear magnetic resonance (NMR) imaging and differential scanning calorimetry (DSC). The effect of the synthesized dimeric ionic liquid on the interfacial resistance of gel polymer electrolytes is described. Differences in the SEM images of lithium electrodes after lithium deposition with and without the 1,1'-pentyl-bis(2,3-dimethylimidazolium) bis(trifluoromethane-sulfonyl)imide (PDMITFSI) ionic liquid in gel polymer electrolytes are clearly discernible. This occurs because the PDMITFSI ionic liquid with hydrophobic moieties and polar groups modulates lithium deposit pathways onto the lithium metal anode. Moreover, high anodic stability for a gel polymer electrolyte with the PDMITFSI ionic liquid was clearly observed.

  1. Preparation and characterization of plasticized palm-based polyurethane solid polymer electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Daud, Farah Nadia; Ahmad, Azizan; Badri, Khairiah Haji [School of Chemical Science and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan (Malaysia)

    2013-11-27

    Palm-based polyurethane solid polymer electrolyte was prepared via prepolymerization method between palm kernel oil based polyols (PKO-p) and 2,4’-diphenylmethane diisocyanate (2,4’-MDI) in acetone at room temperature with the vary amount of lithium trifuoromethanesulfonate (LiCF{sub 3}SO{sub 3}) salt and polyethylene glycol (PEG). The film was analyzed using attenuated total reflection infrared (ATR-IR) spectroscopy, electrochemical impedance spectroscopy (EIS) and X-ray diffractometry (XRD). EIS result indicated ionic conductivity obtained with 30 wt% LiCF3SO3 increased to 6.55 × 10{sup −6} S cm{sup −1} when 10 wt.% of plasticizer was added into the system. FTIR analysis showed the interaction between lithium ions and amine (-N-H) at 3600–3100 cm{sup −1}, carbonyl (-C=O) at 1750–1650 cm{sup −1} and ether (-C-O-C-) at 1150–1000 cm{sup −1} of the polyurethane forming polymer-salt complexes. The XRD result confirmed that LiCF{sub 3}SO{sub 3} salt completely dissociated within the polyurethane film with the absence of crystalline peaks of LiCF{sub 3}SO{sub 3}.

  2. Preparation and characterization of plasticized palm-based polyurethane solid polymer electrolyte

    International Nuclear Information System (INIS)

    Daud, Farah Nadia; Ahmad, Azizan; Badri, Khairiah Haji

    2013-01-01

    Palm-based polyurethane solid polymer electrolyte was prepared via prepolymerization method between palm kernel oil based polyols (PKO-p) and 2,4’-diphenylmethane diisocyanate (2,4’-MDI) in acetone at room temperature with the vary amount of lithium trifuoromethanesulfonate (LiCF 3 SO 3 ) salt and polyethylene glycol (PEG). The film was analyzed using attenuated total reflection infrared (ATR-IR) spectroscopy, electrochemical impedance spectroscopy (EIS) and X-ray diffractometry (XRD). EIS result indicated ionic conductivity obtained with 30 wt% LiCF3SO3 increased to 6.55 × 10 −6 S cm −1 when 10 wt.% of plasticizer was added into the system. FTIR analysis showed the interaction between lithium ions and amine (-N-H) at 3600–3100 cm −1 , carbonyl (-C=O) at 1750–1650 cm −1 and ether (-C-O-C-) at 1150–1000 cm −1 of the polyurethane forming polymer-salt complexes. The XRD result confirmed that LiCF 3 SO 3 salt completely dissociated within the polyurethane film with the absence of crystalline peaks of LiCF 3 SO 3

  3. Improved electrolyte for lithium-thionyl chloride battery. [Patent application

    Energy Technology Data Exchange (ETDEWEB)

    Shipman, W.H.; McCartney, J.F.

    1980-12-17

    A lithium, thionyl chloride battery is provided with an electrolyte which makes it safe under a reverse voltage condition. The electrolyte is niobium pentachloride which is dissolved in the thionyl chloride.

  4. Failure Analysis of Short-Circuited Lithium-Ion Battery with Nickel-Manganese-Cobalt/Graphite Electrode.

    Science.gov (United States)

    Lee, Seung-Mi; Kim, Jea-Yeon; Byeon, Jai-Won

    2018-09-01

    Accidental failures and explosions of lithium-ion batteries have been reported in recent years. To determine the root causes and mechanisms of these failures from the perspective of material degradation, failure analysis was conducted for an intentionally shorted lithium-ion battery. The battery was subjected to electrical overcharging and mechanical pressing to simulate internal short-circuiting. After in situ measurement of the temperature increase during the short-circuiting of the electrodes, the disassembled battery components (i.e., the anode, cathode, and separator) were analyzed by scanning electron microscopy and energy-dispersive X-ray spectroscopy. Regardless of the simulated short-circuit method (mechanical or electrical), damage was observed in the shorted batteries. Numerous small cracks and chemical reaction products were observed on the electrode surface, along with pore shielding on the separator. The event of short-circuiting increased the surface temperature of the battery to approximately 90 °C, which prompted the deterioration and decomposition of the electrolyte, thus affecting the overall battery performance; this was attributed to the decomposition of the lithium salt at 60 °C. The gas generation due to the breakdown of the electrolyte causes pressure accumulation inside the cell; therefore, the electrolyte leaks.

  5. An Empirical Rate Constant Based Model to Study Capacity Fading in Lithium Ion Batteries

    Directory of Open Access Journals (Sweden)

    Srivatsan Ramesh

    2015-01-01

    Full Text Available A one-dimensional model based on solvent diffusion and kinetics to study the formation of the SEI (solid electrolyte interphase layer and its impact on the capacity of a lithium ion battery is developed. The model uses the earlier work on silicon oxidation but studies the kinetic limitations of the SEI growth process. The rate constant of the SEI formation reaction at the anode is seen to play a major role in film formation. The kinetics of the reactions for capacity fading for various battery systems are studied and the rate constants are evaluated. The model is used to fit the capacity fade in different battery systems.

  6. Synthesis and characterization of ionomers as polymer electrolytes for energy conversion devices

    Science.gov (United States)

    Oh, Hyukkeun

    Single-ion conducting electrolytes present a unique alternative to traditional binary salt conductors used in lithium-ion batteries. Secondary lithium batteries are considered as one of the leading candidates to replace the combustible engines in automotive technology, however several roadblocks are present which prevent their widespread commercialization. Power density, energy density and safety properties must be improved in order to enable the current secondary lithium battery technology to compete with existing energy technologies. It has been shown theoretically that single-ion electrolytes can eliminate the salt concentration gradient and polarization loss in the cell that develops in a binary salt system, resulting in substantial improvements in materials utilization for high power and energy densities. While attempts to utilize single-ion conducting electrolytes in lithium-ion battery systems have been made, the low ionic conductivities prevented the successful operation of the battery cells in ambient conditions. This work focuses on designing single-ion conducting electrolytes with high ionic conductivities and electrochemical and mechanical stability which enables the stable charge-discharge performance of battery cells. Perfluorosulfonate ionomers are known to possess exceptionally high ionic conductivities due to the electron-withdrawing effect caused by the C-F bonds which stabilizes the negative charge of the anion, leading to a large number of free mobile cations. The effect of perfluorinated sulfonic acid side chains on transport properties of proton exchange membrane polymers was examinated via a comparison of three ionomers, having different side chain structures and a similar polymer backbone. The three different side chain structures were aryl-, pefluoro alkyl-, and alkyl-sulfonic acid groups, respectively. All ionomers were synthesized and characterized by 1H and 19F NMR. A novel ionomer synthesized with a pendant perfluorinated sulfonic acid

  7. Homogeneous lithium electrodeposition with pyrrolidinium-based ionic liquid electrolytes.

    Science.gov (United States)

    Grande, Lorenzo; von Zamory, Jan; Koch, Stephan L; Kalhoff, Julian; Paillard, Elie; Passerini, Stefano

    2015-03-18

    In this study, we report on the electroplating and stripping of lithium in two ionic liquid (IL) based electrolytes, namely N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl) imide (Pyr14FSI) and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI), and mixtures thereof, both on nickel and lithium electrodes. An improved method to evaluate the Li cycling efficiency confirmed that homogeneous electroplating (and stripping) of Li is possible with TFSI-based ILs. Moreover, the presence of native surface features on lithium, directly observable via scanning electron microscope imaging, was used to demonstrate the enhanced electrolyte interphase (SEI)-forming ability, that is, fast cathodic reactivity of this class of electrolytes and the suppressed dendrite growth. Finally, the induced inhomogeneous deposition enabled us to witness the SEI cracking and revealed previously unreported bundled Li fibers below the pre-existing SEI and nonrod-shaped protuberances resulting from Li extrusion.

  8. Nanoporous Polymer-Ceramic Composite Electrolytes for Lithium Metal Batteries

    KAUST Repository

    Tu, Zhengyuan; Kambe, Yu; Lu, Yingying; Archer, Lynden A.

    2013-01-01

    A nanoporous composite material that offers the unique combination of high room-temperature ionic conductivity and high mechanical modulus is reported. When used as the separator/electrolyte in lithium batteries employing metallic lithium as anode

  9. Synthesis of Lithium Fluoride from Spent Lithium Ion Batteries

    Directory of Open Access Journals (Sweden)

    Daniela S. Suarez

    2017-05-01

    Full Text Available Lithium (Li is considered a strategic element whose use has significantly expanded. Its current high demand is due to its use in lithium ion batteries for portable electronic devices, whose manufacture and market are extensively growing every day. These days there is a great concern about the final disposal of these batteries. Therefore, the possibility of developing new methodologies to recycle their components is of great importance, both commercially and environmentally. This paper presents results regarding important operational variables for the dissolution of the lithium and cobalt mixed-oxide (LiCoO2 cathodes from spent lithium ion batteries (LIBs with hydrofluoric acid. The recovery and synthesis of Co and Li compounds were also investigated. The dissolution parameters studied were: temperature, reaction time, solid-liquid ratio, stirring speed, and concentration of HF. The investigated recovery parameters included: pH, temperature, and time with and without stirring. The final precipitation of lithium fluoride was also examined. The results indicate that an increase in the HF concentration, temperature, and reaction time favors the leaching reaction of the LiCoO2. Dissolutions were close to 60%, at 75 °C and 120 min with a HF concentration of 25% (v/v. The recovery of Co and Li were 98% and 80%, respectively, with purities higher than 94%. Co and Li compounds, such as Co3O4 and LiF, were synthesized. Furthermore, it was possible to almost completely eliminate the F− ions as CaF2.

  10. Facile preparation of polymer electrolytes based on the polymerized ionic liquid poly((4-vinylbenzyl)trimethylammonium bis(trifluoromethanesulfonylimide)) for lithium secondary batteries

    International Nuclear Information System (INIS)

    Li, Mingtao; Wang, Lu; Yang, Bolun; Du, Tingting; Zhang, Ying

    2014-01-01

    Graphical abstract: (A) The main components of PIL electrolytes, (B) A PIL electrolyte sample. - Highlights: • A new polymer electrolyte incorporating a DEME-TFSI liquid is prepared. • The ionic conductivity of the electrolytes reaches 7.58 × 10 −4 S cm −1 at 60 °C. • Batteries discharge 130 mAh g −1 at 0.1 C rates with good capacity retention. - Abstract: The polymer electrolytes based on a novel poly((4-vinylbenzyl)trimethylammonium bis(trifluoromethanesulfonylimide)) polymeric ionic liquid (PIL) as polymer host and containing DEME-TFSI ionic liquid, LiTFSI salt and nano silica are prepared. The polymer electrolyte is chemically stable even at a higher temperature of 60 °C in contact with lithium anode. Particularly, the electrolyte exhibits high lithium ion conductivity, wide electrochemical stability window and good lithium stripping/plating performance. When the IL content reaches 60% (the weight ratio of DEME-TFSI/PIL), the PIL electrolyte presents a higher ionic conductivity, and it is 7.58 × 10 −4 S cm −1 at 60 °C. Preliminary battery tests show that Li/LiFePO 4 cells with the PIL electrolytes are capable to deliver above 130 mAh g −1 at 60 °C with very good capacity retention

  11. Aging investigations of a lithium-ion battery electrolyte from a field-tested hybrid electric vehicle

    Science.gov (United States)

    Grützke, Martin; Kraft, Vadim; Hoffmann, Björn; Klamor, Sebastian; Diekmann, Jan; Kwade, Arno; Winter, Martin; Nowak, Sascha

    2015-01-01

    The electrolyte of a used lithium-ion battery from a hybrid electric vehicle (HEV) was investigated. The liquid electrolyte was collected through the pressure valve of these 5 Ah cells. It consists of (29.8 ± 0.2) wt.% dimethyl carbonate (DMC), (21.7 ± 0.1) wt.% ethyl methyl carbonate (EMC), (30.3 ± 0.3) wt.% ethylene carbonate (EC) and (2.2 ± 0.1) wt.% cyclohexyl benzene (CHB) which were identified with GC-MS and quantified with GC-FID. Li+ (1.29 ± 0.04) mol L-1 and PF6- were determined with IC as the main ionic species in the solution. Furthermore, BF4- was clearly identified with IC-ESI-MS, IC-ICP-MS and 11B NMR and quantified to a concentration of (120.8 ± 8.3) mg L-1 with ICP-OES. The presence of POF3 (detected with GC-MS), F-, PO2F2-, HPO3F- and H2PO4- (determined with IC-ESI-MS) can be attributed to the reaction of the conducting salt LiPF6 via PF5 with traces of water. HPO3F- and H2PO4- could only be observed in cells which were opened in a laboratory hood under exposure of air humidity. This experiment was done to simulate escaping electrolyte from an HEV battery pack. Furthermore, several alkyl phosphates (identified with GC-MS and IC-ESI-MS) are present in the solution due to further reaction of the different fluorinated phosphates with organic carbonates.

  12. Plasma-modified polyethylene membrane as a separator for lithium-ion polymer battery

    International Nuclear Information System (INIS)

    Kim, Jun Young; Lee, Yongbeom; Lim, Dae Young

    2009-01-01

    The surface of polyethylene (PE) membranes as a separator for lithium-ion polymer battery was modified with acrylonitrile (AN) using the plasma technology. The plasma-induced acrylonitrile coated PE (PiAN-PE) membrane was characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and contact angle measurement. The electrochemical performance of the lithium-ion polymer cell fabricated with the PE and the PiAN-PE membranes were also analyzed. The surface characterization demonstrates that the enhanced adhesion of the PiAN-PE membrane resulted from the increased polar component of surface energy for the PiAN-PE membrane. The presence of the PiAN induced onto the surface of the membrane via the plasma modification plays a critical role in improving the wettability and electrolyte retention, the interfacial adhesion between the electrodes and the separator, the cycle performance of the resulting lithium-ion polymer cell assembly. The PiAN-PE membrane modified by the plasma treatment holds a great potential to be used as a high-performance and cost-effective separator for lithium-ion polymer battery.

  13. Lithium Organic Borate Salt and Sulfite Functional Electrolytes%有机硼酸锂盐及亚硫酸酯类功能电解质材料

    Institute of Scientific and Technical Information of China (English)

    陈人杰; 何舟影; 吴锋

    2011-01-01

    随着锂离子电池对高安全性、高容量、高功率等性能的技术需求,新型功能电解质材料的研究开发成为锂离子电池新材料领域研发工作的重点.本文对面向锂离子电池应用的功能电解质材料锂盐和添加剂的最新研究进展作了较为全面的阐述,其中重点介绍了本研究团队近年来在面向改善锂离子电池安全性能、提高其温度适应性、增强电解质与电极材料相容特性等方面研究开发的系列基于双草酸硼酸锂[LiBOB]及二氟草酸硼酸锂[LiODFB]等有机硼酸锂盐和亚硫酸酯类等添加剂的新型功能电解质材料,其表现出高的热稳定性和良好的电化学性能.而且,其中的有机硼酸锂盐和亚硫酸酯还可以作为SEI成膜材料进行应用,其在石墨电极表面可形成稳定的SEI膜,有利于改善电池的循环寿命、自放电、库仑效率和不可逆容量衰减.最后,本文探讨了当前存在的问题及未来的研究方向,并对其应用前景进行了展望.%With the rapid development of lithium ion batteries with higher energy density, higher power density and high security, the research of new functional electrolytes has attracted considerable attention in novel materials field for lithium ion batteries.In this paper, the recent research advances of key technologies on the application of lithium salts and additive functional electrolytes in lithium ion batteries are reviewed, especially on the results of our research team focusing on new functional electrolytes based on lithium organic borate salt, such as lithium bis(oxalato) borate [LiBOB]and lithium oxalyldifluoroborate [LiODFB], and sulfite additives for the purpose of improving security, temperature adaptability and the compatibility between electrolytes and electrodes of lithium ion batteries.These electrolytes exhibit high thermal stability and good electrochemical properties.Moreover, lithium organic borate salt and sulfite have been

  14. A bifunctional electrolyte additive for separator wetting and dendrite suppression in lithium metal batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Hao; Xie, Yong; Xiang, Hongfa; Shi, Pengcheng; Liang, Xin; Xu, Wu

    2018-04-01

    Reformulation of electrolyte systems and improvement of separator wettability are vital to electrochemical performances of rechargeable lithium (Li) metal batteries, especially for suppressing Li dendrites. In this work we report a bifunctional electrolyte additive that improves separator wettability and suppresses Li dendrite growth in LMBs. A triblock polyether (Pluronic P123) was introduced as an additive into a commonly used carbonate-based electrolyte. It was found that addition of 0.2~1% (by weight) P123 into the electrolyte could effectively enhance the wettability of polyethylene separator. More importantly, the adsorption of P123 on Li metal surface can act as an artificial solid electrolyte interphase layer and contribute to suppress the growth of Li dendrites. A smooth and dendritic-free morphology can be achieved in the electrolyte with 0.2% P123. The Li||Li symmetric cells with the 0.2% P123 containing electrolyte exhibit a relatively stable cycling stability at high current densities of 1.0 and 3.0 mA cm-2.

  15. Thermodynamics and Ionic Conductivity of Block Copolymer Electrolytes

    OpenAIRE

    Wanakule, Nisita Sidra

    2010-01-01

    Solid electrolytes have been a long-standing goal of the battery industry since they have been considered safer than flammable liquid electrolytes and are capable of producing batteries with higher energy densities. The latter can be achieved by using a lithium metal anode, which is unstable against liquid electrolytes. Past attempts at polymer electrolytes for lithium-anode batteries have failed due to the formation of lithium dendrites after repeated cycling. To overcome this problem, we ha...

  16. Study of Stable Cathodes and Electrolytes for High Specific Density Lithium-Air Battery

    Science.gov (United States)

    Hernandez-Lugo, Dionne M.; Wu, James; Bennett, William; Ming, Yu; Zhu, Yu

    2015-01-01

    Future NASA missions require high specific energy battery technologies, greater than 400 Wh/kg. Current NASA missions are using "state-of-the-art" (SOA) Li-ion batteries (LIB), which consist of a metal oxide cathode, a graphite anode and an organic electrolyte. NASA Glenn Research Center is currently studying the physical and electrochemical properties of the anode-electrolyte interface for ionic liquid based Li-air batteries. The voltage-time profiles for Pyr13FSI and Pyr14TFSI ionic liquids electrolytes studies on symmetric cells show low over-potentials and no dendritic lithium morphology. Cyclic voltammetry measurements indicate that these ionic liquids have a wide electrochemical window. As a continuation of this work, sp2 carbon cathode and these low flammability electrolytes were paired and the physical and electrochemical properties were studied in a Li-air battery system under an oxygen environment.

  17. Capillary Electrophoresis as Analysis Technique for Battery Electrolytes: (i Monitoring Stability of Anions in Ionic Liquids and (ii Determination of Organophosphate-Based Decomposition Products in LiPF6-Based Lithium Ion Battery Electrolytes

    Directory of Open Access Journals (Sweden)

    Marcelina Pyschik

    2017-09-01

    Full Text Available In this work, a method for capillary electrophoresis (CE hyphenated to a high-resolution mass spectrometer was presented for monitoring the stability of anions in ionic liquids (ILs and in commonly used lithium ion battery (LIB electrolytes. The investigated ILs were 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonylimide (PYR13TFSI and 1-methyl-1-propylpyrrolidinium bis(fluorosulfonylimide (PYR13FSI. The method development was conducted by adjusting the following parameters: buffer compositions, buffer concentrations, and the pH value. Also the temperature and the voltage applied on the capillary were optimized. The ILs were aged at room temperature and at 60 °C for 16 months each. At both temperatures, no anionic decomposition products of the FSI− and TFSI− anions were detected. Accordingly, the FSI− and TFSI− anions were thermally stable at these conditions. This method was also applied for the investigation of LIB electrolyte samples, which were aged at 60 °C for one month. The LP30 (50/50 wt. % dimethyl carbonate/ethylene carbonate and 1 M lithium hexafluorophosphate electrolyte was mixed with the additive 1,3-propane sultone (PS and with one of the following organophosphates (OP: dimethyl phosphate (DMP, diethyl phosphate (DEP, and triethyl phosphate (TEP, to investigate the influence of these compounds on the formation of OPs.

  18. Li-Ion Cells Employing Electrolytes With Methyl Propionate and Ethyl Butyrate Co-Solvents

    Science.gov (United States)

    Smart, Marshall C.; Bugga, Ratnakumar V.

    2011-01-01

    Future NASA missions aimed at exploring Mars and the outer planets require rechargeable batteries that can operate at low temperatures to satisfy the requirements of such applications as landers, rovers, and penetrators. A number of terrestrial applications, such as hybrid electric vehicles (HEVs) and electric vehicles (EVs) also require energy storage devices that can operate over a wide temperature range (i.e., -40 to +70 C), while still providing high power capability and long life. Currently, the state-of-the-art lithium-ion system has been demonstrated to operate over a wide range of temperatures (-30 to +40 C); however, the rate capability at the lower temperatures is very poor. These limitations at very low temperatures are due to poor electrolyte conductivity, poor lithium intercalation kinetics over the electrode surface layers, and poor ionic diffusion in the electrode bulk. Two wide-operating-temperature-range electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed include further optimization of electrolytes containing methyl propionate (MP) and ethyl butyrate (EB), which are effective co-solvents, to widen the operating temperature range beyond the baseline systems. Attention was focused on further optimizing ester-based electrolyte formulations that have exhibited the best performance at temperatures ranging from -60 to +60 C, with an emphasis upon improving the rate capability at -20 to -40 C. This was accomplished by increasing electrolyte salt concentration to 1.20M and increasing the ester content to 60 percent by volume to increase the ionic conductivity at low temperatures. Two JPL-developed electrolytes 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %) operate effectively over a wide

  19. Virus-Assembled Flexible Electrode-Electrolyte Interfaces for Enhanced Polymer-Based Battery Applications

    Directory of Open Access Journals (Sweden)

    Ayan Ghosh

    2012-01-01

    Full Text Available High-aspect-ratio cobalt-oxide-coated Tobacco mosaic virus (TMV- assembled polytetrafluoroethylene (PTFE nonstick surfaces were integrated with a solvent-free polymer electrolyte to create an anode-electrolyte interface for use in lithium-ion batteries. The virus-assembled PTFE surfaces consisted primarily of cobalt oxide and were readily intercalated with a low-molecular-weight poly (ethylene oxide (PEO based diblock copolymer electrolyte to produce a solid anode-electrolyte system. The resulting polymer-coated virus-based system was then peeled from the PTFE backing to produce a flexible electrode-electrolyte component. Electrochemical studies indicated the virus-structured metal-oxide PEO-based interface was stable and displayed robust charge transfer kinetics. Combined, these studies demonstrate the development of a novel solid-state electrode architecture with a unique peelable and flexible processing attribute.

  20. Influence of Adhesive System on Performance of SiO/C Lithium-ion Battery

    Directory of Open Access Journals (Sweden)

    Teng Xin

    2015-01-01

    Full Text Available Silicon based anode material is turning into the research hot point of lithium-ion battery material field due to Si inside supporting higher capacity. Furthermore binder applied as major accessory material of anode system could bring anode material & current collector together, thus the influence given by binder system to battery performance becomes the key point. The paper describes the procedure of adopting commercial LiCoO2 SiO/C as composite material & electrolyte, with using styrene butadiene rubber and acrylic acid copolymer as binder to figure out lithium-ion battery with 2.5Ah, which is testified to present better performance on cold temperature & cycle life plus having a little bit swelling compared with the lithium-ion battery using only styrene butadiene rubber as binder.

  1. A high pressure x-ray photoelectron spectroscopy experimental method for characterization of solid-liquid interfaces demonstrated with a Li-ion battery system

    Energy Technology Data Exchange (ETDEWEB)

    Maibach, Julia; Xu, Chao; Gustafsson, Torbjörn; Edström, Kristina [Department of Chemistry–Ångström Laboratory, Uppsala University, Box 538, SE-751 21 Uppsala (Sweden); Eriksson, Susanna K. [Department of Chemistry–Ångström Laboratory, Uppsala University, Box 523, SE-751 20 Uppsala (Sweden); Åhlund, John [VG Scienta AB, Box 15120, SE-750 15 Uppsala (Sweden); Siegbahn, Hans; Rensmo, Håkan; Hahlin, Maria, E-mail: maria.hahlin@physics.uu.se [Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala (Sweden)

    2015-04-15

    We report a methodology for a direct investigation of the solid/liquid interface using high pressure x-ray photoelectron spectroscopy (HPXPS). The technique was demonstrated with an electrochemical system represented by a Li-ion battery using a silicon electrode and a liquid electrolyte of LiClO{sub 4} in propylene carbonate (PC) cycled versus metallic lithium. For the first time the presence of a liquid electrolyte was realized using a transfer procedure where the sample was introduced into a 2 mbar N{sub 2} environment in the analysis chamber without an intermediate ultrahigh vacuum (UHV) step in the load lock. The procedure was characterized in detail concerning lateral drop gradients as well as stability of measurement conditions over time. The X-ray photoelectron spectroscopy (XPS) measurements demonstrate that the solid substrate and the liquid electrolyte can be observed simultaneously. The results show that the solid electrolyte interphase (SEI) composition for the wet electrode is stable within the probing time and generally agrees well with traditional UHV studies. Since the methodology can easily be adjusted to various high pressure photoelectron spectroscopy systems, extending the approach towards operando solid/liquid interface studies using liquid electrolytes seems now feasible.

  2. Lithium sulfur batteries and electrolytes and sulfur cathodes thereof

    Science.gov (United States)

    Visco, Steven J.; Goncharenko, Nikolay; Nimon, Vitaliy; Petrov, Alexei; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Katz, Bruce D.; Loginova, Valentina

    2017-05-23

    Lithium sulfur battery cells that use water as an electrolyte solvent provide significant cost reductions. Electrolytes for the battery cells may include water solvent for maintaining electroactive sulfur species in solution during cell discharge and a sufficient amount of a cycle life-enhancing compound that facilitates charging at the cathode. The combination of these two components enhances one or more of the following cell attributes: energy density, power density and cycle life. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, for example, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage. Sulfur cathodes, and methods of fabricating lithium sulfur cells, in particular for loading lithium sulfide into the cathode structures, provide further advantages.

  3. High elastic modulus polymer electrolytes suitable for preventing thermal runaway in lithium batteries

    Science.gov (United States)

    Mullin, Scott; Panday, Ashoutosh; Balsara, Nitash Pervez; Singh, Mohit; Eitouni, Hany Basam; Gomez, Enrique Daniel

    2014-04-22

    A polymer that combines high ionic conductivity with the structural properties required for Li electrode stability is useful as a solid phase electrolyte for high energy density, high cycle life batteries that do not suffer from failures due to side reactions and dendrite growth on the Li electrodes, and other potential applications. The polymer electrolyte includes a linear block copolymer having a conductive linear polymer block with a molecular weight of at least 5000 Daltons, a structural linear polymer block with an elastic modulus in excess of 1.times.10.sup.7 Pa and an ionic conductivity of at least 1.times.10.sup.-5 Scm.sup.-1. The electrolyte is made under dry conditions to achieve the noted characteristics. In another aspect, the electrolyte exhibits a conductivity drop when the temperature of electrolyte increases over a threshold temperature, thereby providing a shutoff mechanism for preventing thermal runaway in lithium battery cells.

  4. Further studies on the lithium phosphorus oxynitride solid electrolyte

    International Nuclear Information System (INIS)

    Pichonat, Tristan; Lethien, Christophe; Tiercelin, Nicolas; Godey, Sylvie; Pichonat, Emmanuelle; Roussel, Pascal; Colmont, Marie; Rolland, Paul Alain

    2010-01-01

    First step in the way to the fabrication of an all-solid microbattery for autonomous wireless sensor node, amorphous thin solid films of lithium phosphorus oxynitride (LiPON) were prepared by radio-frequency sputtering of a mixture target of P 2 O 5 /Li 2 O in ambient nitrogen atmosphere. The morphology, composition, and ionic conductivity were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and A.C. impedance spectroscopy. With a thickness of 1.4 μm, the obtained LiPON amorphous layer provided an ionic conductivity close to 6 x 10 -7 S cm -1 at room temperature. MicroRaman UV spectroscopy study was successfully carried out for the first time on LiPON thin films to complete the characterization and bring further information on LiPON structure.

  5. Fermi Potential across Working Solid Oxide Cells with Zirconia or Ceria Electrolytes

    DEFF Research Database (Denmark)

    Jacobsen, Torben; Chatzichristodoulou, Christodoulos; Mogensen, Mogens Bjerg

    2014-01-01

    A solid electrolyte will always possess a finite electronic conductivity, in particular electrolytes like doped ceria that easily get reduced and become mixed ionic and electronic conductors. This given rise too high leak currents through the solid oxide cell (SOC). Especially, problems have been...... driving the O2-ions is not the Fermi potential, which is the potential of the electrons, but the Galvani potential (or inner potential) (1). The concepts of potentials describing the electrical situation of a solid electrolyte is shown i Fig. 1, and an example of the Fermi potential (π) and Galvani...

  6. Development of Lithium-Stuffed Garnet-Type Oxide Solid Electrolytes with High Ionic Conductivity for Application to All-Solid-State Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Inada, Ryoji, E-mail: inada@ee.tut.ac.jp; Yasuda, Satoshi; Tojo, Masaru; Tsuritani, Keiji; Tojo, Tomohiro; Sakurai, Yoji [Department of Electrical and Electronic Engineering, Toyohashi University of Technology, Toyohashi (Japan)

    2016-07-20

    All-solid-state lithium-ion batteries are expected to be one of the next generations of energy storage devices because of their high energy density, high safety, and excellent cycle stability. Although oxide-based solid electrolyte (SE) materials have rather lower conductivity and poor deformability than sulfide-based ones, they have other advantages, such as their chemical stability and ease of handling. Among the various oxide-based SEs, lithium-stuffed garnet-type oxide, with the formula of Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} (LLZ), has been widely studied because of its high conductivity above 10{sup −4} S cm{sup −1} at room temperature, excellent thermal performance, and stability against Li metal anode. Here, we present our recent progress for the development of garnet-type SEs with high conductivity by simultaneous substitution of Ta{sup 5+} into the Zr{sup 4+} site and Ba{sup 2+} into the La{sup 3+} site in LLZ. Li{sup +} concentration was fixed to 6.5 per chemical formulae, so that the formula of our Li garnet-type oxide is expressed as Li{sub 6.5}La{sub 3−x}Ba{sub x}Zr{sub 1.5−x}Ta{sub 0.5+x}O{sub 12} (LLBZT) and Ba contents x are changed from 0 to 0.3. As a result, all LLBZT samples have a cubic garnet structure without containing any secondary phases. The lattice parameters of LLBZT decrease with increasing Ba{sup 2+} contents x ≤ 0.10 while increase with x from 0.10 to 0.30, possibly due to the simultaneous change of Ba{sup 2+} and Ta{sup 5+} substitution levels. The relative densities of LLBZT are in a range between 89 and 93% and are not influenced in any significant way by the compositions. From the AC impedance spectroscopy measurements, the total (bulk + grain) conductivity at 27°C of LLBZT shows its maximum value of 8.34 × 10{sup −4} S cm{sup −1} at x = 0.10, which is slightly higher than the conductivity (= 7.94 × 10{sup −4} S cm{sup −1}) of LLZT without substituting Ba (x = 0). The activation energy of the conductivity

  7. Formation of Reversible Solid Electrolyte Interface on Graphite Surface from Concentrated Electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Dongping; Tao, Jinhui; Yan, Pengfei; Henderson, Wesley A.; Li, Qiuyan; Shao, Yuyan; Helm, Monte L.; Borodin, Oleg; Graff, Gordon L.; Polzin, Bryant; Wang, Chong-Min; Engelhard, Mark; Zhang, Ji-Guang; De Yoreo, James J.; Liu, Jun; Xiao, Jie

    2017-02-10

    Interfacial phenomena have always been key determinants for the performance of energy storage technologies. The solid electrolyte interfacial (SEI) layer, pervasive on the surfaces of battery electrodes for numerous chemical couples, directly affects the ion transport, charge transfer and lifespan of the entire energy system. Almost all SEI layers, however, are unstable resulting in the continuous consumption of the electrolyte. Typically, this leads to the accumulation of degradation products on/restructuring of the electrode surface and thus increased cell impedance, which largely limits the long-term operation of the electrochemical reactions. Herein, a completely new SEI formation mechanism has been discovered, in which the electrolyte components reversibly self-assemble into a protective surface coating on a graphite electrode upon changing the potential. In contrast to the established wisdom regarding the necessity of employing the solvent ethylene carbonate (EC) to form a protective SEI layer on graphite, a wide range of EC-free electrolytes are demonstrated for the reversible intercalation/deintercalation of Li+ cations within a graphite lattice, thereby providing tremendous flexibility in electrolyte tailoring for battery couples. This novel finding is broadly applicable and provides guidance for how to control interfacial reactions through the relationship between ion aggregation and solvent decomposition at polarized interfaces.

  8. Toward fast and cost-effective ink-jet printing of solid electrolyte for lithium microbatteries

    Science.gov (United States)

    Delannoy, P.-E.; Riou, B.; Lestriez, B.; Guyomard, D.; Brousse, T.; Le Bideau, J.

    2015-01-01

    Ink-jet printing of ionogel for low-cost microbattery is presented. Such an approach allows to provide liquid-like electrolyte performances for all-solid microdevices. Ink-jet printing process is possible thanks to sol precursor of the ionogel. This full silica based ionogels confining ionic liquid are known to be thermal resistant, serving safety and technologies requiring solder reflow. High ionic conductivity and compatibility with porous composite electrodes allow reaching good electrochemical cycling performance: full Li-ion cell with LiFePO4 and Li4Ti5O12 porous composite electrodes shows a surface capacity of 300 μAh cm-2 for more than 100 cycles. Such surface capacities are very competitive as compared to those obtained for microdevices based on expensive PVD processes.

  9. Electrochemical properties of ether-based electrolytes for lithium/sulfur rechargeable batteries

    International Nuclear Information System (INIS)

    Barchasz, Céline; Leprêtre, Jean-Claude; Patoux, Sébastien; Alloin, Fannie

    2013-01-01

    Highlights: ► Liquid electrolyte composition for lithium/sulfur secondary batteries. ► Carbonate-based electrolytes prove not to be compatible with the sulfur electrode. ► Poor electrochemical performances related to low polysulfide solubility. ► Increase in the discharge capacity using ether solvents with high solvating ability such as PEGDME. ► Evidence of DIOX polymerization during cycling. -- Abstract: The lithium/sulfur (Li/S) battery is a promising electrochemical system that has a high theoretical capacity of 1675 mAh g −1 . However, the system suffers from several drawbacks: poor active material conductivity, active material dissolution, and use of the highly reactive lithium metal electrode. In this study, we investigated the electrolyte effects on electrochemical performances of the Li/S cell, by acting on the solvent composition. As conventional carbonate-based electrolytes turned out to be unusable in Li/S cells, alternative ether solvents had to be considered. Different kinds of solvent structures were investigated by changing the ether/alkyl moieties ratio to vary the lithium polysulfide solubility. This allowed to point out the importance of the solvent solvation ability on the discharge capacity. As the end of discharge is linked to the positive electrode passivation, an electrolyte having high solvation ability reduces the polysulfide precipitation and delays the positive electrode passivation

  10. Highly Quantitative Electrochemical Characterization of Non-Aqueous Electrolytes & Solid Electrolyte Interphases

    Energy Technology Data Exchange (ETDEWEB)

    Sergiy V. Sazhin; Kevin L. Gering; Mason K. Harrup; Harry W. Rollins

    2012-10-01

    The methods to measure solid electrolyte interphase (SEI) electrochemical properties and SEI formation capability of non-aqueous electrolyte solutions are not adequately addressed in the literature. And yet, there is a strong demand in new electrolyte generations that promote stabilized SEIs and have an influence to resolve safety, calendar life and other limitations of Li-ion batteries. To fill this gap, in situ electrochemical approach with new descriptive criteria for highly quantitative characterization of SEI and electrolytes is proposed. These criteria are: SEI formation capacity, SEI corrosion rate, SEI maintenance rate, and SEI kinetic stability. These criteria are associated with battery parameters like irreversible capacity, self-discharge, shelf-life, power, etc. Therefore, they are especially useful for electrolyte development and standard fast screening, allowing a skillful approach to narrow down the search for the best electrolyte. The characterization protocol also allows retrieving information on interfacial resistance for SEI layers and the electrochemical window of electrolytes, the other important metrics of characterization. The method validation was done on electrolyte blends containing phosphazenes, developed at Idaho National Laboratory, as 1.2M LiPF6 [80 % EC-MEC (2:8) (v/v) + 20% Phosphazene variety] (v/v), which were targeted for safer electrolyte variations.

  11. In-situ study of the dendritic growth in lithium/polymer electrolyte-salt/lithium cells; Etude in-situ de la croissance dendritique dans des cellules lithium/POE-sel/lithium

    Energy Technology Data Exchange (ETDEWEB)

    Brissot, C.; Rosso, M.; Chazalviel, J.N. [Ecole Polytechnique, 91 - Palaiseau (France); Baudry, P.; Lascaud, S. [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches

    1996-12-31

    The in-situ observation of dendritic growth in lithium/polymer electrolyte-LiTFSI/lithium battery cells shows that dendrites grow up with about the same rate as anion migration. Memory effects have been evidenced in cycling experiments and limit the dendrites length. An overall movement of the electrolyte due to variations of electrolyte concentration in the vicinity of the electrodes has been observed too. (J.S.) 13 refs.

  12. In-situ study of the dendritic growth in lithium/polymer electrolyte-salt/lithium cells; Etude in-situ de la croissance dendritique dans des cellules lithium/POE-sel/lithium

    Energy Technology Data Exchange (ETDEWEB)

    Brissot, C; Rosso, M; Chazalviel, J N [Ecole Polytechnique, 91 - Palaiseau (France); Baudry, P; Lascaud, S [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches

    1997-12-31

    The in-situ observation of dendritic growth in lithium/polymer electrolyte-LiTFSI/lithium battery cells shows that dendrites grow up with about the same rate as anion migration. Memory effects have been evidenced in cycling experiments and limit the dendrites length. An overall movement of the electrolyte due to variations of electrolyte concentration in the vicinity of the electrodes has been observed too. (J.S.) 13 refs.

  13. A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes

    Science.gov (United States)

    Liu, Nian; Lu, Zhenda; Zhao, Jie; McDowell, Matthew T.; Lee, Hyun-Wook; Zhao, Wenting; Cui, Yi

    2014-03-01

    Silicon is an attractive material for anodes in energy storage devices, because it has ten times the theoretical capacity of its state-of-the-art carbonaceous counterpart. Silicon anodes can be used both in traditional lithium-ion batteries and in more recent Li-O2 and Li-S batteries as a replacement for the dendrite-forming lithium metal anodes. The main challenges associated with silicon anodes are structural degradation and instability of the solid-electrolyte interphase caused by the large volume change (~300%) during cycling, the occurrence of side reactions with the electrolyte, and the low volumetric capacity when the material size is reduced to a nanometre scale. Here, we propose a hierarchical structured silicon anode that tackles all three of these problems. Our design is inspired by the structure of a pomegranate, where single silicon nanoparticles are encapsulated by a conductive carbon layer that leaves enough room for expansion and contraction following lithiation and delithiation. An ensemble of these hybrid nanoparticles is then encapsulated by a thicker carbon layer in micrometre-size pouches to act as an electrolyte barrier. As a result of this hierarchical arrangement, the solid-electrolyte interphase remains stable and spatially confined, resulting in superior cyclability (97% capacity retention after 1,000 cycles). In addition, the microstructures lower the electrode-electrolyte contact area, resulting in high Coulombic efficiency (99.87%) and volumetric capacity (1,270 mAh cm-3), and the cycling remains stable even when the areal capacity is increased to the level of commercial lithium-ion batteries (3.7 mAh cm-2).

  14. Enhancement in ionic conductivity on solid polymer electrolytes containing large conducting species

    Energy Technology Data Exchange (ETDEWEB)

    Praveen, D. [Department of Physics, Amrita Viswha Vidyapeetham, Bangalore, India, E-mail: d-praveen@blr.amrita.edu (India); Damle, Ramakrishna [Department of Physics, Bangalore University, Bangalore, India. E-mail: ramkrishnadamle@bub.ernet.in (India)

    2016-05-23

    Solid Polymer Electrolytes (SPEs) lack better conducting properties at ambient temperatures. Various methods to enhance their ionic conductivity like irradiation with swift heavy ions, γ-rays, swift electrons and quenching at low temperature etc., have been explored in the literature. Among these, one of the oldest methods is incorporation of different conducting species into the polymer matrix and/or addition of nano-sized inert particles into SPEs. Various new salts like LiBr, Mg(ClO{sub 4}){sub 2}, NH{sub 4}I etc., have already been tried in the past with some success. Also various nanoparticles like Al{sub 2}O{sub 3}, TiO{sub 2} etc., have been tried in the past. In this article, we have investigated an SPE containing Rubidium as a conducting species. Rubidium has a larger ionic size compared to lithium and sodium ions which have been investigated in the recent past. In the present article, we have investigated the conductivity of large sized conducting species and shown the enhancement in the ionic conductivity by addition of nano-sized inert particles.

  15. Enhancement in ionic conductivity on solid polymer electrolytes containing large conducting species

    International Nuclear Information System (INIS)

    Praveen, D.; Damle, Ramakrishna

    2016-01-01

    Solid Polymer Electrolytes (SPEs) lack better conducting properties at ambient temperatures. Various methods to enhance their ionic conductivity like irradiation with swift heavy ions, γ-rays, swift electrons and quenching at low temperature etc., have been explored in the literature. Among these, one of the oldest methods is incorporation of different conducting species into the polymer matrix and/or addition of nano-sized inert particles into SPEs. Various new salts like LiBr, Mg(ClO_4)_2, NH_4I etc., have already been tried in the past with some success. Also various nanoparticles like Al_2O_3, TiO_2 etc., have been tried in the past. In this article, we have investigated an SPE containing Rubidium as a conducting species. Rubidium has a larger ionic size compared to lithium and sodium ions which have been investigated in the recent past. In the present article, we have investigated the conductivity of large sized conducting species and shown the enhancement in the ionic conductivity by addition of nano-sized inert particles.

  16. Performance of Lithium Polymer Cells with Polyacrylonitrile based Electrolyte

    DEFF Research Database (Denmark)

    Perera, Kumudu; Dissanayake, M.A.K.L.; Skaarup, Steen

    2006-01-01

    The performance of lithium polymer cells fabricated with Polyacrylonitrile (PAN) based electrolytes was studied using cycling voltammetry and continuous charge discharge cycling. The electrolytes consisted of PAN, ethylene carbonate (EC), propylene carbonate (PC) and lithium...... trifluoromethanesulfonate (LiCF3SO3 – LiTF). The polymer electrode material was polypyrrole (PPy) doped with dodecyl benzene sulfonate (DBS). The cells were of the form, Li / PAN : EC : PC : LiCF3SO3 / PPy : DBS. Polymer electrodes of three different thicknesses were studied using cycling at different scan rates. All cells...

  17. Comparison of Vitros Dry Slide Technology for Determination of Lithium Ions with Other Methods

    Directory of Open Access Journals (Sweden)

    Nafija Serdarević

    2006-05-01

    Full Text Available The lithium ions concentration in human serum was determined using Dry-slide technology Vitros 250 Analyser (Ortho Clinical Diagnostic, atomic absorption spectrometry (AAS method Perkin Elmer 403 and ion-selective electrode (ISE potentiometry AVL 9181. We compared lithium ions results in sample sera between these methods. Our reference method was AAS. We analyzed lithium ions concentration in 23 sera samples of patients after oral administration of lithium carbonate (3x 300mg Jadran, Galen Laboratory Rijeka, by dry-slide technology, AAS and ISE methods. The quality control, precision, reproducibility and accuracy for Vitros dry slide technology were assessed. We established that the main difference between AAS method and dry slide technology was not statistically significant at p< 0.05 according to Student t-test. Therefore, the dry slide technology may be a useful alternative or it may even replace other methods, such as AAS. The main difference between dry slide technology and ISE methods was statistically significant at p<0.05 using Student t-test. By ISE method, we obtained considerably higher results, which may be explained by the presence of electrolytes or medicaments interfering with lithium ions.

  18. Ion conduction in crystalline superionic solids and its applications

    Science.gov (United States)

    Chandra, Angesh

    2014-06-01

    Superionic solids an area of multidisciplinary research activity, incorporates to study the physical, chemical and technological aspects of rapid ion movements within the bulk of the special class of ionic materials. It is an emerging area of materials science, as these solids show tremendous technological scopes to develop wide variety of solid state electrochemical devices such as batteries, fuel cells, supercapacitors, sensors, electrochromic displays (ECDs), memories, etc. These devices have wide range of applicabilities viz. power sources for IC microchips to transport vehicles, novel sensors for controlling atmospheric pollution, new kind of memories for computers, smart windows/display panels, etc. The field grew with a rapid pace since then, especially with regards to designing new materials as well as to explore their device potentialities. Amongst the known superionic solids, fast Ag+ ion conducting crystalline solid electrolytes are attracted special attention due to their relatively higher room temperature conductivity as well as ease of materials handling/synthesis. Ion conduction in these electrolytes is very much interesting part of today. In the present review article, the ion conducting phenomenon and some device applications of crystalline/polycrystalline superionic solid electrolytes have been reviewed in brief. Synthesis and characterization tools have also been discussed in the present review article.

  19. Lithium-ion storage capacitors achieved by CVD graphene/TaC/Ta-wires and carbon hollow spheres

    International Nuclear Information System (INIS)

    Zhao, Liwei; Li, Hongji; Li, Mingji; Xu, Sheng; Li, Cuiping; Qu, Changqing; Zhang, Lijun; Yang, Baohe

    2016-01-01

    Highlights: • Graphene/TaC/Ta wire electrode was prepared by CVD. • Carbon hollow spheres as a solid electrolyte were prepared by hydrothermal. • Specific capacitance of assembled capacitor reached 593 F g −1 at 10 A g −1 . • The capacitor provided high energy and power densities (132 W h kg −1 /3.17 kW kg −1 ). • The hybrid capacitor also exhibited a high stability during long endurance tests. - Abstract: Lithium-ion storage capacitors were assembled using graphene/tantalum carbide/tantalum wire electrodes and carbon hollow spheres as electrolyte. The graphene/tantalum carbide layers were prepared by electron-assisted hot filament chemical vapor deposition; the carbon hollow spheres were synthesized by hydrothermal reaction and pyrolysis treatment. The specific capacitance of the capacitor was 593 F g −1 at a current density of 10 A g −1 . The capacitor showed excellent cycling stability, retaining 91.2% of its initial capacitance after 8000 cycles. Moreover, the capacitor provided a high specific energy density of 132 W h kg −1 at a high power density of 3.17 kW kg −1 . The high energy density is attributed to the widened operation window ranging from 0 to 3.0 V. The graphene layer of the electrode and carbon hollow spheres in electrolyte synergistic affect influence on the electrochemical performance of the capacitor are discussed. In addition, the use of a low-cost lithium salt, lithium chloride, is also featured in this paper.

  20. Renewable and superior thermal-resistant cellulose-based composite nonwoven as lithium-ion battery separator.

    Science.gov (United States)

    Zhang, Jianjun; Liu, Zhihong; Kong, Qingshan; Zhang, Chuanjian; Pang, Shuping; Yue, Liping; Wang, Xuejiang; Yao, Jianhua; Cui, Guanglei

    2013-01-01

    A renewable and superior thermal-resistant cellulose-based composite nonwoven was explored as lithium-ion battery separator via an electrospinning technique followed by a dip-coating process. It was demonstrated that such nanofibrous composite nonwoven possessed good electrolyte wettability, excellent heat tolerance, and high ionic conductivity. The cells using the composite separator displayed better rate capability and enhanced capacity retention, when compared to those of commercialized polypropylene separator under the same conditions. These fascinating characteristics would endow this renewable composite nonwoven a promising separator for high-power lithium-ion battery.