Electron-deficient anthraquinone derivatives as cathodic material for lithium ion batteries

Science.gov (United States)

Takeda, Takashi; Taniki, Ryosuke; Masuda, Asuna; Honma, Itaru; Akutagawa, Tomoyuki

2016-10-01

We studied the electronic and structural properties of electron-deficient anthraquinone (AQ) derivatives, Me4N4AQ and TCNAQ, and investigated their charge-discharge properties in lithium ion batteries along with those of AQ. Cyclic voltammogram, X-ray structure analysis and theoretical calculations revealed that these three acceptors have different features, such as different electron-accepting properties with different reduction processes and lithium coordination abilities, and different packing arrangements with different intermolecular interactions. These differences greatly affect the charge-discharge properties of lithium ion batteries that use these compounds as cathode materials. Among these compounds, Me4N4AQ showed a high charge/discharge voltage (2.9-2.5 V) with high cyclability (>65% of the theoretical capacity after 30 cycles; no decrease after 15 cycles). These results provide insight into more in-depth design principles for lithium ion batteries using AQ derivatives as cathodic materials.

Cathodes for lithium ion batteries: the benefits of using nanostructured materials

International Nuclear Information System (INIS)

Bazito, Fernanda F.C.; Torresi, Roberto M.

2006-01-01

Commercially available lithium ion cells, which are the most advanced among rechargeable batteries available so far, employ microcrystalline transition metal oxides as cathodes, which function as Li insertion hosts. In search for better electrochemical performance the use of nanomaterials in place of these conventional ones has emerged as excellent alternative. In this review we present a brief introduction about the motivations to use nanostructured materials as cathodes in lithium ion batteries. To illustrate such advantages we present some examples of research directed toward preparations and electrochemical data of the most used cathodes in nanoscale, such as LiCoO 2 , LiMn 2 O 4 , LiMnO 2 , LiV 2 O 5 e LiFePO 4 . (author)

New polyanion-based cathode materials for alkali-ion batteries

Science.gov (United States)

Yaghoobnejad Asl, Hooman

A number of new materials have been discovered through exploratory synthesis with the aim to be studied as the positive electrode (cathode) in Li-ion and Na-ion batteries. The focus has been set on the ease of synthesis, cost and availability of active ingredients in the battery, and decent cycle-life performance through a combination of iron and several polyanionic ligands. An emphasis has been placed also on phosphite (HPO32-) as a polyanionic ligand, mainly due to the fact that it has not been studied seriously before as a polyanion for cathode materials. The concept of mixed polyanions, for example, boro-phosphate and phosphate-nitrates were also explored. In each case the material was first made and purified via different synthetic strategies, and the crystal structure, which dominantly controls the performance of the materials, has been extensively studied through Single-Crystal X-ray Diffraction (SCXRD) or synchrotron-based Powder X-ray Diffraction (PXRD). This investigation yielded four new compositions, namely Li3Fe 2(HPO3)3Cl, LiFe(HPO3)2, Li0.8Fe(H2O)2B[P2O8]•H 2O and AFePO4NO3 (A = NH4/Li, K). Furthermore, for each material the electrochemical performance for insertion of Li+ ion has been studied by means of various electrochemical techniques to reveal the nature of alkali ion insertion. In addition Na-ion intercalation has been studied for boro-phosphate and AFePO4NO3. Additionally a novel synthesis procedure has been reported for tavorite LiFePO4F 1-x(OH)x, where 0 ≤ x ≤ 1, an important class of cathode materials. The results obtained clearly demonstrate the importance of crystal structure on the cathode performance through structural and compositional effects. Moreover these findings may contribute to the energy storage community by providing insight into the solid-state science of electrode material synthesis and proposing new alternative compositions based on sustainable materials.

Theoretical evaluation of high-energy lithium metal phosphate cathode materials in Li-ion batteries

Science.gov (United States)

Howard, Wilmont F.; Spotnitz, Robert M.

Lithium metal phosphates (olivines) are emerging as long-lived, safe cathode materials in Li-ion batteries. Nano-LiFePO 4 already appears in high-power applications, and LiMnPO 4 development is underway. Current and emerging Fe- and Mn-based intercalants, however, are low-energy producers compared to Ni and Co compounds. LiNiPO 4, a high voltage olivine, has the potential for superior energy output (>10.7 Wh in 18650 batteries), compared with commercial Li(Co,Ni)O 2 derivatives (up to 9.9 Wh). Speculative Co and Ni olivine cathode materials charged to above 4.5 V will require significant advances in electrolyte compositions and nanotechnology before commercialization. The major drivers toward 5 V battery chemistries are the inherent abuse tolerance of phosphates and the economic benefit of LiNiPO 4: it can produce 34% greater energy per dollar of cell material cost than LiAl 0.05Co 0.15Ni 0.8O 2, today's "standard" cathode intercalant in Li-ion batteries.

Synthesis and investigation of novel cathode materials for sodium ion batteries

Science.gov (United States)

Sawicki, Monica

Environmental pollution and eventual depletion of fossil fuels and lithium has increased the need for research towards alternative electrical energy storage systems. In this context, research in sodium ion batteries (NIBs) has become more prevalent since the price in lithium has increased due to its demand and reserve location. Sodium is an abundant resource that is low cost, and safe; plus its chemical properties are similar to that of Li which makes the transition into using Na chemistry for ion battery systems feasible. In this study, we report the effects of processing conditions on the electrochemical properties of Na-ion batteries made of the NaCrO2 cathode. NaCrO2 is synthesized via solid state reactions. The as-synthesized powder is then subjected to high-energy ball milling under different conditions which reduces particle size drastically and causes significant degradation of the specific capacity for NaCrO2. X-ray diffraction reveals that lattice distortion has taken place during high-energy ball milling and in turn affects the electrochemical performance of the cathode material. This study shows that a balance between reducing particle size and maintaining the layered structure is essential to obtain high specific capacity for the NaCrO2 cathode. In light of the requirements for grid scale energy storage: ultra-long cycle life (> 20,000 cycles and calendar life of 15 to 20 years), high round trip efficiency (> 90%), low cost, sufficient power capability, and safety; the need for a suitable cathode materials with excellent capacity retention such as Na2MnFe(CN)6 and K2MnFe(CN)6 will be investigated. Prussian blue (A[FeIIIFeII (CN)6]•xH2O, A=Na+ or K+ ) and its analogues have been investigated as an alkali ion host for use as a cathode material. Their structure (FCC) provides large ionic channels along the direction enabling facile insertion and extraction of alkali ions. This material is also capable of more than one Na ion insertion per unit formula

Manganese Sesquioxide as Cathode Material for Multivalent Zinc Ion Battery with High Capacity and Long Cycle Life

International Nuclear Information System (INIS)

Jiang, Baozheng; Xu, Chengjun; Wu, Changle; Dong, Liubing; Li, Jia; Kang, Feiyu

2017-01-01

Highlights: • Manganese oxides with Mn(III) state is firstly reported to store zinc ion. • Zinc ion battery with α-Mn 2 O 3 cathode is assembled. • Storage mechanism of zinc ion in α-Mn 2 O 3 is investigated. - Abstract: Rechargeable zinc ion battery is considered as one of the most potential energy storage devices for large-scale energy storage system due to its safety, low-cost, high capacity and nontoxicity. However, only a few cathode materials have been studied for rechargeable zinc ion batteries. Here, we firstly report manganese sesquioxide (Mn 2 O 3 ) with Mn(III) state as cathode material for rechargeable zinc ion battery. The α-Mn 2 O 3 cathode displays a reversible capacity of 148 mAh g −1 , which is relatively high among all the reported cathode materials for ZIB. The cathode also exhibits good rate capability and excellent cycling stability with a long cycle life up to 2000 times. The ion storage mechanism of α-Mn 2 O 3 in zinc ion battery was also revealed. The pristine α-Mn 2 O 3 undergoes a reversible phase transition from bixbyite structure to layered-type zinc birnessite during the electrochemical zinc ion insertion and extraction. The results not only benefit for the practical application of rechargeable zinc ion battery, but also broaden the horizons of understanding the electrochemical behavior and mechanism of rechargeable zinc ion batteries.

Sulfurized carbon: a class of cathode materials for high performance lithium/sulfur batteries

Directory of Open Access Journals (Sweden)

Sheng S. Zhang

2013-12-01

Full Text Available Liquid electrolyte lithium/sulfur (Li/S batteries cannot come into practical applications because of many problems such as low energy efficiency, short cycle life, and fast self-discharge. All these problems are related to the dissolution of lithium polysulfide, a series of sulfur reduction intermediates, in the liquid electrolyte, and resulting parasitic reactions with the Li anode. Covalently binding sulfur onto carbon surface is a solution to completely eliminate the dissolution of lithium polysulfide and make the Li/S battery viable for practical applications. This can be achieved by replacing elemental sulfur with sulfurized carbon as the cathode material. This article reviews the current efforts on this subject and discusses the syntheses, electrochemical properties, and prospects of the sulfurized carbon as a cathode material in the rechargeable Li/S batteries.

A new high power thermal battery cathode material

International Nuclear Information System (INIS)

Faul, I.

1986-01-01

Smaller and lighter thermal batteries are major aims of the battery research programme at RAE Farnborough. Modern designs of thermal batteries, for use as power supplies in weapon systems, almost invariably use the Li:molten salt:FeS/sub 2/ system because of the significant increase in energy density achieved in comparison with the earlier Ca/CaCrO/sub 4/ couple. The disadvantage of the FeS/sub 2/ system is that the working cell voltage, between 1.5 and 2.0 V, is significantly lower so leading to more cells per battery than the earlier system. Further work at RAE and MSA (Britain) Ltd showed that the poor thermal stability of TiS/sub 2/ limited its use in thermal batteries, whilst the more stable V/sub 6/O/sub 13/ oxidised the electrolyte, giving poor efficiencies. However, the resulting reduced vanadium oxide material, subsequently called lithiated vanadium oxide (LVO), was found to be an excellent high voltage thermal battery cathode, being the subject of both UK and US patents. In this study both V/sub 6/O/sub 13/ made by the direct stoichiometric reaction of V/sub 2/O/sub 5/ and V and also by thermal decomposition of NH/sub 4/VO/sub 3/ under argon, have been used with equal success as the starting material for the preparation of LVO

High-Capacity Cathode Material with High Voltage for Li-Ion Batteries.

Science.gov (United States)

Shi, Ji-Lei; Xiao, Dong-Dong; Ge, Mingyuan; Yu, Xiqian; Chu, Yong; Huang, Xiaojing; Zhang, Xu-Dong; Yin, Ya-Xia; Yang, Xiao-Qing; Guo, Yu-Guo; Gu, Lin; Wan, Li-Jun

2018-03-01

Electrochemical energy storage devices with a high energy density are an important technology in modern society, especially for electric vehicles. The most effective approach to improve the energy density of batteries is to search for high-capacity electrode materials. According to the concept of energy quality, a high-voltage battery delivers a highly useful energy, thus providing a new insight to improve energy density. Based on this concept, a novel and successful strategy to increase the energy density and energy quality by increasing the discharge voltage of cathode materials and preserving high capacity is proposed. The proposal is realized in high-capacity Li-rich cathode materials. The average discharge voltage is increased from 3.5 to 3.8 V by increasing the nickel content and applying a simple after-treatment, and the specific energy is improved from 912 to 1033 Wh kg -1 . The current work provides an insightful universal principle for developing, designing, and screening electrode materials for high energy density and energy quality. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Preparation and electrochemical performance of sulfur-alumina cathode material for lithium-sulfur batteries

International Nuclear Information System (INIS)

Dong, Kang; Wang, Shengping; Zhang, Hanyu; Wu, Jinping

2013-01-01

Highlights: ► Micron-sized alumina was synthesized as adsorbent for lithium-sulfur batteries. ► Sulfur-alumina material was synthesized via crystallizing nucleation. ► The Al 2 O 3 can provide surface area for the deposition of Li 2 S and Li 2 S 2 . ► The discharge capacity of the battery is improved during the first several cycles. - Abstract: Nano-sized sulfur particles exhibiting good adhesion with conducting acetylene black and alumina composite materials were synthesized by means of an evaporated solvent and a concentrated crystallization method for use as the cathodes of lithium-sulfur batteries. The composites were characterized and examined by X-ray diffraction, environmental scanning electron microscopy and electrochemical methods, such as cyclic voltammetry, electrical impedance spectroscopy and charge–discharge tests. Micron-sized flaky alumina was employed as an adsorbent for the cathode material. The initial discharge capacity of the cathode with the added alumina was 1171 mAh g −1 , and the remaining capacity was 585 mAh g −1 after 50 cycles at 0.25 mA cm −2 . Compared with bare sulfur electrodes, the electrodes containing alumina showed an obviously superior cycle performance, confirming that alumina can contribute to reducing the dissolution of polysulfides into electrolytes during the sulfur charge–discharge process

Turning Waste Chemicals into Wealth-A New Approach To Synthesize Efficient Cathode Material for an Li-O2 Battery.

Science.gov (United States)

Yao, Ying; Wu, Feng

2017-09-20

An Li-O 2 battery requires the oxygen-breathing cathode to be highly electronically conductive, rapidly oxygen diffusive, structurally stable, and often times electrocatalytically active. Catalyst-decorated porous carbonaceous materials are the chosen air cathode in this regard. Alternatively, biomass-derived carbonaceous materials possess great ability to remove heavy and toxic metal ions from waste, forming a metal-adsorbed porous carbonaceous material. The similar structure between the air cathode and the metal-adsorbed biomass-derived carbon nicely bridges these two irrelevant areas. In this study, we investigated the electrochemical activity of a biochar material Ag-ESB directly synthesized from ethanol sludge residue in a rechargeable aprotic Li-O 2 battery. Ag ions were adsorbed from sewage and became Ag nanoparticles with uniform coverage on the biochar surface. The as-prepared material exhibits good electrochemical behavior in battery testing, especially toward the battery efficiency and cyclability. This study provides the possibility of synthetically efficient cathode material by reusing "waste" such as biofuel sludge residue. It is an economically and environmentally friendly approach both for an energy-storage system and for waste recycling.

Battery designs with high capacity anode materials and cathode materials

Energy Technology Data Exchange (ETDEWEB)

Masarapu, Charan; Anguchamy, Yogesh Kumar; Han, Yongbong; Deng, Haixia; Kumar, Sujeet; Lopez, Herman A.

2017-10-03

Improved high energy capacity designs for lithium ion batteries are described that take advantage of the properties of high specific capacity anode active compositions and high specific capacity cathode active compositions. In particular, specific electrode designs provide for achieving very high energy densities. Furthermore, the complex behavior of the active materials is used advantageously in a radical electrode balancing design that significantly reduced wasted electrode capacity in either electrode when cycling under realistic conditions of moderate to high discharge rates and/or over a reduced depth of discharge.

Comprehensive Enhancement of Nanostructured Lithium-Ion Battery Cathode Materials via Conformal Graphene Dispersion.

Science.gov (United States)

Chen, Kan-Sheng; Xu, Rui; Luu, Norman S; Secor, Ethan B; Hamamoto, Koichi; Li, Qianqian; Kim, Soo; Sangwan, Vinod K; Balla, Itamar; Guiney, Linda M; Seo, Jung-Woo T; Yu, Xiankai; Liu, Weiwei; Wu, Jinsong; Wolverton, Chris; Dravid, Vinayak P; Barnett, Scott A; Lu, Jun; Amine, Khalil; Hersam, Mark C

2017-04-12

Efficient energy storage systems based on lithium-ion batteries represent a critical technology across many sectors including consumer electronics, electrified transportation, and a smart grid accommodating intermittent renewable energy sources. Nanostructured electrode materials present compelling opportunities for high-performance lithium-ion batteries, but inherent problems related to the high surface area to volume ratios at the nanometer-scale have impeded their adoption for commercial applications. Here, we demonstrate a materials and processing platform that realizes high-performance nanostructured lithium manganese oxide (nano-LMO) spinel cathodes with conformal graphene coatings as a conductive additive. The resulting nanostructured composite cathodes concurrently resolve multiple problems that have plagued nanoparticle-based lithium-ion battery electrodes including low packing density, high additive content, and poor cycling stability. Moreover, this strategy enhances the intrinsic advantages of nano-LMO, resulting in extraordinary rate capability and low temperature performance. With 75% capacity retention at a 20C cycling rate at room temperature and nearly full capacity retention at -20 °C, this work advances lithium-ion battery technology into unprecedented regimes of operation.

Highly Graphitic Carbon Nanofibers Web as a Cathode Material for Lithium Oxygen Batteries

Directory of Open Access Journals (Sweden)

Hyungkyu Han

2018-01-01

Full Text Available The lithium oxygen battery is a promising energy storage system due to its high theoretical energy density and ability to use oxygen from air as a “fuel”. Although various carbonaceous materials have been widely used as a cathode material due to their high electronic conductivity and facial processability, previous studies mainly focused on the electrochemical properties associated with the materials (such as graphene and carbon nanotubes and the electrode configuration. Recent reports demonstrated that the polarization associated with cycling could be significantly increased by lithium carbonates generated from the reaction between the carbon cathode and an electrolyte, which indicates that the physicochemical properties of the carbon cathode could play an important role on the electrochemical performances. However, there is no systematic study to understand these phenomena. Here, we systematically explore the electrochemical properties of carbon nanofibers (CNF webs with different graphitization degree as a cathode for Li oxygen batteries. The physicochemical properties and electrochemical properties of CNF webs were carefully monitored before and after cycling. CNF webs are prepared at 1000, 1200 and 1400 °C. CNF web pyrolyzed at 1400 °C shows lowered polarization and improved cycle retention compared to those of CNF webs pyrolyzed at 1000 and 1200 °C.

Recent Progress in the Design of Advanced Cathode Materials and Battery Models for High-Performance Lithium-X (X = O2 , S, Se, Te, I2 , Br2 ) Batteries.

Science.gov (United States)

Xu, Jiantie; Ma, Jianmin; Fan, Qinghua; Guo, Shaojun; Dou, Shixue

2017-07-01

Recent advances and achievements in emerging Li-X (X = O 2 , S, Se, Te, I 2 , Br 2 ) batteries with promising cathode materials open up new opportunities for the development of high-performance lithium-ion battery alternatives. In this review, we focus on an overview of recent important progress in the design of advanced cathode materials and battery models for developing high-performance Li-X (X = O 2 , S, Se, Te, I 2 , Br 2 ) batteries. We start with a brief introduction to explain why Li-X batteries are important for future renewable energy devices. Then, we summarize the existing drawbacks, major progress and emerging challenges in the development of cathode materials for Li-O 2 (S) batteries. In terms of the emerging Li-X (Se, Te, I 2 , Br 2 ) batteries, we systematically summarize their advantages/disadvantages and recent progress. Specifically, we review the electrochemical performance of Li-Se (Te) batteries using carbonate-/ether-based electrolytes, made with different electrode fabrication techniques, and of Li-I 2 (Br 2 ) batteries with various cell designs (e.g., dual electrolyte, all-organic electrolyte, with/without cathode-flow mode, and fuel cell/solar cell integration). Finally, the perspective on and challenges for the development of cathode materials for the promising Li-X (X = O 2 , S, Se, Te, I 2 , Br 2 ) batteries is presented. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intercalation of Mg-ions in layered V2O5 cathode materials for rechargeable Mg-ion batteries

DEFF Research Database (Denmark)

Sørensen, Daniel Risskov; Johannesen, Pætur; Christensen, Christian Kolle

The development of functioning rechargeable Mg-ion batteries is still in its early stage, and a coarse screening of suitable cathode materials is still on-going. Within the intercalation-type cathodes, layered crystalline materials are of high interest as they are known to perform well in Li-ion...... intercalation batteries and are also increasingly being explored for Na-ion batteries. Here, we present an investigation of the layered material orthorhombic V2O5, which is a classical candidate for an ion-intercalation material having a high theoretical capacity1. We present discharge-curves for the insertion...... discharge. This indicates that the degradation is highly associated with formation of ion-blocking layers on the anode....

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

Preparation and electrochemical performance of sulfur-alumina cathode material for lithium-sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Dong, Kang [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China); Wang, Shengping, E-mail: spwang@cug.edu.cn [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China); Zhang, Hanyu; Wu, Jinping [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China)

2013-06-01

Highlights: ► Micron-sized alumina was synthesized as adsorbent for lithium-sulfur batteries. ► Sulfur-alumina material was synthesized via crystallizing nucleation. ► The Al{sub 2}O{sub 3} can provide surface area for the deposition of Li{sub 2}S and Li{sub 2}S{sub 2}. ► The discharge capacity of the battery is improved during the first several cycles. - Abstract: Nano-sized sulfur particles exhibiting good adhesion with conducting acetylene black and alumina composite materials were synthesized by means of an evaporated solvent and a concentrated crystallization method for use as the cathodes of lithium-sulfur batteries. The composites were characterized and examined by X-ray diffraction, environmental scanning electron microscopy and electrochemical methods, such as cyclic voltammetry, electrical impedance spectroscopy and charge–discharge tests. Micron-sized flaky alumina was employed as an adsorbent for the cathode material. The initial discharge capacity of the cathode with the added alumina was 1171 mAh g{sup −1}, and the remaining capacity was 585 mAh g{sup −1} after 50 cycles at 0.25 mA cm{sup −2}. Compared with bare sulfur electrodes, the electrodes containing alumina showed an obviously superior cycle performance, confirming that alumina can contribute to reducing the dissolution of polysulfides into electrolytes during the sulfur charge–discharge process.

Copper sulfates as cathode materials for Li batteries

Science.gov (United States)

Schwieger, Jonathan N.; Kraytsberg, Alexander; Ein-Eli, Yair

As lithium battery technology sets out to bridge the gap between portable electronics and the electrical automotive industry, cathode materials still stand as the bottleneck regarding performances. In the realm of highly attractive polyanion-type structures as high-voltage cathode materials, the sulfate group (SO 4) 2- possesses an acknowledged superiority over other contenders in terms of open circuit voltage arising from the inductive effect of strong covalent S-O bonds. In parallel, novel lithium insertion mechanisms are providing alternatives to traditional intercalation, enabling reversible multi-electron processes securing high capacities. Combining both of these advantageous features, we report here the successful electrochemical reactivity of copper sulfate pentahydrate (CuSO 4·5H 2O) with respect to lithium insertion via a two-electron displacement reaction entailing the extrusion of metallic copper at a dual voltage of 3.2 V and 2.7 V followed by its reversible insertion at 3.5 V and 3.8 V. At this stage, cyclability was still shown to be limited due to the irreversible degradation to a monohydrate structure owing to constitutional water loss.

Strategies toward High-Performance Cathode Materials for Lithium-Oxygen Batteries.

Science.gov (United States)

Wang, Kai-Xue; Zhu, Qian-Cheng; Chen, Jie-Sheng

2018-05-11

Rechargeable aprotic lithium (Li)-O 2 batteries with high theoretical energy densities are regarded as promising next-generation energy storage devices and have attracted considerable interest recently. However, these batteries still suffer from many critical issues, such as low capacity, poor cycle life, and low round-trip efficiency, rendering the practical application of these batteries rather sluggish. Cathode catalysts with high oxygen reduction reaction (ORR) and evolution reaction activities are of particular importance for addressing these issues and consequently promoting the application of Li-O 2 batteries. Thus, the rational design and preparation of the catalysts with high ORR activity, good electronic conductivity, and decent chemical/electrochemical stability are still challenging. In this Review, the strategies are outlined including the rational selection of catalytic species, the introduction of a 3D porous structure, the formation of functional composites, and the heteroatom doping which succeeded in the design of high-performance cathode catalysts for stable Li-O 2 batteries. Perspectives on enhancing the overall electrochemical performance of Li-O 2 batteries based on the optimization of the properties and reliability of each part of the battery are also made. This Review sheds some new light on the design of highly active cathode catalysts and the development of high-performance lithium-O 2 batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transition-metal chlorides as conversion cathode materials for Li-ion batteries

International Nuclear Information System (INIS)

Li Ting; Chen, Zhong X.; Cao, Yu L.; Ai, Xin P.; Yang, Han X.

2012-01-01

Insoluble AgCl and soluble CuCl 2 were selected and investigated as model compounds of transition-metal chlorides for electrochemical conversion cathode materials. The experimental results demonstrated that the AgCl nanocrystals can convert reversibly to metallic Ag with nearly full utilization of its one-electron redox capacity (187 mAh g −1 ). Similarly, the CuCl 2 -filled mesoporous carbon can realize a reversible two-electron transfer reaction, giving a very high reversible capacity of 466 mAh g −1 after 20 cycles. These data imply that the metal chlorides can undergo complete electrochemical conversion utilizing their full oxidation states for electrical energy storage as previously reported metal fluorides, possibly being used as high capacity cathode materials for Li-ion batteries.

Copper sulfates as cathode materials for Li batteries

Energy Technology Data Exchange (ETDEWEB)

Schwieger, Jonathan N.; Kraytsberg, Alexander; Ein-Eli, Yair [Technion Israel Institute of Technology, Department of Materials Engineering, Technion City, Haifa 32000 (Israel)

2011-02-01

As lithium battery technology sets out to bridge the gap between portable electronics and the electrical automotive industry, cathode materials still stand as the bottleneck regarding performances. In the realm of highly attractive polyanion-type structures as high-voltage cathode materials, the sulfate group (SO{sub 4}){sup 2-} possesses an acknowledged superiority over other contenders in terms of open circuit voltage arising from the inductive effect of strong covalent S-O bonds. In parallel, novel lithium insertion mechanisms are providing alternatives to traditional intercalation, enabling reversible multi-electron processes securing high capacities. Combining both of these advantageous features, we report here the successful electrochemical reactivity of copper sulfate pentahydrate (CuSO{sub 4}.5H{sub 2}O) with respect to lithium insertion via a two-electron displacement reaction entailing the extrusion of metallic copper at a dual voltage of 3.2 V and 2.7 V followed by its reversible insertion at 3.5 V and 3.8 V. At this stage, cyclability was still shown to be limited due to the irreversible degradation to a monohydrate structure owing to constitutional water loss. (author)

Carbon nanotube: nanodiamond Li-ion battery cathodes with increased thermal conductivity

Science.gov (United States)

Salgado, Ruben; Lee, Eungiee; Shevchenko, Elena V.; Balandin, Alexander A.

2016-10-01

Prevention of excess heat accumulation within the Li-ion battery cells is a critical design consideration for electronic and photonic device applications. Many existing approaches for heat removal from batteries increase substantially the complexity and overall weight of the battery. Some of us have previously shown a possibility of effective passive thermal management of Li-ion batteries via improvement of thermal conductivity of cathode and anode material1. In this presentation, we report the results of our investigation of the thermal conductivity of various Li-ion cathodes with incorporated carbon nanotubes and nanodiamonds in different layered structures. The cathodes were synthesized using the filtration method, which can be utilized for synthesis of commercial electrode-active materials. The thermal measurements were conducted with the "laser flash" technique. It has been established that the cathode with the carbon nanotubes-LiCo2 and carbon nanotube layered structure possesses the highest in-plane thermal conductivity of 206 W/mK at room temperature. The cathode containing nanodiamonds on carbon nanotubes structure revealed one of the highest cross-plane thermal conductivity values. The in-plane thermal conductivity is up to two orders-of-magnitude greater than that in conventional cathodes based on amorphous carbon. The obtained results demonstrate a potential of carbon nanotube incorporation in cathode materials for the effective thermal management of Li-ion high-powered density batteries.

Turning Waste Chemicals into Wealth—A New Approach To Synthesize Efficient Cathode Material for an Li–O ₂ Battery

Energy Technology Data Exchange (ETDEWEB)

Yao, Ying; Wu, Feng (Beijing Inst. Tech.)

2017-03-20

An Li–O₂ battery requires the oxygen-breathing cathode to be highly electronically conductive, rapidly oxygen diffusive, structurally stable, and often times electrocatalytically active. Catalyst-decorated porous carbonaceous materials are the chosen air cathode in this regard. Alternatively, biomass-derived carbonaceous materials possess great ability to remove heavy and toxic metal ions from waste, forming a metal-adsorbed porous carbonaceous material. The similar structure between the air cathode and the metal-adsorbed biomass-derived carbon nicely bridges these two irrelevant areas. In this study, we investigated the electrochemical activity of a biochar material Ag-ESB directly synthesized from ethanol sludge residue in a rechargeable aprotic Li–O₂ battery. Ag ions were adsorbed from sewage and became Ag nanoparticles with uniform coverage on the biochar surface. The as-prepared material exhibits good electrochemical behavior in battery testing, especially toward the battery efficiency and cyclability. This study provides the possibility of synthetically efficient cathode material by reusing “waste” such as biofuel sludge residue. It is an economically and environmentally friendly approach both for an energy-storage system and for waste recycling.

Monitoring local redox processes in LiNi0.5Mn1.5O4 battery cathode material by in operando EPR spectroscopy

Science.gov (United States)

Niemöller, Arvid; Jakes, Peter; Eurich, Svitlana; Paulus, Anja; Kungl, Hans; Eichel, Rüdiger-A.; Granwehr, Josef

2018-01-01

Despite the multitude of analytical methods available to characterize battery cathode materials, identifying the factors responsible for material aging is still challenging. We present the first investigation of transient redox processes in a spinel cathode during electrochemical cycling of a lithium ion battery by in operando electron paramagnetic resonance (EPR). The battery contains a LiNi0.5Mn1.5O4 (LNMO) spinel cathode, which is a material whose magnetic interactions are well understood. The evolution of the EPR signal in combination with electrochemical measurements shows the impact of Mn3+ on the Li+ motion inside the spinel. Moreover, state of charge dependent linewidth variations confirm the formation of a solid solution for slow cycling, which is taken over by mixed models of solid solution and two-phase formation for fast cycling due to kinetic restrictions and overpotentials. Long-term measurements for 480 h showed the stability of the investigated LNMO, but also small amounts of cathode degradation products became visible. The results point out how local, exchange mediated magnetic interactions in cathode materials are linked with battery performance and can be used for material characterization.

Particle size effect of Ni-rich cathode materials on lithium ion battery performance

International Nuclear Information System (INIS)

Hwang, Ilkyu; Lee, Chul Wee; Kim, Jae Chang; Yoon, Songhun

2012-01-01

Graphical abstract: The preparation condition of Ni-rich cathode materials was investigated. When the retention time was short, a poor cathode performance was observed. For long retention time condition, cathode performance displayed a best result at pH 12. Highlights: ► Ni-rich cathode materials (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) were prepared by co-precipitation method using separate addition of Al salt. ► Particle size of Ni-rich cathode materials became larger with increase of retention time and solution pH. ► Cathode performance was poor for low retention time. ► Optimal pH for co-precipitation was 12. -- Abstract: Herein, Ni-rich cathode materials (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) in lithium ion batteries are prepared by a separate addition of Ni/Co salt and Al sol solution using a continuously stirred tank reactor. Retention time and solution pH were controlled in order to obtain high performance cathode material. Particle size increase was observed with a higher retention time of the reactants. Also, primary and secondary particles became smaller according to an increase of solution pH, which was probably due to a decrease of growth rate. From the cathode application, a high discharge capacity (175 mAh g −1 ), a high initial efficiency (90%) and a good cycleability were observed in the cathode material prepared under pH 12 condition, which was attributed to its well-developed layered property and the optimal particle size. However, rate capability was inversely proportional to the particle size, which was clarified by a decrease of charge-transfer resistance measured in the electrochemical impedance spectroscopy.

2013 Estorm - Invited Paper - Cathode Materials Review

Energy Technology Data Exchange (ETDEWEB)

Daniel, Claus [ORNL; Mohanty, Debasish [ORNL; Li, Jianlin [ORNL; Wood III, David L [ORNL

2014-01-01

The electrochemical potential of cathode materials defines the positive side of the terminal voltage of a battery. Traditionally, cathode materials are the energy-limiting or voltage-limiting electrode. One of the first electrochemical batteries, the voltaic pile invented by Alessandro Volta in 1800 (Phil. Trans. Roy. Soc. 90, 403 431) had a copper-zinc galvanic element with a terminal voltage of 0.76 V. Since then, the research community has increased capacity and voltage for primary (nonrechargeable) batteries and round-trip efficiency for secondary (rechargeable) batteries. Successful secondary batteries have been the lead acid with a lead oxide cathode and a terminal voltage of 2.1 V and later the NiCd with a nickel(III) oxide hydroxide cathode and a 1.2 V terminal voltage. The relatively low voltage of those aqueous systems and the low round-trip efficiency due to activation energies in the conversion reactions limited their use. In 1976, Wittingham (J. Electrochem. Soc., 123, 315) and Besenhard (J Power Sources 1(3), 267) finally enabled highly reversible redox reactions by intercalation of lithium ions instead of by chemical conversion. In 1980, Goodenough and Mizushima (Mater. Res. Bull. 15, 783 789) demonstrated a high-energy and high-power LiCoO2 cathode, allowing for an increase of terminal voltage far beyond 3 V. Over the past four decades, the international research community has further developed cathode materials of many varieties. Current state-of-the-art cathodes demonstrate voltages beyond any known electrolyte stability window, bringing electrolyte research once again to the forefront of battery research.

Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches

International Nuclear Information System (INIS)

Hausbrand, R.; Cherkashinin, G.; Ehrenberg, H.; Gröting, M.; Albe, K.; Hess, C.; Jaegermann, W.

2015-01-01

Graphical abstract: - Highlights: • Description of recent in operando and in situ analysis methodology. • Surface science approach using photoemission for analysis of cathode surfaces and interfaces. • Ageing and fatigue of layered oxide Li-ion battery cathode materials from the atomistic point of view. • Defect formation and electronic structure evolution as causes for cathode degradation. • Significance of interfacial energy alignment and contact potential for side reactions. - Abstract: This overview addresses the atomistic aspects of degradation of layered LiMO 2 (M = Ni, Co, Mn) oxide Li-ion battery cathode materials, aiming to shed light on the fundamental degradation mechanisms especially inside active cathode materials and at their interfaces. It includes recent results obtained by novel in situ/in operando diffraction methods, modelling, and quasi in situ surface science analysis. Degradation of the active cathode material occurs upon overcharge, resulting from a positive potential shift of the anode. Oxygen loss and eventual phase transformation resulting in dead regions are ascribed to changes in electronic structure and defect formation. The anode potential shift results from loss of free lithium due to side reactions occurring at electrode/electrolyte interfaces. Such side reactions are caused by electron transfer, and depend on the electron energy level alignment at the interface. Side reactions at electrode/electrolyte interfaces and capacity fade may be overcome by the use of suitable solid-state electrolytes and Li-containing anodes

Li2C2, a High-Capacity Cathode Material for Lithium Ion Batteries.

Science.gov (United States)

Tian, Na; Gao, Yurui; Li, Yurong; Wang, Zhaoxiang; Song, Xiaoyan; Chen, Liquan

2016-01-11

As a typical alkaline earth metal carbide, lithium carbide (Li2C2) has the highest theoretical specific capacity (1400 mA h g(-1)) among all the reported lithium-containing cathode materials for lithium ion batteries. Herein, the feasibility of using Li2C2 as a cathode material was studied. The results show that at least half of the lithium can be extracted from Li2C2 and the reversible specific capacity reaches 700 mA h g(-1). The C≡C bond tends to rotate to form C4 (C≡C⋅⋅⋅C≡C) chains during lithium extraction, as indicated with the first-principles molecular dynamics (FPMD) simulation. The low electronic and ionic conductivity are believed to be responsible for the potential gap between charge and discharge, as is supported with density functional theory (DFT) calculations and Arrhenius fitting results. These findings illustrate the feasibility to use the alkali and alkaline earth metal carbides as high-capacity electrode materials for secondary batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Computational Screening for Design of Optimal Coating Materials to Suppress Gas Evolution in Li-Ion Battery Cathodes.

Science.gov (United States)

Min, Kyoungmin; Seo, Seung-Woo; Choi, Byungjin; Park, Kwangjin; Cho, Eunseog

2017-05-31

Ni-rich layered oxides are attractive materials owing to their potentially high capacity for cathode applications. However, when used as cathodes in Li-ion batteries, they contain a large amount of Li residues, which degrade the electrochemical properties because they are the source of gas generation inside the battery. Here, we propose a computational approach to designing optimal coating materials that prevent gas evolution by removing residual Li from the surface of the battery cathode. To discover promising coating materials, the reactions of 16 metal phosphates (MPs) and 45 metal oxides (MOs) with the Li residues, LiOH, and Li 2 CO 3 are examined within a thermodynamic framework. A materials database is constructed according to density functional theory using a hybrid functional, and the reaction products are obtained according to the phases in thermodynamic equilibrium in the phase diagram. In addition, the gravimetric efficiency is calculated to identify coating materials that can eliminate Li residues with a minimal weight of the coating material. Overall, more MP and MO materials react with LiOH than with Li 2 CO 3 . Specifically, MPs exhibit better reactivity to both Li residues, whereas MOs react more with LiOH. The reaction products, such as Li-containing phosphates or oxides, are also obtained to identify the phases on the surface of a cathode after coating. On the basis of the Pareto-front analysis, P 2 O 5 could be an optimal material for the reaction with both Li residuals. Finally, the reactivity of the coating materials containing 3d/4d transition metal elements is better than that of materials containing other types of elements.

Fe-N-C catalyst modified graphene sponge as a cathode material for lithium-oxygen battery

International Nuclear Information System (INIS)

Yu, Ling; Shen, Yue; Huang, Yunhui

2014-01-01

Highlights: • Hydrothermally-synthesized graphene sponge is excellent skeleton of Li-O 2 cathode. • Fe-N-C catalyst loaded on GS was attained via pyrolysis of FePc and GS composites. • High capacity and good cyclability were achieved with Fe-N-GS air electrode. • The synergy of porous structure and catalytic activity leads to the high performance. - Abstract: The cathode of a lithium-oxygen battery needs the synergism of a porous conducting material and a catalyst to facilitate the formation and decomposition of lithium peroxide. Here we introduce a graphene sponge (GS) modified with Fe-N-C catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). The porous, 3-dimensional conductive and free standing nature of the graphene sponge makes it become excellent skeleton of cathode for lithium-oxygen battery. The Fe-N-C catalyst nanoparticles dispersed uniformly on the graphene sheets show excellent catalytic reactivity in both discharge and charge processes. This kind of composite material greatly improves the capacity and cyclability of the lithium-oxygen battery. With dimethyl sulphoxide as electrolyte, the capacity reaches 6762 mAh g −1 which is twice of the pure graphene sponge. In addition, the cell containing Fe-N-GS air electrode exhibits stable cyclic performance and effective reduction of charge potential plateau, indicating that Fe-N-GS is promising as an OER catalyst in rechargeable lithium-air batteries

Recycling of spent lithium-ion battery cathode materials by ammoniacal leaching

International Nuclear Information System (INIS)

Ku, Heesuk; Jung, Yeojin; Jo, Minsang; Park, Sanghyuk; Kim, Sookyung; Yang, Donghyo; Rhee, Kangin; An, Eung-Mo; Sohn, Jeongsoo; Kwon, Kyungjung

2016-01-01

Highlights: • Ammoniacal leaching is used to recover spent Li-ion battery cathode materials. • Leaching agents consist of ammonia, ammonium sulfite and ammonium carbonate. • Ammonium sulfite is a reductant and ammonium carbonate acts as pH buffer. • Co and Cu can be fully leached while Mn and Al are not leached. • Co recovery via ammoniacal leaching is economical compared to acid leaching. - Abstract: As the production and consumption of lithium ion batteries (LIBs) increase, the recycling of spent LIBs appears inevitable from an environmental, economic and health viewpoint. The leaching behavior of Ni, Mn, Co, Al and Cu from treated cathode active materials, which are separated from a commercial LIB pack in hybrid electric vehicles, is investigated with ammoniacal leaching agents based on ammonia, ammonium carbonate and ammonium sulfite. Ammonium sulfite as a reductant is necessary to enhance leaching kinetics particularly in the ammoniacal leaching of Ni and Co. Ammonium carbonate can act as a pH buffer so that the pH of leaching solution changes little during leaching. Co and Cu can be fully leached out whereas Mn and Al are hardly leached and Ni shows a moderate leaching efficiency. It is confirmed that the cathode active materials are a composite of LiMn_2O_4, LiCo_xMn_yNi_zO_2_, Al_2O_3 and C while the leach residue is composed of LiNi_xMn_yCo_zO_2, LiMn_2O_4, Al_2O_3, MnCO_3 and Mn oxides. Co recovery via the ammoniacal leaching is believed to gain a competitive edge on convenitonal acid leaching both by reducing the sodium hydroxide expense for increasing the pH of leaching solution and by removing the separation steps of Mn and Al.

High-Thermal- and Air-Stability Cathode Material with Concentration-Gradient Buffer for Li-Ion Batteries.

Science.gov (United States)

Shi, Ji-Lei; Qi, Ran; Zhang, Xu-Dong; Wang, Peng-Fei; Fu, Wei-Gui; Yin, Ya-Xia; Xu, Jian; Wan, Li-Jun; Guo, Yu-Guo

2017-12-13

Delivery of high capacity with high thermal and air stability is a great challenge in the development of Ni-rich layered cathodes for commercialized Li-ion batteries (LIBs). Herein we present a surface concentration-gradient spherical particle with varying elemental composition from the outer end LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM) to the inner end LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA). This cathode material with the merit of NCM concentration-gradient protective buffer and the inner NCA core shows high capacity retention of 99.8% after 200 cycles at 0.5 C. Furthermore, this cathode material exhibits much improved thermal and air stability compared with bare NCA. These results provide new insights into the structural design of high-performance cathodes with high energy density, long life span, and storage stability materials for LIBs in the future.

Novel copper redox-based cathode materials for room-temperature sodium-ion batteries

Science.gov (United States)

Xu, Shu-Yin; Wu, Xiao-Yan; Li, Yun-Ming; Hu, Yong-Sheng; Chen, Li-Quan

2014-11-01

Layered oxides of P2-type Na0.68Cu0.34Mn0.66O2, P2-type Na0.68Cu0.34Mn0.50Ti0.16O2, and O'3-type NaCu0.67Sb0.33O2 were synthesized and evaluated as cathode materials for room-temperature sodium-ion batteries. The first two materials can deliver a capacity of around 70 mAh/g. The Cu2+ is oxidized to Cu3+ during charging, and the Cu3+ goes back to Cu2+ upon discharging. This is the first demonstration of the highly reversible change of the redox couple of Cu2+/Cu3+ with high storage potential in secondary batteries.

Cathode Composition in a Saltwater Metal-Air Battery

Directory of Open Access Journals (Sweden)

William Shen

2017-01-01

Full Text Available Metal-air batteries consist of a solid metal anode and an oxygen cathode of ambient air, typically separated by an aqueous electrolyte. Here, simple saltwater-based models of aluminum-air and zinc-air cells are used to determine the differences between theoretical cell electric potentials and experimental electric potentials. A substantial difference is observed. It is also found that the metal cathode material is crucial to cell electric potential, despite the cathode not participating in the net reaction. Finally, the material composition of the cathode appears to have a more significant impact on cell potential than the submerged surface area of the cathode.

Recycling of spent lithium-ion battery cathode materials by ammoniacal leaching

Energy Technology Data Exchange (ETDEWEB)

Ku, Heesuk; Jung, Yeojin; Jo, Minsang; Park, Sanghyuk [Department of Energy & Mineral Resources Engineering, Sejong University, Seoul 05006 (Korea, Republic of); Kim, Sookyung [Urban Mine Department, Korea Institute of Geoscience and Mineral Resources, 124 Gwahang-no, Yuseong-gu, Daejeon (Korea, Republic of); Yang, Donghyo, E-mail: ydh@kigam.re.kr [Urban Mine Department, Korea Institute of Geoscience and Mineral Resources, 124 Gwahang-no, Yuseong-gu, Daejeon (Korea, Republic of); Rhee, Kangin; An, Eung-Mo; Sohn, Jeongsoo [Urban Mine Department, Korea Institute of Geoscience and Mineral Resources, 124 Gwahang-no, Yuseong-gu, Daejeon (Korea, Republic of); Kwon, Kyungjung, E-mail: kfromberk@gmail.com [Department of Energy & Mineral Resources Engineering, Sejong University, Seoul 05006 (Korea, Republic of)

2016-08-05

Highlights: • Ammoniacal leaching is used to recover spent Li-ion battery cathode materials. • Leaching agents consist of ammonia, ammonium sulfite and ammonium carbonate. • Ammonium sulfite is a reductant and ammonium carbonate acts as pH buffer. • Co and Cu can be fully leached while Mn and Al are not leached. • Co recovery via ammoniacal leaching is economical compared to acid leaching. - Abstract: As the production and consumption of lithium ion batteries (LIBs) increase, the recycling of spent LIBs appears inevitable from an environmental, economic and health viewpoint. The leaching behavior of Ni, Mn, Co, Al and Cu from treated cathode active materials, which are separated from a commercial LIB pack in hybrid electric vehicles, is investigated with ammoniacal leaching agents based on ammonia, ammonium carbonate and ammonium sulfite. Ammonium sulfite as a reductant is necessary to enhance leaching kinetics particularly in the ammoniacal leaching of Ni and Co. Ammonium carbonate can act as a pH buffer so that the pH of leaching solution changes little during leaching. Co and Cu can be fully leached out whereas Mn and Al are hardly leached and Ni shows a moderate leaching efficiency. It is confirmed that the cathode active materials are a composite of LiMn{sub 2}O{sub 4}, LiCo{sub x}Mn{sub y}Ni{sub z}O{sub 2,} Al{sub 2}O{sub 3} and C while the leach residue is composed of LiNi{sub x}Mn{sub y}Co{sub z}O{sub 2}, LiMn{sub 2}O{sub 4}, Al{sub 2}O{sub 3}, MnCO{sub 3} and Mn oxides. Co recovery via the ammoniacal leaching is believed to gain a competitive edge on convenitonal acid leaching both by reducing the sodium hydroxide expense for increasing the pH of leaching solution and by removing the separation steps of Mn and Al.

High Performance Cathodes for Li-Air Batteries

Energy Technology Data Exchange (ETDEWEB)

Xing, Yangchuan

2013-08-22

The overall objective of this project was to develop and fabricate a multifunctional cathode with high activities in acidic electrolytes for the oxygen reduction and evolution reactions for Li-air batteries. It should enable the development of Li-air batteries that operate on hybrid electrolytes, with acidic catholytes in particular. The use of hybrid electrolytes eliminates the problems of lithium reaction with water and of lithium oxide deposition in the cathode with sole organic electrolytes. The use of acid electrolytes can eliminate carbonate formation inside the cathode, making air breathing Li-air batteries viable. The tasks of the project were focused on developing hierarchical cathode structures and bifunctional catalysts. Development and testing of a prototype hybrid Li-air battery were also conducted. We succeeded in developing a hierarchical cathode structure and an effective bifunctional catalyst. We accomplished integrating the cathode with existing anode technologies and made a pouch prototype Li-air battery using sulfuric acid as catholyte. The battery cathodes contain a nanoscale multilayer structure made with carbon nanotubes and nanofibers. The structure was demonstrated to improve battery performance substantially. The bifunctional catalyst developed contains a conductive oxide support with ultra-low loading of platinum and iridium oxides. The work performed in this project has been documented in seven peer reviewed journal publications, five conference presentations, and filing of two U.S. patents. Technical details have been documented in the quarterly reports to DOE during the course of the project.

Oxide materials as positive electrodes of lithium-ion batteries

International Nuclear Information System (INIS)

Makhonina, Elena V; Pervov, Vladislav S; Dubasova, Valeriya S

2004-01-01

The published data on oxide materials as positive electrodes for lithium-ion batteries are described systematically. The mechanisms of structural changes in cathode materials occurring during the operation of lithium-ion batteries and the problems concerned with their selection are discussed. Modern trends in optimising cathode materials and lithium-ion batteries on the whole are considered.

Preparation of mesohollow and microporous carbon nanofiber and its application in cathode material for lithium–sulfur batteries

International Nuclear Information System (INIS)

Wu, Yuanhe; Gao, Mingxia; Li, Xiang; Liu, Yongfeng; Pan, Hongge

2014-01-01

Highlights: • Mesohollow and microporous carbon fibers were prepared via electrospinning and carbonization. • Sulfur (S) incorporated into the porous fibers by thermal heating in 60 wt.%, forming composite. • S fills fully in the micropores and partially in the mesohollows of the carbon fibers. • The composite shows high capacity and capacity retention as cathode material for Li–S batteries. • Mesohollow and microporous structure is effective in improving the property of S cathode. - Abstract: Mesohollow and microporous carbon nanofibers (MhMpCFs) were prepared by a coaxial electrospinning with polyacrylonitrile (PAN) and polymethylmethacrylate (PMMA) as outer and inner spinning solutions followed by a carbonization. The carbon fibers were thermal treated with sublimed sulfur to form S/MhMpCFs composite, which was used as cathode material for lithium–sulfur batteries. Electrochemical study shows that the S/MhMpCFs cathode material provides a maximum capacity of 815 mA h/g after several cycles of activation, and the capacity retains 715 mA h/g after 70 cycles, corresponding to a retention of 88%. The electrochemical property of the S/MhMpCFs composite is much superior than the S-incorporated solid carbon fibers prepared from electrospinning of single PAN. The mechanism of the enhanced electrochemical property of the S/MhMpCFs composite is discussed

Development of cathode material for lithium-ion batteries

Directory of Open Access Journals (Sweden)

Rustam Mukhtaruly Turganaly

2014-08-01

Full Text Available The electrochemical characteristics of the cathode material coated with carbon layer has been developed. Various carbon coating methods. There  has been carried out a comparative electrochemical analysis of the coated and uncoated with carbon cathode material. 

High performance Li3V2(PO4)3/C composite cathode material for lithium ion batteries studied in pilot scale test

International Nuclear Information System (INIS)

Chen Zhenyu; Dai Changsong; Wu Gang; Nelson, Mark; Hu Xinguo; Zhang Ruoxin; Liu Jiansheng; Xia Jicai

2010-01-01

Li 3 V 2 (PO 4 ) 3 /C composite cathode material was synthesized via carbothermal reduction process in a pilot scale production test using battery grade raw materials with the aim of studying the feasibility for their practical applications. XRD, FT-IR, XPS, CV, EIS and battery charge-discharge tests were used to characterize the as-prepared material. The XRD and FT-IR data suggested that the as-prepared Li 3 V 2 (PO 4 ) 3 /C material exhibits an orderly monoclinic structure based on the connectivity of PO 4 tetrahedra and VO 6 octahedra. Half cell tests indicated that an excellent high-rate cyclic performance was achieved on the Li 3 V 2 (PO 4 ) 3 /C cathodes in the voltage range of 3.0-4.3 V, retaining a capacity of 95% (96 mAh/g) after 100 cycles at 20C discharge rate. The low-temperature performance of the cathode was further evaluated, showing 0.5C discharge capacity of 122 and 119 mAh/g at -25 and -40 o C, respectively. The discharge capacity of graphite//Li 3 V 2 (PO 4 ) 3 batteries with a designed battery capacity of 14 Ah is as high as 109 mAh/g with a capacity retention of 92% after 224 cycles at 2C discharge rates. The promising high-rate and low-temperature performance observed in this work suggests that Li 3 V 2 (PO 4 ) 3 /C is a very strong candidate to be a cathode in a next-generation Li-ion battery for electric vehicle applications.

Sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Liang, Chengdu; Dudney, Nancy J.; Howe, Jane Y.

2017-08-01

The invention is directed in a first aspect to a sulfur-carbon composite material comprising: (i) a bimodal porous carbon component containing therein a first mode of pores which are mesopores, and a second mode of pores which are micropores; and (ii) elemental sulfur contained in at least a portion of said micropores. The invention is also directed to the aforesaid sulfur-carbon composite as a layer on a current collector material; a lithium ion battery containing the sulfur-carbon composite in a cathode therein; as well as a method for preparing the sulfur-composite material.

Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts.

Science.gov (United States)

Cheng, Fangyi; Chen, Jun

2012-03-21

Because of the remarkably high theoretical energy output, metal-air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal-air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal-air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic-organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal-air batteries (219 references).

Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium-sulfur batteries

Science.gov (United States)

Kim, Hoon; Lee, Joungphil; Ahn, Hyungmin; Kim, Onnuri; Park, Moon Jeong

2015-06-01

Elemental sulfur is one of the most attractive cathode active materials in lithium batteries because of its high theoretical specific capacity. Despite the positive aspect, lithium-sulfur batteries have suffered from severe capacity fading and limited rate capability. Here we report facile large-scale synthesis of a class of organosulfur compounds that could open a new chapter in designing cathode materials to advance lithium-sulfur battery technologies. Porous trithiocyanuric acid crystals are synthesized for use as a soft template, where the ring-opening polymerization of elemental sulfur takes place along the thiol surfaces to create three-dimensionally interconnected sulfur-rich phases. Our lithium-sulfur cells display discharge capacity of 945 mAh g-1 after 100 cycles at 0.2 C with high-capacity retention of 92%, as well as lifetimes of 450 cycles. Particularly, the organized amine groups in the crystals increase Li+-ion transfer rate, affording a rate performance of 1210, mAh g-1 at 0.1 C and 730 mAh g-1 at 5 C.

Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium–sulfur batteries

Science.gov (United States)

Kim, Hoon; Lee, Joungphil; Ahn, Hyungmin; Kim, Onnuri; Park, Moon Jeong

2015-01-01

Elemental sulfur is one of the most attractive cathode active materials in lithium batteries because of its high theoretical specific capacity. Despite the positive aspect, lithium–sulfur batteries have suffered from severe capacity fading and limited rate capability. Here we report facile large-scale synthesis of a class of organosulfur compounds that could open a new chapter in designing cathode materials to advance lithium–sulfur battery technologies. Porous trithiocyanuric acid crystals are synthesized for use as a soft template, where the ring-opening polymerization of elemental sulfur takes place along the thiol surfaces to create three-dimensionally interconnected sulfur-rich phases. Our lithium–sulfur cells display discharge capacity of 945 mAh g−1 after 100 cycles at 0.2 C with high-capacity retention of 92%, as well as lifetimes of 450 cycles. Particularly, the organized amine groups in the crystals increase Li+-ion transfer rate, affording a rate performance of 1210, mAh g−1 at 0.1 C and 730 mAh g−1 at 5 C. PMID:26065407

Four-electron transfer tandem tetracyanoquinodimethane for cathode-active material in lithium secondary battery

Science.gov (United States)

Kurimoto, Naoya; Omoda, Ryo; Mizumo, Tomonobu; Ito, Seitaro; Aihara, Yuichi; Itoh, Takahito

2018-02-01

Quinoid compounds are important candidates of organic active materials for lithium-ion batteries. However, its high solubility to organic electrolyte solutions and low redox potential are known as their major drawbacks. To circumvent these issues, we have designed and synthesized a tandem-tetracyanoquinonedimethane type cathode-active material, 11,11,12,12,13,13,14,14-octacyano-1,4,5,8-anthradiquinotetramethane (OCNAQ), that has four redox sites per molecule, high redox potential and suppressed solubility to electrolyte solution. Synthesized OCNAQ has been found to have two-step redox reactions by cyclic voltammetry, and each step consists of two-electron reactions. During charge-discharge tests using selected organic cathode-active materials with a lithium metal anode, the cell voltages obtained from OCNAQ are higher than those for 11,11-dicyanoanthraquinone methide (AQM) as expected, due to the strong electron-withdrawing effect of the cyano groups. Unfortunately, even with the use of the organic active material, the issue of dissolution to the electrolyte solution cannot be suppressed completely; however, appropriate choice of the electrolyte solutions, glyme-based electrolyte solutions in this study, give considerable improvement of the cycle retention (98% and 56% at 10 and 100 cycles at 0.5C, respectively). The specific capacity and energy density obtained in this study are 206 mAh g-1 and 554 mWh g-1 with respect to the cathode active material.

Cathode refunctionalization as a lithium ion battery recycling alternative

Science.gov (United States)

Ganter, Matthew J.; Landi, Brian J.; Babbitt, Callie W.; Anctil, Annick; Gaustad, Gabrielle

2014-06-01

An approach to battery end-of-life (EOL) management is developed involving cathode refunctionalization, which enables remanufacturing of the cathode from EOL materials to regain the electrochemical performance. To date, the optimal end-of-life management of cathode materials is based on economic value and environmental impact which can influence the methods and stage of recycling. Traditional recycling methods can recover high value metal elements (e.g. Li, Co, Ni), but still require synthesis of new cathode from a mix of virgin and recovered materials. Lithium iron phosphate (LiFePO4) has been selected for study as a representative cathode material due to recent mass adoption and limited economic recycling drivers due to the low inherent cost of iron. Refunctionalization of EOL LiFePO4 cathode was demonstrated through electrochemical and chemical lithiation methods where the re-lithiated LiFePO4 regained the original capacity of 150-155 mAh g-1. The environmental impact of the new recycling technique was determined by comparing the embodied energy of cathode material originating from virgin, recycled, and refunctionalized materials. The results demonstrate that the LiFePO4 refunctionalization process, through chemical lithiation, decreases the embodied energy by 50% compared to cathode production from virgin materials.

Electroactive materials for rechargeable batteries

Science.gov (United States)

Wu, Huiming; Amine, Khalil; Abouimrane, Ali

2015-04-21

An as-prepared cathode for a secondary battery, the cathode including an alkaline source material including an alkali metal oxide, an alkali metal sulfide, an alkali metal salt, or a combination of any two or more thereof.

Polycarbonyl(quinonyl) organic compounds as cathode materials for sustainable lithium ion batteries

International Nuclear Information System (INIS)

Zeng, Ronghua; Xing, Lidan; Qiu, Yongcai; Wang, Yating; Huang, Wenna; Li, Weishan; Yang, Shihe

2014-01-01

Highlights: • Quinonyl compounds containing –OH groups are reported as cathode of sustainable Li-ion battery. • Lithiation potential of these compounds is positively correlated to -OH group number on them. • These compounds exhibit a discharge plateau of 3 V and deliver a capacity of over 180 mAh g -1 at 20 mA g -1 . - Abstract: Suitably designed organic compounds are promising renewable electrode materials for lithium ion batteries (LIBs) with minimal environmental impacts and no CO 2 release. Herein we report a series of polycarbonyl organic compounds with different number of hydroxyl groups, which can be obtained from renewable plants, as cathode materials for LIBs. Density functional theory (DFT) calculations based on the natural bond orbital (NBO) reveal a positive correlation between the reduction potentials and the number of hydroxyl groups, which is borne out experimentally. Anthraquinone (AQ) with three or four -OH groups has the structural advantages for improving the discharge plateaus. Mechanistic studies show that AQ containing neighbouring carbonyl groups and hydroxyl groups facilitates the formation of six or five-membered rings with lithium ion. Charge/discharge tests show that AQ, 1,5-DHAQ, 1,2,7-THAQ, and 1,2,5,8-THAQ can achieve initial discharge capacities of 215, 190, 186 and 180 mAh g -1 at a current density of 20 mA g -1 , corresponding to 84%, 85%, 89% and 91% of their theoretical capacities, respectively

Studies of selected synthesis procedures of the conducting LiFePO{sub 4}-based composite cathode materials for Li-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Ojczyk, W.; Marzec, J.; Swierczek, K.; Zajac, W.; Molenda, J. [Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow (Poland); Molenda, M.; Dziembaj, R. [Faculty of Chemistry, Jagiellonian University, ul. R. Ingardena 3, 30-060 Krakow (Poland)

2007-11-15

In this paper technological aspects of a synthesis of phospho-olivine LiFePO{sub 4} based composite cathode materials for lithium batteries are presented. An effective synthesis route yielding a highly conductive composite cathode material was developed. The structural, electrical and electrochemical properties of these materials were investigated. It was shown that the enhanced conductivity of the cathode material is due to the presence of a thin layer of the reduced material which has metallic properties, which is formed on the grain surfaces of the phospho-olivine. We propose a synthesis route yielding LiFePO{sub 4}/Fe{sub 2}P composite material. (author)

Polyamidoamine dendrimer-based binders for high-loading lithium–sulfur battery cathodes

Energy Technology Data Exchange (ETDEWEB)

Bhattacharya, Priyanka; Nandasiri, Manjula I.; Lv, Dongping; Schwarz, Ashleigh M.; Darsell, Jens T.; Henderson, Wesley A.; Tomalia, Donald A.; Liu, Jun; Zhang, Ji-Guang; Xiao, Jie

2016-01-01

Lithium-sulfur (Li-S) batteries are regarded as one of the most promising candidates for next generation energy storage systems because of their ultra high theoretical specific energy. To realize the practical application of Li-S batteries, however, a high S active material loading is essential (>70 wt% in the carbon-sulfur (C-S) composite cathode and >2 mg cm-2 in the electrode). A critical challenge to achieving this high capacity in practical electrodes is the dissolution of the longer lithium polysulfide reaction intermediates in the electrolyte (resulting in loss of active material from the cathode and contamination of the anode due to the polysulfide shuttle mechanism). The binder material used for the cathode is therefore crucial as this is a key determinant of the bonding interactions between the active material (S) and electronic conducting support (C), as well as the maintenance of intimate contact between the electrode materials and current collector. The battery performance can thus be directly correlated with the choice of binder, but this has received only minimal attention in the relevant Li-S battery published literature. Here, we investigated the application of polyamidoamine (PAMAM) dendrimers as functional binders in Li-S batteries—a class of materials which has been unexplored for electrode design. By using dendrimers, it is demonstrated that high S loadings (>4 mg cm-2) can be easily achieved using "standard" (not specifically tailored) materials and simple processing methods. An exceptional electrochemical cycling performance was obtained (as compared to cathodes with conventional linear polymeric binders such as carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR)) with >100 cycles and 85-98% capacity retention, thus demonstrating the significant utility of this new binder architecture which exhibits critical physicochemical properties and flexible nanoscale design parameters (CNDP's).

One-step facile synthesis of Ni2P/C as cathode material for Ni/Zn aqueous secondary battery

Science.gov (United States)

Li, JiLan; Chen, ChangGuo

2018-01-01

Nickel phosphides/carbon(Ni2P/C) composites have been successfully synthesized via a simple one-pot hydrothermal method using glucose as carbon source for the first time. By contrast, the pure Ni2P was prepared under the same conditions without glucose. The results show that glucose not only provide the carbon source, but also prevent the aggregation of Ni2P particles. The as-obtained Ni2P/C composites and pure Ni2P were used as cathode material for alkaline Ni/Zn battery. Owing to unique Ni2P/C composites and loose, Ultra thin flower-like shape the synthesized Ni2P/C material delivers high capacity of 176 mAh g-1 at 1 A g-1 and 82 mAh g-1 at 5 A g-1 current density in Ni2P/C-Zn battery. Moreover, it shows a good cycling life that capacity fading only about 6.2% after 1500 cycles. All of these indicate that the prepared Ni2P/C composites may be a new promising cathode material for Ni-Zn rechargeable battery.

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.

Graphene Modified LiFePO4 Cathode Materials for High Power Lithium ion Batteries

International Nuclear Information System (INIS)

Zhou, X.; Wang, F.; Zhu, Y.; Liu, Z.

2011-01-01

Graphene-modified LiFePO 4 composite has been developed as a Li-ion battery cathode material with excellent high-rate capability and cycling stability. The composite was prepared with LiFePO 4 nanoparticles and graphene oxide nanosheets by spray-drying and annealing processes. The LiFePO 4 primary nanoparticles embedded in micro-sized spherical secondary particles were wrapped homogeneously and loosely with a graphene 3D network. Such a special nanostructure facilitated electron migration throughout the secondary particles, while the presence of abundant voids between the LiFePO 4 nanoparticles and graphene sheets was beneficial for Li + diffusion. The composite cathode material could deliver a capacity of 70 mAh g -1 at 60C discharge rate and showed a capacity decay rate of <15% when cycled under 10C charging and 20C discharging for 1000 times.

Innovative application of ionic liquid to separate Al and cathode materials from spent high-power lithium-ion batteries.

Science.gov (United States)

Zeng, Xianlai; Li, Jinhui

2014-04-30

Because of the increasing number of electric vehicles, there is an urgent need for effective recycling technologies to recapture the significant amount of valuable metals contained in spent lithium-ion batteries (LiBs). Previous studies have indicated, however, that Al and cathode materials were quite difficult to separate due to the strong binding force supplied by the polyvinylidene fluoride (PVDF), which was employed to bind cathode materials and Al foil. This research devoted to seek a new method of melting the PVDF binder with heated ionic liquid (IL) to separate Al foil and cathode materials from the spent high-power LiBs. Theoretical analysis based on Fourier's law was adopted to determine the heat transfer mechanism of cathode material and to examine the relationship between heating temperature and retention time. All the experimental and theoretic results show that peel-off rate of cathode materials from Al foil could reach 99% when major process parameters were controlled at 180°C heating temperature, 300 rpm agitator rotation, and 25 min retention time. The results further imply that the application of IL for recycling Al foil and cathode materials from spent high-power LiBs is highly efficient, regardless of the application source of the LiBs or the types of cathode material. This study endeavors to make a contribution to an environmentally sound and economically viable solution to the challenge of spent LiB recycling. Copyright © 2014 Elsevier B.V. All rights reserved.

Novel Carbon Materials in the Cathode Formulation for High Rate Rechargeable Hybrid Aqueous Batteries

Directory of Open Access Journals (Sweden)

Xiao Zhu

2017-11-01

Full Text Available Novel carbon materials, carbon nanotubes (CNTs and porous graphene (PG, were exploited and used as conductive additives to improve the rate performance of LiMn2O4 cathode for the rechargeable aqueous Zn/LiMn2O4 battery, namely the rechargeable hybrid aqueous battery (ReHAB. Thanks to the long-range conductivity and stable conductive network provided by CNTs, the rate and cycling performances of LiMn2O4 cathode in ReHAB are highly improved—up to about 100 mAh·g−1 capacity is observed at 10 C (1 C = 120 mAh·g−1. Except for CNTs, porous graphene (PG with a high surface area, an abundant porous structure, and an excellent electrical conductivity facilitates the transportation of Li ions and electrons, which can also obviously enhance the rate capability of the ReHAB. This is important because the ReHAB could be charged/discharged in a few minutes, and this leads to potential application of the ReHAB in automobile industry.

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.

High-Capacity Micrometer-Sized Li 2 S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

KAUST Repository

Yang, Yuan

2012-09-19

Li 2S is a high-capacity cathode material for lithium metal-free rechargeable batteries. It has a theoretical capacity of 1166 mAh/g, which is nearly 1 order of magnitude higher than traditional metal oxides/phosphates cathodes. However, Li 2S is usually considered to be electrochemically inactive due to its high electronic resistivity and low lithium-ion diffusivity. In this paper, we discover that a large potential barrier (∼1 V) exists at the beginning of charging for Li 2S. By applying a higher voltage cutoff, this barrier can be overcome and Li 2S becomes active. Moreover, this barrier does not appear again in the following cycling. Subsequent cycling shows that the material behaves similar to common sulfur cathodes with high energy efficiency. The initial discharge capacity is greater than 800 mAh/g for even 10 μm Li 2S particles. Moreover, after 10 cycles, the capacity is stabilized around 500-550 mAh/g with a capacity decay rate of only ∼0.25% per cycle. The origin of the initial barrier is found to be the phase nucleation of polysulfides, but the amplitude of barrier is mainly due to two factors: (a) charge transfer directly between Li 2S and electrolyte without polysulfide and (b) lithium-ion diffusion in Li 2S. These results demonstrate a simple and scalable approach to utilizing Li 2S as the cathode material for rechargeable lithium-ion batteries with high specific energy. © 2012 American Chemical Society.

Chromium (V) compounds as cathode material in electrochemical power sources

Science.gov (United States)

Delnick, F.M.; Guidotti, R.A.; McCarthy, D.K.

A cathode for use in a thermal battery, comprising a chromium (V) compound. The preferred materials for this use are Ca/sub 5/(CrO/sub 4/)/sub 3/Cl, Ca/sub 5/(CrO/sub 4/)OH, and Cr/sub 2/O/sub 5/. The chromium (V) compound can be employed as a cathode material in ambient temperature batteries when blended with a suitably conductive filler, preferably carbon black.

Rechargeable quasi-solid state lithium battery with organic crystalline cathode

Science.gov (United States)

Hanyu, Yuki; Honma, Itaru

2012-01-01

Utilization of metal-free low-cost high-capacity organic cathodes for lithium batteries has been a long-standing goal, but critical cyclability problems owing to dissolution of active materials into the electrolyte have been an inevitable obstacle. For practical utilisation of numerous cathode-active compounds proposed over the past decades, a novel battery construction strategy is required. We have designed a solid state cell that accommodates organic cathodic reactions in solid phase. The cell was successful at achieving high capacity exceeding 200 mAh/g with excellent cycleability. Further investigations confirmed that our strategy is effective for numerous other redox-active organic compounds. This implies hundreds of compounds dismissed before due to low cycleability would worth a re-visit under solid state design. PMID:22693655

Cathodes and electrolytes for rechargeable magnesium batteries and methods of manufacture

Science.gov (United States)

Kumta, Prashant N.; Saha, Partha; Datta, Moni Kanchan; Manivannan, Ayyakkannu

2018-04-17

The invention relates to Chevrel-phase materials and methods of preparing these materials utilizing a precursor approach. The Chevrel-phase materials are useful in assembling electrodes, e.g., cathodes, for use in electrochemical cells, such as rechargeable batteries. The Chevrel-phase materials have a general formula of Mo6Z8 and the precursors have a general formula of MxMo6Z8. The cathode containing the Chevrel-phase material in accordance with the invention can be combined with a magnesium-containing anode and an electrolyte.

Improving lithium-ion battery performances by adding fly ash from coal combustion on cathode film

Energy Technology Data Exchange (ETDEWEB)

Dyartanti, Endah Retno; Jumari, Arif, E-mail: arifjumari@yahoo.com; Nur, Adrian; Purwanto, Agus [Research Group of Battery & Advanced Material, Department of Chemical Engineering, Sebelas Maret University, Jl. Ir. Sutami 36 A Kentingan, Surakarta Indonesia 57126 (Indonesia)

2016-02-08

A lithium battery is composed of anode, cathode and a separator. The performance of lithium battery is also influenced by the conductive material of cathode film. In this research, the use of fly ash from coal combustion as conductive enhancer for increasing the performances of lithium battery was investigated. Lithium iron phosphate (LiFePO{sub 4}) was used as the active material of cathode. The dry fly ash passed through 200 mesh screen, LiFePO{sub 4} and acethylene black (AB), polyvinylidene fluoride (PVDF) as a binder and N-methyl-2-pyrrolidone (NMP) as a solvent were mixed to form slurry. The slurry was then coated, dried and hot pressed to obtain the cathode film. The ratio of fly ash and AB were varied at the values of 1%, 2%, 3%, 4% and 5% while the other components were at constant. The anode film was casted with certain thickness and composition. The performance of battery lithium was examined by Eight Channel Battery Analyzer, the composition of the cathode film was examined by XRD (X-Ray Diffraction), and the structure and morphology of the anode film was analyzed by SEM (Scanning Electron Microscope). The composition, structure and morphology of cathode film was only different when fly ash added was 4% of AB or more. The addition of 2% of AB on cathode film gave the best performance of 81.712 mAh/g on charging and 79.412 mAh/g on discharging.

Improving the Performance of Layered Oxide Cathode Materials with Football-Like Hierarchical Structure for Na-Ion Batteries by Incorporating Mg2+ into Vacancies in Na-Ion Layers.

Science.gov (United States)

Li, Zheng-Yao; Wang, Huibo; Chen, Dongfeng; Sun, Kai; Yang, Wenyun; Yang, Jinbo; Liu, Xiangfeng; Han, Songbai

2018-04-09

The development of advanced cathode materials is still a great interest for sodium-ion batteries. The feasible commercialization of sodium-ion batteries relies on the design and exploitation of suitable electrode materials. This study offers a new insight into material design to exploit high-performance P2-type cathode materials for sodium-ion batteries. The incorporation of Mg 2+ into intrinsic Na + vacancies in Na-ion layers can lead to a high-performance P2-type cathode material for sodium-ion batteries. The materials prepared by the coprecipitation approach show a well-defined morphology of secondary football-like hierarchical structures. Neutron power diffraction and refinement results demonstrate that the incorporation of Mg 2+ into intrinsic vacancies can enlarge the space for Na-ion diffusion, which can increase the d-spacing of the (0 0 2) peak and the size of slabs but reduce the chemical bond length to result in an enhanced rate capability and cycling stability. The incorporation of Mg 2+ into available vacancies and a unique morphology make Na 0.7 Mg 0.05 Mn 0.8 Ni 0.1 Co 0.1 O 2 a promising cathode, which can be charged and discharged at an ultra-high current density of 2000 mA g -1 with an excellent specific capacity of 60 mAh g -1 . This work provides a new insight into the design of electrode materials for sodium-ion batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Construction of tubular polypyrrole-wrapped biomass-derived carbon nanospheres as cathode materials for lithium–sulfur batteries

International Nuclear Information System (INIS)

Yu, Qiuhong; Lu, Yang; Peng, Tao; Hou, Xiaoyi; Luo, Rongjie; Wang, Yange; Yan, Hailong; Luo, Yongsong; Liu, Xianming; Kim, Jang-Kyo

2017-01-01

A promising hybrid material composed of tubular polypyrrole (T-PPy)-wrapped monodisperse biomass-derived carbon nanospheres (BCSs) was first synthesized successfully via a simple hydrothermal approach by using watermelon juice as the carbon source, and further used as an anchoring object for sulfur (S) of lithium–sulfur (Li–S) batteries. The use of BCSs with hydrophilic nature as a framework could provide large interface areas between the active materials and electrolyte, and improve the dispersion of T-PPy, which could help in the active material utilization. As a result, BCS@T-PPy/S as a cathode material exhibited a high capacity of 1143.6 mA h g −1 and delivered a stable capacity up to 685.8 mA h g −1 after 500 cycles at 0.5 C, demonstrating its promising application for rechargeable Li–S batteries. (paper)

Structural and Electrical Properties of Lithium-Ion Rechargeable Battery Using the LiFePO4/Carbon Cathode Material.

Science.gov (United States)

Kim, Young-Sung; Jeoung, Tae-Hoon; Nam, Sung-Pill; Lee, Seung-Hwan; Kim, Jea-Chul; Lee, Sung-Gap

2015-03-01

LiFePO4/C composite powder as cathode material and graphite powder as anode material for Li-ion batteries were synthesized by using the sol-gel method. An electrochemical improvement of LiFePO4 materials has been achieved by adding polyvinyl alcohol as a carbon source into as-prepared materials. The samples were characterized by elemental analysis (EA), X-ray diffraction (XRD), and field emission scanning electron microscopy (FE-EM). The chemical composition of LiFePO4/C powders was in a good agreement with that of the starting solution. The capacity loss after 500 cycles of LiFePO4/C cell is 11.1% in room temperature. These superior electrochemical properties show that LiFePO4/C composite materials are promising candidates as cathode materials.

Innovative application of ionic liquid to separate Al and cathode materials from spent high-power lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Zeng, Xianlai; Li, Jinhui, E-mail: jinhui@tsinghua.edu.cn

2014-04-01

Highlights: • Manual dismantling is superior in spent high-power LiBs recycling. • Heated ionic liquid can effectively separate Al and cathode materials. • Fourier’s law was adopted to determine the heat transfer mechanism. • The process of spent LiBs recycling with heated ionic liquid dismantling was proposed. - Abstract: Because of the increasing number of electric vehicles, there is an urgent need for effective recycling technologies to recapture the significant amount of valuable metals contained in spent lithium-ion batteries (LiBs). Previous studies have indicated, however, that Al and cathode materials were quite difficult to separate due to the strong binding force supplied by the polyvinylidene fluoride (PVDF), which was employed to bind cathode materials and Al foil. This research devoted to seek a new method of melting the PVDF binder with heated ionic liquid (IL) to separate Al foil and cathode materials from the spent high-power LiBs. Theoretical analysis based on Fourier’s law was adopted to determine the heat transfer mechanism of cathode material and to examine the relationship between heating temperature and retention time. All the experimental and theoretic results show that peel-off rate of cathode materials from Al foil could reach 99% when major process parameters were controlled at 180 °C heating temperature, 300 rpm agitator rotation, and 25 min retention time. The results further imply that the application of IL for recycling Al foil and cathode materials from spent high-power LiBs is highly efficient, regardless of the application source of the LiBs or the types of cathode material. This study endeavors to make a contribution to an environmentally sound and economically viable solution to the challenge of spent LiB recycling.

Solution-combustion synthesized aluminium-doped spinel (LiAl(subx)Mn(sub2-x)O(sub4) as a high-performance lithium-ion battery cathode material

CSIR Research Space (South Africa)

Kebede, MA

2015-06-01

Full Text Available High-performing (LiAl(subx)Mn(sub2-x)O(sub4) (x = 0, 0.125, 0.25, 0.375, and 0.5) spinel cathode materials for lithium-ion battery were developed using a solution combustion method. The as-synthesized cathode materials have spinel cubic structure...

Optimization of Layered Cathode Materials for Lithium-Ion Batteries

Directory of Open Access Journals (Sweden)

Christian Julien

2016-07-01

Full Text Available This review presents a survey of the literature on recent progress in lithium-ion batteries, with the active sub-micron-sized particles of the positive electrode chosen in the family of lamellar compounds LiMO2, where M stands for a mixture of Ni, Mn, Co elements, and in the family of yLi2MnO3•(1 − yLiNi½Mn½O2 layered-layered integrated materials. The structural, physical, and chemical properties of these cathode elements are reported and discussed as a function of all the synthesis parameters, which include the choice of the precursors and of the chelating agent, and as a function of the relative concentrations of the M cations and composition y. Their electrochemical properties are also reported and discussed to determine the optimum compositions in order to obtain the best electrochemical performance while maintaining the structural integrity of the electrode lattice during cycling.

Quantifying the environmental impact of a Li-rich high-capacity cathode material in electric vehicles via life cycle assessment.

Science.gov (United States)

Wang, Yuqi; Yu, Yajuan; Huang, Kai; Chen, Bo; Deng, Wensheng; Yao, Ying

2017-01-01

A promising Li-rich high-capacity cathode material (xLi 2 MnO 3 ·(1-x)LiMn 0.5 Ni 0.5 O 2 ) has received much attention with regard to improving the performance of lithium-ion batteries in electric vehicles. This study presents an environmental impact evaluation of a lithium-ion battery with Li-rich materials used in an electric vehicle throughout the life cycle of the battery. A comparison between this cathode material and a Li-ion cathode material containing cobalt was compiled in this study. The battery use stage was found to play a large role in the total environmental impact and high greenhouse gas emissions. During battery production, cathode material manufacturing has the highest environmental impact due to its complex processing and variety of raw materials. Compared to the cathode with cobalt, the Li-rich material generates fewer impacts in terms of human health and ecosystem quality. Through the life cycle assessment (LCA) results and sensitivity analysis, we found that the electricity mix and energy efficiency significantly influence the environmental impacts of both battery production and battery use. This paper also provides a detailed life cycle inventory, including firsthand data on lithium-ion batteries with Li-rich cathode materials.

Capacity Fade Analysis of Sulfur Cathodes in Lithium–Sulfur Batteries

Science.gov (United States)

Yan, Jianhua; Liu, Xingbo

2016-01-01

Rechargeable lithium–sulfur (Li–S) batteries are receiving ever‐increasing attention due to their high theoretical energy density and inexpensive raw sulfur materials. However, their rapid capacity fade has been one of the key barriers for their further improvement. It is well accepted that the major degradation mechanisms of S‐cathodes include low electrical conductivity of S and sulfides, precipitation of nonconductive Li2S2 and Li2S, and poly‐shuttle effects. To determine these degradation factors, a comprehensive study of sulfur cathodes with different amounts of electrolytes is presented here. A survey of the fundamentals of Li–S chemistry with respect to capacity fade is first conducted; then, the parameters obtained through electrochemical performance and characterization are used to determine the key causes of capacity fade in Li–S batteries. It is confirmed that the formation and accumulation of nonconductive Li2S2/Li2S films on sulfur cathode surfaces are the major parameters contributing to the rapid capacity fade of Li–S batteries. PMID:27981001

A versatile single molecular precursor for the synthesis of layered oxide cathode materials for Li-ion batteries.

Science.gov (United States)

Li, Maofan; Liu, Jiajie; Liu, Tongchao; Zhang, Mingjian; Pan, Feng

2018-02-01

A carbonyl-bridged single molecular precursor LiTM(acac) 3 [transition metal (TM) = cobalt/manganese/nickel (Co/Mn/Ni), acac = acetylacetone], featuring a one-dimensional chain structure, was designed and applied to achieve the layered oxide cathode materials: LiTMO 2 (TM = Ni/Mn/Co, NMC). As examples, layered oxides, primary LiCoO 2 , binary LiNi 0.8 Co 0.2 O 2 and ternary LiNi 0.5 Mn 0.3 Co 0.2 O 2 were successfully prepared to be used as cathode materials. When they are applied to lithium-ion batteries (LIBs), all exhibit good electrochemical performance because of their unique morphology and great uniformity of element distribution. This versatile precursor is predicted to accommodate many other metal cations, such as aluminum (Al 3+ ), iron (Fe 2+ ), and sodium (Na + ), because of the flexibility of organic ligand, which not only facilitates the doping-modification of the NMC system, but also enables synthesis of Na-ion layered oxides. This opens a new direction of research for the synthesis of high-performance layered oxide cathode materials for LIBs.

Cathodes and electrolytes for rechargeable magnesium batteries and methods of manufacture

Energy Technology Data Exchange (ETDEWEB)

Kumta, Prashant N.; Saha, Partha; Datta, Moni Kanchan; Manivannan, Ayyakkannu

2018-04-17

The invention relates to Chevrel-phase materials and methods of preparing these materials utilizing a precursor approach. The Chevrel-phase materials are useful in assembling electrodes, e.g., cathodes, for use in electrochemical cells, such as rechargeable batteries. The Chevrel-phase materials have a general formula of Mo₆Z₈ and the precursors have a general formula of M_xMo₆Z₈. The cathode containing the Chevrel-phase material in accordance with the invention can be combined with a magnesium-containing anode and an electrolyte.

Atomistic Insights into FeF3 Nanosheet: An Ultrahigh-Rate and Long-Life Cathode Material for Li-Ion Batteries.

Science.gov (United States)

Yang, Zhenhua; Zhao, Shu; Pan, Yanjun; Wang, Xianyou; Liu, Hanghui; Wang, Qun; Zhang, Zhijuan; Deng, Bei; Guo, Chunsheng; Shi, Xingqiang

2018-01-24

Iron fluoride with high operating voltage and theoretical energy density has been proposed as a high-performance cathode material for Li-ion batteries. However, the inertness of pristine bulk FeF 3 results in poor Li kinetics and cycling life. Developing nanosheet-based electrode materials is a feasible strategy to solve these problems. Herein, on the basis of first-principles calculations, first the stability of FeF 3 (012) nanosheet with different atomic terminations under different environmental conditions was systematically studied, then the Li-ion adsorption and diffusion kinetics were thoroughly probed, and finally the voltages for different Li concentrations were given. We found that F-terminated nanosheet is energetically favorable in a wide range of chemical potential, which provide a vehicle for lithium ion diffusion. Our Li-ion adsorption and diffusion kinetics study revealed that (1) the formation of Li dimer is the most preferred, (2) the Li diffusion energy barrier of Li dimer is lower than isolated Li atom (0.17 eV for Li dimer vs 0.22 eV for Li atom), and (3) the diffusion coefficient of Li is 1.06 × 10 -6 cm 2 ·s -1 , which is orders of magnitude greater than that of Li diffusion in bulk FeF 3 (10 -13 -10 -11 cm 2 ·s -1 ). Thus, FeF 3 nanosheet can act as an ultrahigh-rate cathode material for Li-ion batteries. More importantly, the calculated voltage and specific capacity of Li on the FeF 3 (012) nanosheet demonstrate that it has a much more stable voltage profile than bulk FeF 3 for a wide range of Li concentration. So, few layers FeF 3 nanosheet provides the desired long-life energy density in Li-ion batteries. These above findings in the current study shed new light on the design of ultrahigh-rate and long-life FeF 3 cathode material for Li-ion batteries.

Super high energy density of Li3V2(PO4)3 as cathode materials for lithium ion batteries

Science.gov (United States)

Noerochim, Lukman; Amin, Mochammad Karim Al; Susanti, Diah; Triwibowo, Joko

2018-04-01

Lithium ion batteries have many advantages such as high energy density, no memory effect, long time cycleability and friendly environment. One type of cathode material that can be developed is Li3V2(PO4)3. In this study has been carried out the synthesis of Li3V2(PO4)3 with a hydrothermal temperature variation of 140, 160 and 180 °C and calcination temperature at 800 °C. SEM images show that the morphology of Li3V2(PO4)3 has irregular flakes with a size between 1-10 µm. CV results show redox reaction occurs in the range between 3 V to 4.8 V with the highest specific discharge capacity of 136 mAh/g for specimen with temperature hydrothermal and calcination are 180 °C and 800 °C. This result demonstrates that Li3V2(PO4)3 has a great potential as cathode material for lithium ion battery.

Lithium recycling and cathode material regeneration from acid leach liquor of spent lithium-ion battery via facile co-extraction and co-precipitation processes.

Science.gov (United States)

Yang, Yue; Xu, Shengming; He, Yinghe

2017-06-01

A novel process for extracting transition metals, recovering lithium and regenerating cathode materials based on facile co-extraction and co-precipitation processes has been developed. 100% manganese, 99% cobalt and 85% nickel are co-extracted and separated from lithium by D2EHPA in kerosene. Then, Li is recovered from the raffinate as Li 2 CO 3 with the purity of 99.2% by precipitation method. Finally, organic load phase is stripped with 0.5M H 2 SO 4 , and the cathode material LiNi 1/3 Co 1/3 Mn 1/3 O 2 is directly regenerated from stripping liquor without separating metal individually by co-precipitation method. The regenerative cathode material LiNi 1/3 Co 1/3 Mn 1/3 O 2 is miro spherical morphology without any impurities, which can meet with LiNi 1/3 Co 1/3 Mn 1/3 O 2 production standard of China and exhibits good electrochemical performance. Moreover, a waste battery management model is introduced to guarantee the material supply for spent battery recycling. Copyright © 2017 Elsevier Ltd. All rights reserved.

Recent Progress in Advanced Materials for Lithium Ion Batteries

Directory of Open Access Journals (Sweden)

Jiajun Chen

2013-01-01

Full Text Available The development and commercialization of lithium ion batteries is rooted in material discovery. Promising new materials with high energy density are required for achieving the goal toward alternative forms of transportation. Over the past decade, significant progress and effort has been made in developing the new generation of Li-ion battery materials. In the review, I will focus on the recent advance of tin- and silicon-based anode materials. Additionally, new polyoxyanion cathodes, such as phosphates and silicates as cathode materials, will also be discussed.

Advanced characterization of lithium battery materials with positrons

International Nuclear Information System (INIS)

Barbiellini, Bernardo; Kuriplach, Jan

2017-01-01

Cathode materials are crucial to improved battery performance, in part because there are not yet materials that can maintain high power and stable cycling with a capacity comparable to that of anode materials. Our parameter-free, gradient-corrected model for electron-positron correlations predicts that spectroscopies based on positron annihilation can be deployed to study the effect of lithium intercalation in the oxide matrix of the cathode. The positron characteristics in oxides can be reliably computed using methods based on first-principles. Thus, we can enable a fundamental characterization of lithium battery materials involving positron annihilation spectroscopy and first-principles calculations. The detailed information one can extract from positron experiments could be useful for understanding and optimizing both battery materials and bi-functional catalysts for oxygen reduction and evolution. (paper)

Mesoporous LiMnPO4/C nanoparticles as high performance cathode material for lithium ion batteries

International Nuclear Information System (INIS)

Wen, Fang; Shu, Hongbo; Zhang, Yuanyuan; Wan, Jiajia; Huang, Weihua; Yang, Xiukang; Yu, Ruizhi; Liu, Li; Wang, Xianyou

2016-01-01

LiMnPO 4 has been considered as one of the most promising high voltage cathode materials for next-generation lithium ion batteries. However, LiMnPO 4 suffers from intrinsic drawbacks of extremely low electronic conductivity and ionic diffusivity between LiMnPO 4 /MnPO 4 . In this paper, mesoporous LiMnPO 4 nanoparticles are synthesized successfully via a facile glycine-assisted solvothermal rout. The as-prepared mesoporous LiMnPO 4 /C nanoparticles present well-defined abundant mesoporous structure (diameter of 3 ∼ 10 nm), uniform carbon layer (thickness of 3 ∼ 4 nm), high specific surface area (90.1 m 2 /g). As a result, the mesoporous LiMnPO 4 /C nanoparticles achieve excellent electrochemical performance as cathode materials for lithium ion batteries. It demonstrates a high discharge capacity of 167.7, 161.6, 156.4, 148.4 and 128.7 mAh/g at 0.1, 0.5, 1, 2 and 5C, and maintains a discharge capacity of 130.0 mAh/g after 100 cycles at 1C. The good electrochemical performance is attributed to its special interpenetrating mesoporous structure in LiMnPO 4 nanoparticles, which significantly enhances the ionic and electronic transport and additional capacitive behavior to compensate the sluggish kinetics.

Synthesis of Co-Al-Cl LDH by cathodic material reprocessing from cellular phone batteries

Energy Technology Data Exchange (ETDEWEB)

Amaral, Fabio Augusto do; Machado, Erica Oliveira; Freitas, Leonardo Luis de; Santana, Laiane Kalita; Canobre, Sheila Cristina, E-mail: fabioamaral@yahoo.com.br, E-mail: fabioamaral@iqufu.ufu.br [Universidade Federal de Uberlandia (UFU/LAETE), (Brazil). Inst. de Quimica. Lab. de Armazenamento de Energia e Tratamento de Efluente

2014-08-15

The aim of this paper was the recovering of the cathodic material from discarded lithium ion batteries for obtainment of the lamellar double hydroxides (LDHs) by the co-precipitation method at variable pH in HCl and H{sub 2}O{sub 2} 1:1 (v/v) acid solution containing Co and Al (extracted from cathodic material composed of LiCoO{sub 2} and aluminum foil). These metals were precipitated in LiOH at pH 9 or 11, or NH{sub 4}OH at pH 9 and submitted to the hydrothermal treatment (HT) to improve the structural organization of the LDHs lamellae. After precipitation, the resulting solids were structurally characterized by XRD for phase identification and calculation of the unit cell parameter, thermally by TGA for the identification of the mass loss and morphologically by SEM. The sample obtained by precipitation with LiOH at pH 11 / hydrothermal treatment showed diffraction peaks similar to hydrotalcite, morphological and thermal characteristics similar to the pattern Co-Al-Cl LDH obtained by co-precipitation at constant pH 8. (author)

Free energy for protonation reaction in lithium-ion battery cathode materials

International Nuclear Information System (INIS)

Benedek, R.; Thackeray, M. M.; van de Walle, A.

2008-01-01

Calculations are performed of free energies for proton-for-lithium-ion exchange reactions in lithium-ion battery cathode materials. First-principles calculations are employed for the solid phases and tabulated ionization potential and hydration energy data for aqueous ions. Layered structures, spinel LiMn 2 O 4 , and olivine LiFePO 4 are considered. Protonation is most favorable energetically in layered systems, such as Li 2 MnO 3 and LiCoO 2 . Less favorable are ion-exchange in spinel LiMn 2 O 4 and LiV 3 O 8 . Unfavorable is the substitution of protons for Li in olivine LiFePO 4 , because of the large distortion of the Fe and P coordination polyhedra. The reaction free energy scales roughly linearly with the volume change in the reaction

Studies on bare and Mg-doped LiCoO2 as a cathode material for lithium ion batteries

CSIR Research Space (South Africa)

Reddy, MV

2014-05-01

Full Text Available at ScienceDirect Electrochimica Acta jo ur nal ho me p age: www.elsev ier .com/ locate /e lec tac ta Graphical Abstract Electrochimica Acta xxx (2013) xxx–xxx Studies on Bare and Mg-doped LiCoO2 as a cathode material for Lithium ion Batteries M.V. Reddy... for Lithium ion Batteries M.V. Reddy∗, Thor Wei Jie, Charl J. Jafta, Kenneth I. Ozoemena, Mkhulu K. Mathe, A. Sree Kumaran Nair, Soo Soon Peng, M. Sobri Idris, Geetha Balakrishna, Fabian I. Ezema, B.V.R. Chowdari • Layered compounds, Li...

Recycling of spent lithium-ion battery cathode materials by ammoniacal leaching.

Science.gov (United States)

Ku, Heesuk; Jung, Yeojin; Jo, Minsang; Park, Sanghyuk; Kim, Sookyung; Yang, Donghyo; Rhee, Kangin; An, Eung-Mo; Sohn, Jeongsoo; Kwon, Kyungjung

2016-08-05

As the production and consumption of lithium ion batteries (LIBs) increase, the recycling of spent LIBs appears inevitable from an environmental, economic and health viewpoint. The leaching behavior of Ni, Mn, Co, Al and Cu from treated cathode active materials, which are separated from a commercial LIB pack in hybrid electric vehicles, is investigated with ammoniacal leaching agents based on ammonia, ammonium carbonate and ammonium sulfite. Ammonium sulfite as a reductant is necessary to enhance leaching kinetics particularly in the ammoniacal leaching of Ni and Co. Ammonium carbonate can act as a pH buffer so that the pH of leaching solution changes little during leaching. Co and Cu can be fully leached out whereas Mn and Al are hardly leached and Ni shows a moderate leaching efficiency. It is confirmed that the cathode active materials are a composite of LiMn2O4, LiCoxMnyNizO2, Al2O3 and C while the leach residue is composed of LiNixMnyCozO2, LiMn2O4, Al2O3, MnCO3 and Mn oxides. Co recovery via the ammoniacal leaching is believed to gain a competitive edge on convenitonal acid leaching both by reducing the sodium hydroxide expense for increasing the pH of leaching solution and by removing the separation steps of Mn and Al. Copyright © 2016 Elsevier B.V. All rights reserved.

Organic anodes and sulfur/selenium cathodes for advanced Li and Na batteries

Science.gov (United States)

Luo, Chao

To address energy crisis and environmental pollution induced by fossil fuels, there is an urgent demand to develop sustainable, renewable, environmental benign, low cost and high capacity energy storage devices to power electric vehicles and enhance clean energy approaches such as solar energy, wind energy and hydroenergy. However, the commercial Li-ion batteries cannot satisfy the critical requirements for next generation rechargeable batteries. The commercial electrode materials (graphite anode and LiCoO 2 cathode) are unsustainable, unrenewable and environmental harmful. Organic materials derived from biomasses are promising candidates for next generation rechargeable battery anodes due to their sustainability, renewability, environmental benignity and low cost. Driven by the high potential of organic materials for next generation batteries, I initiated a new research direction on exploring advanced organic compounds for Li-ion and Na-ion battery anodes. In my work, I employed croconic acid disodium salt and 2,5-Dihydroxy-1,4-benzoquinone disodium salt as models to investigate the effects of size and carbon coating on electrochemical performance for Li-ion and Na-ion batteries. The results demonstrate that the minimization of organic particle size into nano-scale and wrapping organic materials with graphene oxide can remarkably enhance the rate capability and cycling stability of organic anodes in both Li-ion and Na-ion batteries. To match with organic anodes, high capacity sulfur and selenium cathodes were also investigated. However, sulfur and selenium cathodes suffer from low electrical conductivity and shuttle reaction, which result in capacity fading and poor lifetime. To circumvent the drawbacks of sulfur and selenium, carbon matrixes such as mesoporous carbon, carbonized polyacrylonitrile and carbonized perylene-3, 4, 9, 10-tetracarboxylic dianhydride are employed to encapsulate sulfur, selenium and selenium sulfide. The resulting composites exhibit

Silver-coated LiVPO4F composite with improved electrochemical performance as cathode material for lithium-ion batteries

Science.gov (United States)

Yang, Bo; Yang, Lin

2015-12-01

Nano-structured LiVPO4F/Ag composite cathode material has been successfully synthesized via a sol-gel route. The structural and physical properties, as well as the electrochemical performance of the material are compared with those of the pristine LiVPO4F. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that Ag particles are uniformly dispersed on the surface of LiVPO4F without destroying the crystal structure of the bulk material. An analysis of the electrochemical measurements show that the Ag-modified LiVPO4F material exhibits high discharge capacity, good cycle performance (108.5 mAh g-1 after 50th cycles at 0.1 C, 93% of initial discharge capacity) and excellent rate behavior (81.8 mAh g-1 for initial discharge capacity at 5 C). The electrochemical impedance spectroscopy (EIS) results reveal that the adding of Ag decreases the charge-transfer resistance (Rct) of LiVPO4F cathode. This study demonstrates that Ag-coating is a promising way to improve the electrochemical performance of the pristine LiVPO4F for lithium-ion batteries cathode material.

An all-organic rechargeable battery using bipolar polyparaphenylene as a redox-active cathode and anode.

Science.gov (United States)

Zhu, L M; Lei, A W; Cao, Y L; Ai, X P; Yang, H X

2013-01-21

An all-organic rechargeable battery is realized by use of polyparaphenylene as both cathode- and anode-active material. This new battery can operate at a high voltage of 3.0 V with fairly high capacity, offering a renewable and cheaper alternative to conventional batteries.

Is alpha-V₂O₅ a cathode material for Mg insertion batteries?

Energy Technology Data Exchange (ETDEWEB)

Sa, Niya; Wang, Hao; Proffit, Danielle L.; Lipson, Albert L.; Key, Baris; Liu, Miao; Feng, Zhenxing; Fister, Timothy T.; Ren, Yang; Sun, Cheng-Jun; Vaughey, John T.; Fenter, Paul A.; Persson, Kristin A.; Burrell, Anthony K.

2016-08-01

When designing a high energy density battery, one of the critical features is a high voltage, high capacity cathode material. In the development of Mg batteries, oxide cathodes that can reversibly intercalate Mg, while at the same time being compatible with an electrolyte that can deposit Mg reversibly are rare. Herein, we report the compatibility of Mg anodes with a-V₂O₅ by employing magnesium bis(trifluoromethane sulfonyl)imide in diglyme electrolytes at very low water levels. Electrolytes that contain a high water level do not reversibly deposit Mg, but interestingly these electrolytes appear to enable much higher capacities for an a-V₂O₅ cathode. Solid state NMR indicates that the major source of the higher capacity in high water content electrolytes originates from reversible proton insertion. In contrast, we found that lowering the water level of the magnesium bis(trifluoromethane sulfonyl)imide in diglyme electrolyte is critical to achieve reversible Mg deposition and direct evidence for reversible Mg intercalation is shown. Findings we report here elucidate the role of proton intercalation in water-containing electrolytes and clarify numerous conflicting reports of Mg insertion into a-V₂O₅.

High performance Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C composite cathode material for lithium ion batteries studied in pilot scale test

Energy Technology Data Exchange (ETDEWEB)

Chen Zhenyu [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Dai Changsong, E-mail: changsd@hit.edu.c [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Wu Gang; Nelson, Mark [Materials Physics and Applications Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Hu Xinguo [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Zhang Ruoxin; Liu Jiansheng; Xia Jicai [Battery Material Business Division, Guangzhou Tinci Materials Technology Co., Ltd., Guangzhou 510760 (China)

2010-12-01

Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C composite cathode material was synthesized via carbothermal reduction process in a pilot scale production test using battery grade raw materials with the aim of studying the feasibility for their practical applications. XRD, FT-IR, XPS, CV, EIS and battery charge-discharge tests were used to characterize the as-prepared material. The XRD and FT-IR data suggested that the as-prepared Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C material exhibits an orderly monoclinic structure based on the connectivity of PO{sub 4} tetrahedra and VO{sub 6} octahedra. Half cell tests indicated that an excellent high-rate cyclic performance was achieved on the Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C cathodes in the voltage range of 3.0-4.3 V, retaining a capacity of 95% (96 mAh/g) after 100 cycles at 20C discharge rate. The low-temperature performance of the cathode was further evaluated, showing 0.5C discharge capacity of 122 and 119 mAh/g at -25 and -40 {sup o}C, respectively. The discharge capacity of graphite//Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} batteries with a designed battery capacity of 14 Ah is as high as 109 mAh/g with a capacity retention of 92% after 224 cycles at 2C discharge rates. The promising high-rate and low-temperature performance observed in this work suggests that Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C is a very strong candidate to be a cathode in a next-generation Li-ion battery for electric vehicle applications.

High-Capacity, High-Voltage Composite Oxide Cathode Materials

Science.gov (United States)

Hagh, Nader M.

2015-01-01

This SBIR project integrates theoretical and experimental work to enable a new generation of high-capacity, high-voltage cathode materials that will lead to high-performance, robust energy storage systems. At low operating temperatures, commercially available electrode materials for lithium-ion (Li-ion) batteries do not meet energy and power requirements for NASA's planned exploration activities. NEI Corporation, in partnership with the University of California, San Diego, has developed layered composite cathode materials that increase power and energy densities at temperatures as low as 0 degC and considerably reduce the overall volume and weight of battery packs. In Phase I of the project, through innovations in the structure and morphology of composite electrode particles, the partners successfully demonstrated an energy density exceeding 1,000 Wh/kg at 4 V at room temperature. In Phase II, the team enhanced the kinetics of Li-ion transport and electronic conductivity at 0 degC. An important feature of the composite cathode is that it has at least two components that are structurally integrated. The layered material is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated and deliver a large amount of energy with stable cycling.

Synthesis-microstructure-performance relationship of layered transition metal oxides as cathode for rechargeable sodium batteries prepared by high-temperature calcination.

Science.gov (United States)

Xie, Man; Luo, Rui; Lu, Jun; Chen, Renjie; Wu, Feng; Wang, Xiaoming; Zhan, Chun; Wu, Huiming; Albishri, Hassan M; Al-Bogami, Abdullah S; El-Hady, Deia Abd; Amine, Khalil

2014-10-08

Research on sodium batteries has made a comeback because of concern regarding the limited resources and cost of lithium for Li-ion batteries. From the standpoint of electrochemistry and economics, Mn- or Fe-based layered transition metal oxides should be the most suitable cathode candidates for affordable sodium batteries. Herein, this paper reports a novel cathode material, layered Na1+x(Fey/2Niy/2Mn1-y)1-xO2 (x = 0.1-0.5), synthesized through a facile coprecipitation process combined with subsequent calcination. For such cathode material calcined at 800 °C for 20 h, the Na/Na1+x(Fey/2Niy/2Mn1-y)1-xO2 (x = 0.4) electrode exhibited a good capacity of 99.1 mAh g(-1) (cycled at 1.5-4.0 V) and capacity retention over 87% after 50 cycles. Optimization of this material would make layered transition metal oxides a strong candidate for the Na-ion battery cathode.

The preparation and graphene surface coating NaTi_2(PO_4)_3 as cathode material for lithium ion batteries

International Nuclear Information System (INIS)

Li, Na; Wang, Yanping; Rao, Richuan; Dong, Xiongzi; Zhang, Xianwen; Zhu, Sane

2017-01-01

Graphical abstract: The NaTi_2(PO_4)_3/graphene composite is used directly as cathode electrode material for lithium-ion battery by using metal lithium as an anode electrode. Meanwhile, the electrochemical properties of the composite in this system is firstly studied in detail. The NaTi_2(PO_4)_3/graphene composite exhibits the better rate and cyclic performance than NaTi_2(PO_4)_3, which is ascribed to its stable 3-D framework and the enhanced electronic conduction resulting from the graphene sheets surface modification. - Highlights: • The graphene coated NaTi_2(PO_4)_3 was prepared by a simple sol-gel method followed by calcination. • The electrochemical properties of the NaTi_2(PO_4)_3/graphene composite was firstly studied in detail when used as cathode electrode material for lithium-ion batteries. • The electrochemical reaction mechanism of NaTi_2(PO_4)_3/graphene composite was investigated by ex situ XRD. - Abstract: The graphene coated NaTi_2(PO_4)_3 has been fabricated via a simple sol-gel process followed by calcination. The NaTi_2(PO_4)_3/graphene (NTP/G) composite is used directly as cathode electrode material for lithium-ion battery and the electrochemical properties of the composite in this system is firstly studied in detail. In the charge-discharge process, two Li"+ can occupy octahedral M (2) site and be reversibly intercalated into the 3D framework of NTP through the ion conduction channel where almost all of Na"+ are immobilized to sustain the framework. At 5C rate, the capacity retention of the NTP/G composite after 800 cycles is still up to 82.7%. The superior electrochemical properties of NTP/G is ascribed to its stable 3-D framework and the enhanced electronic conduction resulting from the graphene sheets surface modification.

Fe/Fe3C decorated 3-D porous nitrogen-doped graphene as a cathode material for rechargeable Li–O2 batteries

International Nuclear Information System (INIS)

Lai, Yanqing; Chen, Wei; Zhang, Zhian; Qu, Yaohui; Gan, Yongqing; Li, Jie

2016-01-01

Graphical abstract: Fe/Fe 3 C decorated 3-D porous N-doped graphene are prepaed by a one-step carbonization process, with MOF as the structure-directing agent. The method provides a simple and scalable route for preparing 3-D porous graphene materials.The as-prepared material possesses an excellent bi-functional electrocatalytic activity. While applied as the cathode materials of Li–O 2 batteries, the cell exihibits high capacity and considerable rate capability. - Highlights: • A facile simple strategy is employed to in-situ fabricate Fe/Fe 3 C decorated 3-D porous nitrogen-doped graphene. • MIL-100(Fe), a kind of metal-organic framework, is proved playing a structure-directing role in this advanced synthesis route. • This material possesses excellent bi-functional electro-catalytic activity for ORR and OER and shows good electrochemical performance while used as cathode material for Li–O 2 batteries. • The MOF-assisted synthesis method would be a promising new strategy for the synthesis of 3-D porous graphene materials. - Abstract: Fe/Fe 3 C decorated 3-D porous N-doped graphene (F-PNG) is designed and synthesized via a one-step carbonization route. During the process, MIL-100(Fe), a kind of metal organic frameworks (MOFs) plays a structure-directing role. It is found that F-PNG with 3-D porous structure is constituted by N-doped graphene and extremely small Fe/Fe 3 C particles uniformly distribute on the surface of graphene. This rationally designed F-PNG possesses excellent oxygen reduction reaction and oxygen evolution reaction bifunctional electrocatalytic activity. While the material is explored as a cathode of Li–O 2 batteries, it exhibits excellent electrochemical performances, delivering a discharge voltage platform of ∼2.91 V and a charge voltage platform of ∼3.52 V at 0.1 mA cm −2 , showing a good cycle performance and having a discharge capacity of ∼7150 mAh g −1 carbon+catalyst at 0.1 mA cm −2 . The excellent performance of

A high-capacity, low-cost layered sodium manganese oxide material as cathode for sodium-ion batteries.

Science.gov (United States)

Guo, Shaohua; Yu, Haijun; Jian, Zelang; Liu, Pan; Zhu, Yanbei; Guo, Xianwei; Chen, Mingwei; Ishida, Masayoshi; Zhou, Haoshen

2014-08-01

A layered sodium manganese oxide material (NaMn3 O5 ) is introduced as a novel cathode materials for sodium-ion batteries. Structural characterizations reveal a typical Birnessite structure with lamellar stacking of the synthetic nanosheets. Electrochemical tests reveal a particularly large discharge capacity of 219 mAh g(-1) in the voltage rang of 1.5-4.7 V vs. Na/Na(+) . With an average potential of 2.75 V versus sodium metal, layered NaMn3 O5 exhibits a high energy density of 602 Wh kg(-1) , and also presents good rate capability. Furthermore, the diffusion coefficient of sodium ions in the layered NaMn3 O5 electrode is investigated by using the galvanostatic intermittent titration technique. The results greatly contribute to the development of room-temperature sodium-ion batteries based on earth-abundant elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-throughput theoretical design of lithium battery materials

International Nuclear Information System (INIS)

Ling Shi-Gang; Gao Jian; Xiao Rui-Juan; Chen Li-Quan

2016-01-01

The rapid evolution of high-throughput theoretical design schemes to discover new lithium battery materials is reviewed, including high-capacity cathodes, low-strain cathodes, anodes, solid state electrolytes, and electrolyte additives. With the development of efficient theoretical methods and inexpensive computers, high-throughput theoretical calculations have played an increasingly important role in the discovery of new materials. With the help of automatic simulation flow, many types of materials can be screened, optimized and designed from a structural database according to specific search criteria. In advanced cell technology, new materials for next generation lithium batteries are of great significance to achieve performance, and some representative criteria are: higher energy density, better safety, and faster charge/discharge speed. (topical review)

Characterization of LiFePO{sub 4} cathode by addition of graphene for lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Honggowiranto, Wagiyo, E-mail: wagiyo@batan.go.id; Kartini, Evvy, E-mail: kartini@batan.go.id [Center for Science and Technology Advanced Materials, National Nuclear Energy Agency Kawasan Puspiptek Serpong, Tangerang Selatan 15314 (Indonesia)

2016-02-08

The improvement of LiFePO{sub 4} (LFP) cathode performance has been performed by addition of Graphene (LFP+Graphene). The cathode was prepared from the active material with 5 wt % graphene and 10 wt % polyvinylidene fluoride in an n-methyl pyrrolidone solvent. Another cathode material used only 5% artificial graphite for comparison (LFP+Graphite). The crystal structure, microstructure, electronic conductivity, electrochemical impedance spectroscopy (EIS) of the cathodes were characterized by X-ray diffraction, SEM, and Impedance spectroscopy, respectively. Two half cell coin batteries were assembled using a lithium metal as an anode and LiPf{sub 6} as an electrolyte, and two cathodes (LFP+Graphene) and (LFP+Graphite). Charge discharge performance of battery was characterized by Battery analyser (BTS 8). The electronic conductivity of cathode with grapheme increased of about one order magnitude compared with the only cathode with graphite, namely from 1.97E-7S/cm (LFP+Graphite) to 1.92E-6S/cm (LFP+Graphene). The charge-discharge capacity after 10{sup th} cycles of LiFePO{sub 4} with graphene decreased of about 0.68% from 114.3 mAh/g to113.1 mAh/g, while LFP with graphite decreased of about 2.84% from 110.2 mAh/g to 107.1 mAh, at 0.1C-rates. It could be concluded that the addition of graphene has increased the ionic conductivity, and improved performance of the LFP lithium ion battery, such as higher capacity and better efficiency.

Layered P2-Na 2/3 Co 1/2 Ti 1/2 O 2 as a high-performance cathode material for sodium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Sabi, Noha; Doubaji, Siham; Hashimoto, Kazuki; Komaba, Shinichi; Amine, Khalil; Solhy, Abderrahim; Manoun, Bouchaib; Bilal, Essaid; Saadoune, Ismael

2017-02-01

Layered oxides are regarded as promising cathode materials for sodium-ion batteries. We present Na2/3Co1/2Ti1/2O2 as a potential new cathode material for sodium-ion batteries. The crystal features and morphology of the pristine powder were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The cathode material is evaluated in galvanostatic charge-discharge and galvanostatic intermittent titration tests, as well as ex-situ X-ray diffraction analysis. Synthesized by a high-temperature solid state reaction, Na2/3Co1/2Ti1/2O2 crystallizes in P2-type structure with P6(3)/mmc space group. The material presents reversible electrochemical behavior and delivers a specific discharge capacity of 100 mAh g(-1) when tested in Na half cells between 2.0 and 4.2 V (vs. Na+/Na), with capacity retention of 98% after 50 cycles. Furthermore, the electrochemical cycling of this titanium-containing material evidenced a reduction of the potential jumps recorded in the NaxCoO2 parent phase, revealing a positive impact of Ti substitution for Co. The ex-situ XRD measurements confirmed the reversibility and stability of the material. No structural changes were observed in the XRD patterns, and the P2-type structure was stable during the charge/discharge process between 2.0 and 4.2 V vs. Na+/Na. These outcomes will contribute to the progress of developing low cost electrode materials for sodium-ion batteries. (C) 2017 Elsevier B.V. All rights reserved.

Material and energy flows in the materials production, assembly, and end-of-life stages of the automotive lithium-ion battery life cycle

Energy Technology Data Exchange (ETDEWEB)

Dunn, J.B.; Gaines, L.; Barnes, M.; Wang, M.; Sullivan, J. (Energy Systems)

2012-06-21

This document contains material and energy flows for lithium-ion batteries with an active cathode material of lithium manganese oxide (LiMn{sub 2}O{sub 4}). These data are incorporated into Argonne National Laboratory's Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET) model, replacing previous data for lithium-ion batteries that are based on a nickel/cobalt/manganese (Ni/Co/Mn) cathode chemistry. To identify and determine the mass of lithium-ion battery components, we modeled batteries with LiMn{sub 2}O{sub 4} as the cathode material using Argonne's Battery Performance and Cost (BatPaC) model for hybrid electric vehicles, plug-in hybrid electric vehicles, and electric vehicles. As input for GREET, we developed new or updated data for the cathode material and the following materials that are included in its supply chain: soda ash, lime, petroleum-derived ethanol, lithium brine, and lithium carbonate. Also as input to GREET, we calculated new emission factors for equipment (kilns, dryers, and calciners) that were not previously included in the model and developed new material and energy flows for the battery electrolyte, binder, and binder solvent. Finally, we revised the data included in GREET for graphite (the anode active material), battery electronics, and battery assembly. For the first time, we incorporated energy and material flows for battery recycling into GREET, considering four battery recycling processes: pyrometallurgical, hydrometallurgical, intermediate physical, and direct physical. Opportunities for future research include considering alternative battery chemistries and battery packaging. As battery assembly and recycling technologies develop, staying up to date with them will be critical to understanding the energy, materials, and emissions burdens associated with batteries.

Material and Energy Flows in the Materials Production, Assembly, and End-of-Life Stages of the Automotive Lithium-Ion Battery Life Cycle

Energy Technology Data Exchange (ETDEWEB)

Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States); Gaines, Linda [Argonne National Lab. (ANL), Argonne, IL (United States); Barnes, Matthew [Argonne National Lab. (ANL), Argonne, IL (United States); Sullivan, John L. [Argonne National Lab. (ANL), Argonne, IL (United States); Wang, Michael [Argonne National Lab. (ANL), Argonne, IL (United States)

2014-01-01

This document contains material and energy flows for lithium-ion batteries with an active cathode material of lithium manganese oxide (LiMn₂O₄). These data are incorporated into Argonne National Laboratory’s Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET) model, replacing previous data for lithium-ion batteries that are based on a nickel/cobalt/manganese (Ni/Co/Mn) cathode chemistry. To identify and determine the mass of lithium-ion battery components, we modeled batteries with LiMn₂O₄ as the cathode material using Argonne’s Battery Performance and Cost (BatPaC) model for hybrid electric vehicles, plug-in hybrid electric vehicles, and electric vehicles. As input for GREET, we developed new or updated data for the cathode material and the following materials that are included in its supply chain: soda ash, lime, petroleum-derived ethanol, lithium brine, and lithium carbonate. Also as input to GREET, we calculated new emission factors for equipment (kilns, dryers, and calciners) that were not previously included in the model and developed new material and energy flows for the battery electrolyte, binder, and binder solvent. Finally, we revised the data included in GREET for graphite (the anode active material), battery electronics, and battery assembly. For the first time, we incorporated energy and material flows for battery recycling into GREET, considering four battery recycling processes: pyrometallurgical, hydrometallurgical, intermediate physical, and direct physical. Opportunities for future research include considering alternative battery chemistries and battery packaging. As battery assembly and recycling technologies develop, staying up to date with them will be critical to understanding the energy, materials, and emissions burdens associated with batteries.

Deposition and characterization of thin films of materials with application in cathodes for lithium rechargeable micro batteries

International Nuclear Information System (INIS)

Lopez I, J.

2007-01-01

In this thesis work is reported the deposition and characterization of thin films of materials of the type LiMO 2 , with M=Co and Ni, which have application in cathodes for micro-batteries of lithium ions. In the last years some investigators have reported that the electrochemical operation of the lithium ions batteries it can improve recovering the cathode, in bundle form, with some metal oxides as the Al 2 O 3 ; for that the study of the formation of thin films in bilayer form LiMO 2 /AI 2 O 3 is of interest in the development of lithium ions micro batteries. The thin films were deposited using the laser ablation technique studying the effect of some deposit parameters in the properties of the one formed material, as: laser fluence, substrate temperature and working atmosphere, with the purpose of optimizing it. In the case of the LiCoO 2 it was found that to use an inert atmosphere of argon allows to obtain the material with the correct composition. Additionally, with the use of a temperature in the substrate of 150 C is possible to obtain to the material with certain crystallinity grade that to the subjected being to a post-deposit thermal treatment at 300 C for three hours, it gives as result a totally crystalline material. In the case of the thin films of LiNiO 2 , it was necessary to synthesize the oxide starting from a reaction of solid state among nickel oxide (NiO) and lithium oxide (Li 2 O) obtaining stoichiometric LiNiO 2 . For the formation of the thin films of LiNiO 2 it was used an argon atmosphere and the laser fluence was varied, the deposits were carried out to two different substrates temperatures, atmosphere and 160 C. In both cases the material it was recovered with an alumina layer, found that this layer didn't modify the structural properties of the base oxide (LiCoO 2 and LiNiO 2 ). (Author)

In Situ Analysis of the Li-O2 Battery with Thermally Reduced Graphene Oxide Cathode: Influence of Water Addition

DEFF Research Database (Denmark)

Storm, Mie Møller; Christensen, Mathias Kjærgård; Younesi, Reza

2016-01-01

The Li-O2 battery technology holds the promise to deliver a battery with significantly increased specific energy compared to today's Li-ion batteries. As a cathode support material, reduced graphene oxide has received increasing attention in the Li-O2 battery community due to the possibility...... of increased discharge capacity, increased battery cyclability, and decreased, charging, overpotential. In this. article we investigate the effect of water on a thermally, redircedigraphene, oxide cathode in a Li-O2 battery. Differential electrochemical mass spectrciscnieveals a, decreased electron count......-of-the cathode and not only on addition of water to the electrolyte as demonstrated by the solution-based mechanism In situ synchrotron X-ray diffraction experiment using a new design of a capillary-based Li-O2 cell with a thermally reduced graphene oxide cathode shows formation of LiOH along with Li2O2....

Advanced Nanostructured Cathode for Ultra High Specific Energy Lithium Ion Batteries, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — Integrate advanced nanotechnology with energy storage technology to develop advanced cathode materials for use in Li-ion batteries while maintaining a high level of...

Recycling of LiCo0.59Mn0.26Ni0.15O2 cathodic material from spent Li-ion batteries by the method of the citrate gel combustion

Directory of Open Access Journals (Sweden)

Senćanski Jelena V.

2017-01-01

Full Text Available The Li-ion batteries are the main power source for the high technology devices, such as mobile phones and electric vehicles. Because of that, the number of spent Li-ion batteries significantly increases. Today, the number of active mobile phones crossed 7.19 billion. It is estimated that the mass of the spent lithium ion batteries in China will exceed 500,000 t by 2020. The trouble is in the ingredients of these batteries. They contain Li, Co, Mn, Ni, Cu, Al and toxic and flammable electrolytes which have a harmful affection to the environment. Because of that, the recycling procedure attracts raising attention of researches. Several commercial spent Li-ion batteries were recycled by the relatively fast, economic and simple procedure. The three ways of separating the cathode material from Al collector were examined after the manual dismantling of the components of batteries with the Li(Co–Mn–NiO2 as cathode material. These were: 1. dissolution of the Al collector in the alkali medium, 2. peeling off with N-methylpyrrolidone and 3. thermal decomposition of the adhesive at 700°C. The procedure with the highest yield was the one with the dissolution in alkali medium. The chemical analysis of the single batteries'' components (the crust, Al/Cu collector, cathode material were done by the atomic absorption spectrometry. The components, before the analysis, were dissolved. The re-synthesis of the cathode material by the method of the citrate gel combustion was done after the separating the cathode material and dissolving it in the nitric acid. The obtained product was, after annealing, characterized by the methods of X-ray diffraction and Raman spectroscopy. The recycled product was LiCo0.59Mn0.26Ni0.15O2 stoichiometry, with the hexagonal layered structure α-NaFeO2 type. The functionalization of the resynthesized material was examined in the 1 M solution LiClO4 in the propylene carbonate, by galvanostatic charging, with the current density of 0

Mechanical characterization and modeling for anodes and cathodes in lithium-ion batteries

Science.gov (United States)

Wang, Lubing; Yin, Sha; Zhang, Chao; Huan, Yong; Xu, Jun

2018-07-01

Mechanical properties of electrode materials have significant influence over electrochemical properties as well as mechanical integrity of lithium-ion battery cells. Here, anode and cathode in a commercially available 18650 NCA (Nickel Cobalt Aluminum Oxide)/graphite cell were comprehensively studied by tensile tests considering material anisotropy, SOC (state of charge), strain rate and electrolyte content. Results showed that the mechanical properties of both electrodes were highly dependent on strain rate and electrolyte content; however, anode was SOC dependent while cathode was not. Besides, coupled effects of strain rate and SOC of anodes were also discussed. SEM (scanning electron microscope) images of surfaces and cross-sections of electrodes showed the fracture morphology. In addition, mechanical behavior of Cu foil separated from anode with different SOC values were studied and compared. Finally, constitutive models of electrodes considering both strain rate and anisotropy effects were established. This study reveals the relationship between electrochemical dependent mechanical behavior of the electrodes. The established mechanical models of electrodes can be applied to the numerical computation of battery cells. Results are essential to predict the mechanical responses as well as the deformation of battery cell under various loading conditions, facilitating safer battery design and manufacturing.

Modeling study of a Li–O2 battery with an active cathode

International Nuclear Information System (INIS)

Li, Xianglin; Huang, Jing; Faghri, Amir

2015-01-01

In this study, a new organic lithium oxygen (Li–O 2 ) battery structure is proposed to enhance battery capacity. The electrolyte is forced to recirculate through the cathode and then saturated with oxygen in a tank external to the battery. The forced convection enhances oxygen transport and alleviates the problem of electrode blockage during discharge. A two dimensional, transient, non-isothermal simulation model is developed to study the heat and mass transfer within the battery and validate the proposed design. Results show that this novel active cathode design improves the battery capacity at all discharge current densities. The capacity of the Li–O 2 battery is increased by 15.5 times (from 12.2 mAh g −1 to 201 mAh g −1 ) at the discharge current of 2.0 mA cm −2 when a conventional passive electrode is replaced by the newly designed active electrode. Furthermore, a cathode with non-uniform porosity is suggested and simulation results show that it can reach a higher discharge capacity without decreasing its power density. Detailed mass transport processes in the battery are also studied. - Highlights: • Electrolyte is circulated through the cathode and externally saturated with oxygen. • A two-dimensional, transient, non-isothermal model is developed for a Li–O 2 battery. • The new design's capacity can be 15.5 times that of a battery with passive cathode. • A cathode with non-uniform porosity is proposed to further enhance battery capacity

Nanoscale visualization of redox activity at lithium-ion battery cathodes.

Science.gov (United States)

Takahashi, Yasufumi; Kumatani, Akichika; Munakata, Hirokazu; Inomata, Hirotaka; Ito, Komachi; Ino, Kosuke; Shiku, Hitoshi; Unwin, Patrick R; Korchev, Yuri E; Kanamura, Kiyoshi; Matsue, Tomokazu

2014-11-17

Intercalation and deintercalation of lithium ions at electrode surfaces are central to the operation of lithium-ion batteries. Yet, on the most important composite cathode surfaces, this is a rather complex process involving spatially heterogeneous reactions that have proved difficult to resolve with existing techniques. Here we report a scanning electrochemical cell microscope based approach to define a mobile electrochemical cell that is used to quantitatively visualize electrochemical phenomena at the battery cathode material LiFePO4, with resolution of ~100 nm. The technique measures electrode topography and different electrochemical properties simultaneously, and the information can be combined with complementary microscopic techniques to reveal new perspectives on structure and activity. These electrodes exhibit highly spatially heterogeneous electrochemistry at the nanoscale, both within secondary particles and at individual primary nanoparticles, which is highly dependent on the local structure and composition.

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....

Synthesis and properties of Li{sub 2}MnO{sub 3}-based cathode materials for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Xue, Leigang; Zhang, Shu; Li, Shuli; Lu, Yao; Toprakci, Ozan [Fiber and Polymer Science Program, Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, NC 27695-8301 (United States); Xia, Xin [Fiber and Polymer Science Program, Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, NC 27695-8301 (United States); College of Textile and Clothing, Xinjiang University, Xinjiang, Urumchi 830046 (China); Chen, Chen [College of Textile and Clothing, Xinjiang University, Xinjiang, Urumchi 830046 (China); Hu, Yi [Fiber and Polymer Science Program, Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, NC 27695-8301 (United States); Engineering Research Center for Eco-Dyeing and Finishing of Textiles, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018 (China); Zhang, Xiangwu, E-mail: xiangwu_zhang@ncsu.edu [Fiber and Polymer Science Program, Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, NC 27695-8301 (United States)

2013-11-15

Highlights: •0.3Li{sub 2}MnO{sub 3}·0.5LiMn{sub 0.5}Ni{sub 0.5}O{sub 2}·0.2LiCoO{sub 2} was synthesized by a co-precipitation method. •The preparation method is simple and this material is inexpensive due to the high contents of Mn and Ni. •The material could be charged to a high potential to extract more lithium without structural damage. •A relatively high capacity of 178 mAh g{sup −1} is delivered between 2.0 and 4.6 V with excellent cycling performance. -- Abstract: Lithium-ion batteries have been wildly used in various portable electronic devices and the application targets are currently moving from small-sized mobile devices to large-scale electric vehicles and grid energy storage. Therefore, lithium-ion batteries with higher energy densities are in urgent need. For high-energy cathodes, Li{sub 2}MnO{sub 3}–LiMO{sub 2} layered–layered (M = Mn, Co, Ni) materials are of significant interest due to their high specific capacities over wide operating potential windows. Here, three Li{sub 2}MnO{sub 3}-based cathode materials with α-NaFeO{sub 2} structure were prepared by a facile co-precipitation method and subsequent heat treatment. Among these three materials, 0.3Li{sub 2}MnO{sub 3}·0.5LiMn{sub 0.5}Ni{sub 0.5}O{sub 2}·0.2LiCoO{sub 2} shows the best lithium storage capability. This cathode material is composed of uniform nanosized particles with diameters ranging from 100 to 200 nm, and it could be charged to a high cutoff potential to extract more lithium, resulting in a high capacity of 178 mAh g{sup −1} between 2.0 and 4.6 V with almost no capacity loss over 100 cycles.

"Electron/Ion Sponge"-Like V-Based Polyoxometalate: Toward High-Performance Cathode for Rechargeable Sodium Ion Batteries.

Science.gov (United States)

Liu, Jilei; Chen, Zhen; Chen, Shi; Zhang, Bowei; Wang, Jin; Wang, Huanhuan; Tian, Bingbing; Chen, Minghua; Fan, Xiaofeng; Huang, Yizhong; Sum, Tze Chien; Lin, Jianyi; Shen, Ze Xiang

2017-07-25

One key challenge facing room temperature Na-ion batteries lies in identifying earth-abundant, environmentally friendly and safe materials that can provide efficient Na + storage sites in Na-ion batteries. Herein, we report such a material, polyoxometalate Na 2 H 8 [MnV 13 O 38 ] (NMV), with entirely different composition and structure from those cathode compounds reported before. Ex-situ XPS and FTIR analyses reveal that NMV cathode behaves like an "electron/Na-ion sponge", with 11 electrons/Na + acceptability per mole, which has a decisive contribution to the high capacity. The extraordinary structural features, evidenced by X-ray crystallographic analysis, of Na 2 H 8 [MnV 13 O 38 ] with a flexible 2D lamellar network and 1D open channels provide diverse Na ion migration pathways, yielding good rate capability. First-principle calculations demonstrate that a super-reduced state, [MnV 13 O 38 ] 20- , is formed with slightly expanded size (ca. 7.5%) upon Na + insertion compared to the original [MnV 13 O 38 ] 9- . This "ion sponge" feature ensures the good cycling stability. Consequently, benefiting from the combinations of "electron/ion sponge" with diverse Na + diffusion channels, when revealed as the cathode materials for Na-ion batteries, Na 2 H 8 [MnV 13 O 38 ]/G exhibits a high specific capacity (ca. 190 mA h/g at 0.1 C), associates with a good rate capability (130 mA h/g at 1 C), and a good capacity retention (81% at 0.2 C). Our results promote better understanding of the storage mechanism in polyoxometalate host, enrich the existing rechargeable SIBs cathode chemistry, and enlighten an exciting direction for exploring promising cathode materials for Na-ion batteries.

Synthesis and electrochemical characterization of nano-CeO2-coated nanostructure LiMn2O4 cathode materials for rechargeable lithium batteries

International Nuclear Information System (INIS)

Arumugam, D.; Kalaignan, G. Paruthimal

2010-01-01

LiMn 2 O 4 spinel cathode materials were coated with 0.5, 1.0, and 1.5 wt.% CeO 2 by a polymeric process, followed by calcination at 850 o C for 6 h in air. The surface-coated LiMn 2 O 4 cathode materials were physically characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron microscopy (XPS). XRD patterns of CeO 2 -coated LiMn 2 O 4 revealed that the coating did not affect the crystal structure or the Fd3m space group of the cathode materials compared to uncoated LiMn 2 O 4 . The surface morphology and particle agglomeration were investigated using SEM, TEM image showed a compact coating layer on the surface of the core materials that had average thickness of about 20 nm. The XPS data illustrated that the CeO 2 completely coated the surface of the LiMn 2 O 4 core cathode materials. The galvanostatic charge and discharge of the uncoated and CeO 2 -coated LiMn 2 O 4 cathode materials were measured in the potential range of 3.0-4.5 V (0.5 C rate) at 30 o C and 60 o C. Among them, the 1.0 wt.% of CeO 2 -coated spinel LiMn 2 O 4 cathode satisfies the structural stability, high reversible capacity and excellent electrochemical performances of rechargeable lithium batteries.

Silicon oxide based high capacity anode materials for lithium ion batteries

Science.gov (United States)

Deng, Haixia; Han, Yongbong; Masarapu, Charan; Anguchamy, Yogesh Kumar; Lopez, Herman A.; Kumar, Sujeet

2017-03-21

Silicon oxide based materials, including composites with various electrical conductive compositions, are formulated into desirable anodes. The anodes can be effectively combined into lithium ion batteries with high capacity cathode materials. In some formulations, supplemental lithium can be used to stabilize cycling as well as to reduce effects of first cycle irreversible capacity loss. Batteries are described with surprisingly good cycling properties with good specific capacities with respect to both cathode active weights and anode active weights.

Carbon/Sulfur Composite Cathodes for Flexible Lithium/Sulfur Batteries: Status and Prospects

International Nuclear Information System (INIS)

Zhao, Yan; Zhang, Yongguang; Bakenova, Zagipa; Bakenov, Zhumabay

2015-01-01

High specific energy and low cost flexible lithium/sulfur batteries have attracted significant attention as a promising power source to enable future flexible and wearable electronic devices. Here, we review recent progress in the development of free-standing sulfur composite cathodes, with special emphasis on electrode material selectivity and battery structural design. The mini-review is organized based on the dimensionality of different scaffold materials, namely one-dimensional carbon nanotube (CNT), two-dimensional graphene, and three-dimensional CNT/graphene composite, respectively. Finally, the opportunities and perspectives of the future research directions are discussed.

Oxyphosphorus-containing polymers as binders for battery cathodes

Science.gov (United States)

Pratt, Russell Clayton; Mullin, Scott Allen; Eitouni, Hany Basam

2018-05-29

A class of polymeric phosphorous esters can be used as binders for battery cathodes. Metal salts can be added to the polymers to provide ionic conductivity. The polymeric phosphorous esters can be formulated with other polymers either as mixtures or as copolymers to provide additional desirable properties. Examples of such properties include even higher ionic conductivity and improved mechanical properties. Furthermore, cathodes that include the polymeric phosphorous esters can be assembled with a polymeric electrolyte separator and an anode to form a complete battery.

Hydrothermal synthesis and rate capacity studies of Li3V2(PO4)3 nanorods as cathode material for lithium-ion batteries

International Nuclear Information System (INIS)

Liu Haowen; Cheng Cuixia; Huang Xintang; Li Jinlin

2010-01-01

It is an effective method by synthesizing one-dimensional nanostructure to improve the rate performances of cathode materials for Li-ion batteries. In this paper, Li 3 V 2 (PO 4 ) 3 nanorods were successfully prepared by hydrothermal reaction method. The structure, composition and shape of the prepared were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scan electron microscope (SEM) and transmission electron microscope (TEM), respectively. The data indicate the as-synthesis powders are defect-rich nanorods and the sizes are the length of several hundreds of nanometers to 1 μm and the diameter of about 60 nm. The preferential growth direction of the prepared material was the [1 2 0]. The electrodes consisting of the Li 3 V 2 (PO 4 ) 3 nanorods show the better discharge capacities at high rates over a potential range of 3.0-4.6 V. These results can be attributed to the shorter distance of electron transport and the fact that ion diffusion in the electrode material is limited by the nanorod radius. All these results indicate that the resulting Li 3 V 2 (PO 4 ) 3 nanorods are promising cathode materials in lithium-ion batteries.

Mitigating Voltage Decay of Li-Rich Cathode Material via Increasing Ni Content for Lithium-Ion Batteries.

Science.gov (United States)

Shi, Ji-Lei; Zhang, Jie-Nan; He, Min; Zhang, Xu-Dong; Yin, Ya-Xia; Li, Hong; Guo, Yu-Guo; Gu, Lin; Wan, Li-Jun

2016-08-10

Li-rich layered materials have been considered as the most promising cathode materials for future high-energy-density lithium-ion batteries. However, they suffer from severe voltage decay upon cycling, which hinders their further commercialization. Here, we report a Li-rich layered material 0.5Li2MnO3·0.5LiNi0.8Co0.1Mn0.1O2 with high nickel content, which exhibits much slower voltage decay during long-term cycling compared to conventional Li-rich materials. The voltage decay after 200 cycles is 201 mV. Combining in situ X-ray diffraction (XRD), ex situ XRD, ex situ X-ray photoelectron spectroscopy, and scanning transmission electron microscopy, we demonstrate that nickel ions act as stabilizing ions to inhibit the Jahn-Teller effect of active Mn(3+) ions, improving d-p hybridization and supporting the layered structure as a pillar. In addition, nickel ions can migrate between the transition-metal layer and the interlayer, thus avoiding the formation of spinel-like structures and consequently mitigating the voltage decay. Our results provide a simple and effective avenue for developing Li-rich layered materials with mitigated voltage decay and a long lifespan, thereby promoting their further application in lithium-ion batteries with high energy density.

Lipon coatings for high voltage and high temperature Li-ion battery cathodes

Energy Technology Data Exchange (ETDEWEB)

Dudney, Nancy J.; Liang, Chengdu; Nanda, Jagjit; Veith, Gabriel M.; Kim, Yoongu; Martha, Surendra Kumar

2017-12-05

A lithium ion battery includes an anode and a cathode. The cathode includes a lithium, manganese, nickel, and oxygen containing compound. An electrolyte is disposed between the anode and the cathode. A protective layer is deposited between the cathode and the electrolyte. The protective layer includes pure lithium phosphorus oxynitride and variations that include metal dopants such as Fe, Ti, Ni, V, Cr, Cu, and Co. A method for making a cathode and a method for operating a battery are also disclosed.

Polyoxometalate flow battery

Science.gov (United States)

Anderson, Travis M.; Pratt, Harry D.

2016-03-15

Flow batteries including an electrolyte of a polyoxometalate material are disclosed herein. In a general embodiment, the flow battery includes an electrochemical cell including an anode portion, a cathode portion and a separator disposed between the anode portion and the cathode portion. Each of the anode portion and the cathode portion comprises a polyoxometalate material. The flow battery further includes an anode electrode disposed in the anode portion and a cathode electrode disposed in the cathode portion.

Novel iron-cobalt derivatised lithium iron phosphate nanocomposite for lithium ion battery cathode

CSIR Research Space (South Africa)

Ikpo, CO

2013-01-01

Full Text Available Described herein is the electrochemical study conducted on lithium ion battery cathode material consisting of composite of lithium iron phosphate (LiFePO(sub4), iron-cobalt derivatised carbon nanotubes (FeCo-CNT) and polyaniline (PA) nanomaterials...

Cathode materials produced by spray flame synthesis for lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Hamid, NoorAshrina Binti A.

2013-07-03

Lithium ion batteries are one of the most enthralling rechargeable energy storage systems for portable application due to their high energy density. Nevertheless, with respect to electromobility innovation towards better electrochemical properties such as higher energy and power density is required. Altering the cathode material used in Li-ion batteries is favorable since the mass- and volume performance is closely related to the cathode electrode mass. Instead of using LiCoO{sub 2} as cathode electrode, LiFePO{sub 4} has gained serious attention as this material owns a high theoretical capacity of 170 mAh g{sup -1}. It is non-toxic, cheap and consists of abundant materials but suffers from low electronic and ionic conductivity. Utilization of nanotechnology methods in combination with composite formation is known to cure this problem effectively. In this work, a new combination of techniques using highly scalable gas-phase synthesis namely spray-flame synthesis and subsequent solid-state reaction has been used to synthesize nanocomposite LiFePO{sub 4}/C. At first this work deals with the formation and characterization of nanosize FePO{sub 4} from a solution of iron(III)acetylacetonate and tributyl phosphate in toluene using spray-flame synthesis. It was shown that a subsequent solid state reaction with Li{sub 2}CO{sub 3} and glucose yielded a LiFePO{sub 4}/C nanocomposite with very promising electrochemical properties. Based on these initial findings the influence of two synthesis parameter - carbon content and annealing temperature - was investigated towards the physicochemical properties of LiFePO{sub 4}/C. It was shown that an annealing temperature of 700 C leads to high purity composite materials consisting of crystalline LiFePO{sub 4} with crystallite sizes well below 100 nm and amorphous carbon consisting of disordered and graphite-like carbon. Variation of glucose amount between 10 and 30 wt% resulted in carbon contents between 2.1 and 7.3 wt%. In parallel

Cathode materials produced by spray flame synthesis for lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Hamid, NoorAshrina Binti A.

2013-07-03

Lithium ion batteries are one of the most enthralling rechargeable energy storage systems for portable application due to their high energy density. Nevertheless, with respect to electromobility innovation towards better electrochemical properties such as higher energy and power density is required. Altering the cathode material used in Li-ion batteries is favorable since the mass- and volume performance is closely related to the cathode electrode mass. Instead of using LiCoO{sub 2} as cathode electrode, LiFePO{sub 4} has gained serious attention as this material owns a high theoretical capacity of 170 mAh g{sup -1}. It is non-toxic, cheap and consists of abundant materials but suffers from low electronic and ionic conductivity. Utilization of nanotechnology methods in combination with composite formation is known to cure this problem effectively. In this work, a new combination of techniques using highly scalable gas-phase synthesis namely spray-flame synthesis and subsequent solid-state reaction has been used to synthesize nanocomposite LiFePO{sub 4}/C. At first this work deals with the formation and characterization of nanosize FePO{sub 4} from a solution of iron(III)acetylacetonate and tributyl phosphate in toluene using spray-flame synthesis. It was shown that a subsequent solid state reaction with Li{sub 2}CO{sub 3} and glucose yielded a LiFePO{sub 4}/C nanocomposite with very promising electrochemical properties. Based on these initial findings the influence of two synthesis parameter - carbon content and annealing temperature - was investigated towards the physicochemical properties of LiFePO{sub 4}/C. It was shown that an annealing temperature of 700 C leads to high purity composite materials consisting of crystalline LiFePO{sub 4} with crystallite sizes well below 100 nm and amorphous carbon consisting of disordered and graphite-like carbon. Variation of glucose amount between 10 and 30 wt% resulted in carbon contents between 2.1 and 7.3 wt%. In parallel

Electrochemical Characteristics of Layered Transition Metal Oxide Cathode Materials for Lithium Ion Batteries: Surface, Bulk Behavior, and Thermal Properties.

Science.gov (United States)

Tian, Chixia; Lin, Feng; Doeff, Marca M

2018-01-16

Layered lithium transition metal oxides, in particular, NMCs (LiNi x Co y Mn z O 2 ) represent a family of prominent lithium ion battery cathode materials with the potential to increase energy densities and lifetime, reduce costs, and improve safety for electric vehicles and grid storage. Our work has focused on various strategies to improve performance and to understand the limitations to these strategies, which include altering compositions, utilizing cation substitutions, and charging to higher than usual potentials in cells. Understanding the effects of these strategies on surface and bulk behavior and correlating structure-performance relationships advance our understanding of NMC materials. This also provides information relevant to the efficacy of various approaches toward ensuring reliable operation of these materials in batteries intended for demanding traction and grid storage applications. In this Account, we start by comparing NMCs to the isostructural LiCoO 2 cathode, which is widely used in consumer batteries. Effects of changing the metal content (Ni, Mn, Co) upon structure and performance of NMCs are briefly discussed. Our early work on the effects of partial substitution of Al, Fe, and Ti for Co on the electrochemical and bulk structural properties is then covered. The original aim of this work was to reduce the Co content (and thus the raw materials cost) and to determine the effect of the substitutions on the electrochemical and bulk structural properties. More recently, we have turned to the application of synchrotron and advanced microscopy techniques to understand both bulk and surface characteristics of the NMCs. Via nanoscale-to-macroscale spectroscopy and atomically resolved imaging techniques, we were able to determine that the surfaces of NMC undergo heterogeneous reconstruction from a layered structure to rock salt under a variety of conditions. Interestingly, formation of rock salt also occurs under abuse conditions. The surface

Electrochemical performance of La2O3/Li2O/TiO2 nano-particle coated cathode material LiFePO4.

Science.gov (United States)

Wang, Hong; Yang, Chi; Liu, Shu-Xin

2014-09-01

Cathode material, LiFePO4 was modified by coating with a thin layer of La2O3/Li2O/TiO2 nano-particles for improving its performance for lithium ion batteries. The morphology and structure of the modified cathode material were characterized by powder X-ray diffraction, scanning electron microcopy and AES. The performance of the battery with the modified cathode material, including cycling stability, C-rate discharge was examined. The results show that the battery composed of the coated cathode materials can discharge at a large current density and show stable cycling performance in the range from 2.5 to 4.0 V. The rate of Li ion diffusion increases in the battery with the La2O3/Li2O/TiO2-coated LiFePO4 as a cathode and the coating layer may acts as a faster ion conductor (La(2/3-x)Li(3x)TiO3).

Lithium nickel cobalt manganese oxide synthesized using alkali chloride flux: morphology and performance as a cathode material for lithium ion batteries.

Science.gov (United States)

Kim, Yongseon

2012-05-01

Li(Ni(0.8)Co(0.1)Mn(0.1))O(2) (NCM811) was synthesized using alkali chlorides as a flux and the performance as a cathode material for lithium ion batteries was examined. Primary particles of the powder were segregated and grown separately in the presence of liquid state fluxes, which induced each particle to be composed of one primary particle with well-developed facet planes, not the shape of agglomerates as appears with commercial NCMs. The new NCM showed far less gas emission during high temperature storage at charged states, and higher volumetric capacity thanks to its high bulk density. The material is expected to provide optimal performances for pouch type lithium ion batteries, which require high volumetric capacity and are vulnerable to deformation caused by gas generation from the electrode materials.

Vanadium Oxyfluoride/Few-Layer Graphene Composite as a High-Performance Cathode Material for Lithium Batteries.

Science.gov (United States)

Cambaz, Musa Ali; Vinayan, B P; Clemens, Oliver; Munnangi, Anji Reddy; Chakravadhanula, Venkata Sai Kiran; Kübel, Christian; Fichtner, Maximilian

2016-04-18

Metal oxyfluoride compounds are gathering significant interest as cathode materials for lithium ion batteries at the moment because of their high theoretical capacity and resulting high energy density. In this regard, a new and direct approach is presented to synthesize phase-pure vanadium oxyfluoride (VO2F). The structure of VO2F was identified by Rietveld refinement of the powder X-ray diffraction (XRD) pattern. It crystallizes in a perovskite-type structure with disorder of the oxide and fluoride ions. The as-synthesized VO2F was tested as a cathode material for lithium ion batteries after being surface-coated with few-layer graphene. The VO2F delivered a first discharge capacity of 254 mA h g(-1) and a reversible capacity of 208 mA h g(-1) at a rate of C/20 for the first 20 cycles with an average discharge voltage of 2.84 V, yielding an energy density of 591 W h kg(-1). Improved rate capability that outperforms the previous report has been achieved, showing a discharge capacity of 150 mA h g(-1) for 1 C. The structural changes during lithium insertion and extraction were monitored by ex-situ XRD analysis of the electrodes discharged and charged to various stages. Lithium insertion results in an irreversible structural change of the anion lattice from (3)/4 cubic close packing to hexagonal close packing to accommodate the inserted lithium ions while keeping the overall space-group symmetry. For the first time we have revealed a structural change for the ReO3-type structure of as-prepared VO2F to the RhF3 structure after lithiation/delithiation, with structural changes that have not been observed in previous reports. Furthermore, the new synthetic approach described here would be a platform for the synthesis of new oxyfluoride compounds.

Exfoliation and reassembly of cobalt oxide nanosheets into a reversible lithium-ion battery cathode.

Science.gov (United States)

Compton, Owen C; Abouimrane, Ali; An, Zhi; Palmeri, Marc J; Brinson, L Catherine; Amine, Khalil; Nguyen, SonBinh T

2012-04-10

An exfoliation-reassembly-activation (ERA) approach to lithium-ion battery cathode fabrication is introduced, demonstrating that inactive HCoO(2) powder can be converted into a reversible Li(1-x) H(x) CoO(2) thin-film cathode. This strategy circumvents the inherent difficulties often associated with the powder processing of the layered solids typically employed as cathode materials. The delamination of HCoO(2) via a combination of chemical and mechanical exfoliation generates a highly processable aqueous dispersion of [CoO(2) ](-) nanosheets that is critical to the ERA approach. Following vacuum-assisted self-assembly to yield a thin-film cathode and ion exchange to activate this material, the generated cathodes exhibit excellent cyclability and discharge capacities approaching that of low-temperature-prepared LiCoO(2) (~83 mAh g(-1) ), with this good electrochemical performance attributable to the high degree of order in the reassembled cathode. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Feasibility of Cathode Surface Coating Technology for High-Energy Lithium-ion and Beyond-Lithium-ion Batteries.

Science.gov (United States)

Kalluri, Sujith; Yoon, Moonsu; Jo, Minki; Liu, Hua Kun; Dou, Shi Xue; Cho, Jaephil; Guo, Zaiping

2017-12-01

Cathode material degradation during cycling is one of the key obstacles to upgrading lithium-ion and beyond-lithium-ion batteries for high-energy and varied-temperature applications. Herein, we highlight recent progress in material surface-coating as the foremost solution to resist the surface phase-transitions and cracking in cathode particles in mono-valent (Li, Na, K) and multi-valent (Mg, Ca, Al) ion batteries under high-voltage and varied-temperature conditions. Importantly, we shed light on the future of materials surface-coating technology with possible research directions. In this regard, we provide our viewpoint on a novel hybrid surface-coating strategy, which has been successfully evaluated in LiCoO 2 -based-Li-ion cells under adverse conditions with industrial specifications for customer-demanding applications. The proposed coating strategy includes a first surface-coating of the as-prepared cathode powders (by sol-gel) and then an ultra-thin ceramic-oxide coating on their electrodes (by atomic-layer deposition). What makes it appealing for industry applications is that such a coating strategy can effectively maintain the integrity of materials under electro-mechanical stress, at the cathode particle and electrode- levels. Furthermore, it leads to improved energy-density and voltage retention at 4.55 V and 45 °C with highly loaded electrodes (≈24 mg.cm -2 ). Finally, the development of this coating technology for beyond-lithium-ion batteries could be a major research challenge, but one that is viable. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface-initiated growth of thin oxide coatings for Li-sulfur battery cathodes

Energy Technology Data Exchange (ETDEWEB)

Lee, Kyu Tae; Black, Robert; Yim, Taeeun; Ji, Xiulei; Nazar, Linda F. [University of Waterloo, Department of Chemistry, Waterloo, ON (Canada)

2012-12-15

The concept of surface-initiated growth of oxides on functionalized carbons is introduced as a method to inhibit the dissolution of polysulfide ions in Li-S battery cathode materials. MO{sub x} (M: Si, V) thin layers are homogeneously coated on nanostructured carbon-sulfur composites. The coating significantly inhibits the dissolution of polysulfides on cycling, resulting in enhanced cycle performance and coulombic efficiency of the Li-S battery. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Lithium position and occupancy fluctuations in a cathode during charge/discharge cycling of lithium-ion battery

International Nuclear Information System (INIS)

Sharma, N.; Yu, D.; Zhu, Y.; Wu, Y.; Peterson, V. K.

2012-01-01

Lithium-ion batteries are undergoing rapid development to meet the energy demands of the transportation and renewable energy-generation sectors. The capacity of a lithium-ion battery is dependent on the amount of lithium that can be reversibly incorporated into the cathode. Neutron diffraction provides greater sensitivity towards lithium relative to other diffraction techniques. In conjunction with the penetration depth afforded by neutron diffraction, the information concerning lithium gained in a neutron diffraction study allows commercial lithium-ion batteries to be explored with respect to the lithium content in the whole cathode. Furthermore, neutron diffraction instruments featuring area detectors that allow relatively fast acquisitions enable perturbations of lithium location and occupancy in the cathode during charge/discharge cycling to be determined in real time. Here, we present the time, current, and temperature dependent lithium transfer occurring within a cathode functioning under conventional charge-discharge cycling. The lithium location and content, oxygen positional parameter, and lattice parameter of the Li 1+y Mn 2 0 4 cathode are measured and linked to the battery's charge/discharge characteristics (performance). We determine that the lithium-transfer mechanism involves two crystallographic sites, and that the mechanism differs between discharge and charge, explaining the relative ease of discharging (compared with charging) this material. Furthermore, we find that the rate of change of the lattice is faster on charging than discharging, and is dependent on the lithium insertion/ extraction processes (e.g. dependent on how the site occupancies evolve). Using in situ neutron diffraction data the atomic-scale understanding of cathode functionality is revealed, representing detailed information that can be used to direct improvements in battery performance at both the practical and fundamental level.

Reduced graphene oxide encapsulated sulfur spheres for the lithium-sulfur battery cathode

Directory of Open Access Journals (Sweden)

Feiyan Liu

Full Text Available Reduced graphene oxide (rGO encapsulated sulfur spheres for the Li-S batteries were prepared via the redox reaction between sodium polysulfide. XRD spectra showed that the diffraction peak of graphite oxide (GO at 10° disappeared, while the relatively weak diffraction peak at 27° belongs to graphene emerged. FT-IR spectra showed that the vibrations of the functional groups of GO, such as 3603 cm−1, 1723 cm−1and 1619 cm−1 which contributed from OH, COC and CO respectively, disappeared when compared to the spectra of GSC. SEM observations indicated that the optimum experimental condition followed as: mass ratio of GO and S was 1:1, 10% NaOH was used to adjust the pH. EDX analysis showed that the sulfur content reached at 68.8% of the composite material. The resultant electric resistance was nearly less than GO’s resistance in three orders of magnitude under same condition. Further electrochemical performance tests showed a coulombic efficiency was 96% from the first cycle capacity was 827 mAh g−1, to 388 mAh g−1 in the 100 cycles. This study carries substantial significance to the development of Li-S battery cathode materials. Keywords: Lithium-sulfur battery, Graphene, Sulfur spheres, Cathode material

Novel sodium intercalated (NH4)2V6O16 platelets: High performance cathode materials for lithium-ion battery.

Science.gov (United States)

Fei, Hailong; Wu, Xiaomin; Li, Huan; Wei, Mingdeng

2014-02-01

A simple and versatile method for preparation of novel sodium intercalated (NH4)2V6O16 is developed via a simple hydrothermal route. It is found that ammonium sodium vanadium bronze displays higher discharge capacity and better rate cyclic stability than ammonium vanadium bronze as lithium-ion battery cathode material because of smaller charge transfer resistance, which would favor superior discharge capacity and rate performance. Crown Copyright © 2013. Published by Elsevier Inc. All rights reserved.

Is overprotection of the sulfur cathode good for Li-S batteries?

Science.gov (United States)

Gao, Tian; Shao, Jie; Li, Xingxing; Zhu, Guobin; Lu, Qiujian; Han, Yuyao; Qu, Qunting; Zheng, Honghe

2015-08-11

How to restrain the dissolution of polysulfides from the sulfur cathode is the current research focus of Li-S batteries. Here, we find that moderate dissolution of polysulfides is of great importance for high-efficiency and stable discharge/charge cycling. Both overprotection and inadequate protection of the sulfur cathode are unfavorable for the cycling of Li-S batteries.

Synthesis and characterization of cathode, anode and electrolyte materials for rechargeable lithium batteries

Science.gov (United States)

Yang, Shoufeng

Two new classes of cathode materials were studied: iron phosphate/sulfate materials and layered manganese oxides, both of which are low cost and had shown some potential. The first class of materials have poor conductivity and cyclability. I studied a number of methods for increasing the conductivity, and determined that grinding the material with carbon black was as effective as special in-situ coatings. The optimum carbon loading was determined to be between 6 and 15 wt%. Too much carbon reduces the volumetric energy density, whereas too little significantly increased cell polarization (reduced the rate of reaction). The kinetic and thermodynamic stability of LiFePO 4 was also studied and it was determined that over discharge protection will be needed as irreversible Li3PO4 can be formed at low potentials. A novel hydrothermal synthesis method was developed, but the significant level of Fe on the Li site reduces the reaction rate too much. In the case of the layered manganese oxide, cation substitution with Co and Ni is found to be effective in avoiding Jahn-Teller effects and improving electrochemistry. A wide range of tin compounds have been suggested as lithium storage media for advanced anode materials, as tin can store over 4 Li per Sn atom. Lithium hexafluorophosphate, LiPF6, is presently the salt of choice for LiCoO2 batteries, but it is expensive and dissolves some manganese compounds. The lithium bis(oxolato)borate (BOB) salt was recently reported, and I made a study of its use in cells with the LiFePO4 cathode and the tin anode. During its synthesis, it became clear that LiBOB is very reactive with many solvents, and these complexes were characterized to better understand this new material. In LiBOB the lithium is five coordinated, an unstable configuration for the lithium ion so that water and many other solvents rapidly react to make a six coordination. Only in the case of ethylene carbonate was the lithium found to be four coordinated. The Li

Study of Poly (3,4-ethylenedioxythiophene)/MnO2 as Composite Cathode Materials for Aluminum-Air Battery

International Nuclear Information System (INIS)

Kuo, Yu-Lin; Wu, Ching-Chen; Chang, Wen-Sheng; Yang, Ching-Ru; Chou, Hung-Lung

2015-01-01

Highlights: • Open-tunnel structure of MnO 2 catalysts were prepared by the hydrothermal method. • PEDOT was deposited on MnO 2 /carbon paper by oxidative chemical vapor deposition. • PEDOT/α-MnO 2 /10AA composite cathode shows the highest discharge performance. • The enhancement on discharge performance was due to the clear charge transfer. - Abstract: This study focuses on the development of the composite electrode materials for an aluminum-air battery and improving the oxygen reduction reaction (ORR) of the air electrode by matching alpha- and beta- manganese dioxide (MnO 2 ) with poly-(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer. The catalyst powders of α-MnO 2 and β-MnO 2 are prepared by hydrothermal method with different precursors, while PEDOT conducting polymer is subsequently deposited on the screen-printed electrodes (MnO 2 /carbon paper) by oxidative chemical vapor deposition (oCVD). Material characteristics of prepared MnO 2 powder and PEDOT layer are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman scattering spectroscopy. The half-cell polarization curve test is found to be strongly depended on the crystalline phases of MnO 2 . From experimental observations and a density functional theory (DFT) study, the conductivity of PEDOT/α-MnO 2 is found to be higher than PEDOT/β-MnO 2 contributed to structural effect mediated improvements in charge transfer. As a result, integrating the deposition of PEDOT on α-MnO 2 /carbon paper as composite cathode is suitable for the use in aluminum-air battery

A Hollow-Structured Manganese Oxide Cathode for Stable Zn-MnO₂ Batteries.

Science.gov (United States)

Guo, Xiaotong; Li, Jianming; Jin, Xu; Han, Yehu; Lin, Yue; Lei, Zhanwu; Wang, Shiyang; Qin, Lianjie; Jiao, Shuhong; Cao, Ruiguo

2018-05-05

Aqueous rechargeable zinc-manganese dioxide (Zn-MnO₂) batteries are considered as one of the most promising energy storage devices for large scale-energy storage systems due to their low cost, high safety, and environmental friendliness. However, only a few cathode materials have been demonstrated to achieve stable cycling for aqueous rechargeable Zn-MnO₂ batteries. Here, we report a new material consisting of hollow MnO₂ nanospheres, which can be used for aqueous Zn-MnO₂ batteries. The hollow MnO₂ nanospheres can achieve high specific capacity up to ~405 mAh g −1 at 0.5 C. More importantly, the hollow structure of birnessite-type MnO₂ enables long-term cycling stability for the aqueous Zn-MnO₂ batteries. The excellent performance of the hollow MnO₂ nanospheres should be due to their unique structural properties that enable the easy intercalation of zinc ions.

Facile Synthesis of V2O5 Hollow Spheres as Advanced Cathodes for High-Performance Lithium-Ion Batteries

Directory of Open Access Journals (Sweden)

Xingyuan Zhang

2017-01-01

Full Text Available Three-dimensional V2O5 hollow structures have been prepared through a simple synthesis strategy combining solvothermal treatment and a subsequent thermal annealing. The V2O5 materials are composed of microspheres 2–3 μm in diameter and with a distinct hollow interior. The as-synthesized V2O5 hollow microspheres, when evaluated as a cathode material for lithium-ion batteries, can deliver a specific capacity as high as 273 mAh·g−1 at 0.2 C. Benefiting from the hollow structures that afford fast electrolyte transport and volume accommodation, the V2O5 cathode also exhibits a superior rate capability and excellent cycling stability. The good Li-ion storage performance demonstrates the great potential of this unique V2O5 hollow material as a high-performance cathode for lithium-ion batteries.

Rapid Thermal Annealing of Cathode-Garnet Interface toward High-Temperature Solid State Batteries.

Science.gov (United States)

Liu, Boyang; Fu, Kun; Gong, Yunhui; Yang, Chunpeng; Yao, Yonggang; Wang, Yanbin; Wang, Chengwei; Kuang, Yudi; Pastel, Glenn; Xie, Hua; Wachsman, Eric D; Hu, Liangbing

2017-08-09

High-temperature batteries require the battery components to be thermally stable and function properly at high temperatures. Conventional batteries have high-temperature safety issues such as thermal runaway, which are mainly attributed to the properties of liquid organic electrolytes such as low boiling points and high flammability. In this work, we demonstrate a truly all-solid-state high-temperature battery using a thermally stable garnet solid-state electrolyte, a lithium metal anode, and a V 2 O 5 cathode, which can operate well at 100 °C. To address the high interfacial resistance between the solid electrolyte and cathode, a rapid thermal annealing method was developed to melt the cathode and form a continuous contact. The resulting interfacial resistance of the solid electrolyte and V 2 O 5 cathode was significantly decreased from 2.5 × 10 4 to 71 Ω·cm 2 at room temperature and from 170 to 31 Ω·cm 2 at 100 °C. Additionally, the diffusion resistance in the V 2 O 5 cathode significantly decreased as well. The demonstrated high-temperature solid-state full cell has an interfacial resistance of 45 Ω·cm 2 and 97% Coulombic efficiency cycling at 100 °C. This work provides a strategy to develop high-temperature all-solid-state batteries using garnet solid electrolytes and successfully addresses the high contact resistance between the V 2 O 5 cathode and garnet solid electrolyte without compromising battery safety or performance.

LiCaFeF6: A zero-strain cathode material for use in Li-ion batteries

Science.gov (United States)

de Biasi, Lea; Lieser, Georg; Dräger, Christoph; Indris, Sylvio; Rana, Jatinkumar; Schumacher, Gerhard; Mönig, Reiner; Ehrenberg, Helmut; Binder, Joachim R.; Geßwein, Holger

2017-09-01

A new zero-strain LiCaFeF6 cathode material for reversible insertion and extraction of lithium ions is presented. LiCaFeF6 is synthesized by a solid-state reaction and processed to a conductive electrode composite via high-energy ball-milling. In the first cycle, a discharge capacity of 112 mAh g-1 is achieved in the voltage range from 2.0 V to 4.5 V. The electrochemically active redox couple is Fe3+/Fe2+ as confirmed by Mössbauer spectroscopy and X-ray absorption spectroscopy. The compound has a trigonal colquiriite-type crystal structure (space group P 3 bar 1 c). By means of in situ and ex situ XRD as well as X-ray absorption fine structure spectroscopy a reversible response to Li uptake/release is found. For an uptake of 0.8 mol Li per formula unit only minimal changes occur in the lattice parameters causing a total change in unit cell volume of less than 0.5%. The spatial distribution of cations in the crystal structure as well as the linkage between their corresponding fluorine octahedra is responsible for this very small structural response. With its zero-strain behaviour this material is expected to exhibit only negligible mechanical degradation. It may be used as a cathode material in future lithium-ion batteries with strongly improved safety and cycle life.

Carbon black as an alternative cathode material for electrical energy recovery and transfer in a microbial battery.

Science.gov (United States)

Zhang, Xueqin; Guo, Kun; Shen, Dongsheng; Feng, Huajun; Wang, Meizhen; Zhou, Yuyang; Jia, Yufeng; Liang, Yuxiang; Zhou, Mengjiao

2017-08-01

Rather than the conventional concept of viewing conductive carbon black (CB) to be chemically inert in microbial electrochemical cells (MECs), here we confirmed the redox activity of CB for its feasibility as an electron sink in the microbial battery (MB). Acting as the cathode of a MB, the solid-state CB electrode showed the highest electron capacity equivalent of 18.58 ± 0.46 C/g for the unsintered one and the lowest capacity of 2.29 ± 0.48 C/g for the one sintered under 100% N 2 atmosphere. The capacity vibrations of CBs were strongly in coincidence with the abundances of C=O moiety caused by different pretreatments and it implied one plausible mechanism based on CB's surface functionality for its electron capturing. Once subjected to electron saturation, CB could be completely regenerated by different strategies in terms of electrochemical discharging or donating electrons to biologically-catalyzed nitrate reduction. Surface characterization also revealed that CB's regeneration fully depended on the reversible shift of C=O moiety, further confirming the functionality-based mechanism for CB's feasibility as the role of MB's cathode. Moreover, resilience tests demonstrated that CB cathode was robust for the multi-cycles charging-discharging operations. These results imply that CB is a promising alternative material for the solid-state cathode in MBs.

Preparation and enhanced electrochemical properties of nano-sulfur/poly(pyrrole-co-aniline) cathode material for lithium/sulfur batteries

International Nuclear Information System (INIS)

Qiu Linlin; Zhang Shichao; Zhang Lan; Sun, Mingming; Wang Weikun

2010-01-01

Poly(pyrrole-co-aniline) (PPyA) copolymer nanofibers were prepared by chemical oxidation method with cetyltrimethyl ammonium chloride (CTAC) as template, and the nano-sulfur/poly(pyrrole-co-aniline) (S/PPyA) composite material in lithium batteries was achieved via co-heating the mixture of PPyA and sublimed sulfur at 160 deg. C for 24 h. The component and structure of the materials were characterized by FTIR, Raman, XRD, and SEM. PPyA with nanofiber network structure was employed as a conductive matrix, adsorbing agent and firm reaction chamber for the sulfur cathode materials. The nano-dispersed composite exhibited a specific capacity up to 1285 mAh g -1 in the initial cycle and remained 866 mAh g -1 after 40 cycles.

Polymer-Templated LiFePO4/C Nanonetworks as High-Performance Cathode Materials for Lithium-Ion Batteries.

Science.gov (United States)

Fischer, Michael G; Hua, Xiao; Wilts, Bodo D; Castillo-Martínez, Elizabeth; Steiner, Ullrich

2018-01-17

Lithium iron phosphate (LFP) is currently one of the main cathode materials used in lithium-ion batteries due to its safety, relatively low cost, and exceptional cycle life. To overcome its poor ionic and electrical conductivities, LFP is often nanostructured, and its surface is coated with conductive carbon (LFP/C). Here, we demonstrate a sol-gel based synthesis procedure that utilizes a block copolymer (BCP) as a templating agent and a homopolymer as an additional carbon source. The high-molecular-weight BCP produces self-assembled aggregates with the precursor-sol on the 10 nm scale, stabilizing the LFP structure during crystallization at high temperatures. This results in a LFP nanonetwork consisting of interconnected ∼10 nm-sized particles covered by a uniform carbon coating that displays a high rate performance and an excellent cycle life. Our "one-pot" method is facile and scalable for use in established battery production methodologies.

Octahedral magnesium manganese oxide molecular sieves as the cathode material of aqueous rechargeable magnesium-ion battery

International Nuclear Information System (INIS)

Zhang, Hongyu; Ye, Ke; Shao, Shuangxi; Wang, Xin; Cheng, Kui; Xiao, Xue; Wang, Guiling; Cao, Dianxue

2017-01-01

Highlights: • The mico-sheet Mg-OMS-1 is synthesized by a simple hydrothermal method. • The mechanism of Mg 2+ insertion/deinsertion from Mg-OMS-1 is explored. • The electrode exhibits a good electrochemical performance in MgCl 2 electrolyte. - Abstract: Aqueous magnesium-ion batteries have shown the desired properties of high safety characteristics, similar electrochemical properties to lithium and low cost for energy storage applications. The micro-sheet morphology of todorokite-type magnesium manganese oxide molecular sieve (Mg-OMS-1) material, which applies as a novel cathode material for magnesium-ion battery, is obtained by the simple hydrothermal method. The structure and morphology of the particles are confirmed by X-ray power diffraction, X-ray photoelectron spectroscopy, inductively coupled plasma, scanning and transmission electron microscopy. The electrochemical performance of Mg-OMS-1 is researched by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and constant current charge-discharge measurement. Mg-OMS-1 shows a good battery behavior for Mg 2+ insertion and deinsertion in the aqueous electrolyte. When discharging at 10 mA g −1 in 0.2 mol dm −3 MgCl 2 aqueous electrolyte, the initial discharge capacity reaches 300 mAh g −1 . The specific capacity retention rate is 83.7% after cycling 300 times at 100 mA g −1 in 0.5 mol dm −3 MgCl 2 electrolyte with a columbic efficiency of nearly 100%.

Effect of entropy change of lithium intercalation in cathodes and anodes on Li-ion battery thermal management

Energy Technology Data Exchange (ETDEWEB)

Viswanathan, Vilayanur V.; Choi, Daiwon; Wang, Donghai; Xu, Wu; Towne, Silas; Williford, Ralph E.; Zhang, Ji-Guang; Liu, Jun; Yang, Zhenguo [Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (United States)

2010-06-01

The entropy changes ({delta}S) in various cathode and anode materials, as well as in complete Li-ion batteries, were measured using an electrochemical thermodynamic measurement system (ETMS). LiCoO{sub 2} has a much larger entropy change than electrodes based on LiNi{sub x}Co{sub y}Mn{sub z}O{sub 2} and LiFePO{sub 4}, while lithium titanate based anodes have lower entropy change compared to graphite anodes. The reversible heat generation rate was found to be a significant portion of the total heat generation rate. The appropriate combinations of cathode and anode were investigated to minimize reversible heat generation rate across the 0-100% state of charge (SOC) range. In addition to screening for battery electrode materials with low reversible heat, the techniques described in this paper can be a useful engineering tool for battery thermal management in stationary and transportation applications. (author)

Co-intercalation of Mg(2+) and Na(+) in Na(0.69)Fe2(CN)6 as a High-Voltage Cathode for Magnesium Batteries.

Science.gov (United States)

Kim, Dong-Min; Kim, Youngjin; Arumugam, Durairaj; Woo, Sang Won; Jo, Yong Nam; Park, Min-Sik; Kim, Young-Jun; Choi, Nam-Soon; Lee, Kyu Tae

2016-04-06

Thanks to the advantages of low cost and good safety, magnesium metal batteries get the limelight as substituent for lithium ion batteries. However, the energy density of state-of-the-art magnesium batteries is not high enough because of their low operating potential; thus, it is necessary to improve the energy density by developing new high-voltage cathode materials. In this study, nanosized Berlin green Fe2(CN)6 and Prussian blue Na(0.69)Fe2(CN)6 are compared as high-voltage cathode materials for magnesium batteries. Interestingly, while Mg(2+) ions cannot be intercalated in Fe2(CN)6, Na(0.69)Fe2(CN)6 shows reversible intercalation and deintercalation of Mg(2+) ions, although they have the same crystal structure except for the presence of Na(+) ions. This phenomenon is attributed to the fact that Mg(2+) ions are more stable in Na(+)-containing Na(0.69)Fe2(CN)6 than in Na(+)-free Fe2(CN)6, indicating Na(+) ions in Na(0.69)Fe2(CN)6 plays a crucial role in stabilizing Mg(2+) ions. Na(0.69)Fe2(CN)6 delivers reversible capacity of approximately 70 mA h g(-1) at 3.0 V vs Mg/Mg(2+) and shows stable cycle performance over 35 cycles. Therefore, Prussian blue analogues are promising structures for high-voltage cathode materials in Mg batteries. Furthermore, this co-intercalation effect suggests new avenues for the development of cathode materials in hybrid magnesium batteries that use both Mg(2+) and Na(+) ions as charge carriers.

Cathode materials: A personal perspective

Energy Technology Data Exchange (ETDEWEB)

Goodenough, John B. [Texas Materials Institute, University of Texas at Austin, ETC 9.102, 1 University Station, Austin, TX 78712-1063 (United States)

2007-12-06

A thermodynamically stable rechargeable battery has a voltage limited by the window of the electrolyte. An aqueous electrolyte has a window of 1.2 eV, which prevents achieving the high energy density desired for many applications. A non-aqueous electrolyte with a window of 5 eV requires Li{sup +} rather than H{sup +} as the working ion. Early experiments with Li{sub x}TiS{sub 2} cathodes showed competitive capacity and rate capability, but problems with a lithium anode made the voltage of a safe cell based on a sulfide cathode too low to be competitive with a nickel/metal-hydride battery. Transition-metal oxides can give voltages of 4.5 V versus Li{sup +}/Li{sup 0}. However, the challenge with oxides has been to obtain a competitive capacity and rate capability while retaining a high voltage with low-cost, environmentally friendly cathode materials. Comparisons will be made between layered Li{sub 1-x}MO{sub 2}, spinels Li{sub 1-x}[M{sub 2}]O{sub 4}, and olivines Li{sub 1-x}MPO{sub 4} having 0 < x < 1. Although higher capacities can be obtained with layered Li{sub 1-x}MO{sub 2} compounds, which have enabled the wireless revolution, their metastability makes them unlikely to be used in power applications. The spinel and olivine framework structures have been shown to be capable of charge/discharge rates of over 10C with a suitable temperature range for plug-in hybrid vehicles. (author)

Olivine-type cathode for rechargeable batteries: Role of chelating agents

International Nuclear Information System (INIS)

Kandhasamy, Sathiyaraj; Singh, Pritam; Thurgate, Stephen; Ionescu, Mihail; Appadoo, Dominique; Minakshi, Manickam

2012-01-01

Highlights: ► Olivine powder was synthesized by sol–gel method using a range of chelating agents. ► Role of chelating agents in olivine cathode was investigated for battery application. ► Battery was fabricated with olivine cathode, Zn anode and aqueous electrolyte. ► Synergetic effect of additives (CA + TEA + PVP) led to improved storage capacity. - Abstract: Olivine (LiCo 1/3 Mn 1/3 Ni 1/3 PO 4 ) powders were synthesized at 550–600 °C for 6 h in air by a sol–gel method using multiple chelating agents and used as a cathode material for rechargeable batteries. Range of chelating agents like a weak organic acid (citric acid – CA), emulsifier (triethanolamine – TEA) and non-ionic surfactant (polyvinylpyrrolidone – PVP) in sol–gel wet chemical synthesis were used. The dependence of the physicochemical properties of the olivine powders such as particle size, morphology, structural bonding and crystallinity on the chelating agent was extensively investigated. Among the chelating agents used, unique cycling behavior (75 mAh/g after 25 cycles) is observed for the PVP assisted olivine. This is due to volumetric change in trapped organic layer for first few cycles. The trapped organic species in the electrode–electrolyte interface enhances the rate of lithium ion diffusion with better capacity retention. In contrast, CA and TEA showed a gradual capacity fade of 30 and 38 mAh/g respectively after multiple cycles. The combination of all the three mixed chelating agents showed an excellent electrochemical behavior of 100 mAh/g after multiple cycles and the synergistic effect of these agents are discussed.

Polyanion-Type Electrode Materials for Sodium-Ion Batteries.

Science.gov (United States)

Ni, Qiao; Bai, Ying; Wu, Feng; Wu, Chuan

2017-03-01

Sodium-ion batteries, representative members of the post-lithium-battery club, are very attractive and promising for large-scale energy storage applications. The increasing technological improvements in sodium-ion batteries (Na-ion batteries) are being driven by the demand for Na-based electrode materials that are resource-abundant, cost-effective, and long lasting. Polyanion-type compounds are among the most promising electrode materials for Na-ion batteries due to their stability, safety, and suitable operating voltages. The most representative polyanion-type electrode materials are Na 3 V 2 (PO 4 ) 3 and NaTi 2 (PO 4 ) 3 for Na-based cathode and anode materials, respectively. Both show superior electrochemical properties and attractive prospects in terms of their development and application in Na-ion batteries. Carbonophosphate Na 3 MnCO 3 PO 4 and amorphous FePO 4 have also recently emerged and are contributing to further developing the research scope of polyanion-type Na-ion batteries. However, the typical low conductivity and relatively low capacity performance of such materials still restrict their development. This paper presents a brief review of the research progress of polyanion-type electrode materials for Na-ion batteries, summarizing recent accomplishments, highlighting emerging strategies, and discussing the remaining challenges of such systems.

Polyanion‐Type Electrode Materials for Sodium‐Ion Batteries

Science.gov (United States)

Ni, Qiao; Wu, Feng

2017-01-01

Sodium‐ion batteries, representative members of the post‐lithium‐battery club, are very attractive and promising for large‐scale energy storage applications. The increasing technological improvements in sodium‐ion batteries (Na‐ion batteries) are being driven by the demand for Na‐based electrode materials that are resource‐abundant, cost‐effective, and long lasting. Polyanion‐type compounds are among the most promising electrode materials for Na‐ion batteries due to their stability, safety, and suitable operating voltages. The most representative polyanion‐type electrode materials are Na3V2(PO4)3 and NaTi2(PO4)3 for Na‐based cathode and anode materials, respectively. Both show superior electrochemical properties and attractive prospects in terms of their development and application in Na‐ion batteries. Carbonophosphate Na3MnCO3PO4 and amorphous FePO4 have also recently emerged and are contributing to further developing the research scope of polyanion‐type Na‐ion batteries. However, the typical low conductivity and relatively low capacity performance of such materials still restrict their development. This paper presents a brief review of the research progress of polyanion‐type electrode materials for Na‐ion batteries, summarizing recent accomplishments, highlighting emerging strategies, and discussing the remaining challenges of such systems. PMID:28331782

The preparation and graphene surface coating NaTi{sub 2}(PO{sub 4}){sub 3} as cathode material for lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Li, Na; Wang, Yanping; Rao, Richuan; Dong, Xiongzi [Department of Chemical and Chemical Engineering, Hefei normal University, Hefei, Anhui 230601 (China); Zhang, Xianwen, E-mail: 18326056237@163.com [Institute of Advanced Energy Technology & Equipment, Hefei University of Technology, 193 Tunxi Road, Hefei, Anhui 230009 (China); Zhu, Sane, E-mail: sdjnlina@163.com [Department of Chemistry and Materials Engineering, Hefei University, Hefei, Anhui 230601 (China)

2017-03-31

Graphical abstract: The NaTi{sub 2}(PO{sub 4}){sub 3}/graphene composite is used directly as cathode electrode material for lithium-ion battery by using metal lithium as an anode electrode. Meanwhile, the electrochemical properties of the composite in this system is firstly studied in detail. The NaTi{sub 2}(PO{sub 4}){sub 3}/graphene composite exhibits the better rate and cyclic performance than NaTi{sub 2}(PO{sub 4}){sub 3}, which is ascribed to its stable 3-D framework and the enhanced electronic conduction resulting from the graphene sheets surface modification. - Highlights: • The graphene coated NaTi{sub 2}(PO{sub 4}){sub 3} was prepared by a simple sol-gel method followed by calcination. • The electrochemical properties of the NaTi{sub 2}(PO{sub 4}){sub 3}/graphene composite was firstly studied in detail when used as cathode electrode material for lithium-ion batteries. • The electrochemical reaction mechanism of NaTi{sub 2}(PO{sub 4}){sub 3}/graphene composite was investigated by ex situ XRD. - Abstract: The graphene coated NaTi{sub 2}(PO{sub 4}){sub 3} has been fabricated via a simple sol-gel process followed by calcination. The NaTi{sub 2}(PO{sub 4}){sub 3}/graphene (NTP/G) composite is used directly as cathode electrode material for lithium-ion battery and the electrochemical properties of the composite in this system is firstly studied in detail. In the charge-discharge process, two Li{sup +} can occupy octahedral M (2) site and be reversibly intercalated into the 3D framework of NTP through the ion conduction channel where almost all of Na{sup +} are immobilized to sustain the framework. At 5C rate, the capacity retention of the NTP/G composite after 800 cycles is still up to 82.7%. The superior electrochemical properties of NTP/G is ascribed to its stable 3-D framework and the enhanced electronic conduction resulting from the graphene sheets surface modification.

Sphere-shaped hierarchical cathode with enhanced growth of nanocrystal planes for high-rate and cycling-stable li-ion batteries.

Science.gov (United States)

Zhang, Linjing; Li, Ning; Wu, Borong; Xu, Hongliang; Wang, Lei; Yang, Xiao-Qing; Wu, Feng

2015-01-14

High-energy and high-power Li-ion batteries have been intensively pursued as power sources in electronic vehicles and renewable energy storage systems in smart grids. With this purpose, developing high-performance cathode materials is urgently needed. Here we report an easy and versatile strategy to fabricate high-rate and cycling-stable hierarchical sphered cathode Li(1.2)Ni(0.13)Mn(0.54)Co(0.13)O2, by using an ionic interfusion method. The sphere-shaped hierarchical cathode is assembled with primary nanoplates with enhanced growth of nanocrystal planes in favor of Li(+) intercalation/deintercalation, such as (010), (100), and (110) planes. This material with such unique structural features exhibits outstanding rate capability, cyclability, and high discharge capacities, achieving around 70% (175 mAh g(-1)) of the capacity at 0.1 C rate within about 2.1 min of ultrafast charging. Such cathode is feasible to construct high-energy and high-power Li-ion batteries.

Functionalized NbS2 as cathode for Li- and Na-ion batteries

KAUST Repository

Zhu, Jiajie

2017-07-27

Cathodes of Li- and Na-ion batteries usually have capacities <200 mAh/g, significantly less than the anodes. Two-dimensional materials can overcome this limitation but suffer from low voltages. In this context, we investigate NbS2 functionalized by O, F, and Cl as a cathode material by first-principles calculations, considering both the conversion and intercalation mechanisms. NbS2O2 shows a higher voltage than NbS2 for both Li and Na, but the voltage decreases drastically for increasing ion coverage. Even higher voltages and favorable dependences on the ion coverage are achieved by F and Cl functionalization. We obtain NbS2F2 and NbS2Cl2 energy densities of 1223 mW h/g and 823 mW h/g for lithiation and 1086 mW h/g and 835 mW h/g for sodiation, respectively. These values are higher than those for most state-of-the-art cathode materials (∼600 mW h/g). In addition, low diffusion barriers enable high cycling rates.

Functionalized NbS2 as cathode for Li- and Na-ion batteries

KAUST Repository

Zhu, Jiajie; Alshareef, Husam N.; Schwingenschlö gl, Udo

2017-01-01

Cathodes of Li- and Na-ion batteries usually have capacities <200 mAh/g, significantly less than the anodes. Two-dimensional materials can overcome this limitation but suffer from low voltages. In this context, we investigate NbS2 functionalized by O, F, and Cl as a cathode material by first-principles calculations, considering both the conversion and intercalation mechanisms. NbS2O2 shows a higher voltage than NbS2 for both Li and Na, but the voltage decreases drastically for increasing ion coverage. Even higher voltages and favorable dependences on the ion coverage are achieved by F and Cl functionalization. We obtain NbS2F2 and NbS2Cl2 energy densities of 1223 mW h/g and 823 mW h/g for lithiation and 1086 mW h/g and 835 mW h/g for sodiation, respectively. These values are higher than those for most state-of-the-art cathode materials (∼600 mW h/g). In addition, low diffusion barriers enable high cycling rates.

Synthesis of LiFePO4/Graphene Nano composite and Its Electrochemical Properties as Cathode Material for Li-Ion Batteries

International Nuclear Information System (INIS)

Ma, X.; Chen, G.; Liu, Q.; Zeng, G.; Wu, T.

2014-01-01

LiFePO 4 /graphene nano composite was successfully synthesized by rheological phase method and its electrochemical properties as the cathode materials for lithium ion batteries were measured. As the iron source in the synthesis, FeOOH nano rods anchored on graphene were first synthesized. The FeOOH nano rods precursors and the final LiFePO 4 /graphene nano composite products were characterized by XRD, SEM, and TEM. While the FeOOH precursors were nano rods with 5-10 nm in diameter and 10-50 nm in length, the LiFePO 4 were nanoparticles with 20-100 nm in size. Compared with the electrochemical properties of LiFePO 4 particles without graphene nano sheets, it is clear that the graphene nano sheets can improve the performances of LiFePO 4 as the cathode material for lithium ion batteries. The as-synthesized LiFePO 4 /graphene nano composite showed high capacities and good cyclabilities. When measured at room temperature and at the rate of 0.1 C (1 C = 170 mA g -1 ), the composite showed a discharge capacity of 156 mA h g -1 in the first cycle and a capacity retention of 96% after 15 cycles. The improved performances of the composite are believed to be the result of the three-dimensional conducting network formed by the flexible and planar graphene nano sheets.

Synthesis of LiFePO4/Graphene Nanocomposite and Its Electrochemical Properties as Cathode Material for Li-Ion Batteries

Directory of Open Access Journals (Sweden)

Xiaoling Ma

2015-01-01

Full Text Available LiFePO4/graphene nanocomposite was successfully synthesized by rheological phase method and its electrochemical properties as the cathode materials for lithium ion batteries were measured. As the iron source in the synthesis, FeOOH nanorods anchored on graphene were first synthesized. The FeOOH nanorods precursors and the final LiFePO4/graphene nanocomposite products were characterized by XRD, SEM, and TEM. While the FeOOH precursors were nanorods with 5–10 nm in diameter and 10–50 nm in length, the LiFePO4 were nanoparticles with 20–100 nm in size. Compared with the electrochemical properties of LiFePO4 particles without graphene nanosheets, it is clear that the graphene nanosheets can improve the performances of LiFePO4 as the cathode material for lithium ion batteries. The as-synthesized LiFePO4/graphene nanocomposite showed high capacities and good cyclabilities. When measured at room temperature and at the rate of 0.1C (1C = 170 mA g−1, the composite showed a discharge capacity of 156 mA h g−1 in the first cycle and a capacity retention of 96% after 15 cycles. The improved performances of the composite are believed to be the result of the three-dimensional conducting network formed by the flexible and planar graphene nanosheets.

Nano-sized LiFePO4/C composite with core-shell structure as cathode material for lithium ion battery

International Nuclear Information System (INIS)

Liu, Yang; Zhang, Min; Li, Ying; Hu, Yemin; Zhu, Mingyuan; Jin, Hongming; Li, Wenxian

2015-01-01

Graphical abstract: Nano-sized LiFePO4/C composite with core-shell structure was fabricated via a well-designed approach as cathode material forlithium ion battery. The nano-sized LiFePO4/C composite with whole carbon shell coating layer showed an excellent electrical performance. - Abstract: Nano-sized composite with LiFePO 4 -core and carbon-shell was synthesized via a facile route followed by heat treatment at 650 °C. X-ray diffraction (XRD) shows that the core is well crystallized LiFePO 4 . The electron microscopy (SEM and TEM) observations show that the core-shell structured LiFePO 4 /C composite coating with whole carbon shell layer of ∼2.8 nm, possesses a specific surface area of 51 m 2 g −1 . As cathode material for lithium ion battery, the core-shell LiFePO 4 /C composite exhibits high initial capacity of 161 mAh g −1 at 0.1 C, excellent high-rate discharge capacity of 135 mAh g −1 at 5 C and perfect cycling retention of 99.6% at 100 th cycle. All these promising results should be contributed to the core-shell nanostructure which prevents collapse of the particle structure in the long-term charge and discharge cycles, as well as the large surface area of the nano-sized LiFePO 4 /C composite which enhances the electronic conductivity and shortens the distance of lithium ion diffusion

Using elastin protein to develop highly efficient air cathodes for lithium-O2 batteries

International Nuclear Information System (INIS)

Guo, Guilue; Ang, Huixiang; Tan, Huiteng; Zhang, Yu; Guo, Yuanyuan; Fong, Eileen; Yan, Qingyu; Yao, Xin

2016-01-01

Transition metal-nitrogen/carbon (M-N/C, M = Fe, Co) catalysts are synthesized using environmentally friendly histidine-tag-rich elastin protein beads, metal sulfate and water soluble carbon nanotubes followed by post-annealing and acid leaching processes. The obtained catalysts are used as cathode materials in lithium-O 2 batteries. It has been discovered that during discharge, Li 2 O 2 nanoparticles first nucleate and grow around the bead-decorated CNT regions (M-N/C centres) and coat on the catalysts at a high degree of discharge. The Fe-N/C catalyst-based cathodes deliver a capacity of 12 441 mAh g −1 at a current density of 100 mA g −1 . When they were cycled at a limited capacity of 800 mAh g −1 at current densities of 200 or 400 mA g −1 , these cathodes showed stable charge voltages of ∼3.65 or 3.90 V, corresponding to energy efficiencies of ∼71.2 or 65.1%, respectively. These results are considerably superior to those of the cathodes based on bare annealed CNTs, which prove that the Fe-N/C catalysts developed here are promising for use in non-aqueous lithium-O 2 battery cathodes. (paper)

Using elastin protein to develop highly efficient air cathodes for lithium-O2 batteries

Science.gov (United States)

Guo, Guilue; Yao, Xin; Ang, Huixiang; Tan, Huiteng; Zhang, Yu; Guo, Yuanyuan; Fong, Eileen; Yan, Qingyu

2016-01-01

Transition metal-nitrogen/carbon (M-N/C, M = Fe, Co) catalysts are synthesized using environmentally friendly histidine-tag-rich elastin protein beads, metal sulfate and water soluble carbon nanotubes followed by post-annealing and acid leaching processes. The obtained catalysts are used as cathode materials in lithium-O2 batteries. It has been discovered that during discharge, Li2O2 nanoparticles first nucleate and grow around the bead-decorated CNT regions (M-N/C centres) and coat on the catalysts at a high degree of discharge. The Fe-N/C catalyst-based cathodes deliver a capacity of 12 441 mAh g-1 at a current density of 100 mA g-1. When they were cycled at a limited capacity of 800 mAh g-1 at current densities of 200 or 400 mA g-1, these cathodes showed stable charge voltages of ˜3.65 or 3.90 V, corresponding to energy efficiencies of ˜71.2 or 65.1%, respectively. These results are considerably superior to those of the cathodes based on bare annealed CNTs, which prove that the Fe-N/C catalysts developed here are promising for use in non-aqueous lithium-O2 battery cathodes.

Manganese Dioxide As Rechargeable Magnesium Battery Cathode

International Nuclear Information System (INIS)

Ling, Chen; Zhang, Ruigang

2017-01-01

Rechargeable magnesium battery (rMB) has received increased attention as a promising alternative to current Li-ion technology. However, the lack of appropriate cathode that provides high-energy density and good sustainability greatly hinders the development of practical rMBs. To date, the successful Mg 2+ -intercalation was only achieved in only a few cathode hosts, one of which is manganese dioxide. This review summarizes the research activity of studying MnO 2 in magnesium cells. In recent years, the cathodic performance of MnO 2 was impressively improved to the capacity of >150–200 mAh g −1 at voltage of 2.6–2.8 V with cyclability to hundreds or more cycles. In addition to reviewing electrochemical performance, we sketch a mechanistic picture to show how the fundamental understanding about MnO 2 cathode has been changed and how it paved the road to the improvement of cathode performance.

Manganese Dioxide As Rechargeable Magnesium Battery Cathode

Energy Technology Data Exchange (ETDEWEB)

Ling, Chen, E-mail: chen.ling@toyota.com; Zhang, Ruigang [Toyota Research Institute of North America, Ann Arbor, MI (United States)

2017-11-03

Rechargeable magnesium battery (rMB) has received increased attention as a promising alternative to current Li-ion technology. However, the lack of appropriate cathode that provides high-energy density and good sustainability greatly hinders the development of practical rMBs. To date, the successful Mg{sup 2+}-intercalation was only achieved in only a few cathode hosts, one of which is manganese dioxide. This review summarizes the research activity of studying MnO{sub 2} in magnesium cells. In recent years, the cathodic performance of MnO{sub 2} was impressively improved to the capacity of >150–200 mAh g{sup −1} at voltage of 2.6–2.8 V with cyclability to hundreds or more cycles. In addition to reviewing electrochemical performance, we sketch a mechanistic picture to show how the fundamental understanding about MnO{sub 2} cathode has been changed and how it paved the road to the improvement of cathode performance.

Electrochemical Performance of a V2O5 Cathode for a Sodium Ion Battery

Science.gov (United States)

Van Nghia, Nguyen; Long, Pham Duy; Tan, Ta Anh; Jafian, Samuel; Hung, I.-Ming

2017-06-01

In this paper, layered vanadium pentoxide (V2O5) is employed as a cathode material for a sodium ion battery. The V2O5 particle sizes range from 200 nm to 500 nm and the shapes of the aggregated V2O5 particles are non-homogeneous and irregular. The material exhibits a first discharge capacity of approximately 208.1 mAh g-1. The structure of V2O5 changes to a NaxV2O5 structure after Na+ insertion at the first discharge; the structure of NaxV2O5 remains stable␣during cycling. After 40 cycles, the discharge capacity retains 61.2% of the capacity of the second cycle. The capacity of V2O5 at a high charge/discharge current rate of 1.0 C is 49.1% of capacity at 0.1 C. Furthermore, the capacity returns to the initial value as the discharge rate returns to 0.1 C. The results of electrochemical performance tests indicate that V2O5 is a potential cathode material for sodium ion batteries.

Moessbauer study of FePO4 cathode for lithium- and sodium-ion batteries

International Nuclear Information System (INIS)

Tetsuaki Nishida; Masahiro Tokunaga; Toshiharu Nishizumi; Takafumi Yamamoto; Tomoyuki Shiratsuchi; Shigeto Okada; Jun-ichi Yamaki

2005-01-01

LiFePO 4 of olivine type has attracted much interest as a rare-metal free cathode for lithium-ion battery. The present authors' group has found a low-cost preparation method for new cathode material FePO 4 (P 321 ) from an aqueous solution of metallic iron and P 2 O 5 . A cathode pellet was prepared by mixing FePO 4 , acetylene black (AB) and polytetrafluoroethylene (PTFE) binder at a mass ratio of 70:25:5. Electrochemical cathode performance was investigated under a constant current density of 0.1 mA/cm 2 with a coin-type cell with an anode of metallic Li and Na for Li- and Na-ion batteries, respectively. Moessbauer spectra were measured by a constant accele- ration method with a Moessbauer source of 57 Co(Pd) and an α-Fe foil as a reference of the isomer shift. Moessbauer spectra of the original cathode pellet top left and right) composed of amorphous FePO 4 indicate that all the Fe III atoms have a tetrahedral symmetry. After discharging the Li-(second left) and Na-batteries (second right), all the Fe III were reduced to octahedral Fe II . The reduction of Fe III to Fe II indicates penetration of Li + and Na + into the FePO 4 cathode which accompanies an electron capture; Li + (or Na + ) + Fe III PO 4 + e - = LiFe II PO 4 (or NaFe II PO 4 ) After charging the Li-cell (bottom left), all the Fen atoms were oxidized to tetrahedral Fe III , while 69 % of Fe II was oxidized to Fe III in the Na-ion cell (bottom right) due to a lower cell voltage: 4.0 V. Oxidation of Fe II to Fe III reflects a release of Li + or Na + ions from the FePO 4 cathode to the electrolyte, i.e., an inverse reaction of eq.

Vanadium Pentoxide-Based Composite Synthesized Using Microwave Water Plasma for Cathode Material in Rechargeable Magnesium Batteries

Directory of Open Access Journals (Sweden)

Tatsuhiko Yajima

2013-10-01

Full Text Available Multivalent cation rechargeable batteries are expected to perform well as high-capacity storage devices. Rechargeable magnesium batteries have an advantage in terms of resource utilization and safety. Here, we report on sulfur-doped vanadium pentoxide (S-V2O5 as a potential material for the cathodes of such a battery; S-V2O5 showed a specific capacity of 300 mAh·g−1. S-V2O5 was prepared by a method using a low-temperature plasma generated by carbon felt and a 2.45 GHz microwave generator. This study investigates the ability of S-V2O5 to achieve high capacity when added to metal oxide. The highest recorded capacity (420 mAh·g−1 was reached with MnO2 added to composite SMn-V2O5, which has a higher proportion of included sulfur than found in S-V2O5. Results from transmission electron microscopy, energy-dispersive X-ray spectroscopy, Micro-Raman spectroscopy, and X-ray photoelectron spectroscopy show that the bulk of the SMn-V2O5 was the orthorhombic V2O5 structure; the surface was a xerogel-like V2O5 and a solid solution of MnO2 and sulfur.

Effect of Metal (Mn, Ti) Doping on NCA Cathode Materials for Lithium Ion Batteries

OpenAIRE

Wan, Dao Yong; Fan, Zhi Yu; Dong, Yong Xiang; Baasanjav, Erdenebayar; Jun, Hang-Bae; Jin, Bo; Jin, En Mei; Jeong, Sang Mun

2018-01-01

NCA (LiNi0.85Co0.10Al0.05-x MxO2, M=Mn or Ti, x < 0.01) cathode materials are prepared by a hydrothermal reaction at 170°C and doped with Mn and Ti to improve their electrochemical properties. The crystalline phases and morphologies of various NCA cathode materials are characterized by XRD, FE-SEM, and particle size distribution analysis. The CV, EIS, and galvanostatic charge/discharge test are employed to determine the electrochemical properties of the cathode materials. Mn and Ti doping res...

Recent Development of Carbonaceous Materials for Lithium–Sulphur Batteries

Directory of Open Access Journals (Sweden)

Xingxing Gu

2016-11-01

Full Text Available The effects of climate change are just beginning to be felt, and as such, society must work towards strategies of reducing humanity’s impact on the environment. Due to the fact that energy production is one of the primary contributors to greenhouse gas emissions, it is obvious that more environmentally friendly sources of power are required. Technologies such as solar and wind power are constantly being improved through research; however, as these technologies are often sporadic in their power generation, efforts must be made to establish ways to store this sustainable energy when conditions for generation are not ideal. Battery storage is one possible supplement to these renewable energy technologies; however, as current Li-ion technology is reaching its theoretical capacity, new battery technology must be investigated. Lithium–sulphur (Li–S batteries are receiving much attention as a potential replacement for Li-ion batteries due to their superior capacity, and also their abundant and environmentally benign active materials. In the spirit of environmental harm minimization, efforts have been made to use sustainable carbonaceous materials for applications as carbon–sulphur (C–S composite cathodes, carbon interlayers, and carbon-modified separators. This work reports on the various applications of carbonaceous materials applied to Li–S batteries, and provides perspectives for the future development of Li–S batteries with the aim of preparing a high energy density, environmentally friendly, and sustainable sulphur-based cathode with long cycle life.

Investigation of Thermal Stability of P2-NaxCoO2 Cathode Materials for Sodium Ion Batteries Using Real-Time Electron Microscopy.

Science.gov (United States)

Hwang, Sooyeon; Lee, Yongho; Jo, Eunmi; Chung, Kyung Yoon; Choi, Wonchang; Kim, Seung Min; Chang, Wonyoung

2017-06-07

Here, we take advantage of in situ transmission electron microscopy (TEM) to investigate the thermal stability of P2-type Na x CoO 2 cathode materials for sodium ion batteries, which are promising candidates for next-generation lithium ion batteries. A double-tilt TEM heating holder was used to directly characterize the changes in the morphology and the crystallographic and electronic structures of the materials with increase in temperature. The electron diffraction patterns and the electron energy loss spectra demonstrated the presence of cobalt oxides (Co 3 O 4 , CoO) and even metallic cobalt (Co) at higher temperatures as a result of reduction of Co ions and loss of oxygen. The bright-field TEM images revealed that the surface of Na x CoO 2 becomes porous at high temperatures. Higher cutoff voltages result in degrading thermal stability of Na x CoO 2 . The observations herein provide a valuable insight that thermal stability is one of the important factors to be considered in addition to the electrochemical properties when developing new electrode materials for novel battery systems.

Towards highly stable storage of sodium ions: a porous Na(3)V(2)(PO(4))(3)/C cathode material for sodium-ion batteries.

Science.gov (United States)

Shen, Wei; Wang, Cong; Liu, Haimei; Yang, Wensheng

2013-10-18

A porous Na3 V2 (PO4 )3 cathode material coated uniformly with a layer of approximately 6 nm carbon has been synthesized by the sol-gel method combined with a freeze-drying process. The special porous morphology and structure significantly increases the specific surface area of the material, which greatly enlarges the contact area between the electrode and electrolyte, and consequently supplies more active sites for sodium ions. When employed as a cathode material of sodium-ion batteries, this porous Na3 V2 (PO4 )3 /C exhibits excellent rate performance and cycling stability; for instance, it shows quite a flat potential plateau at 3.4 V in the potential window of 2.7-4.0 V versus Na(+) /Na and delivers an initial capacity as high as 118.9 and 98.0 mA h g(-1) at current rates of 0.05 and 0.5 C, respectively, and after 50 cycles, a good capacity retention of 92.7 and 93.6 % are maintained. Moreover, even when the discharge current density is increased to 5 C (590 mA g(-1) ), an initial capacity of 97.6 mA h g(-1) can still be achieved, and an exciting capacity retention of 88.6 % is obtained after 100 cycles. The good cycle performance, excellent rate capability, and moreover, the low cost of Na3 V2 (PO4 )3 /C suggest that this material is a promising cathode for large-scale sodium-ion rechargeable batteries. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-capacity lithium-ion battery conversion cathodes based on iron fluoride nanowires and insights into the conversion mechanism.

Science.gov (United States)

Li, Linsen; Meng, Fei; Jin, Song

2012-11-14

The increasing demands from large-scale energy applications call for the development of lithium-ion battery (LIB) electrode materials with high energy density. Earth abundant conversion cathode material iron trifluoride (FeF(3)) has a high theoretical capacity (712 mAh g(-1)) and the potential to double the energy density of the current cathode material based on lithium cobalt oxide. Such promise has not been fulfilled due to the nonoptimal material properties and poor kinetics of the electrochemical conversion reactions. Here, we report for the first time a high-capacity LIB cathode that is based on networks of FeF(3) nanowires (NWs) made via an inexpensive and scalable synthesis. The FeF(3) NW cathode yielded a discharge capacity as high as 543 mAh g(-1) at the first cycle and retained a capacity of 223 mAh g(-1) after 50 cycles at room temperature under the current of 50 mA g(-1). Moreover, high-resolution transmission electron microscopy revealed the existence of continuous networks of Fe in the lithiated FeF(3) NWs after discharging, which is likely an important factor for the observed improved electrochemical performance. The loss of active material (FeF(3)) caused by the increasingly ineffective reconversion process during charging was found to be a major factor responsible for the capacity loss upon cycling. With the advantages of low cost, large quantity, and ease of processing, these FeF(3) NWs are not only promising battery cathode materials but also provide a convenient platform for fundamental studies and further improving conversion cathodes in general.

Preparation and Characterisation of LiFePO4/CNT Material for Li-Ion Batteries

Directory of Open Access Journals (Sweden)

Rushanah Mohamed

2011-01-01

Full Text Available Li-ion battery cathode materials were synthesised via a mechanical activation and thermal treatment process and systematically studied. LiFePO4/CNT composite cathode materials were successfully prepared from LiFePO4 material. The synthesis technique involved growth of carbon nanotubes onto the LiFePO4 using a novel spray pyrolysis-modified CVD technique. The technique yielded LiFePO4/CNT composite cathode material displaying good electrochemical activity. The composite cathode exhibited excellent electrochemical performances with 163 mAh/g discharge capacity with 94% cycle efficiency at a 0.1 C discharge rate in the first cycle, with a capacity fade of approximately 10% after 30 cycles. The results indicate that carbon nanotube addition can enable LiFePO4 to display a higher discharge capacity at a fast rate with high efficiency. The research is of potential interest for the application of carbon nanotubes as a new conducting additive in cathode preparation and for the development of high-power Li-ion batteries for hybrid electric vehicles.

Advanced carbon materials/olivine LiFePO4 composites cathode for lithium ion batteries

Science.gov (United States)

Gong, Chunli; Xue, Zhigang; Wen, Sheng; Ye, Yunsheng; Xie, Xiaolin

2016-06-01

In the past two decades, LiFePO4 has undoubtly become a competitive candidate for the cathode material of the next-generation LIBs due to its abundant resources, low toxicity and excellent thermal stability, etc. However, the poor electronic conductivity as well as low lithium ion diffusion rate are the two major drawbacks for the commercial applications of LiFePO4 especially in the power energy field. The introduction of highly graphitized advanced carbon materials, which also possess high electronic conductivity, superior specific surface area and excellent structural stability, into LiFePO4 offers a better way to resolve the issue of limited rate performance caused by the two obstacles when compared with traditional carbon materials. In this review, we focus on advanced carbon materials such as one-dimensional (1D) carbon (carbon nanotubes and carbon fibers), two-dimensional (2D) carbon (graphene, graphene oxide and reduced graphene oxide) and three-dimensional (3D) carbon (carbon nanotubes array and 3D graphene skeleton), modified LiFePO4 for high power lithium ion batteries. The preparation strategies, structure, and electrochemical performance of advanced carbon/LiFePO4 composite are summarized and discussed in detail. The problems encountered in its application and the future development of this composite are also discussed.

High performance screen printable lithium-ion battery cathode ink based on C-LiFePO4

International Nuclear Information System (INIS)

Sousa, R.E.; Oliveira, J.; Gören, A.; Miranda, D.; Silva, M.M.; Hilliou, Loic; Costa, C.M.; Lanceros-Mendez, S.

2016-01-01

Highlights: • C-LiFePO 4 paste was been prepared for screen-printing technique. • The inks produced have a Newtonian viscosity of 3 Pa.s for this printing technique. • C-LiFePO 4 inks present a 48.2 mAh.g −1 after 50 cycles at 5C. • This ink is suitable in the development of printed lithium ion batteries. - Abstract: Lithium-ion battery cathodes have been fabricated by screen-printing through the development of C-LiFePO 4 inks. It is shown that shear thinning polymer solutions in N-methyl-2-pyrrolidone (NMP) with Newtonian viscosity above 0.4 Pa s are the best binders for formulating a cathode paste with satisfactory film forming properties. The paste shows an elasticity of the order of 500 Pa and, after shear yielding, shows an apparent viscosity of the order of 3 Pa s for shear rates corresponding to those used during screen-printing. The screen-printed cathode produced with a thickness of 26 μm shows a homogeneous distribution of the active material, conductive additive and polymer binder. The total resistance and diffusion coefficient of the cathode are ∼ 450 Ω and 2.5 × 10 −16 cm 2 s −1 , respectively. The developed cathodes show an initial discharge capacity of 48.2 mAh g −1 at 5C and a discharge value of 39.8 mAh g −1 after 50 cycles. The capacity retention of 83% represents 23% of the theoretical value (charge and/or discharge process in twenty minutes), demonstrating the good performance of the battery. Thus, the developed C-LiFePO 4 based inks allow to fabricate screen-printed cathodes suitable for printed lithium-ion batteries.

Comparative study on experiments and simulation of blended cathode active materials for lithium ion batteries

International Nuclear Information System (INIS)

Appiah, Williams Agyei; Park, Joonam; Van Khue, Luu; Lee, Yunju; Choi, Jaecheol; Ryou, Myung-Hyun; Lee, Yong Min

2016-01-01

We simulate the electrochemical properties of Li-ion cells consisting of a blended cathode composed of LiMn 2 O 4 and LiNi 0.6 Co 0.2 Mn 0.2 O 2 and an artificial graphite anode using the Li-ion battery model available in COMSOL MULTIPHYSICS 4.4 along with a capacity fade model. The discharge profiles of the pure and blended cathodes at various current rates obtained through simulations and experimental results are well matched. By combining two capacity fade models available in literature, namely the solid electrolyte interphase (SEI) growth model and the Mn 2+ dissolution model, the cycling performance of the pure LiMn 2 O 4 cells at 25 °C are successfully simulated and found to be in a good agreement with the experimental results. The blended cathode exhibits better capacity retention than the pure LiMn 2 O 4 during cycling. We also observed that at high powers, the gravimetric energy density of the LiMn 2 O 4 cathode exceeds that of the LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathode; the reverse effect is seen at low powers. Further, we were able to easily modulate the energy and power densities of the blended cathode system by changing the blend ratio in our simulation model.

Cathodes for lithium-air battery cells with acid electrolytes

Science.gov (United States)

Xing, Yangchuan; Huang, Kan; Li, Yunfeng

2016-07-19

In various embodiments, the present disclosure provides a layered metal-air cathode for a metal-air battery. Generally, the layered metal-air cathode comprises an active catalyst layer, a transition layer bonded to the active catalyst layer, and a backing layer bonded to the transition layer such that the transition layer is disposed between the active catalyst layer and the backing layer.

Electrospun single crystalline fork-like K2V8O21 as high-performance cathode materials for lithium-ion batteries

Science.gov (United States)

Hao, Pengfei; Zhu, Ting; Su, Qiong; Lin, Jiande; Cui, Rong; Cao, Xinxin; Wang, Yaping; Pan, Anqiang

2018-06-01

Single crystalline fork-like potassium vanadate (K2V8O21) has been successfully prepared through electrospinning combined with a subsequent annealing process. The as-obtained K2V8O21 forks show a unique layer-by-layer stacked structure with conductive carbon. When used as cathode materials for lithium-ion batteries, the as-prepared fork-like materials exhibit high specific discharge capacity and excellent cyclic stability. High specific discharge capacity of 200.2 mA h g-1 and 131.5 mA h g-1 can be delivered at the current densities of 50 mA g-1 and 500 mA g-1, respectively. Furthermore, the K2V8O21 electrodes exhibit excellent long-term cycling stability that maintain a capacity of 108.3 mA h g-1 after 300 cycles at 500 mA g-1 with a fading rate of only 0.054% per cycle, revealing their potential applications in next generation high-performance lithium-ion batteries.

Short-range contacts govern the performance of industry-relevant battery cathodes

Science.gov (United States)

Morelly, Samantha L.; Alvarez, Nicolas J.; Tang, Maureen H.

2018-05-01

Fundamental understanding of how processing affects composite battery electrode structure and performance is still lacking, especially for industry-relevant electrodes with low fractions of inactive material. This work combines rheology, electronic conductivity measurements, and battery rate capability tests to prove that short-range electronic contacts are more important to cathode rate capability than either ion transport or long-range electronic conductivity. LiNi0.33Mn0.33Co0.33O2, carbon black, and polyvinylidene difluoride in 1-methyl-2-pyrrolidinone represent a typical commercial electrode with films. Improvements in battery rate capability at constant electrode porosity do not correlate to electronic conductivity, but rather show an optimum fraction of free carbon. Simple comparison of rate capability in electrodes with increased total carbon loading (3 wt%) shows improvement for all fractions of free carbon. These results clearly indicate that ion transport cannot be limiting and highlight the critical importance of short-range electronic contacts for controlling battery performance.

Synthesis of hierarchical porous honeycomb carbon for lithium-sulfur battery cathode with high rate capability and long cycling stability

International Nuclear Information System (INIS)

Qu, Yaohui; Zhang, Zhian; Zhang, Xiahui; Ren, Guodong; Wang, Xiwen; Lai, Yanqing; Liu, Yexiang; Li, Jie

2014-01-01

Highlights: • A novel HPHC was prepared by a simple template process. • The HPHC as matrix to load sulfur for Lithium-Sulfur battery cathodes. • S-HPHC cathode shows high rate capability and long cycling stability. • The sulfur-HPHC composite presents electrochemical stability up to 300 cycles at 1.5 C. - Abstract: Sulfur has a high specific capacity of 1675 mAh g −1 as lithium battery cathode, but its rapid capacity fading due to polysulfides dissolution presents a significant challenge for practical applications. Here we report a novel hierarchical porous honeycomb carbon (HPHC) for lithium-sulfur battery cathode with effective trapping of polysulfides. The HPHC was prepared by a simple template process, and a sulfur-carbon composite based on HPHC was synthesized for lithium-sulfur batteries by a melt-diffusion method. It is found that the elemental sulfur was dispersed inside the three-dimensionally hierarchical pores of HPHC based on the analyses. Electrochemical tests reveal that the sulfur-HPHC composite shows high rate capability and long cycling stability as cathode materials. The sulfur-HPHC composite with sulfur content of 66.3 wt% displays an initial discharge capacity of 923 mAh g −1 and a reversible discharge capacity of 564 mAh g −1 after 100 cycles at 2 C charge-discharge rate. In particular, the sulfur-HPHC composite presents a long term cycling stability up to 300 cycles at 1.5 C. The results illustrate that the electrochemical reaction constrained inside the interconnected macro/meso/micropores of HPHC would be the dominant factor for the excellent high rate capability and long cycling stability of the sulfur cathode, and the three-dimensionally honeycomb carbon network would be a promising carbon matrix structure for lithium-sulfur battery cathode

Advanced Cathode Material For High Energy Density Lithium-Batteries, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — Advanced cathode materials having high red-ox potential and high specific capacity offer great promise to the development of high energy density lithium-based...

Advanced Electrode Materials for High Energy Next Generation Li ion Batteries

Science.gov (United States)

Hayner, Cary Michael

Lithium ion batteries are becoming an increasingly ubiquitous part of modern society. Since their commercial introduction by Sony in 1991, lithium-ion batteries have grown to be the most popular form of electrical energy storage for portable applications. Today, lithium-ion batteries power everything from cellphones and electric vehicles to e-cigarettes, satellites, and electric aircraft. Despite the commercialization of lithium-ion batteries over twenty years ago, it remains the most active field of energy storage research for its potential improvement over current technology. In order to capitalize on these opportunities, new materials with higher energy density and storage capacities must be developed. Unfortunately, most next-generation materials suffer from rapid capacity degradation or severe loss of capacity when rapidly discharged. In this dissertation, the development of novel anode and cathode materials for advanced high-energy and high-power lithium-ion batteries is reported. In particular, the application of graphene-based materials to stabilize active material is emphasized. Graphene, a unique two-dimensional material composed of atomically thin carbon sheets, has shown potential to address unsatisfactory rate capability, limited cycling performance and abrupt failure of these next-generation materials. This dissertation covers four major subjects: development of silicon-graphene composites, impact of carbon vacancies on graphene high-rate performance, iron fluoride-graphene composites, and ternary iron-manganese fluoride synthesis. Silicon is considered the most likely material to replace graphite as the anode active material for lithium-ion batteries due to its ability to alloy with large amounts of lithium, leading to significantly higher specific capacities than the graphite standard. However, Si also expands in size over 300% upon lithiation, leading to particle fracture and isolation from conductive support, resulting in cell failure within a few

One-Pot Synthesis of Lithium-Rich Cathode Material with Hierarchical Morphology.

Science.gov (United States)

Luo, Kun; Roberts, Matthew R; Hao, Rong; Guerrini, Niccoló; Liberti, Emanuela; Allen, Christopher S; Kirkland, Angus I; Bruce, Peter G

2016-12-14

Lithium-rich transition metal oxides, Li 1+x TM 1-x O 2 (TM, transition metal), have attracted much attention as potential candidate cathode materials for next generation lithium ion batteries because their high theoretical capacity. Here we present the synthesis of Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2 using a facile one-pot resorcinol-formaldehyde method. Structural characterization indicates that the material adopts a hierarchical porous morphology consisting of uniformly distributed small pores and disordered large pore structures. The material exhibits excellent electrochemical cycling stability and a good retention of capacity at high rates. The material has been shown to be both advantageous in terms of gravimetric and volumetric capacities over state of the art commercial cathode materials.

Conductive framework of inverse opal structure for sulfur cathode in lithium-sulfur batteries.

Science.gov (United States)

Jin, Lu; Huang, Xiaopeng; Zeng, Guobo; Wu, Hua; Morbidelli, Massimo

2016-09-07

As a promising cathode inheritor for lithium-ion batteries, the sulfur cathode exhibits very high theoretical volumetric capacity and energy density. In its practical applications, one has to solve the insulating properties of sulfur and the shuttle effect that deteriorates cycling stability. The state-of-the-art approaches are to confine sulfur in a conductive matrix. In this work, we utilize monodisperse polystyrene nanoparticles as sacrificial templates to build polypyrrole (PPy) framework of an inverse opal structure to accommodate (encapsulate) sulfur through a combined in situ polymerization and melting infiltration approach. In the design, the interconnected conductive PPy provides open channels for sulfur infiltration, improves electrical and ionic conductivity of the embedded sulfur, and reduces polysulfide dissolution in the electrolyte through physical and chemical adsorption. The flexibility of PPy and partial filling of the inverse opal structure endure possible expansion and deformation during long-term cycling. It is found that the long cycling stability of the cells using the prepared material as the cathode can be substantially improved. The result demonstrates the possibility of constructing a pure conductive polymer framework to accommodate insulate sulfur in ion battery applications.

Thermal Characteristics of Conversion-Type FeOF Cathode in Li-ion Batteries

Directory of Open Access Journals (Sweden)

Liwei Zhao

2017-10-01

Full Text Available Rutile FeOF was used as a conversion-type cathode material for Li-ion batteries. In the present study, 0.6Li, 1.4Li, and 2.7Li per mole lithiation reactions were carried out by changing the electrochemical discharge reaction depth. The thermal characteristics of the FeOF cathode were investigated by thermogravimetric mass spectrometric (TG-MS and differential scanning calorimeter (DSC systems. No remarkable HF release was detected, even up to 700 °C, which indicated a low toxic risk for the FeOF cathode. Changes in the thermal properties of the FeOF cathode via different conversion reaction depths in the associated electrolyte were studied by changing the cathode/electrolyte ratio in the mixture. LiFeOF was found to exothermically react with the electrolyte at about 210 °C. Similar exothermic reactions were found with charged FeOF cathodes because of the irreversible Li ions. Among the products of the conversion reaction of FeOF, Li2O was found to exothermically react with the electrolyte at about 120 °C, which induced the main thermal risk of the FeOF cathode. It suggests that the oxygen-containing conversion-type cathodes have a higher thermal risk than the oxygen-free ones, but controlling the cathode/electrolyte ratio in cells successfully reduced the thermal risk. Finally, the thermal stability of the FeOF cathode was evaluated in comparison with FeF3 and LiFePO4 cathodes.

Nano-structures Enhanced Novel Composite Electrode Material for Batteries, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — Integrate advanced nanotechnology with energy storage technology to develop advanced cathode material for use in Li-ion batteries while maintaining high level of...

Textile Inspired Lithium-Oxygen Battery Cathode with Decoupled Oxygen and Electrolyte Pathways.

Science.gov (United States)

Xu, Shaomao; Yao, Yonggang; Guo, Yuanyuan; Zeng, Xiaoqiao; Lacey, Steven D; Song, Huiyu; Chen, Chaoji; Li, Yiju; Dai, Jiaqi; Wang, Yanbin; Chen, Yanan; Liu, Boyang; Fu, Kun; Amine, Khalil; Lu, Jun; Hu, Liangbing

2018-01-01

The lithium-air (Li-O 2 ) battery has been deemed one of the most promising next-generation energy-storage devices due to its ultrahigh energy density. However, in conventional porous carbon-air cathodes, the oxygen gas and electrolyte often compete for transport pathways, which limit battery performance. Here, a novel textile-based air cathode is developed with a triple-phase structure to improve overall battery performance. The hierarchical structure of the conductive textile network leads to decoupled pathways for oxygen gas and electrolyte: oxygen flows through the woven mesh while the electrolyte diffuses along the textile fibers. Due to noncompetitive transport, the textile-based Li-O 2 cathode exhibits a high discharge capacity of 8.6 mAh cm -2 , a low overpotential of 1.15 V, and stable operation exceeding 50 cycles. The textile-based structure can be applied to a range of applications (fuel cells, water splitting, and redox flow batteries) that involve multiple phase reactions. The reported decoupled transport pathway design also spurs potential toward flexible/wearable Li-O 2 batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of entropy changes in anodes and cathodes on the thermal behavior of lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Williford, Ralph E.; Viswanathan, Vilayanur V.; Zhang, Ji-Guang [Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (United States)

2009-04-01

The entropy changes ({delta}S) in various cathode and anode materials, as well as complete Li-ion batteries, were measured using an electrochemical thermodynamic measurement system (ETMS). A thermal model based on the fundamental properties of individual electrodes was used to obtain transient and equilibrium temperature distributions of Li-ion batteries. The results from theoretical simulations were compared with results obtained in experimental measurements. We found that the detailed shape of the entropy curves strongly depends on the manufacturer of the materials even for the same nominal compositions. LiCoO{sub 2} has a much larger entropy change than LiNi{sub x}Co{sub y}Mn{sub z}O{sub 2}. This means that LiNi{sub x}Co{sub y}Mn{sub z}O{sub 2} is much more thermodynamically stable than LiCoO{sub 2}. The temperatures around the positive terminal of a prismatic battery are consistently higher than those at the negative terminal, due to differences in the thermal conductivities of the different terminal connectors. When all other simulation parameters are the same, simulations that use a battery-averaged entropy tend to overestimate the predicted temperatures when compared with simulations that use individual entropies for the anode and the cathode, due to computational averaging. (author)

Cathode architectures for alkali metal / oxygen batteries

Science.gov (United States)

Visco, Steven J; Nimon, Vitaliy; De Jonghe, Lutgard C; Volfkovich, Yury; Bograchev, Daniil

2015-01-13

Electrochemical energy storage devices, such as alkali metal-oxygen battery cells (e.g., non-aqueous lithium-air cells), have a cathode architecture with a porous structure and pore composition that is tailored to improve cell performance, especially as it pertains to one or more of the discharge/charge rate, cycle life, and delivered ampere-hour capacity. A porous cathode architecture having a pore volume that is derived from pores of varying radii wherein the pore size distribution is tailored as a function of the architecture thickness is one way to achieve one or more of the aforementioned cell performance improvements.

Effect of Metal (Mn, Ti Doping on NCA Cathode Materials for Lithium Ion Batteries

Directory of Open Access Journals (Sweden)

Dao Yong Wan

2018-01-01

Full Text Available NCA (LiNi0.85Co0.10Al0.05-x MxO2, M=Mn or Ti, x < 0.01 cathode materials are prepared by a hydrothermal reaction at 170°C and doped with Mn and Ti to improve their electrochemical properties. The crystalline phases and morphologies of various NCA cathode materials are characterized by XRD, FE-SEM, and particle size distribution analysis. The CV, EIS, and galvanostatic charge/discharge test are employed to determine the electrochemical properties of the cathode materials. Mn and Ti doping resulted in cell volume expansion. This larger volume also improved the electrochemical properties of the cathode materials because Mn4+ and Ti4+ were introduced into the octahedral lattice space occupied by the Li-ions to expand the Li layer spacing and, thereby, improved the lithium diffusion kinetics. As a result, the NCA-Ti electrode exhibited superior performance with a high discharge capacity of 179.6 mAh g−1 after the first cycle, almost 23 mAh g−1 higher than that obtained with the undoped NCA electrode, and 166.7 mAh g−1 after 30 cycles. A good coulombic efficiency of 88.6% for the NCA-Ti electrode is observed based on calculations in the first charge and discharge capacities. In addition, the NCA-Ti cathode material exhibited the best cycling stability of 93% up to 30 cycles.

Synthesis and characterization of high-density LiFePO4/C composites as cathode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Chang Zhaorong; Lv Haojie; Tang Hongwei; Li Huaji; Yuan Xiaozi; Wang Haijiang

2009-01-01

To achieve a high-energy-density lithium electrode, high-density LiFePO 4 /C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO 4 as a precursor, glucose as a C source, and Li 2 CO 3 as a Li source, in a pipe furnace under an atmosphere of 5% H 2 -95% N 2 . The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO 4 /carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO 4 /carbon composite powder with a carbon content of 7% reached 1.80 g m -3 . The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g -1 , respectively, with a volume capacity of 300.6 mAh cm -3 , at a 0.1C rate. At a rate of 5C, the LiFePO 4 /carbon composite shows a high discharge capacity of 98.3 mAh g -1 and a volume capacity of 176.94 mAh cm -3 .

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.

Detailed investigation of Na2.24FePO4CO3 as a cathode material for Na-ion batteries

Science.gov (United States)

Huang, Weifeng; Zhou, Jing; Li, Biao; Ma, Jin; Tao, Shi; Xia, Dingguo; Chu, Wangsheng; Wu, Ziyu

2014-01-01

Na-ion batteries are gaining an increased recognition as the next generation low cost energy storage devices. Here, we present a characterization of Na3FePO4CO3 nanoplates as a novel cathode material for sodium ion batteries. First-principles calculations reveal that there are two paths for Na ion migration along b and c axis. In-situ and ex-situ Fe K-edge X-ray absorption near edge structure (XANES) point out that in Na3FePO4CO3 both Fe2+/Fe3+ and Fe3+/Fe4+ redox couples are electrochemically active, suggesting also the existence of a two-electron intercalation reaction. Ex-situ X-ray powder diffraction data demonstrates that the crystalline structure of Na3FePO4CO3 remains stable during the charging/discharging process within the range 2.0–4.55 V. PMID:24595232

Three-dimensional graphene/LiFePO4 nanostructures as cathode materials for flexible lithium-ion batteries

International Nuclear Information System (INIS)

Ding, Y.H.; Ren, H.M.; Huang, Y.Y.; Chang, F.H.; Zhang, P.

2013-01-01

Graphical abstract: Graphene/LiFePO 4 composites as a high-performance cathode material for flexible lithium-ion batteries have been prepared by using a co-precipitation method to synthesize graphene/LiFePO4 powders as precursors and then followed by a solvent evaporation process. - Highlights: • Flexible LiFePO 4 /graphene films were prepared first time by a solvent evaporation process. • The flexible electrode exhibited a high discharge capacity without conductive additives. • Graphene network offers the electrode adequate strength to withstand repeated flexing. - Abstract: Three-dimensional graphene/LiFePO 4 nanostructures for flexible lithium-ion batteries were successfully prepared by solvent evaporation method. Structural characteristics of flexible electrodes were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Electrochemical performance of graphene/LiFePO 4 was examined by a variety of electrochemical testing techniques. The graphene/LiFePO 4 nanostructures showed high electrochemical properties and significant flexibility. The composites with low graphene content exhibited a high capacity of 163.7 mAh g −1 at 0.1 C and 114 mAh g −1 at 5 C without further incorporation of conductive agents

NiCo2O4 surface coating Li[Ni0.03Mn1.97]O4 micro-/nano- spheres as cathode material for high-performance lithium ion battery

Science.gov (United States)

Ye, Pan; Dong, Hui; Xu, Yunlong; Zhao, Chongjun; Liu, Dong

2018-01-01

Here we report a novel transitional metal oxide (NiCo2O4) coated Li[Ni0.03Mn1.97]O4 micro-/nano- spheres as high-performance Li-ion battery cathode material. A thin layer of ∼10 nm NiCo2O4 was formed by simple wet-chemistry approach adjacent to the surface of Li[Ni0.03Mn1.97]O4 micro-/nano- spheres, leading to significantly enhanced battery electrochemical performance. The optimized sample(1 wt%) not only delivers excellent discharge capacity and cycling stability improvement at both room temperature and elevated temperatures, but also effectively prevents Mn dissolution while retaining its coating structure intact according to XRF and TEM results. The CV and EIS break-down analysis indicated a much faster electrochemical reaction kinetics, more reversible electrode process and greatly reduced charge transfer and Warburg resistance, clearly illustrating the dual role of NiCo2O4 coating to boost electron transport and Li+ diffusion, and alleviation of manganese dissolving. This approach may render as an efficient technique to realize high-performance lithium ion battery cathode material.

Development of thin film cathodes for lithium-ion batteries in the material system Li–Mn–O by r.f. magnetron sputtering

International Nuclear Information System (INIS)

Fischer, J.; Adelhelm, C.; Bergfeldt, T.; Chang, K.; Ziebert, C.; Leiste, H.; Stüber, M.; Ulrich, S.; Music, D.; Hallstedt, B.; Seifert, H.J.

2013-01-01

Today most commercially available lithium ion batteries are still based on the toxic and expensive LiCoO 2 as a standard cathode material. However, lithium manganese based cathode materials are cheaper and environmentally friendlier. In this work cubic-LiMn 2 O 4 spinel, monoclinic-Li 2 MnO 3 and orthorhombic-LiMnO 2 thin films have been synthesized by non-reactive r.f. magnetron sputtering from two ceramic targets (LiMn 2 O 4 , LiMnO 2 ) in a pure argon discharge. The deposition parameters, namely target power and working gas pressure, were optimized in a combination with a post deposition heat treatment with respect to microstructure and electrochemical behavior. The chemical composition was determined using inductively coupled plasma optical emission spectroscopy and carrier gas hot extraction. The films' crystal structure, phase evolution and morphology were investigated by X-ray diffraction, micro Raman spectroscopy and scanning electron microscopy. Due to the fact that these thin films consist of the pure active material without any impurities, such as binders or conductive additives like carbon black, they are particularly well suited for measurements of the intrinsic physical properties, which is essential for fundamental understanding. The electrochemical behavior of the cubic and the orthorhombic films was investigated by galvanostatic cycling in half cells against metallic lithium. The cubic spinel films exhibit a maximum specific capacity of ∼ 82 mAh/g, while a specific capacity of nearly 150 mAh/g can be reached for the orthorhombic counterparts. These films are promising candidates for future all solid state battery applications. - Highlights: ► Synthesis of 3 Li–Mn–O structures by one up-scalable thin film deposition method ► Formation of o-LiMnO 2 by r.f. magnetron sputtering in combination with post-annealing ► Discharge capacity with o-LiMnO 2 cathodes twice as high as for c-LiMn 2 O 4 ► Thin film deposition of m-Li 2 MnO 3 and

A Novel Battery Cathode Material Based on intercalation Chemistry: Redox Reactions of the 2,5-Dimercapto-1,3,4-Thiadiazole/V2O5 Xerogel System

National Research Council Canada - National Science Library

Shouji, Eiichi

1998-01-01

.... Elemental analysis gives a composition for the intercalation material of (POLYDMcT)0.25.V2O5.1.4H2O. The cyclic voltammetry and galvanostatic discharge behavior of the parent V2O5 xerogel and the new intercalation material are directly compared. The (POLYDMcT)0.25.V2O5.1.4H2O hybrid composite material is shown to have superior discharge behavior, making it an attractive candidate material for use as a cathode in lithium secondary batteries.

Synthesis and Electrochemical Properties of Ni Doped Spinel LiNixMn2-xO4 (0 ≤ x ≤ 0.5) Cathode Materials for Li-Ion Battery

CSIR Research Space (South Africa)

Kebede, M

2013-11-01

Full Text Available Spherical pristine LiMn2O4 and Ni doped LiNixMn2-xO4 (x=0.1, 0.2, 0.3, 0.4, 0.5) cathode materials for lithium ion battery with high first cycle discharge capacity and excellent cycle performance were synthesized using the solution...

Capacity extended bismuth-antimony cathode for high-performance liquid metal battery

Science.gov (United States)

Dai, Tao; Zhao, Yue; Ning, Xiao-Hui; Lakshmi Narayan, R.; Li, Ju; Shan, Zhi-wei

2018-03-01

Li-Bi based liquid metal batteries (LMBs) have attracted interest due to their potential for solving grid scale energy storage problems. In this study, the feasibility of replacing the bismuth cathode with a bismuth-antimony alloy cathode in lithium based LMBs is investigated. The influence of the Bi:Sb ratio on voltage characteristics is evaluated via the constant current discharge method and electrochemical titration. On observing the cross section of the electrode at various stages of discharge, it is determined that both Sb and Bi form solid intermetallics with Li on the cathode. Additionally, the addition of Bi not only reduces the melting temperature of the Bi:Sb intermetallic but also actively contributes to the electrode capacity. Thereafter, a Li|LiCl-LiF|Sb-Bi liquid metal battery with 3 A h nameplate capacity, assembled and cycled at 1 C rate, is found to possess a stable capacity for over 160 cycles. The overall performance of this battery is discussed in the context of cost effectiveness, energy and coulombic efficiencies.

Effect of microstructure on low temperature electrochemical properties of LiFePO4/C cathode material

International Nuclear Information System (INIS)

Zhao, Nannan; Zhi, Xiaoke; Wang, Li; Liu, Yanhui; Liang, Guangchuan

2015-01-01

Graphical abstract: The low temperature performance of Li-ion batteries and LiFePO 4 /C composites was discussed. A conclusion that cathode material is the main limitation for the low temperature performance was come up, by comparing the low temperature performance of 18650 Li-ion batteries with LiMn 2 O 4 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 and LiFePO 4 /C as cathode materials. The low temperature performance results indicate the LiFePO 4 /C microstructure is the main factor influencing the low temperature performance of LiFePO 4 . A new LiFePO 4 /C with pomegranate-like spherical structure was proposed in this paper, which shows superior low temperature performance, which can be attributed to its uniform fine primary particles and smaller primary particles. - Highlights: • Low temperature performance of Li-ion battery and LiFePO 4 /C composite was discussed. • Cathode material mainly decided the low temperature performance of Li-ion battery. • LiFePO 4 /C microstructure mainly affects its low temperature performance. • Pomegranate-like spherical structure LiFePO 4 /C has good low temperature performance. - Abstract: The low-temperature electrochemical performance of Li-ion batteries is mainly determined by the choice of cathode material, as evident from a comparison of the low-temperature electrochemical performance of the 18650 batteries with the LiMn 2 O 4 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , and LiFePO 4 /C as the cathode, respectively, at −20 °C. LiFePO 4 /C materials with different morphologies and microstructures were prepared by different methods. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), galvanostatic charge–discharge measurements and EIS. The low-temperature performance of the samples and those of the coin cells utilizing the materials as cathodes were measured. The results indicate that the microstructure of LiFePO 4 /C is a key factor determining the low

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.

Silver nanowires as catalytic cathodes for stabilizing lithium-oxygen batteries

Science.gov (United States)

Kwak, Won-Jin; Jung, Hun-Gi; Lee, Seon-Hwa; Park, Jin-Bum; Aurbach, Doron; Sun, Yang-Kook

2016-04-01

Silver nanowires have been investigated as a catalytic cathode material for lithium-oxygen batteries. Their high aspect ratio contributes to the formation of a corn-shaped layer structure of the poorly crystalline lithium peroxide (Li2O2) nanoparticles produced by oxygen reduction in poly-ether based electrolyte solutions. The nanowire morphology seems to provide the necessary large contact area and facile electron supply for a very effective oxygen reduction reaction. The unique morphology and structure of the Li2O2 deposits and the catalytic nature of the silver nano-wires promote decomposition of Li2O2 at low potentials (below 3.4 V) upon the oxygen evolution. This situation avoids decomposition of the solution species and oxidation of the electrodes during the anodic (charge) reactions, leading to high electrical efficiently of lithium-oxygen batteries.

Strategies to curb structural changes of lithium/transition metal oxide cathode materials and the changes’ effects on thermal and cycling stability

International Nuclear Information System (INIS)

Yu Xiqian; Hu Enyuan; Bak, Seongmin; Zhou Yong-Ning; Yang Xiao-Qing

2016-01-01

Structural transformation behaviors of several typical oxide cathode materials during a heating process are reviewed in detail to provide in-depth understanding of the key factors governing the thermal stability of these materials. We also discuss applying the information about heat induced structural evolution in the study of electrochemically induced structural changes. All these discussions are expected to provide valuable insights for designing oxide cathode materials with significantly improved structural stability for safe, long-life lithium ion batteries, as the safety of lithium-ion batteries is a critical issue; it is widely accepted that the thermal instability of the cathodes is one of the most critical factors in thermal runaway and related safety problems. (topical review)

Carbon Quantum Dot Surface-Engineered VO2 Interwoven Nanowires: A Flexible Cathode Material for Lithium and Sodium Ion Batteries.

Science.gov (United States)

Balogun, Muhammad-Sadeeq; Luo, Yang; Lyu, Feiyi; Wang, Fuxin; Yang, Hao; Li, Haibo; Liang, Chaolun; Huang, Miao; Huang, Yongchao; Tong, Yexiang

2016-04-20

The use of electrode materials in their powdery form requires binders and conductive additives for the fabrication of the cells, which leads to unsatisfactory energy storage performance. Recently, a new strategy to design flexible, binder-, and additive-free three-dimensional electrodes with nanoscale surface engineering has been exploited in boosting the storage performance of electrode materials. In this paper, we design a new type of free-standing carbon quantum dot coated VO2 interwoven nanowires through a simple fabrication process and demonstrate its potential to be used as cathode material for lithium and sodium ion batteries. The versatile carbon quantum dots that are vastly flexible for surface engineering serve the function of protecting the nanowire surface and play an important role in the diffusion of electrons. Also, the three-dimensional carbon cloth coated with VO2 interwoven nanowires assisted in the diffusion of ions through the inner and the outer surface. With this unique architecture, the carbon quantum dot nanosurface engineered VO2 electrode exhibited capacities of 420 and 328 mAh g(-1) at current density rate of 0.3 C for lithium and sodium storage, respectively. This work serves as a milestone for the potential replacement of lithium ion batteries and next generation postbatteries.

Polymorphs of LiFeSO4F as cathode materials for lithium ion batteries - a first principle computational study.

Science.gov (United States)

Chung, Sai Cheong; Barpanda, Prabeer; Nishimura, Shin-Ichi; Yamada, Yuki; Yamada, Atsuo

2012-06-28

We have investigated polymorphs of LiFeSO4F, tavorite and triplite, which have been reported as cathode materials for lithium ion batteries. The predicted voltages are 3.64 and 3.90 V for tavorite and triplite, respectively, which agreed excellently with experimental data. It is found that the lithiated states (LiFeSO4F) of the polymorphs are almost degenerate in energy. The difference in voltage is mainly due to the difference in the stabilities of the delithiated states (FeSO4F). This is rationalized by the Fe(3+)-Fe(3+) repulsion in the edge sharing geometry of the triplite structure.

Review of Battery Technologies for Military Land Vehicles

Science.gov (United States)

2017-01-01

to their incompatible voltage window18 [10]. 5.3.1.3 Lithium Nickel Cobalt Aluminium Oxide ( NCA ) Batteries The NCA cathode (basic chemical...energy (175- 240 Wh/kg). However, Li-ion batteries using NCA cathodes have poor safety properties, similar to Li-ion batteries using LCO cathodes [1...Li-ion batteries using NCA cathodes are available commercially and manufacturers of NCA batteries include Toda Kogyo and BTR New Materials [1

Lithium secondary batteries: Role of polymer cathode morphology

Science.gov (United States)

Naoi, Katsuhiko; Osaka, Tetsuya; Owens, Boone B.

1988-06-01

Electrically conducting polymers have been utilized both as the cathode and as the electrolyte element of Li secondary cells. Polymer cathodes were limited in their suitability for batteries because of the low energy content associated with low levels of doping and the inclusion of complex ionic species in the cathode. Recent studies have indicated that doping levels up to 100 percent can be achieved in polyanilene. High doping levels in combination with controlled morphologies have been found to improve the energy and rate capabilities of polymer cathodes. A morphology-modifying technique was utilized to enhance the charge/discharge characteristics of Li/liquid electrolyte polypyrrole cells. The polymer is electropolymerized in a preferred orientation morphology when the substrate is first precoated with an insulating film of nitrile butadiene rubber (NBR). Modification of the kinetic behavior of the electrode results from variations in the chemical composition of the NBR.

A Spinel-integrated P2-type Layered Composite: High-rate Cathode for Sodium-ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Zheng, Jianming; Yan, Pengfei; Kan, Wang Hay; Wang, Chong M.; Manthiram, Arumugam

2016-01-14

Sodium-ion batteries (SIB) are being intensively investigated, owing to the natural abundance and low cost of Na resources. However, the SIBs still suffer from poor rate capability due to the large ionic radius of Na+ ion and the significant kinetic barrier to Na+-ion transport. Here, we present an Fd-3m spinel-integrated P2-type layered composite (P2 + Fd-3m) material as a high-rate cathode for SIBs. The P2 + Fd-3m composite material Na0.50Ni1/6Co1/6Mn2/3O2 shows significantly enhanced discharge capacity, energy density, and rate capability as compared to the pure P2-type counterpart. The composite delivers a high capacity of 85 mA h g-1 when discharging at a very high current density of 1500 mA g-1 (10C rate) between 2.0 and 4.5 V, validating it as a promising cathode candidate for high-power SIBs. The superior performance is ascribed to the improved kinetics in the presence of the integrated-spinel phase, which facilitates fast electron transport to coordinate with the timely Na+-ion insertion/extraction. The findings of this work also shed light on the importance of developing lattice doping, surface coating, and electrolyte additives to further improve the structural and interfacial stability of P2-type cathode materials and fully realize their practical applications in sodium-ion batteries.

Recent Advances on the Understanding of Structural and Composition Evolution of LMR Cathodes for Li-ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Yan, Pengfei [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA (United States); Zheng, Jianming; Xiao, Jie [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA (United States); Wang, Chong-Min, E-mail: chongmin.wang@pnnl.gov [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA (United States); Zhang, Ji-Guang, E-mail: chongmin.wang@pnnl.gov [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA (United States)

2015-06-08

Lithium-and-manganese-rich (LMR) cathode materials have been regarded as very promising for lithium (Li)-ion battery applications. However, their practical application is still limited by several barriers such as their limited electrochemical stability and rate capability. In this work, we present recent progress on the understanding of structural and compositional evolution of LMR cathode materials, with an emphasis being placed on the correlation between structural/chemical evolution and electrochemical properties. In particular, using Li[Li{sub 0.2}Ni{sub 0.2}Mn{sub 0.6}]O{sub 2} as a typical example, we clearly illustrate the structural characteristics of pristine materials and their dependence on the material-processing history, cycling-induced structural degradation/chemical partition, and their correlation with electrochemical performance degradation. The fundamental understanding that resulted from this work may also guide the design and preparation of new cathode materials based on the ternary system of transitional metal oxides.

Probing the Complexities of Structural Changes in Layered Oxide Cathode Materials for Li-Ion Batteries during Fast Charge-Discharge Cycling and Heating.

Science.gov (United States)

Hu, Enyuan; Wang, Xuelong; Yu, Xiqian; Yang, Xiao-Qing

2018-02-20

The rechargeable lithium-ion battery (LIB) is the most promising energy storage system to power electric vehicles with high energy density and long cycling life. However, in order to meet customers' demands for fast charging, the power performances of current LIBs need to be improved. From the cathode aspect, layer-structured cathode materials are widely used in today's market and will continue to play important roles in the near future. The high rate capability of layered cathode materials during charging and discharging is critical to the power performance of the whole cell and the thermal stability is closely related to the safety issues. Therefore, the in-depth understanding of structural changes of layered cathode materials during high rate charging/discharging and the thermal stability during heating are essential in developing new materials and improving current materials. Since structural changes take place from the atomic level to the whole electrode level, combination of characterization techniques covering multilength scales is quite important. In many cases, this means using comprehensive tools involving diffraction, spectroscopy, and imaging to differentiate the surface from the bulk and to obtain structural/chemical information with different levels of spatial resolution. For example, hard X-ray spectroscopy can yield the bulk information and soft X-ray spectroscopy can give the surface information; X-ray based imaging techniques can obtain spatial resolution of tens of nanometers, and electron-based microcopy can go to angstroms. In addition to challenges associated with different spatial resolution, the dynamic nature of structural changes during high rate cycling and heating requires characterization tools to have the capability of collecting high quality data in a time-resolved fashion. Thanks to the advancement in synchrotron based techniques and high-resolution electron microscopy, high temporal and spatial resolutions can now be achieved. In

A closed-loop process for recycling LiNixCoyMn(1−x−yO2 from mixed cathode materials of lithium-ion batteries

Directory of Open Access Journals (Sweden)

Rujuan Zheng

2017-01-01

Full Text Available With the rapid development of consumer electronics and electric vehicles (EV, a large number of spent lithium-ion batteries (LIBs have been generated worldwide. Thus, effective recycling technologies to recapture a significant amount of valuable metals contained in spent LIBs are highly desirable to prevent the environmental pollution and resource depletion. In this work, a novel recycling technology to regenerate a LiNi1/3Co1/3Mn1/3O2 cathode material from spent LIBs with different cathode chemistries has been developed. By dismantling, crushing, leaching and impurity removing, the LiNi1/3Co1/3Mn1/3O2 (selected as an example of LiNixCoyMn(1−x−yO2 powder can be directly prepared from the purified leaching solution via co-precipitation followed by solid-state synthesis. For comparison purposes, a fresh-synthesized sample with the same composition has also been prepared using the commercial raw materials via the same method. X-ray diffraction (XRD, scanning electron microscopy (SEM and electrochemical measurements have been carried out to characterize these samples. The electrochemical test result suggests that the re-synthesized sample delivers cycle performance and low rate capability which are comparable to those of the fresh-synthesized sample. This novel recycling technique can be of great value to the regeneration of a pure and marketable LiNixCoyMn(1−x−yO2 cathode material with low secondary pollution. Keywords: Spent lithium-ion battery, Cathode material recycling, Acid leaching, Purification, Co-precipitation

Advances in electrode materials for Li-based rechargeable batteries

Energy Technology Data Exchange (ETDEWEB)

Zhang, Hui [China Academy of Space Technology (CAST), Beijing (China); Mao, Chengyu [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Li, Jianlin [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States); Chen, Ruiyong [Korea Inst. of Science and Technology (KIST), Saarbrucken (Germany); Saarland Univ., Saarbrucken (Germany)

2017-07-05

Rechargeable lithium-ion batteries store energy as chemical energy in electrode materials during charge and can convert the chemical energy into electrical energy when needed. Tremendous attention has been paid to screen electroactive materials, to evaluate their structural integrity and cycling reversibility, and to improve the performance of electrode materials. This review discusses recent advances in performance enhancement of both anode and cathode through nanoengineering active materials and applying surface coatings, in order to effectively deal with the challenges such as large volume variation, instable interface, limited cyclability and rate capability. We also introduce and discuss briefly the diversity and new tendencies in finding alternative lithium storage materials, safe operation enabled in aqueous electrolytes, and configuring novel symmetric electrodes and lithium-based flow batteries.

Rechargeable Aqueous Zinc-Ion Battery Based on Porous Framework Zinc Pyrovanadate Intercalation Cathode

KAUST Repository

Xia, Chuan; Guo, Jing; Lei, Yongjiu; Liang, Hanfeng; Zhao, Chao; Alshareef, Husam N.

2017-01-01

metal pyrovanadate compounds. The zinc pyrovanadate nanowires show significantly improved electrochemical performance when used as intercalation cathode for aqueous zinc–ion battery. Specifically, the ZVO cathode delivers high capacities of 213 and 76 m

Vanadium oxide based cpd. useful as a cathode active material - is used in lithium or alkali metal batteries to prolong life cycles

DEFF Research Database (Denmark)

1997-01-01

A mixt. of metallic iron particles and vanadium pentoxide contg. V in its pentavalent state in a liq. is reacted to convert at least some of the pentavalent V to its tetravalent state and form a gel. The liq. phase is then sepd. from the oxide based gel to obtain a solid material(I) comprising Fe......, V and oxygen where at least some of the V is in the tetravalent state. USE-(I) is a cathode active material in electric current producing storage cells. ADVANTAGE-Use of (I) in Li or alkali metal batteries gives prolonged life cycles.Storage cells using (I) have improved capacity during charge...

Li{sub 2}MnSiO{sub 4} as a potential Li-battery cathode material

Energy Technology Data Exchange (ETDEWEB)

Dominko, R.; Bele, M.; Gaberscek, M.; Jamnik, J. [National Institute of Chemistry, P.O.B. 660, SI-1001 Ljubljana (Slovenia); Kokalj, A. [Institute Jozef Stefan, Jamova 39, SI-1000 Ljubljana (Slovenia)

2007-12-06

Recently we synthesized and preliminary characterized a new material for potential use in Li-battery cathodes: Li{sub 2}MnSiO{sub 4}. Although its theoretical capacity is about 330 mAh g{sup -1}, the actual measurements showed a much smaller value (about 120 mAh g{sup -1}). One of the reasons for the poor performance could be the poor electronic conductivity (<10{sup -14} S cm{sup -1} at RT) causing a huge polarization during charge-discharge. However, in the present paper we show that reducing the particle size down to the range of 20-50 nm and additional particle embedment into a carbon phase does not significantly improve the electrochemistry of Li{sub 2}MnSiO{sub 4}. Observations of structural changes during the first charge shows a complete loss of peaks when reaching the nominal composition of ca. Li{sub 1}MnSiO{sub 4}. The peaks are not recovered during subsequent cycling. It is supposed that extraction of Li causes significant structural changes so that the resulting material is only able to reversibly exchange a limited amount of Li. (author)

Transition Metal Hollow Nanocages as Promising Cathodes for the Long-Term Cyclability of Li–O2 Batteries

Directory of Open Access Journals (Sweden)

Amrita Chatterjee

2018-05-01

Full Text Available As a step towards efficient and cost-effective electrocatalytic cathodes for Li–O2 batteries, highly porous hausmannite-type Mn3O4 hollow nanocages (MOHNs of a large diameter of ~250 nm and a high surface area of 90.65 m2·g−1 were synthesized and their physicochemical and electrochemical properties were studied in addition to their formation mechanism. A facile approach using carbon spheres as the template and MnCl2 as the precursor was adopted to suit the purpose. The MOHNs/Ketjenblack cathode-based Li–O2 battery demonstrated an improved cyclability of 50 discharge–charge cycles at a specific current of 400 mA·g−1 and a specific capacity of 600 mAh·g−1. In contrast, the Ketjenblack cathode-based one can sustain only 15 cycles under the same electrolytic system comprised of 1 M LiTFSI/TEGDME. It is surmised that the unique hollow nanocage morphology of MOHNs is responsible for the high electrochemical performance. The hollow nanocages were a result of the aggregation of crystalline nanoparticles of 25–35 nm size, and the mesoscopic pores between the nanoparticles gave rise to a loosely mesoporous structure for accommodating the volume change in the MOHNs/Ketjenblack cathode during electrocatalytic reactions. The improved cyclic stability is mainly due to the faster mass transport of the O2 through the mesoscopic pores. This work is comparable to the state-of-the-art experimentations on cathodes for Li–O2 batteries that focus on the use of non-precious transition materials.

Asymmetric battery having a semi-solid cathode and high energy density anode

Energy Technology Data Exchange (ETDEWEB)

Tan, Taison; Chiang, Yet-Ming; Ota, Naoki; Wilder, Throop; Duduta, Mihai

2017-11-28

Embodiments described herein relate generally to devices, systems and methods of producing high energy density batteries having a semi-solid cathode that is thicker than the anode. An electrochemical cell can include a positive electrode current collector, a negative electrode current collector and an ion-permeable membrane disposed between the positive electrode current collector and the negative electrode current collector. The ion-permeable membrane is spaced a first distance from the positive electrode current collector and at least partially defines a positive electroactive zone. The ion-permeable membrane is spaced a second distance from the negative electrode current collector and at least partially defines a negative electroactive zone. The second distance is less than the first distance. A semi-solid cathode that includes a suspension of an active material and a conductive material in a non-aqueous liquid electrolyte is disposed in the positive electroactive zone, and an anode is disposed in the negative electroactive zone.

Strategies to curb structural changes of lithium/transition metal oxide cathode materials & the changes’ effects on thermal & cycling stability

Science.gov (United States)

Xiqian, Yu; Enyuan, Hu; Seongmin, Bak; Yong-Ning, Zhou; Xiao-Qing, Yang

2016-01-01

Structural transformation behaviors of several typical oxide cathode materials during a heating process are reviewed in detail to provide in-depth understanding of the key factors governing the thermal stability of these materials. We also discuss applying the information about heat induced structural evolution in the study of electrochemically induced structural changes. All these discussions are expected to provide valuable insights for designing oxide cathode materials with significantly improved structural stability for safe, long-life lithium ion batteries, as the safety of lithium-ion batteries is a critical issue; it is widely accepted that the thermal instability of the cathodes is one of the most critical factors in thermal runaway and related safety problems. Project supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies (Grant No. DE-SC0012704).

Synthesis of Li2MnSiO4-graphene composite and its electrochemical performances as a cathode material for lithium ion batteries.

Science.gov (United States)

Kim, Jeonghyun; Song, Taeseup; Park, Hyunjung; Yuh, Junhan; Paik, Ungyu

2014-10-01

The Li2MnSiO4 is a promising candidate as a cathode for lithium ion batteries due to its large theoretical capacity of 330 mA h g(-1) and high thermal stability. However, the problems related to low electronic conductivity and large irreversible capacity at the first cycle limits its practical use as a Li-ion cathode material. We have developed a carbon coated Li2MnSiO4-graphene composite electrode to overcome these problems. Our designed electrode exhibits high reversible capacity of 301 mA h g(-1), with a high initial coulombic efficiency, and a discharge capacity at current rate of 0.5 C, that is double value of carbon coated Li2MnSiO4-carbon black composite electrode. These significant improvements are attributed to fast electron transport along the graphene sheet.

A closed loop process for recycling spent lithium ion batteries

Science.gov (United States)

Gratz, Eric; Sa, Qina; Apelian, Diran; Wang, Yan

2014-09-01

As lithium ion (Li-ion) batteries continue to increase their market share, recycling Li-ion batteries will become mandatory due to limited resources. We have previously demonstrated a new low temperature methodology to separate and synthesize cathode materials from mixed cathode materials. In this study we take used Li-ion batteries from a recycling source and recover active cathode materials, copper, steel, etc. To accomplish this the batteries are shredded and processed to separate the steel, copper and cathode materials; the cathode materials are then leached into solution; the concentrations of nickel, manganese and cobalt ions are adjusted so NixMnyCoz(OH)2 is precipitated. The precipitated product can then be reacted with lithium carbonate to form LiNixMnyCozO2. The results show that the developed recycling process is practical with high recovery efficiencies (∼90%), and 1 ton of Li-ion batteries has the potential to generate 5013 profit margin based on materials balance.

Design of high-performance cathode materials with single-phase pathway for sodium ion batteries: A study on P2-Nax(LiyMn1-y)O2 compounds

Science.gov (United States)

Yang, Lufeng; Li, Xiang; Ma, Xuetian; Xiong, Shan; Liu, Pan; Tang, Yuanzhi; Cheng, Shuang; Hu, Yan-Yan; Liu, Meilin; Chen, Hailong

2018-03-01

Sodium-ion batteries (SIBs) are an emerging electrochemical energy storage technology that has high promise for electrical grid level energy storage. High capacity, long cycle life, and low cost cathode materials are very much desired for the development of high performance SIB systems. Sodium manganese oxides with different compositions and crystal structures have attracted much attention because of their high capacity and low cost. Here we report our investigations into a group of promising lithium doped sodium manganese oxide cathode materials with exceptionally high initial capacity of ∼223 mAh g-1 and excellent capacity retentions, attributed primarily to the absence of phase transformation in a wide potential range of electrochemical cycling, as confirmed by in-operando X-ray diffraction (XRD), Rietveld refinement, and high-resolution 7Li solid-state NMR characterizations. The systematic study of structural evolution and the correlation with the electrochemical behavior of the doped cathode materials provides new insights into rational design of high-performance intercalation compounds by tailoring the composition and the crystal structure evolution in electrochemical cycling.

Modeling the Effects of the Cathode Composition of a Lithium Iron Phosphate Battery on the Discharge Behavior

Directory of Open Access Journals (Sweden)

Won Il Cho

2013-10-01

Full Text Available This paper reports a modeling methodology to predict the effects on the discharge behavior of the cathode composition of a lithium iron phosphate (LFP battery cell comprising a LFP cathode, a lithium metal anode, and an organic electrolyte. A one-dimensional model based on a finite element method is presented to calculate the cell voltage change of a LFP battery cell during galvanostatic discharge. To test the validity of the modeling approach, the modeling results for the variations of the cell voltage of the LFP battery as a function of time are compared with the experimental measurements during galvanostatic discharge at various discharge rates of 0.1C, 0.5C, 1.0C, and 2.0C for three different compositions of the LFP cathode. The discharge curves obtained from the model are in good agreement with the experimental measurements. On the basis of the validated modeling approach, the effects of the cathode composition on the discharge behavior of a LFP battery cell are estimated. The modeling results exhibit highly nonlinear dependencies of the discharge behavior of a LFP battery cell on the discharge C-rate and cathode composition.

Nickel foam-supported polyaniline cathode prepared with electrophoresis for improvement of rechargeable Zn battery performance

Science.gov (United States)

Xia, Yang; Zhu, Derong; Si, Shihui; Li, Degeng; Wu, Sen

2015-06-01

Porous nickel foam is used as a substrate for the development of rechargeable zinc//polyaniline battery, and the cathode electrophoresis of PANI microparticles in non-aqueous solution is applied to the fabrication of Ni foam supported PANI electrode, in which the corrosion of the nickel foam substrate is prohibited. The Ni foam supported PANI cathode with high loading is prepared by PANI electrophoretic deposition, and followed by PANI slurry casting under vacuum filtration. The electrochemical charge storage performance for PANI material is significantly improved by using nickel foam substrate via the electrophoretic interlayer. The specific capacity of the nickel foam-PANI electrode with the electrophoretic layer is higher than the composite electrode without the electrophoretic layer, and the specific capacity of PANI supported by Ni foam reaches up to 183.28 mAh g-1 at the working current of 2.5 mA cm-2. The present electrophoresis deposition method plays the facile procedure for the immobilization of PANI microparticles onto the surface of non-platinum metals, and it becomes feasible to the use of the Ni foam supported PANI composite cathode for the Zn/PANI battery in weak acidic electrolyte.

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.

Application of Spent Li-Ion Batteries Cathode in Methylene Blue Dye Discoloration

Directory of Open Access Journals (Sweden)

Eric M. Garcia

2017-01-01

Full Text Available This paper aims to present the mechanism study of methylene blue (MB discoloration using spent Li-ion battery cathode tape and hydrogen peroxide. The recycled cathode used in this work is composed of 72% of LiCoO2, 18% of carbon, and 10% of Al. The value found for surface area is 8.9 m2/g and the ZCP value occurs in pH = 2.95. Different from what is proposed in the literature, the most likely mechanism of methylene blue discoloration is the oxidation/delitiation of LiCoO2 and the reduction of H2O2 forming OH∙. Thus, in this paper, an important and promising alternative for discoloration of textile industry dyes using spent Li-ion battery cathode is presented.

Phosphorus Enrichment as a New Composition in the Solid Electrolyte Interphase of High-Voltage Cathodes and Its Effects on Battery Cycling

Energy Technology Data Exchange (ETDEWEB)

Yan, Pengfei; Zheng, Jianming; Kuppan, Saravanan; Li, Qiuyan; Lv, Dongping; Xiao, Jie; Chen, Guoying; Zhang, Jiguang; Wang, Chong M.

2015-11-10

Immersion of a solid into liquid often leads to the modification of both the structure and chemistry of surface of the solid, which subsequently affects the chemical and physical properties of the system. For the case of the rechargeable lithium ion battery, such a surface modification is termed as solid electrolyte interphase (SEI) layer, which has been perceived to play critical role for the stable operation of the batteries. However, the structure and chemical composition of SEI layer and its spatial distribution and dependence on the battery operating condition remain unclear. By using aberration corrected scanning transmission electron microscopy coupled with ultra-high sensitive energy dispersive x-ray spectroscopy, we probed the structure and chemistry of SEI layer on several high voltage cathodes. We show that layer-structured cathodes, when cycled at a high cut off voltage, can form a P-rich SEI layer on their surface, which is a direct evidence of Li-salt (LiPF6) decomposition. Our systematical investigations indicate such cathode/Li-salt side reaction shows strong dependence on structure of the cathode materials, operating voltage and temperature, indicating the feasibility of SEI engineering. These findings provide us valuable insights into the complex interface between the high-voltage cathode and the electrolyte.

Electrochemical performances of LiNi1−xMnxPO4 (x = 0.05–0.2) olivine cathode materials for high voltage rechargeable lithium ion batteries

DEFF Research Database (Denmark)

Karthikprabhu, S.; Karuppasamy, K.; Vikraman, Dhanasekaran

2018-01-01

This study demonstrated to synthesis of carbon-free lithium nickel phosphate (LiNiPO4) and its analogue of manganese doped LiNi1−xMnxPO4 (x = 0.05–0.2) cathode materials by a facile polyol method and their suitability for use in high voltage lithium ion batteries (LIBs). The physicochemical...

Hollow Carbon Nanofiber-Encapsulated Sulfur Cathodes for High Specific Capacity Rechargeable Lithium Batteries

KAUST Repository

Zheng, Guangyuan

2011-10-12

Sulfur has a high specific capacity of 1673 mAh/g as lithium battery cathodes, but its rapid capacity fading due to polysulfides dissolution presents a significant challenge for practical applications. Here we report a hollow carbon nanofiber-encapsulated sulfur cathode for effective trapping of polysulfides and demonstrate experimentally high specific capacity and excellent electrochemical cycling of the cells. The hollow carbon nanofiber arrays were fabricated using anodic aluminum oxide (AAO) templates, through thermal carbonization of polystyrene. The AAO template also facilitates sulfur infusion into the hollow fibers and prevents sulfur from coating onto the exterior carbon wall. The high aspect ratio of the carbon nanofibers provides an ideal structure for trapping polysulfides, and the thin carbon wall allows rapid transport of lithium ions. The small dimension of these nanofibers provides a large surface area per unit mass for Li2S deposition during cycling and reduces pulverization of electrode materials due to volumetric expansion. A high specific capacity of about 730 mAh/g was observed at C/5 rate after 150 cycles of charge/discharge. The introduction of LiNO3 additive to the electrolyte was shown to improve the Coulombic efficiency to over 99% at C/5. The results show that the hollow carbon nanofiber-encapsulated sulfur structure could be a promising cathode design for rechargeable Li/S batteries with high specific energy. © 2011 American Chemical Society.

Synthesis of a Flexible Freestanding Sulfur/Polyacrylonitrile/Graphene Oxide as the Cathode for Lithium/Sulfur Batteries

Directory of Open Access Journals (Sweden)

Huifen Peng

2018-04-01

Full Text Available Rechargeable lithium/sulfur (Li/S batteries have received quite significant attention over the years because of their high theoretical specific capacity (1672 mAh·g−1 and energy density (2600 mAh·g−1 which has led to more efforts for improvement in their electrochemical performance. Herein, the synthesis of a flexible freestanding sulfur/polyacrylonitrile/graphene oxide (S/PAN/GO as the cathode for Li/S batteries by simple method via vacuum filtration is reported. The S/PAN/GO hybrid binder-free electrode is considered as one of the most promising cathodes for Li/S batteries. Graphene oxide (GO slice structure provides effective ion conductivity channels and increases structural stability of the ternary system, resulting in excellent electrochemical properties of the freestanding S/PAN/GO cathode. Additionally, graphene oxide (GO membrane was able to minimize the polysulfides’ dissolution and their shuttle, which was attributed to the electrostatic interactions between the negatively-charged species and the oxygen functional groups on GO. Furthermore, these oxygen-containing functional groups including carboxyl, epoxide and hydroxyl groups provide active sites for coordination with inorganic materials (such as sulfur. It exhibits the initial reversible specific capacity of 1379 mAh·g−1 at a constant current rate of 0.2 C and maintains 1205 mAh·g−1 over 100 cycles (~87% retention. In addition, the freestanding S/PAN/GO cathode displays excellent coulombic efficiency (~100% and rate capability, delivering up to 685 mAh·g−1 capacity at 2 C.

Development of thin film cathodes for lithium-ion batteries in the material system Li–Mn–O by r.f. magnetron sputtering

Energy Technology Data Exchange (ETDEWEB)

Fischer, J., E-mail: julian.fischer@kit.edu [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials, Applied Materials Physics (IAM-AWP), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Adelhelm, C.; Bergfeldt, T. [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials, Applied Materials Physics (IAM-AWP), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Chang, K. [RWTH Aachen University, Materials Chemistry, Kopernikusstrasse 10, 46 52074 Aachen (Germany); Ziebert, C.; Leiste, H.; Stüber, M.; Ulrich, S. [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials, Applied Materials Physics (IAM-AWP), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Music, D.; Hallstedt, B. [RWTH Aachen University, Materials Chemistry, Kopernikusstrasse 10, 46 52074 Aachen (Germany); Seifert, H.J. [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials, Applied Materials Physics (IAM-AWP), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)

2013-01-01

Today most commercially available lithium ion batteries are still based on the toxic and expensive LiCoO{sub 2} as a standard cathode material. However, lithium manganese based cathode materials are cheaper and environmentally friendlier. In this work cubic-LiMn{sub 2}O{sub 4} spinel, monoclinic-Li{sub 2}MnO{sub 3} and orthorhombic-LiMnO{sub 2} thin films have been synthesized by non-reactive r.f. magnetron sputtering from two ceramic targets (LiMn{sub 2}O{sub 4}, LiMnO{sub 2}) in a pure argon discharge. The deposition parameters, namely target power and working gas pressure, were optimized in a combination with a post deposition heat treatment with respect to microstructure and electrochemical behavior. The chemical composition was determined using inductively coupled plasma optical emission spectroscopy and carrier gas hot extraction. The films' crystal structure, phase evolution and morphology were investigated by X-ray diffraction, micro Raman spectroscopy and scanning electron microscopy. Due to the fact that these thin films consist of the pure active material without any impurities, such as binders or conductive additives like carbon black, they are particularly well suited for measurements of the intrinsic physical properties, which is essential for fundamental understanding. The electrochemical behavior of the cubic and the orthorhombic films was investigated by galvanostatic cycling in half cells against metallic lithium. The cubic spinel films exhibit a maximum specific capacity of ∼ 82 mAh/g, while a specific capacity of nearly 150 mAh/g can be reached for the orthorhombic counterparts. These films are promising candidates for future all solid state battery applications. - Highlights: ► Synthesis of 3 Li–Mn–O structures by one up-scalable thin film deposition method ► Formation of o-LiMnO{sub 2} by r.f. magnetron sputtering in combination with post-annealing ► Discharge capacity with o-LiMnO{sub 2} cathodes twice as high as for c

Na2MnSiO4 as an attractive high capacity cathode material for sodium-ion battery

Science.gov (United States)

Law, Markas; Ramar, Vishwanathan; Balaya, Palani

2017-08-01

Here we report a polyanion-based cathode material for sodium-ion batteries, Na2MnSiO4, registering impressive sodium storage performances with discharge capacity of 210 mAh g-1 at an average voltage of 3 V at 0.1 C, along with excellent long-term cycling stability (500 cycles at 1 C). Insertion/extraction of ∼1.5 mol of sodium ion per formula unit of the silicate-based compound is reported and the utilisation of Mn2+ ⇋ Mn4+ redox couple is also demonstrated by ex-situ XPS. Besides, this study involves a systematic investigation of influence of the electrolyte additive (with different content) on the sodium storage performance of Na2MnSiO4. The electrolyte additive forms an optimum protective passivation film on the electrode surface, successfully reducing manganese dissolution.

Methods and apparatuses for making cathodes for high-temperature, rechargeable batteries

Science.gov (United States)

Meinhardt, Kerry D; Sprenkle, Vincent L; Coffey, Gregory W

2014-05-20

The approaches for fabricating cathodes can be adapted to improve control over cathode composition and to better accommodate batteries of any shape and their assembly. For example, a first solid having an alkali metal halide, a second solid having a transition metal, and a third solid having an alkali metal aluminum halide are combined into a mixture. The mixture can be heated in a vacuum to a temperature that is greater than or equal to the melting point of the third solid. When the third solid is substantially molten liquid, the mixture is compressed into a desired cathode shape and then cooled to solidify the mixture in the desired cathode shape.

Synthesis and electrochemical characterization of mesoporous Li2FeSiO4/C composite cathode material for Li-ion batteries

Science.gov (United States)

Kumar, Ajay; Jayakumar, O. D.; Bazzi, Khadije; Nazri, Gholam-Abbas; Naik, Vaman M.; Naik, Ratna

2015-03-01

Lithium iron silicate (Li2FeSiO4) has the potential as cathode for Li ion batteries due to its high theoretical capacity (~ 330 mAh/g) and improved safety. The application of Li2FeSiO4 as cathode material has been challenged by its poor electronic conductivity and slow lithium ion diffusion in the solid phase. In order to solve these problems, we have synthesized mesoporous Li2FeSiO4/C composites by sol-gel method using the tri-block copolymer (P123) as carbon source. The phase purity and morphology of the composite materials were characterized by x-ray diffraction, SEM and TEM. The XRD pattern confirmed the formation of ~ 12 nm size Li2FeSiO4 crystallites in composites annealed at 600 °C for 6 h under argon atmosphere. The electrochemical properties are measured using the composite material as positive electrode in a standard coin cell configuration with lithium as the active anode and the cells were tested using AC impedance spectroscopy, cyclic voltammetry, and galvanostatic charge/discharge cycling. The Li2FeSiO4/C composites showed a discharge capacity of ~ 240 mAh/g at a rate of C/30 at room temperature. The effect of different annealing temperature and synthesis time on the electrochemical performance of Li2FeSiO4/C will be presented.

Synthesis and characterization of high-density LiFePO{sub 4}/C composites as cathode materials for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Chang Zhaorong [College of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007 (China)], E-mail: czr_56@163.com; Lv Haojie; Tang Hongwei; Li Huaji [College of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007 (China); Yuan Xiaozi; Wang Haijiang [Institute for Fuel Cell Innovation, National Research Council of Canada, Vancouver, BC, V6T 1W5 (Canada)

2009-08-01

To achieve a high-energy-density lithium electrode, high-density LiFePO{sub 4}/C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO{sub 4} as a precursor, glucose as a C source, and Li{sub 2}CO{sub 3} as a Li source, in a pipe furnace under an atmosphere of 5% H{sub 2}-95% N{sub 2}. The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO{sub 4}/carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO{sub 4}/carbon composite powder with a carbon content of 7% reached 1.80 g m{sup -3}. The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g{sup -1}, respectively, with a volume capacity of 300.6 mAh cm{sup -3}, at a 0.1C rate. At a rate of 5C, the LiFePO{sub 4}/carbon composite shows a high discharge capacity of 98.3 mAh g{sup -1} and a volume capacity of 176.94 mAh cm{sup -3}.

Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries

Science.gov (United States)

Hameed, A. Shahul; Reddy, M. V.; Nagarathinam, M.; Runčevski, Tomče; Dinnebier, Robert E.; Adams, Stefan; Chowdari, B. V. R.; Vittal, Jagadese J.

2015-11-01

Li-ion batteries (LIBs) are considered as the best available technology to push forward the production of eco-friendly electric vehicles (EVs) and for the efficient utilization of renewable energy sources. Transformation from conventional vehicles to EVs are hindered by the high upfront price of the EVs and are mainly due to the high cost of LIBs. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, an rGO/MOPOF (reduced graphene oxide/Metal-Organic Phosphate Open Framework) nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H2. Firstly, an hydrated nanocomposite, rGO/K2[(VO)2(HPO4)2(C2O4)]·4.5H2O has been prepared by simple magnetic stirring at room temperature which releases water to form the anhydrous cathode material while drying at 90 °C during routine electrode fabrication procedure. The pristine MOPOF material undergoes highly reversible lithium storage, however with capacity fading. Enhanced lithium cycling has been witnessed with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks to increased electronic conductivity and enhanced Li diffusivity.

Influence of thermal-decomposition temperatures on structures and properties of V2O5 as cathode materials for lithium ion battery

Directory of Open Access Journals (Sweden)

Yu Chen

2015-02-01

Full Text Available Submicron spherical V2O5 particles with a uniform size and a lower crystallinity were successfully synthesized by a chemical precipitation-thermal decomposition technique using the commercial V2O5 powders as starting material. The crystal structure and grain morphology of samples were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM, respectively. Electrochemical testing such as discharge–charge cycling (CD and cyclic voltammetry (CV were employed in evaluating their electrochemical properties as cathode materials for lithium ion battery. Results reveal that the crystallinity and crystalline size of V2O5 particles increased when the thermal-decomposition temperature increased from 400 °C to 500 °C, and their adhesiveness was also synchronously increased. This indicate that the thermal-decomposition temperature palyed a significant influence on electrochemical properties of V2O5 cathodes. The V2O5 sample obtained at 400 °C delivered not only a high initial discharge capacity of 330 mA h g−1 and also the good cycle stability during 50 cycles due to its higher values of α in crystal structure and better dispersity in grain morphology.

Habit plane-driven P2-type manganese-based layered oxide as long cycling cathode for Na-ion batteries

Science.gov (United States)

Luo, Rui; Wu, Feng; Xie, Man; Ying, Yao; Zhou, Jiahui; Huang, Yongxin; Ye, Yusheng; Li, Li; Chen, RenJie

2018-04-01

Layered transition metal oxides are considered to be promising candidates as cathode materials for sodium-ion batteries. Herein, a facile solid-state reaction is developed to synthesize hexagons plate-like Na0.67Ni0.25Mn0.75O2+δ (denoted as P2-NNM) material with habit plane formed. The structure of this layered oxide is characterized by XRD, HR-TEM and SAED. The layered material delivers a high reversible capacity of 91.8 mAh g-1 at 0.2 C with a capacity retention of 94.4 % after 280 cycles, superior rate capability and long cycle life (84.2 % capacity retention after 1000 cycle). Ni2+ is an active ion and Ni doping alleviates the Jahn-Teller distortion, and Mn3+/Mn4+ coexist as Mn4+ is desired from the stability perspective. Particularly, CV and XPS results confirm these results. Moreover, the electrode exhibits a quasi-solid-solution reaction during the sodium extraction and insertion. This contribution demonstrates that P2-NNM is a promising cathode electrode for rechargeable long-life sodium-ion batteries.

High capacity anode materials for lithium ion batteries

Science.gov (United States)

Lopez, Herman A.; Anguchamy, Yogesh Kumar; Deng, Haixia; Han, Yongbon; Masarapu, Charan; Venkatachalam, Subramanian; Kumar, Suject

2015-11-19

High capacity silicon based anode active materials are described for lithium ion batteries. These materials are shown to be effective in combination with high capacity lithium rich cathode active materials. Supplemental lithium is shown to improve the cycling performance and reduce irreversible capacity loss for at least certain silicon based active materials. In particular silicon based active materials can be formed in composites with electrically conductive coatings, such as pyrolytic carbon coatings or metal coatings, and composites can also be formed with other electrically conductive carbon components, such as carbon nanofibers and carbon nanoparticles. Additional alloys with silicon are explored.

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.

VOCl as a Cathode for Rechargeable Chloride Ion Batteries.

Science.gov (United States)

Gao, Ping; Reddy, M Anji; Mu, Xiaoke; Diemant, Thomas; Zhang, Le; Zhao-Karger, Zhirong; Chakravadhanula, Venkata Sai Kiran; Clemens, Oliver; Behm, R Jürgen; Fichtner, Maximilian

2016-03-18

A novel room temperature rechargeable battery with VOCl cathode, lithium anode, and chloride ion transporting liquid electrolyte is described. The cell is based on the reversible transfer of chloride ions between the two electrodes. The VOCl cathode delivered an initial discharge capacity of 189 mAh g(-1) . A reversible capacity of 113 mAh g(-1) was retained even after 100 cycles when cycled at a high current density of 522 mA g(-1) . Such high cycling stability was achieved in chloride ion batteries for the first time, demonstrating the practicality of the system beyond a proof of concept model. The electrochemical reaction mechanism of the VOCl electrode in the chloride ion cell was investigated in detail by ex situ X-ray diffraction (XRD), infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The results confirm reversible deintercalation-intercalation of chloride ions in the VOCl electrode. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three-dimensional interconnected cobalt oxide-carbon hollow spheres arrays as cathode materials for hybrid batteries

Directory of Open Access Journals (Sweden)

Jiye Zhan

2016-06-01

Full Text Available Hierarchical porous metal oxides arrays is critical for development of advanced energy storage devices. Herein, we report a facile template-assisted electro-deposition plus glucose decomposition method for synthesis of multilayer CoO/C hollow spheres arrays. The CoO/C arrays consist of multilayer interconnected hollow composite spheres with diameters of ∼350 nm as well as thin walls of ∼20 nm. Hierarchical hollow spheres architecture with 3D porous networks are achieved. As cathode of high-rate hybrid batteries, the multilayer CoO/C hollow sphere arrays exhibit impressive enhanced performances with a high capacity (73.5 mAh g−1 at 2 A g−1, and stable high-rate cycling life (70 mAh g−1 after 12,500 cycles at 2 A g−1. The improved electrochemical performance is owing to the composite hollow-sphere architecture with high contact area between the active materials and electrolyte as well as fast ion/electron transportation path.

Properties of cathode materials in alkaline cells

International Nuclear Information System (INIS)

Salkind, A.J.; McBreen, J.; Freeman, R.; Parkhurst, W.A.

1985-01-01

Conventional and new cathode materials in primary and secondary alkaline cells were investigated for stability, structure, electrochemical reversibility and efficiency. Included were various forms of AgO for reserve-type silver-zinc batteries, a new material - AgNiO/sub 2/ - and several nickel electrodes for nickel-cadmium and nickel-hydrogen cells for aerospace applications. A comparative study was made of the stability of electroformed and chemically prepared AgO. Stability was correlated with impurities detected by XPS and SAM. After the first discharge AgNiO/sub 2/ can be recharged to the monovalent level. The discharge product is predominantly silver. Plastic-bonded nickel electrodes display a second plateau on discharge. Additions of Co(OH)/sub 2/ largely eliminate this

A design strategy of large grain lithium-rich layered oxides for lithium-ion batteries cathode

International Nuclear Information System (INIS)

Jiang, Xiong; Wang, Zhenhua; Rooney, David; Zhang, Xiaoxue; Feng, Jie; Qiao, Jinshuo; Sun, Wang; Sun, Kening

2015-01-01

Highlights: • Ultrasound-assisted mixing lithium was used to synthesize Lithium-rich layered oxides. • Lithium-rich layered oxides composed of large grain had high capacity and high cycling stability. • This unique large grain overcomes stress-induced structural collapse caused by Li-ion insertion/extraction and reduces dissolution of Mn ions. • A new strategy of large grain could be employed to synthesize the other complex architectures for various applications. - Abstract: Li-rich materials are considered the most promising for Li-ion battery cathodes, as high capacity can be achieved. However, poor cycling stability is a critical drawback that leads to poor capacity retention. Here a strategy is used to synthesize a large-grain lithium-rich layered oxides to overcome this difficulty without sacrificing rate capability. This material is designed with micron scale grain with a width of about 300 nm and length of 1–3 μm. This unique structure has a better ability to overcome stress-induced structural collapse caused by Li-ion insertion/extraction and reduce the dissolution of Mn ions, which enable a reversible and stable capacity. As a result, this cathode material delivered a highest discharge capacity of around 308 mAh g −1 at a current density of 30 mA g −1 with retention of 88.3% (according to the highest discharge capacity) after 100 cycles, 190 mAh g −1 at a current density of 300 mA g −1 and almost no capacity fading after 100 cycles. Therefore, Lithium-rich material of large-grain structure is a promising cathode candidate in Lithium-ion batteries with high capacity and high cycle stability for application. This strategy of large grain may furthermore open the door to synthesize the other complex architectures for various applications

New secondary batteries utilizing electronically conductive polymer cathodes

Science.gov (United States)

Martin, Charles R.; White, Ralph E.

1989-01-01

The objectives of this project are to characterize the transport properties in electronically conductive polymers and to assess the utility of these films as cathodes in lithium/polymer secondary batteries. During this research period, progress has been made in a literature survey of the historical background, methods of preparation, the physical and chemical properties, and potential technological applications of polythiophene. Progress has also been made in the characterization of polypyrrole flat films and fibrillar films. Cyclic voltammetry and potential step chronocoulometry were used to gain information on peak currents and potentials switching reaction rates, charge capacity, and charge retention. Battery charge/discharge studies were also performed.

Synthesis and electrochemical properties of Ni doped spinel LiNi (subx)Mn (sub2-x)O(sub)4 (0 ≤ x ≤ 0.5) cathode materials for Li-Ion battery

CSIR Research Space (South Africa)

Kebede, MA

2012-10-01

Full Text Available Spherical pristine LiMn(sub2)O(sub 4) and Ni doped LiNixMn(sub2-x)O(sub)4 (x=0.1, 0.2, 0.3, 0.4, 0.5) cathode materials for lithium ion battery with high first cycle discharge capacity and excellent cycle performance were synthesized using...

Statistical analysis on hollow and core-shell structured vanadium oxide microspheres as cathode materials for Lithium ion batteries

Directory of Open Access Journals (Sweden)

Xing Liang

2018-06-01

Full Text Available In this data, the statistical analyses of vanadium oxide microspheres cathode materials are presented for the research article entitled “Statistical analyses on hollow and core-shell structured vanadium oxides microspheres as cathode materials for Lithium ion batteries” (Liang et al., 2017 [1]. This article shows the statistical analyses on N2 adsorption-desorption isotherm and morphology vanadium oxide microspheres as cathode materials for LIBs. Keywords: Adsorption-desorption isotherm, Pore size distribution, SEM images, TEM images

Solution-combustion synthesized nickel-substituted spinel cathode materials (LiNixMn2-xO4; 0≤x≤0.2) for lithium ion battery: enhancing energy storage, capacity retention, and lithium ion transport

CSIR Research Space (South Africa)

Kebede, MA

2014-01-01

Full Text Available Spherically shaped Ni-substituted LiNi(subx)Mn(sub2-x)O(sub4) (x=0, 0.1, 0.2) spinel cathode materials for lithium ion battery with high first cycle discharge capacity and remarkable cycling performance were synthesized using the solution...

Alkaline and non-aqueous proton-conducting pouch-cell batteries

Science.gov (United States)

Young, Kwo-hsiung; Nei, Jean; Meng, Tiejun

2018-01-02

Provided are sealed pouch-cell batteries that are alkaline batteries or non-aqueous proton-conducing batteries. A pouch cell includes a flexible housing such as is used for pouch cell construction where the housing is in the form of a pouch, a cathode comprising a cathode active material suitable for use in an alkaline battery, an anode comprising an anode active material suitable for use in an alkaline battery, an electrolyte that is optionally an alkaline or proton-conducting electrolyte, and wherein the pouch does not include or require a safety vent or other gas absorbing or releasing system as the anode active material and the cathode active material do not increase the internal atmospheric pressure any more than 2 psig during cycling. The batteries provided function contrary to the art recognized belief that such battery systems were impossible due to unacceptable gas production during cycling.

Multiple imaging mode X-ray computed tomography for distinguishing active and inactive phases in lithium-ion battery cathodes

Science.gov (United States)

Komini Babu, Siddharth; Mohamed, Alexander I.; Whitacre, Jay F.; Litster, Shawn

2015-06-01

This paper presents the use of nanometer scale resolution X-ray computed tomography (nano-CT) in the three-dimensional (3D) imaging of a Li-ion battery cathode, including the separate volumes of active material, binder plus conductive additive, and pore. The different high and low atomic number (Z) materials are distinguished by sequentially imaging the lithium cobalt oxide electrode in absorption and then Zernike phase contrast modes. Morphological parameters of the active material and the additives are extracted from the 3D reconstructions, including the distribution of contact areas between the additives and the active material. This method could provide a better understanding of the electric current distribution and structural integrity of battery electrodes, as well as provide detailed geometries for computational models.

Effect of microstructure on low temperature electrochemical properties of LiFePO{sub 4}/C cathode material

Energy Technology Data Exchange (ETDEWEB)

Zhao, Nannan; Zhi, Xiaoke; Wang, Li; Liu, Yanhui; Liang, Guangchuan, E-mail: liangguangchuan@hebut.edu.cn

2015-10-05

Graphical abstract: The low temperature performance of Li-ion batteries and LiFePO{sub 4}/C composites was discussed. A conclusion that cathode material is the main limitation for the low temperature performance was come up, by comparing the low temperature performance of 18650 Li-ion batteries with LiMn{sub 2}O{sub 4}, LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} and LiFePO{sub 4}/C as cathode materials. The low temperature performance results indicate the LiFePO{sub 4}/C microstructure is the main factor influencing the low temperature performance of LiFePO{sub 4}. A new LiFePO{sub 4}/C with pomegranate-like spherical structure was proposed in this paper, which shows superior low temperature performance, which can be attributed to its uniform fine primary particles and smaller primary particles. - Highlights: • Low temperature performance of Li-ion battery and LiFePO{sub 4}/C composite was discussed. • Cathode material mainly decided the low temperature performance of Li-ion battery. • LiFePO{sub 4}/C microstructure mainly affects its low temperature performance. • Pomegranate-like spherical structure LiFePO{sub 4}/C has good low temperature performance. - Abstract: The low-temperature electrochemical performance of Li-ion batteries is mainly determined by the choice of cathode material, as evident from a comparison of the low-temperature electrochemical performance of the 18650 batteries with the LiMn{sub 2}O{sub 4}, LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2}, and LiFePO{sub 4}/C as the cathode, respectively, at −20 °C. LiFePO{sub 4}/C materials with different morphologies and microstructures were prepared by different methods. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), galvanostatic charge–discharge measurements and EIS. The low-temperature performance of the samples and those of the coin cells utilizing the materials as cathodes were measured. The results

Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries

Science.gov (United States)

Hameed, A. Shahul; Reddy, M. V.; Nagarathinam, M.; Runčevski, Tomče; Dinnebier, Robert E; Adams, Stefan; Chowdari, B. V. R.; Vittal, Jagadese J.

2015-01-01

Li-ion batteries (LIBs) are considered as the best available technology to push forward the production of eco-friendly electric vehicles (EVs) and for the efficient utilization of renewable energy sources. Transformation from conventional vehicles to EVs are hindered by the high upfront price of the EVs and are mainly due to the high cost of LIBs. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, an rGO/MOPOF (reduced graphene oxide/Metal-Organic Phosphate Open Framework) nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H2. Firstly, an hydrated nanocomposite, rGO/K2[(VO)2(HPO4)2(C2O4)]·4.5H2O has been prepared by simple magnetic stirring at room temperature which releases water to form the anhydrous cathode material while drying at 90 °C during routine electrode fabrication procedure. The pristine MOPOF material undergoes highly reversible lithium storage, however with capacity fading. Enhanced lithium cycling has been witnessed with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks to increased electronic conductivity and enhanced Li diffusivity. PMID:26593096

Synthesis, characterization and electrochemical properties of 4.8 V LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} cathode material in lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Chi, Le Ha [Faculty of Engineering Physics and NanoTechnology, College of Technology, 144 Xuan Thuy Road, Hanoi (Viet Nam)] [Vietnamese Academy of Science and Technology, 18 Hoang Quoc Viet Street, Cau Giay District, Hanoi (Viet Nam); Dinh, Nguyen Nang [Faculty of Engineering Physics and NanoTechnology, College of Technology, 144 Xuan Thuy Road, Hanoi (Viet Nam); Brutti, Sergio, E-mail: sergio.brutti@uniroma1.i [Department of Chemistry, University of Rome ' La Sapienza' , P.le Aldo Moro 5, 00185 Rome (Italy); Scrosati, Bruno [Department of Chemistry, University of Rome ' La Sapienza' , P.le Aldo Moro 5, 00185 Rome (Italy)

2010-07-15

In this work the synthesis of a nickel doped cubic manganese spinel has been studied for application as cathode material in secondary lithium batteries. Six different experimental approaches have been tested in order to carry out a screening of the various possible synthetic routes. The used synthetic strategies were wet chemistry (WC), solid state (SS), combustion synthesis (CS), cellulose-based sol-gel synthesis (SG-C), ascorbic acid-based sol-gel synthesis (SG-AA) and resorcinol/formaldehyde-based sol-gel synthesis (SG-RF). The goal of our study is to obtain insights about how the synthesis conditions can be modified in order to achieve a material with improved electrochemical performances in such devices, especially in high current operating regimes. The synthesized materials have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), atomic absorption, inductively coupled plasma (ICP-MS) atomic emission spectroscopy, surface area measurements and tested as high voltage cathodes in Li-ion electrochemical devices.

Performance and cost of materials for lithium-based rechargeable automotive batteries

Science.gov (United States)

Schmuch, Richard; Wagner, Ralf; Hörpel, Gerhard; Placke, Tobias; Winter, Martin

2018-04-01

It is widely accepted that for electric vehicles to be accepted by consumers and to achieve wide market penetration, ranges of at least 500 km at an affordable cost are required. Therefore, significant improvements to lithium-ion batteries (LIBs) in terms of energy density and cost along the battery value chain are required, while other key performance indicators, such as lifetime, safety, fast-charging ability and low-temperature performance, need to be enhanced or at least sustained. Here, we review advances and challenges in LIB materials for automotive applications, in particular with respect to cost and performance parameters. The production processes of anode and cathode materials are discussed, focusing on material abundance and cost. Advantages and challenges of different types of electrolyte for automotive batteries are examined. Finally, energy densities and costs of promising battery chemistries are critically evaluated along with an assessment of the potential to fulfil the ambitious targets of electric vehicle propulsion.

Mechanisms of Degradation and Strategies for the Stabilization of Cathode-Electrolyte Interfaces in Li-Ion Batteries.

Science.gov (United States)

Cabana, Jordi; Kwon, Bob Jin; Hu, Linhua

2018-02-20

Undesired reactions at the interface between a transition metal oxide cathode and a nonaqueous electrolyte bring about challenges to the performance of Li-ion batteries in the form of compromised durability. These challenges are especially severe in extreme conditions, such as above room temperature or at high potentials. The ongoing push to increase the energy density of Li-ion batteries to break through the existing barriers of application in electric vehicles creates a compelling need to address these inefficiencies. This goal requires a combination of deep knowledge of the mechanisms underpinning reactivity, and the ability to assemble multifunctional electrode systems where different components synergistically extend cycle life by imparting interfacial stability, while maintaining, or even increasing, capacity and potential of operation. The barriers toward energy storage at high density apply equally in Li-ion, the leading technology in the battery market, and in related, emerging concepts for high energy density, such as Na-ion and Mg-ion, because they also conceptually rely on electroactive transition metal oxides. Therefore, their relevance is broad and the quest for solutions inevitable. In this Account, we describe mechanisms of reaction that can degrade the interface between a Li-ion battery electrolyte and the cathode, based on an oxide with transition metals that can reach high formal oxidation states. The focus is placed on cathodes that deliver high capacity and operate at high potential because their development would enable Li-ion battery technologies with high capacity for energy storage. Electrode-electrolyte instabilities will be identified beyond the intrinsic potential windows of stability, by linking them to the electroactive transition metals present at the surface of the electrode. These instabilities result in irreversible transformations at these interfaces, with formation of insulating layers that impede transport or material loss due

Advanced materials for sodium-beta alumina batteries: Status, challenges and perspectives

Science.gov (United States)

Lu, Xiaochuan; Xia, Guanguang; Lemmon, John P.; Yang, Zhenguo

The increasing penetration of renewable energy and the trend toward clean, efficient transportation have spurred growing interests in sodium-beta alumina batteries that store electrical energy via sodium ion transport across a β″-Al 2O 3 solid electrolyte at elevated temperatures (typically 300-350 °C). Currently, the negative electrode or anode is metallic sodium in molten state during battery operation; the positive electrode or cathode can be molten sulfur (Na-S battery) or solid transition metal halides plus a liquid phase secondary electrolyte (e.g., ZEBRA battery). Since the groundbreaking works in the sodium-beta alumina batteries a few decades ago, encouraging progress has been achieved in improving battery performance, along with cost reduction. However, there remain issues that hinder broad applications and market penetration of the technologies. To better the Na-beta alumina technologies require further advancement in materials along with component and system design and engineering. This paper offers a comprehensive review on materials of electrodes and electrolytes for the Na-beta alumina batteries and discusses the challenges ahead for further technology improvement.

Advanced materials for sodium-beta alumina batteries: Status, challenges and perspectives

International Nuclear Information System (INIS)

Lu, Xiaochuan; Xia, Guanguang; Lemmon, John P.; Yang, Zhenguo

2010-01-01

The increasing penetration of renewable energy and the trend toward clean, efficient transportation have spurred growing interests in sodium-beta alumina batteries that store electrical energy via sodium ion transport across a β''-Al 2 O 3 solid electrolyte at elevated temperatures (typically 300-350 C). Currently, the negative electrode or anode is metallic sodium in molten state during battery operation; the positive electrode or cathode can be molten sulfur (Na-S battery) or solid transition metal halides plus a liquid phase secondary electrolyte (e.g., ZEBRA battery). Since the groundbreaking works in the sodium-beta alumina batteries a few decades ago, encouraging progress has been achieved in improving battery performance, along with cost reduction. However, there remain issues that hinder broad applications and market penetration of the technologies. To better the Na-beta alumina technologies require further advancement in materials along with component and system design and engineering. This paper offers a comprehensive review on materials of electrodes and electrolytes for the Na-beta alumina batteries and discusses the challenges ahead for further technology improvement. (author)

Synthesis of LiNi0.65Co0.25Mn0.1O2 as cathode material for lithium-ion batteries by rheological phase method

International Nuclear Information System (INIS)

Cheng Cuixia; Tan Long; Hu Anzheng; Liu Haowen; Huang Xintang

2010-01-01

Research highlights: → In this paper, for the first time, rheological phase method, a simple and effective route, was applied to synthesis high capacity cathode material LiNi 0.65 Co 0.25 Mn 0.1 O 2 . → All of the results obtained by X-ray diffraction spectrometer, X-ray photoelectron spectrometer, charge-discharge tests and electrochemical impedance spectroscopy show that the rheological phase production have better properties than that of the report. - Abstract: Rheological phase (RP) method has been successfully applied to synthesize a promising cathode material LiNi 0.65 Co 0.25 Mn 0.1 O 2 . X-ray diffraction, X-ray photoelectron spectroscopy, inductively coupled plasma and transmission electron microscope are used to investigate the structure, composition and morphology, respectively. XRD result shows that the as-prepared powder has a layered α-NaFeO 2 structure. XPS pattern reveals that the Ni ions have valences of 2+ and 3+, and the Co and Mn are 3+, 4+, respectively. The electrode consisting of the obtained powder presents the better electrochemical properties, which is attributed to the fewer amounts of Ni 2+ ions and the smaller particles. All the results suggest that the rheological phase method is a promising technique for the preparation of LiNi 0.65 Co 0.25 Mn 0.1 O 2 cathode material of lithium-ion batteries.

Enhanced performance of Li-O2 battery based on CFx/C composites as cathode materials

International Nuclear Information System (INIS)

Wu, Chaolumen; Wang, Haibin; Liao, Chenbo; Yang, Jun; Li, Lei

2015-01-01

A hybrid air-electrode composed of a mixture of fluorinated carbon (CF x ) and Ketjen black (KB) active carbon composite materials was prepared to improve performance of Li-O 2 battery. In the hybrid air-electrodes, four kinds of CF x materials including fluorinated graphite, fluorinated carbon fiber, fluorinated coke and fluorinated black carbon were utilized as lithium insertion materials. The physical properties and morphologies of the KB and CF x carbon materials were characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Scanning electron microscopy (SEM) measurements. Compared with the conventional KB air-electrode, all the CF x /KB hybrid air-electrodes in Li-O 2 batteries showed higher specific discharge capacity, especially at high current density. Among these CF x /KB hybrid air-electrodes, the fluorinated graphite based electrode showed the best electrochemical performance in Li-O 2 battery due to its highest discharge capacity of the fluorinated graphite material in the Li/CF x primary battery, highest specific surface area, and highest total pore volume. The electrochemical performance of Li-O 2 and Li-air batteries using the hybrid air-electrodes with the different fluorinated graphite: KB weight ratio, including specific charge and discharge capacity, cycling stability and rate capability were systematically investigated. At a current density of 0.5 mA cm −2 , the fluorinated graphite based air-electrode delivered a high specific discharge capacity of 1138 mAh g −1 in Li-O 2 batteries, which was more than four times than that of the conventional KB air-electrode (265 mAh g −1 ) under same testing conditions. The battery assembled with the fluorinated graphite based air-electrode exhibited better cycling stability than that of the battery assembled with the conventional KB air-electrode.

Comparative Issues of Cathode Materials for Li-Ion Batteries

Directory of Open Access Journals (Sweden)

Christian M. Julien

2014-03-01

Full Text Available After an introduction to lithium insertion compounds and the principles of Li-ion cells, we present a comparative study of the physical and electrochemical properties of positive electrodes used in lithium-ion batteries (LIBs. Electrode materials include three different classes of lattices according to the dimensionality of the Li+ ion motion in them: olivine, layered transition-metal oxides and spinel frameworks. Their advantages and disadvantages are compared with emphasis on synthesis difficulties, electrochemical stability, faradaic performance and security issues.

Lithium Diffusion and Magnetism in Battery Cathode Material LixNi1/3Co1/3Mn1/3O2

International Nuclear Information System (INIS)

Månsson, M; Prša, K; Nozaki, H; Sugiyama, J; Wikberg, J M; Sassa, Y; Dahbi, M; Kamazawa, K; Sedlak, K; Watanabe, I

2014-01-01

We have studied low-temperature magnetic properties as well as high-temperature lithium ion diffusion in the battery cathode materials Li x Ni 1/3 Co 1/3 Mn 1/3 O 2 by the use of muon spin rotation/relaxation. Our data reveal that the samples enter into a 2D spin-glass state below T SG ≈ 12 K. We further show that lithium diffusion channels become active for T ≥ T diff ∼ 125 K where the Li-ion hopping-rate [v(T)] starts to increase exponentially. Further, v(T) is found to fit very well to an Arrhenius type equation and the activation energy for the diffusion process is extracted as E a ≈ 100 meV

In-situ time-of-flight neutron diffraction study of the structure evolution of electrode materials in a commercial battery with LiNi0.8Co0.15Al0.05O2 cathode

Science.gov (United States)

Bobrikov, I. A.; Samoylova, N. Yu.; Sumnikov, S. V.; Ivanshina, O. Yu.; Vasin, R. N.; Beskrovnyi, A. I.; Balagurov, A. M.

2017-12-01

A commercial lithium-ion battery with LiNi0.8Co0.15Al0.05O2 (NCA) cathode has been studied in situ using high-intensity and high-resolution neutron diffraction. Structure and phase composition of the battery electrodes have been probed during charge-discharge in different cycling modes. The dependence of the anode composition on the charge rate has been determined quantitatively. Different kinetics of Li (de)intercalation in the graphite anode during charge/discharge process have been observed. Phase separation of the cathode material has not been detected in whole voltage range. Non-linear dependencies of the unit cell parameters, atomic and layer spacing on the lithium content in the cathode have been observed. Measured dependencies of interatomic spacing and interlayer spacing, and unit cell parameters of the cathode structure on the lithium content could be qualitatively explained by several factors, such as variations of oxidation state of cation in oxygen octahedra, Coulomb repulsion of oxygen layers, changes of average effective charge of oxygen layers and van der Waals interactions between MeO2-layers at high level of the NCA delithiation.

Synchrotron radiation-based 61Ni Mössbauer spectroscopic study of Li(Ni1/3Mn1/3Co1/3)O2 cathode materials of lithium ion rechargeable battery

Science.gov (United States)

Segi, Takashi; Masuda, Ryo; Kobayashi, Yasuhiro; Tsubota, Takayuki; Yoda, Yoshitaka; Seto, Makoto

2016-12-01

Layered rocksalt type oxides, such as Li(Ni1/3Mn1/3Co1/3)O2, are widely used as the cathode active materials of lithium-ion rechargeable batteries. Because the nickel ions are associated with the role of the charge compensation at discharge and charge, the 61Ni Mössbauer measurements at 6 K using synchrotron radiation were performed to reveal the role of Ni. The Ni ions of the active materials play two roles for the redox process between the charge and discharge states of lithium-ion batteries. Half of the total Ni ions change to the low-spin Ni3+ with Jahn-Teller distortion from the Ni2+ ions of the discharge state. The remainder exhibit low-spin state divalent Ni ions.

Outstanding Li-storage performance of LiFePO4@MWCNTs cathode material with 3D network structure for lithium-ion batteries

Science.gov (United States)

Sun, Xiaodong; Zhang, Le

2018-05-01

In this work, the MWCNTs-decorated LiFePO4 microspheres (LiFePO4@MWCNTs) with a 3D network structure have been synthesized by a facile and efficient spray-drying approach followed by solid-state reaction in a reduction atmosphere. In the as-prepared composite, the MWCNTs around LiFePO4 nanoparticles can provide 3D conductive networks which greatly facilitate the transport of Li+-ion and electron during the electrochemical reaction. Compared to the pure LiFePO4 material, the LiFePO4@MWCNTs composite as cathode for lithium-ion batteries exhibits significantly improved Li-storage performance in terms of rate capability and cyclic stability. Therefore, we can speculate that the spray-drying approach is a promising route to prepare the high-performance electrode materials with 3D network structure for electrochemical energy storage.

From Metal-Organic Framework to Li2S@C-Co-N Nanoporous Architecture: A High-Capacity Cathode for Lithium-Sulfur Batteries.

Science.gov (United States)

He, Jiarui; Chen, Yuanfu; Lv, Weiqiang; Wen, Kechun; Xu, Chen; Zhang, Wanli; Li, Yanrong; Qin, Wu; He, Weidong

2016-12-27

Owing to the high theoretical specific capacity (1166 mAh g -1 ), lithium sulfide (Li 2 S) has been considered as a promising cathode material for Li-S batteries. However, the polysulfide dissolution and low electronic conductivity of Li 2 S limit its further application in next-generation Li-S batteries. In this report, a nanoporous Li 2 S@C-Co-N cathode is synthesized by liquid infiltration-evaporation of ultrafine Li 2 S nanoparticles into graphitic carbon co-doped with cobalt and nitrogen (C-Co-N) derived from metal-organic frameworks. The obtained Li 2 S@C-Co-N architecture remarkably immobilizes Li 2 S within the cathode structure through physical and chemical molecular interactions. Owing to the synergistic interactions between C-Co-N and Li 2 S nanoparticles, the Li 2 S@C-Co-N composite delivers a reversible capacity of 1155.3 (99.1% of theoretical value) at the initial cycle and 929.6 mAh g -1 after 300 cycles, with nearly 100% Coulombic efficiency and a capacity fading of 0.06% per cycle. It exhibits excellent rate capacities of 950.6, 898.8, and 604.1 mAh g -1 at 1C, 2C, and 4C, respectively. Such a cathode structure is promising for practical applications in high-performance Li-S batteries.

Visualizing redox orbitals and their potentials in advanced lithium-ion battery materials using high-resolution x-ray Compton scattering.

Science.gov (United States)

Hafiz, Hasnain; Suzuki, Kosuke; Barbiellini, Bernardo; Orikasa, Yuki; Callewaert, Vincent; Kaprzyk, Staszek; Itou, Masayoshi; Yamamoto, Kentaro; Yamada, Ryota; Uchimoto, Yoshiharu; Sakurai, Yoshiharu; Sakurai, Hiroshi; Bansil, Arun

2017-08-01

Reduction-oxidation (redox) reactions are the key processes that underlie the batteries powering smartphones, laptops, and electric cars. A redox process involves transfer of electrons between two species. For example, in a lithium-ion battery, current is generated when conduction electrons from the lithium anode are transferred to the redox orbitals of the cathode material. The ability to visualize or image the redox orbitals and how these orbitals evolve under lithiation and delithiation processes is thus of great fundamental and practical interest for understanding the workings of battery materials. We show that inelastic scattering spectroscopy using high-energy x-ray photons (Compton scattering) can yield faithful momentum space images of the redox orbitals by considering lithium iron phosphate (LiFePO 4 or LFP) as an exemplar cathode battery material. Our analysis reveals a new link between voltage and the localization of transition metal 3d orbitals and provides insight into the puzzling mechanism of potential shift and how it is connected to the modification of the bond between the transition metal and oxygen atoms. Our study thus opens a novel spectroscopic pathway for improving the performance of battery materials.

Reaction mechanism and thermal stability study on cathode materials for rechargeable lithium ion batteries

Science.gov (United States)

Fang, Jin

Olivine-type lithium iron phosphate has been a very promising cathode material since it was proposed by Padhi in 1997, low-cost, environmental friendly and stable structure ensure the commercialization of LiFePO 4. In LiFePO4, during charge and discharge process, Li ions are transferred between two phases, Li-poor LialphaFePO 4 and Li-rich Li1-betaFePO4, which implies a significant energy barrier for the new phase nucleation and interface growth, contrary to the fast reaction kinetics experimentally observed. The understanding of the lithiation and delithiation mechanism of this material has spurred a lot of research interests. Many theory models have been proposed to explain the reaction mechanism of LiFePO4, among them, the single phase model claims that the reaction goes through a metastable single phase, and the over potential required to form this single phase is about 30mV, so we studied the driving force to transport lithium ions between Lialpha FePO4 and Li1-betaFePO4 phases and compared the particle sizes effect. Experiment results shows that, the nano-sized (30nm) LiFePO4 has wider solid solution range, lower solid solution formation temperature and faster kinetics than normal LiFePO4 (150nm). Also a 20mV over potential was observed in both samples, either after relaxing the FePO4/LiFePO4 system to equilibrium or transport lithium from one side to the other side, the experiment result is corresponding to theoretical calculation; indicates the reaction might go through single-phase reaction mechanism. The energy and power density of lithium ion battery largely depend on cathode materials. Mn substituted LiFePO4 has a higher voltage than LiFePO4, which results a higher theoretical energy density. Safety issue is one of the most important criterions for batteries, since cathode materials need to maintain stable structure during hundreds of charge and discharge cycles and ranges of application conditions. We have reported that iron-rich compound o-Fe1-yMnyPO4

Poly(2,5-dimercapto-1,3,4-thiadiazole) as a Cathode for Rechargeable Lithium Batteries with Dramatically Improved Performance

KAUST Repository

Gao, Jie

2012-05-29

Organosulfur compounds with multiple thiol groups are promising for high gravimetric energy density electrochemical energy storage. We have synthesized a poly(2,5-dimercapto-1,3,4-thiadiazole) (PDMcT)/poly(3,4-ethylenedioxythiophene) (PEDOT) composite cathode for lithium-ion batteries with a new method and investigated its electrochemical behavior by charge/discharge cycles and cyclic voltammetry (CV) in an ether-based electrolyte. Based on a comparison of the electrochemical performance with a carbonate-based electrolyte, we found a much higher discharge capacity, but also a very attractive cycling performance of PDMcT by using a tetra(ethylene glycol) dimethyl ether (TEGDME)-based electrolyte. The first discharge capacity of the as-synthesized PDMcT/PEDOT composite approached 210 mAh g -1 in the TEGDME-based electrolyte. CV results clearly show that the redox reactions of PDMcT are highly reversible in this TEGDME-based electrolyte. The reversible capacity remained around 120 mAh g -1 after 20 charge/discharge cycles. With improved cycling performance and very low cost, PDMcT could become a very promising cathode material when combined with a TEGDME-based electrolyte. The poor capacity in the carbonate-based electrolyte is a consequence of the irreversible reaction of the DMcT monomer and dimer with the solvent, emphasizing the importance of electrolyte chemistry when studying molecular-based battery materials. The nature of the electrolyte has a dramatic effect on the performance of poly(2,5-dimercapto-1,3,4-thiadiazole) (PDMcT) as a cathode material in lithium-ion batteries. Whereas the use of an ethylene/diethyl carbonate (EC/DEC)-based electrolyte resulted in very poor performance, the use of a tetra(ethylene glycol) dimethyl ether (TEGDME)-based electrolyte dramatically improved the performance in terms of both the discharge capacity and capacity retention (see scheme). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps intended for lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, Xihua; Xie, Yongbing; Cao, Hongbin; Nawaz, Faheem; Zhang, Yi

2014-01-01

Highlights: • A simple process to recycle cathode scraps intended for lithium-ion batteries. • Complete separation of the cathode material from the aluminum foil is achieved. • The recovered aluminum foil is highly pure. • LiNi 1/3 Co 1/3 Mn 1/3 O 2 is directly resynthesized from the separated cathode material. - Abstract: To solve the recycling challenge for aqueous binder based lithium-ion batteries (LIBs), a novel process for recycling and resynthesizing LiNi 1/3 Co 1/3 Mn 1/3 O 2 from the cathode scraps generated during manufacturing process is proposed in this study. Trifluoroacetic acid (TFA) is employed to separate the cathode material from the aluminum foil. The effects of TFA concentration, liquid/solid (L/S) ratio, reaction temperature and time on the separation efficiencies of the cathode material and aluminum foil are investigated systematically. The cathode material can be separated completely under the optimal experimental condition of 15 vol.% TFA solution, L/S ratio of 8.0 mL g −1 , reacting at 40 °C for 180 min along with appropriate agitation. LiNi 1/3 Co 1/3 Mn 1/3 O 2 is successfully resynthesized from the separated cathode material by solid state reaction method. Several kinds of characterizations are performed to verify the typical properties of the resynthesized LiNi 1/3 Co 1/3 Mn 1/3 O 2 powder. Electrochemical tests show that the initial charge and discharge capacities of the resynthesized LiNi 1/3 Co 1/3 Mn 1/3 O 2 are 201 mAh g −1 and 155.4 mAh g −1 (2.8–4.5 V, 0.1 C), respectively. The discharge capacity remains at 129 mAh g −1 even after 30 cycles with a capacity retention ratio of 83.01%

Study on novel functional materials carboxymethyl cellulose lithium (CMC-Li) improve high-performance lithium-ion battery.

Science.gov (United States)

Qiu, Lei; Shao, Ziqiang; Xiang, Pan; Wang, Daxiong; Zhou, Zhenwen; Wang, Feijun; Wang, Wenjun; Wang, Jianquan

2014-09-22

Novel cellulose derivative CMC-Li was synthesized by cotton as raw material. The mechanism of the CMC-Li modified electrode materials by electrospinning was reported. CMC-Li/lithium iron phosphate (LiFePO4, LFP) composite fiber coated with LFP and CMC-Li nanofibers was successfully obtained by electrospinning. Then, CMC-Li/LFP nano-composite fiber was carbonized under nitrogen at a high temperature formed CNF/LFP/Li (CLL) composite nanofibers as cathode material. It can increase the contents of Li+, and improving the diffusion efficiency and specific capacity. The battery with CLL as cathode material retained close to 100% of initial reversible capacity after 200 cycles at 168 mAh g(-1), which was nearly the theoretical specific capacity of LFP. The cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD) and scanning electron microscope (SEM) were characterizing material performance. The batteries have good electrochemical property, outstanding pollution-free, excellent stability. Copyright © 2014 Elsevier Ltd. All rights reserved.

High rate performance of novel cathode material Li1.33Ni1/3Co1/3Mn1/3O2 for lithium ion batteries

International Nuclear Information System (INIS)

Liu Haowen; Tan Long

2011-01-01

Highlights: → A novel cathode material with highly ordered structure has been prepared for the first time. → The charge and discharge current is 1000 mA g -1 and 2000 mA g -1 , respectively. → The results indicate better discharge capacity and cyclability. - Abstract: Li 1.33 Ni 1/3 Co 1/3 Mn 1/3 O 2 with highly ordered structure has been successfully synthesized via a simple co-precipitation process. Charge-discharge tests showed that the initial discharge capacities are 153.0 mAh g -1 and 128.9 mAh g -1 at 5 C (1000 mA g -1 ) and 10 C (2000 mA g -1 ) between 2.5 and 4.5 V, respectively. The average full-charge time of this material is less than 12 min at 5 C and 6 min at 10 C. The electrode material composed of the prepared showed a better cyclability. The excellent high rate performance is attributed to the improved ordered layered structure and the electrical conductivity. The excess Li shorten Li + diffusion distance between these submicron and nano-scaled particles. The results show that Li 1.33 Ni 1/3 Co 1/3 Mn 1/3 O 2 cathode material has potential application in lithium ion batteries.

Sulfur based electrode materials for secondary batteries

Science.gov (United States)

Hao, Yong

Developing next generation secondary batteries has attracted much attention in recent years due to the increasing demand of high energy and high power density energy storage for portable electronics, electric vehicles and renewable sources of energy. This dissertation investigates sulfur based advanced electrode materials in Lithium/Sodium batteries. The electrochemical performances of the electrode materials have been enhanced due to their unique nano structures as well as the formation of novel composites. First, a nitrogen-doped graphene nanosheets/sulfur (NGNSs/S) composite was synthesized via a facile chemical reaction deposition. In this composite, NGNSs were employed as a conductive host to entrap S/polysulfides in the cathode part. The NGNSs/S composite delivered an initial discharge capacity of 856.7 mAh g-1 and a reversible capacity of 319.3 mAh g-1 at 0.1C with good recoverable rate capability. Second, NGNS/S nanocomposites, synthesized using chemical reaction-deposition method and low temperature heat treatment, were further studied as active cathode materials for room temperature Na-S batteries. Both high loading composite with 86% gamma-S8 and low loading composite with 25% gamma-S8 have been electrochemically evaluated and compared with both NGNS and S control electrodes. It was found that low loading NGNS/S composite exhibited better electrochemical performance with specific capacity of 110 and 48 mAh g-1 at 0.1C at the 1st and 300th cycle, respectively. The Coulombic efficiency of 100% was obtained at the 300th cycle. Third, high purity rock-salt (RS), zinc-blende (ZB) and wurtzite (WZ) MnS nanocrystals with different morphologies were successfully synthesized via a facile solvothermal method. RS-, ZB- and WZ-MnS electrodes showed the capacities of 232.5 mAh g-1, 287.9 mAh g-1 and 79.8 mAh g-1 at the 600th cycle, respectively. ZB-MnS displayed the best performance in terms of specific capacity and cyclability. Interestingly, MnS electrodes

Effect of Decreasing Cobalt Content on the Electrochemical Properties and Structural Stability of Li_(1-x)Ni_(y)Co_(z)Al_(0.05)O_(2) Type Cathode Materials

OpenAIRE

Ghatak, Kamalika; Kumar, Hemant; Nadimpalli, Siva; Datta, Dibakar

2017-01-01

In Lithium ion batteries (LIBs), proper design of cathode materials influences its intercalation behavior, overall cost, structural stability, and its impact on environment. At present, the most common type of cathode materials, NCA , has very high cobalt concentration. Since cobalt is toxic and expensive, the existing design of cathode materials is not cost-effective, and environmentally benign. However, these immensely important issues have not yet been properly addressed. Therefore, we hav...

Key electronic states in lithium battery materials probed by soft X-ray spectroscopy

International Nuclear Information System (INIS)

Yang, Wanli; Liu, Xiaosong; Qiao, Ruimin; Olalde-Velasco, Paul; Spear, Jonathan D.; Roseguo, Louis; Pepper, John X.; Chuang, Yi-de; Denlinger, Jonathan D.; Hussain, Zahid

2013-01-01

Highlights: •Key electronic states in battery materials revealed by soft X-ray spectroscopy. •Soft X-ray absorption consistently probes Mn oxidation states in different systems. •Soft X-ray absorption and emission fingerprint battery operations in LiFePO 4 . •Spectroscopic guidelines for selecting/optimizing polymer materials for batteries. •Distinct SEI formation on same electrode material with different crystal orientations. -- Abstract: The formidable challenges for developing a safe, low-cost, high-capacity, and high-power battery necessitate employing advanced tools that are capable of directly probing the key electronic states relevant to battery performance. Synchrotron based soft X-ray spectroscopy directly measures both the occupied and unoccupied states in the vicinity of the Fermi level, including transition-metal-3d and anion-p states. This article presents the basic concepts on how fundamental physics in electronic structure could provide valuable information for lithium-ion battery applications. We then discuss some of our recent studies on transition-metal oxide based cathodes, silicon based anode, and solid-electrolyte-interphase through soft X-ray absorption and emission spectroscopy. We argue that spectroscopic results reveal the evolution of electronic states for fingerprinting, understanding, and optimizing lithium-ion battery operations

A porous C/LiFePO4/multiwalled carbon nanotubes cathode material for Lithium ion batteries

International Nuclear Information System (INIS)

Qin, Guohui; Ma, Qianqian; Wang, Chengyang

2014-01-01

Highlights: •C/LiFePO 4 /MWCNT was synthesized by a incorporation of sol-gel approach and an electro-polymerization progress with a subsequent carbonization progress. •The prepared C/LiFePO 4 /MWCNTs electrode presents high-rate ability, cyclic stability, and a relative volume density. •Such cathode material is an alternative candidate for high power lithium ion batteries. -- Abstract: Three dimensional (3D) porous C/LiFePO 4 /MWCNTs was synthesized by a hybrid of in situ sol gel strategy and a facile electro-polymerization polyaniline technique and a simultaneous sintering progress. In combined with the 3D hierarchical pore topologies and high electronic conduction facilitating the kinetics of both electron transport and lithium ion diffusion within the particles, the optimized electrodes exhibit an ultrahigh rate capacity, stable charge/discharge cycle ability, and a comparative volume capacity. The synthesized LiFePO 4 composite offers a discharge capacity of 169.6mAhg −1 (nearly to its the theoretical capability 170mAhg −1 ) at the C/10 rate and delivers a good rate performance with a capacity of 141.9mAh g −1 at a high rate of 20 C, and stable charge/discharge cycle ability (>95% capacity retention after 200 charge/discharge cycles).This non-organic facile synthesize avenue can be high desirable to prepare high-power electrode materials

Enhancing the stability and performance of a battery cathode using a non-aqueous electrolyte

Energy Technology Data Exchange (ETDEWEB)

Kim, Sung Yeol [Division of Engineering, Brown University, Providence, RI 02912 (United States); Sen, Sujat [Department of Chemistry, Brown University, Providence, RI 02912 (United States); Song, Hyun-Kon [Interdisciplinary School of Green Energy and School of Nano-Biotechnology and Chemical Engineering, Ulsan National Institute of Science and Technology, Banyeon-ri 100, Ulju-gun, Ulsan 689-798 (Korea); Palmore, G. Tayhas R. [Division of Biology and Medicine, Brown University, Providence, RI 02912 (United States)

2010-06-15

For conductive polymers to be considered materials for energy storage, both their electroactivity and stability must be optimized. In this study, a non-aqueous electrolyte (0.2 M LiClO{sub 4} in acetonitrile) was studied for its effect on the charge storage capacity and stability of two materials used in batteries developed in our laboratory, polypyrrole (pPy) and poly(3,4-ethylenedioxythiophene) (PEDOT) doped with 2,2'-azino-bis(3-ethylbenzothiaxoline-6-sulfonic acid (ABTS)). The results are compared to the performance of these materials in an aqueous electrolyte (0.2 M HCl/aq). Loss of ABTS dopant was eliminated principally due to the low solubility of ABTS in acetonitrile, resulting in cathode materials with improved stability in terms of load cycling and performance. (author)

Quantitative description on structure-property relationships of Li-ion battery materials for high-throughput computations

Science.gov (United States)

Wang, Youwei; Zhang, Wenqing; Chen, Lidong; Shi, Siqi; Liu, Jianjun

2017-12-01

Li-ion batteries are a key technology for addressing the global challenge of clean renewable energy and environment pollution. Their contemporary applications, for portable electronic devices, electric vehicles, and large-scale power grids, stimulate the development of high-performance battery materials with high energy density, high power, good safety, and long lifetime. High-throughput calculations provide a practical strategy to discover new battery materials and optimize currently known material performances. Most cathode materials screened by the previous high-throughput calculations cannot meet the requirement of practical applications because only capacity, voltage and volume change of bulk were considered. It is important to include more structure-property relationships, such as point defects, surface and interface, doping and metal-mixture and nanosize effects, in high-throughput calculations. In this review, we established quantitative description of structure-property relationships in Li-ion battery materials by the intrinsic bulk parameters, which can be applied in future high-throughput calculations to screen Li-ion battery materials. Based on these parameterized structure-property relationships, a possible high-throughput computational screening flow path is proposed to obtain high-performance battery materials.

Carbon-Free CoO Mesoporous Nanowire Array Cathode for High-Performance Aprotic Li-O2 Batteries.

Science.gov (United States)

Wu, Baoshan; Zhang, Hongzhang; Zhou, Wei; Wang, Meiri; Li, Xianfeng; Zhang, Huamin

2015-10-21

Although various kinds of catalysts have been developed for aprotic Li-O2 battery application, the carbon-based cathodes are still vulnerable to attacks from the discharge intermediates or products, as well as the accompanying electrolyte decomposition. To ameliorate this problem, the free-standing and carbon-free CoO nanowire array cathode was purposely designed for Li-O2 batteries. The single CoO nanowire formed as a special mesoporous structure, owing even comparable specific surface area and pore volume to the typical Super-P carbon particles. In addition to the highly selective oxygen reduction/evolution reactions catalytic activity of CoO cathodes, both excellent discharge specific capacity and cycling efficiency of Li-O2 batteries were obtained, with 4888 mAh gCoO(-1) and 50 cycles during 500 h period. Owing to the synergistic effect between elaborate porous structure and selective intermediate absorption on CoO crystal, a unique bimodal growth phenomenon of discharge products was occasionally observed, which further offers a novel mechanism to control the formation/decomposition morphology of discharge products in nanoscale. This research work is believed to shed light on the future development of high-performance aprotic Li-O2 batteries.

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.

A mixed iron-manganese based pyrophosphate cathode, Na2Fe0.5Mn0.5P2O7, for rechargeable sodium ion batteries.

Science.gov (United States)

Shakoor, Rana A; Park, Chan Sun; Raja, Arsalan A; Shin, Jaeho; Kahraman, Ramazan

2016-02-07

The development of secondary batteries based on abundant and cheap elements is vital. Among various alternatives to conventional lithium-ion batteries, sodium-ion batteries (SIBs) are promising due to the abundant resources and low cost of sodium. While there are many challenges associated with the SIB system, cathode is an important factor in determining the electrochemical performance of this battery system. Accordingly, ongoing research in the field of SIBs is inclined towards the development of safe, cost effective cathode materials having improved performance. In particular, pyrophosphate cathodes have recently demonstrated decent electrochemical performance and thermal stability. Herein, we report the synthesis, electrochemical properties, and thermal behavior of a novel Na2Fe0.5Mn0.5P2O7 cathode for SIBs. The material was synthesized through a solid state process. The structural analysis reveals that the mixed substitution of manganese and iron has resulted in a triclinic crystal structure (P1[combining macron] space group). Galvanostatic charge/discharge measurements indicate that Na2Fe0.5Mn0.5P2O7 is electrochemically active with a reversible capacity of ∼80 mA h g(-1) at a C/20 rate with an average redox potential of 3.2 V. (vs. Na/Na(+)). It is noticed that 84% of initial capacity is preserved over 90 cycles showing promising cyclability. It is also noticed that the rate capability of Na2Fe0.5Mn0.5P2O7 is better than Na2MnP2O7. Ex situ and CV analyses indicate that Na2Fe0.5Mn0.5P2O7 undergoes a single phase reaction rather than a biphasic reaction due to different Na coordination environment and different Na site occupancy when compared to other pyrophosphate materials (Na2FeP2O7 and Na2MnP2O7). Thermogravimetric analysis (25-550 °C) confirms good thermal stability of Na2Fe0.5Mn0.5P2O7 with only 2% weight loss. Owing to promising electrochemical properties and decent thermal stability, Na2Fe0.5Mn0.5P2O7, can be an attractive cathode for SIBs.

Thermal Conductivity Changes Due to Degradation of Cathode Film Subjected to Charge-Discharge Cycles in a Li Ion Battery

Science.gov (United States)

Jagannadham, K.

2018-05-01

A battery device with graphene platelets as anode, lithium nickel manganese oxide as cathode, and solid-state electrolyte consisting of layers of lithium phosphorous oxynitride and lithium lanthanum titanate is assembled on the stainless steel substrate. The battery in a polymer enclosure is subjected to several electrical tests consisting of charge and discharge cycles at different current and voltage levels. Thermal conductivity of the cathode layer is determined at the end of charge-discharge cycles using transient thermoreflectance. The microstructure and composition of the cathode layer and the interface between the cathode, the anode, and the electrolyte are characterized using scanning electron microscopy and elemental mapping. The decrease in the thermal conductivity of the same cathode observed after each set of electrical test cycles is correlated with the volume changes and formation of low ionic and thermal conductivity lithium oxide and lithium oxychloride at the interface and along porous regions. The interface between the metal current collector and the cathode is also found to be responsible for the increase in thermal resistance. The results indicate that changes in the thermal conductivity of the electrodes provide a measure of the resistance to heat transfer and degradation of ionic transport in the cathode accompanying the charge-discharge cycles in the batteries.

Investigation of different anode materials for aluminium rechargeable batteries

Science.gov (United States)

Muñoz-Torrero, David; Leung, Puiki; García-Quismondo, Enrique; Ventosa, Edgar; Anderson, Marc; Palma, Jesús; Marcilla, Rebeca

2018-01-01

In order to shed some light into the importance of the anodic reaction in reversible aluminium batteries, we investigate here the electrodeposition of aluminium in an ionic liquid electrolyte (BMImCl-AlCl3) using different substrates. We explore the influence of the type of anodic material (aluminium, stainless steel and carbon) and its 3D geometry on the reversibility of the anodic reaction by cyclic voltammetry (CV) and galvanostatic charge-discharge. The shape of the CVs confirms that electrodeposition of aluminium was feasible in the three materials but the highest peak currents and smallest peak separation in the CV of the aluminium anode suggested that this material was the most promising. Interestingly, carbon-based substrates appeared as an interesting alternative due to the high peak currents in CV, moderate overpotentials and dual role as anode and cathode. 3D substrates such as fiber-based carbon paper and aluminium mesh showed significantly smaller overpotentials and higher efficiencies for Al reaction suggesting that the use of 3D substrates in full batteries might result in enhanced power. This is corroborated by polarization testing of full Al-batteries.

Crystallography and Growth of Epitaxial Oxide Films for Fundamental Studies of Cathode Materials Used in Advanced Li-Ion Batteries

Directory of Open Access Journals (Sweden)

Leonid A. Bendersky

2017-05-01

Full Text Available Li-ion battery systems, synthesized as epitaxial thin films, can provide powerful insights into their electrochemical processes. Crystallographic analysis shows that many important cathode oxides have an underlying similarity: their structures can be considered as different ordering schemes of Li and transition metal ions within a pseudo-cubic sublattice of oxygen anions arranged in a face-center cubic (FCC fashion. This oxygen sublattice is compatible with SrTiO3 and similar perovskite oxides, thus perovskites can be used as supporting substrates for growing epitaxial cathode films. The predicted epitaxial growth and crystallographic relations were experimentally verified for different oxide films deposited by pulsed laser deposition (PLD on SrTiO3 or SrRuO3/SrTiO3 of different orientations. The results based on cross-sectional high-resolution TEM of the following films are presented in the paper: (a trigonal LiCoO2; (b orthorhombic LiMnO2; (c monoclinic Li2MnO3; (d compositionally-complex monoclinic Li1.2Mn0.55Ni0.15Co0.1O2. All results demonstrated the feasibility of epitaxial growth for these materials, with the growth following the predicted cube-on-cube orientation relationship between the cubic and pseudo-cubic oxygen sublattices of a substrate and a film, respectively.

Novel hierarchically porous carbon materials obtained from natural biopolymer as host matrixes for lithium-sulfur battery applications.

Science.gov (United States)

Zhang, Bin; Xiao, Min; Wang, Shuanjin; Han, Dongmei; Song, Shuqin; Chen, Guohua; Meng, Yuezhong

2014-08-13

Novel hierarchically porous carbon materials with very high surface areas, large pore volumes and high electron conductivities were prepared from silk cocoon by carbonization with KOH activation. The prepared novel porous carbon-encapsulated sulfur composites were fabricated by a simple melting process and used as cathodes for lithium sulfur batteries. Because of the large surface area and hierarchically porous structure of the carbon material, soluble polysulfide intermediates can be trapped within the cathode and the volume expansion can be alleviated effectively. Moreover, the electron transport properties of the carbon materials can provide an electron conductive network and promote the utilization rate of sulfur in cathode. The prepared carbon-sulfur composite exhibited a high specific capacity and excellent cycle stability. The results show a high initial discharge capacity of 1443 mAh g(-1) and retain 804 mAh g(-1) after 80 discharge/charge cycles at a rate of 0.5 C. A Coulombic efficiency retained up to 92% after 80 cycles. The prepared hierarchically porous carbon materials were proven to be an effective host matrix for sulfur encapsulation to improve the sulfur utilization rate and restrain the dissolution of polysulfides into lithium-sulfur battery electrolytes.

Hydrothermal synthesis of cathode materials

Science.gov (United States)

Chen, Jiajun; Wang, Shijun; Whittingham, M. Stanley

A number of cathodes are being considered for the next generation of lithium ion batteries to replace the expensive LiCoO 2 presently used. Besides the layered oxides, such as LiNi yMn yCo 1-2 yO 2, a leading candidate is lithium iron phosphate with the olivine structure. Although this material is inherently low cost, a manufacturing process that produces electrochemically active LiFePO 4 at a low cost is also required. Hydrothermal reactions are one such possibility. A number of pure phosphates have been prepared using this technique, including LiFePO 4, LiMnPO 4 and LiCoPO 4; this method has also successfully produced mixed metal phosphates, such as LiFe 0.33Mn 0.33Co 0.33PO 4. Ascorbic acid was found to be better than hydrazine or sugar at preventing the formation of ferric ions in aqueous media. When conductive carbons are added to the reaction medium excellent electrochemical behavior is observed.

Surface and in-depth characterization of lithium-ion battery cathodes at different cycle states using confocal micro-X-ray fluorescence-X-ray absorption near edge structure analysis

International Nuclear Information System (INIS)

Menzel, Magnus; Schlifke, Annalena; Falk, Mareike; Janek, Jürgen; Fröba, Michael; Fittschen, Ursula Elisabeth Adriane

2013-01-01

The cathode material LiNi 0.5 Mn 1.5 O 4 for lithium-ion batteries has been studied with confocal micro-X-ray fluorescence (CMXRF) combined with X-ray absorption near edge structure (XANES) at the Mn-K edge and the Ni-K edge. This technique allows for a non-destructive, spatially resolved (x, y and z) investigation of the oxidation states of surface areas and to some extent of deeper layers of the electrode. Until now CMXRF-XANES has been applied to a limited number of applications, mainly geo-science. Here, we introduce this technique to material science applications and show its performance to study a part of a working system. A novel mesoporous LiNi 0.5 Mn 1.5 O 4 material was cycled (charged and discharged) to investigate the effects on the oxidation states at the cathode/electrolyte interface. With this approach the degradation of Mn 3+ to Mn 4+ only observable at the surface of the electrode could be directly shown. The spatially resolved non-destructive analysis provides knowledge helpful for further understanding of deterioration and the development of high voltage battery materials, because of its nondestructive nature it will be also suitable to monitor processes during battery cycling. - Highlights: • The potential of confocal micro-XRF-XANES for spatial resolved species analysis in a part of a working system is shown. • The spatial resolution enables differentiation of the oxidized interface from deeper layers. • With the analytical technique confocal micro-XRF-XANES 3D in-situ analyses of working systems are feasible. • The multidimensional and nondestructive analysis of Li-ion battery cathodes is shown. • The analysis will allow for a deeper understanding of processes at interfaces in battery science and others

Surface and in-depth characterization of lithium-ion battery cathodes at different cycle states using confocal micro-X-ray fluorescence-X-ray absorption near edge structure analysis

Energy Technology Data Exchange (ETDEWEB)

Menzel, Magnus; Schlifke, Annalena [Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg (Germany); Falk, Mareike; Janek, Jürgen [Physikalisch-Chemisches Institut, Justus-Liebig-Universität Gießen, Heinrich-Buff-Ring 58, 35392 Gießen (Germany); Fröba, Michael, E-mail: froeba@chemie.uni-hamburg.de [Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg (Germany); Fittschen, Ursula Elisabeth Adriane, E-mail: ursula.fittschen@chemie.uni-hamburg.de [Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg (Germany)

2013-07-01

The cathode material LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} for lithium-ion batteries has been studied with confocal micro-X-ray fluorescence (CMXRF) combined with X-ray absorption near edge structure (XANES) at the Mn-K edge and the Ni-K edge. This technique allows for a non-destructive, spatially resolved (x, y and z) investigation of the oxidation states of surface areas and to some extent of deeper layers of the electrode. Until now CMXRF-XANES has been applied to a limited number of applications, mainly geo-science. Here, we introduce this technique to material science applications and show its performance to study a part of a working system. A novel mesoporous LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} material was cycled (charged and discharged) to investigate the effects on the oxidation states at the cathode/electrolyte interface. With this approach the degradation of Mn{sup 3+} to Mn{sup 4+} only observable at the surface of the electrode could be directly shown. The spatially resolved non-destructive analysis provides knowledge helpful for further understanding of deterioration and the development of high voltage battery materials, because of its nondestructive nature it will be also suitable to monitor processes during battery cycling. - Highlights: • The potential of confocal micro-XRF-XANES for spatial resolved species analysis in a part of a working system is shown. • The spatial resolution enables differentiation of the oxidized interface from deeper layers. • With the analytical technique confocal micro-XRF-XANES 3D in-situ analyses of working systems are feasible. • The multidimensional and nondestructive analysis of Li-ion battery cathodes is shown. • The analysis will allow for a deeper understanding of processes at interfaces in battery science and others.

Controlling porosity of porous carbon cathode for lithium oxygen batteries: Influence of micro and meso porosity

Science.gov (United States)

Kim, Minjae; Yoo, Eunjoo; Ahn, Wha-Seung; Shim, Sang Eun

2018-06-01

In rechargeable lithium-oxygen (Li-O2) batteries, the porosity of porous carbon materials plays a crucial role in the electrochemical performance serving as oxygen diffusion path and Li ion transfer passage. However, the influence of optimization of porous carbon as an air electrode on cell electrochemical performance remains unclear. To understand the role of carbon porosity in Li-O2 batteries, carbon materials featuring controlled pore sizes and porosity, including C-800 (nearly 96% microporous) and AC-950 (55:45 micro/meso porosity), are designed and synthesized by carbonization using a triazine-based covalent organic polymer (TCOP). We find that the microporous C-800 cathode allows 120 cycles with a limited capacity of 1000 mAh g-1, about 2 and 10 times higher than that of mixed-porosity AC-950 and mesoporous CMK-3, respectively. Meanwhile, the specific discharge capacity of the C-800 electrode at 200 mA g-1 is 6003 mAh g-1, which is lower than that of the 8433 and 9960 mAh g-1 when using AC-950 and CMK-3, respectively. This difference in the electrochemical performance of the porous carbon cathode with different porosity causes to the generation and decomposition of Li2O2 during the charge and discharge cycle, which affects oxygen diffusion and Li ion transfer.

Rechargeable Aqueous Zinc-Ion Battery Based on Porous Framework Zinc Pyrovanadate Intercalation Cathode

KAUST Repository

Xia, Chuan

2017-12-11

In this work, a microwave approach is developed to rapidly synthesize ultralong zinc pyrovanadate (Zn3V2O7(OH)2·2H2O, ZVO) nanowires with a porous crystal framework. It is shown that our synthesis strategy can easily be extended to fabricate other metal pyrovanadate compounds. The zinc pyrovanadate nanowires show significantly improved electrochemical performance when used as intercalation cathode for aqueous zinc–ion battery. Specifically, the ZVO cathode delivers high capacities of 213 and 76 mA h g−1 at current densities of 50 and 3000 mA g−1, respectively. Furthermore, the Zn//ZVO cells show good cycling stability up to 300 cycles. The estimated energy density of this Zn cell is ≈214Wh kg−1, which is much higher than commercial lead–acid batteries. Significant insight into the Zn-storage mechanism in the pyrovanadate cathodes is presented using multiple analytical methods. In addition, it is shown that our prototype device can power a 1.5 V temperature sensor for at least 24 h.

Synthesis of lithium nickel cobalt manganese oxide cathode materials by infrared induction heating

Science.gov (United States)

Hsieh, Chien-Te; Chen, Yu-Fu; Pai, Chun-Ting; Mo, Chung-Yu

2014-12-01

This study adopts an in-situ infrared (IR) sintering incorporated with carbonization technique to synthesize carbon-coated LiNi1/3Co1/3Mn1/3O2 (LNCM) cathode materials for Li-ion batteries. Compared with electric resistance heating, the in-situ IR sintering is capable of rapidly producing highly-crystalline LNCM powders at 900 °C within a short period, i.e., 3 h in this case. Glucose additive is employed to serve a carbon precursor, which is carbonized and coated over the surface of LNCM crystals during the IR sintering process. The electrochemical performance of LNCM cathodes is well examined by charge-discharge cycling at 0.1-5C. An appropriate carbon coating is capable of raising discharge capacity (i.e., 181.5 mAh g-1 at 0.1C), rate capability (i.e., 75.0 mAh g-1 at 5C), and cycling stability (i.e., capacity retention: 94.2% at 1C after 50 cycles) of LNCM cathodes. This enhanced performance can be ascribed to the carbon coating onto the external surface of LNCM powders, creating an outer circuit of charge-transfer pathway and preventing cathode corrosion from direct contact to the electrolyte. Accordingly, the in-situ IR sintering technique offers a potential feasibility for synthesizing cathode materials commercially in large scale.

Fiber Laser Welding Properties of Copper Materials for Secondary Batteries

Directory of Open Access Journals (Sweden)

Young-Tae YOU

2017-11-01

Full Text Available Secondary battery is composed of four main elements: cathodes, anodes, membranes and electrolyte. The cathodes and the anodes are connected to the poles that allow input and output of the current generated while the battery is being charged or discharged. In this study laser welding is conducted for 40 sheets of pure copper material with thickness of 38μm, which are used in currently manufactured lithium-ion batteries, using pulse-wave fiber laser to compare welded joint to standard bolt joint and to determine optimum process parameters. The parameters, which has significant impact on penetration of the pulse waveform laser to the overlapped thin sheets, is the peak power while the size of the weld zone is mainly affected by the pulse irradiation time and the focal position. It is confirmed that overlapping rate is affected by the pulse repetition rate rather than by the pulse irradiation time. At the cross-section of the weld zone, even with the increased peak power, the width of the front bead weld size does not change significantly, but the cross-sectional area becomes larger. This is because the energy density per pulse increases as the peak power increases.DOI: http://dx.doi.org/10.5755/j01.ms.23.4.16316

Electrochemical performance of co-doped Li1.2Mn0.6Ni0.2O2 cathode materials

CSIR Research Space (South Africa)

David, K

2013-04-01

Full Text Available The composite material has a xLi2MnO3·(1-x)LiMO2 (M = Mn, Co, Ni) structure has been considered as one of the most promising cathode materials for advanced lithium-ion batteries due to their low-cost and high capacity (> 200 mAh g−1) between 4.8 V...

Redox‐Flow Batteries: From Metals to Organic Redox‐Active Materials

Science.gov (United States)

Winsberg, Jan; Hagemann, Tino; Janoschka, Tobias; Hager, Martin D.

2016-01-01

Abstract Research on redox‐flow batteries (RFBs) is currently experiencing a significant upturn, stimulated by the growing need to store increasing quantities of sustainably generated electrical energy. RFBs are promising candidates for the creation of smart grids, particularly when combined with photovoltaics and wind farms. To achieve the goal of “green”, safe, and cost‐efficient energy storage, research has shifted from metal‐based materials to organic active materials in recent years. This Review presents an overview of various flow‐battery systems. Relevant studies concerning their history are discussed as well as their development over the last few years from the classical inorganic, to organic/inorganic, to RFBs with organic redox‐active cathode and anode materials. Available technologies are analyzed in terms of their technical, economic, and environmental aspects; the advantages and limitations of these systems are also discussed. Further technological challenges and prospective research possibilities are highlighted. PMID:28070964

Lithium Carbonate Recovery from Cathode Scrap of Spent Lithium-Ion Battery: A Closed-Loop Process.

Science.gov (United States)

Gao, Wenfang; Zhang, Xihua; Zheng, Xiaohong; Lin, Xiao; Cao, Hongbin; Zhang, Yi; Sun, Zhi

2017-02-07

A closed-loop process to recover lithium carbonate from cathode scrap of lithium-ion battery (LIB) is developed. Lithium could be selectively leached into solution using formic acid while aluminum remained as the metallic form, and most of the other metals from the cathode scrap could be precipitated out. This phenomenon clearly demonstrates that formic acid can be used for lithium recovery from cathode scrap, as both leaching and separation reagent. By investigating the effects of different parameters including temperature, formic acid concentration, H 2 O 2 amount, and solid to liquid ratio, the leaching rate of Li can reach 99.93% with minor Al loss into the solution. Subsequently, the leaching kinetics was evaluated and the controlling step as well as the apparent activation energy could be determined. After further separation of the remaining Ni, Co, and Mn from the leachate, Li 2 CO 3 with the purity of 99.90% could be obtained. The final solution after lithium carbonate extraction can be further processed for sodium formate preparation, and Ni, Co, and Mn precipitates are ready for precursor preparation for cathode materials. As a result, the global recovery rates of Al, Li, Ni, Co, and Mn in this process were found to be 95.46%, 98.22%, 99.96%, 99.96%, and 99.95% respectively, achieving effective resources recycling from cathode scrap of spent LIB.

Ultra-flexible lithium ion batteries fabricated by electrodeposition and solvothermal synthesis

International Nuclear Information System (INIS)

Wang, Jian; Zhang, Lei; Zhou, Qingwen; Wu, Wenlu; Zhu, Chao; Liu, Ziqiang; Chang, Shaozhong; Pu, Jun; Zhang, Huigang

2017-01-01

Cathodes have been one of the major challenges of flexible batteries. The traditional slurry-based technologies lead to loose interparticle connection, which is vulnerable upon bending. The direct fabrication of cathode materials requires high temperatures, which may destroy flexible substrates. Here we developed an electrodepostion and solvothermal route to conformally coat cathode material on a flexible scaffold. The monolithic electrode enables an ultra-flexible lithium ion battery because of the close attachment of active materials to flexible scaffolds and the interlock effect between the hard shell and soft core. This ultra-flexible battery retains 58.8% of initial capacity even after bending 4000 cycles.

Electrochemical and ab initio investigations to design a new phenothiazine based organic redox polymeric material for metal-ion battery cathodes.

Science.gov (United States)

Godet-Bar, T; Leprêtre, J-C; Le Bacq, O; Sanchez, J-Y; Deronzier, A; Pasturel, A

2015-10-14

Different N-substituted phenothiazines have been synthesized and their electrochemical behavior has been investigated in CH3CN in order to design the best polyphenothiazine based cathodic material candidate for lithium batteries. These compounds exhibit two successive reversible one-electron oxidation processes. Ab initio calculations demonstrate that the potential of the first process is a result of both the hybridization effects between the substituent and the phenothiazine unit as well as the change of conformation of the phenothiazine heterocycle during the oxidation process. More specifically, we show that an asymmetric molecular orbital spreading throughout an external cycle of the phenothiazine unit and the alkyl fragment is formed only if the alkyl fragment is long enough (from the methyl moiety onwards) and is at the origin of the bent conformation for N-substituted phenothiazines during oxidation. Electrochemical investigations supported by ab initio calculations allow the selection of a phenothiazinyl unit which is then polymerized by a Suzuki coupling strategy to avoid the common solubilization issue in carbonate-based liquid electrolytes of lithium cells. The first electrochemical measurements performed show that phenothiazine derivatives pave the way for a promising family of redox polymers intended to be used as organic positives for lithium batteries.

Fabricating Ir/C Nanofiber Networks as Free-Standing Air Cathodes for Rechargeable Li-CO2 Batteries.

Science.gov (United States)

Wang, Chengyi; Zhang, Qinming; Zhang, Xin; Wang, Xin-Gai; Xie, Zhaojun; Zhou, Zhen

2018-06-07

Li-CO 2 batteries are promising energy storage systems by utilizing CO 2 at the same time, though there are still some critical barriers before its practical applications such as high charging overpotential and poor cycling stability. In this work, iridium/carbon nanofibers (Ir/CNFs) are prepared via electrospinning and subsequent heat treatment, and are used as cathode catalysts for rechargeable Li-CO 2 batteries. Benefitting from the unique porous network structure and the high activity of ultrasmall Ir nanoparticles, Ir/CNFs exhibit excellent CO 2 reduction and evolution activities. The Li-CO 2 batteries present extremely large discharge capacity, high coulombic efficiency, and long cycling life. Moreover, free-standing Ir/CNF films are used directly as air cathodes to assemble Li-CO 2 batteries, which show high energy density and ultralong operation time, demonstrating great potential for practical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlled phase stability of highly Na-active triclinic structure in nanoscale high-voltage Na2-2xCo1+xP2O7 cathode for Na-ion batteries

Science.gov (United States)

Song, Hee Jo; Kim, Jae-Chan; Dar, Mushtaq Ahmad; Kim, Dong-Wan

2018-02-01

With the increasing demand for high energy density in energy-storage systems, a high-voltage cathode is essential in rechargeable Li-ion and Na-ion batteries. The operating voltage of a triclinic-polymorph Na2CoP2O7, also known as the rose form, is above 4.0 V (vs. Na/Na+), which is relatively high compared to that of other cathode materials. Thus, it can be employed as a potential high-voltage cathode material in Na-ion batteries. However, it is difficult to synthesize a pure rose phase because of its low phase stability, thus limiting its use in high-voltage applications. Herein, compositional-engineered, rose-phase Na2-2xCo1+xP2O7/C (x = 0, 0.1 and 0.2) nanopowder are prepared using a wet-chemical method. The Na2-2xCo1+xP2O7/C cathode shows high electrochemical reactivity with Na ions at 4.0 V, delivering high capacity and high energy density.

Thermophysical properties of LiCoO₂-LiMn₂O₄ blended electrode materials for Li-ion batteries.

Science.gov (United States)

Gotcu, Petronela; Seifert, Hans J

2016-04-21

Thermophysical properties of two cathode types for lithium-ion batteries were measured by dependence on temperature. The cathode materials are commercial composite thick films containing LiCoO2 and LiMn2O4 blended active materials, mixed with additives (binder and carbon black) deposited on aluminium current collector foils. The thermal diffusivities of the cathode samples were measured by laser flash analysis up to 673 K. The specific heat data was determined based on measured composite specific heat, aluminium specific heat data and their corresponding measured mass fractions. The composite specific heat data was measured using two differential scanning calorimeters over the temperature range from 298 to 573 K. For a comprehensive understanding of the blended composite thermal behaviour, measurements of the heat capacity of an additional LiMn2O4 sample were performed, and are the first experimental data up to 700 K. Thermal conductivity of each cathode type and their corresponding blended composite layers were estimated from the measured thermal diffusivity, the specific heat capacity and the estimated density based on metallographic methods and structural investigations. Such data are highly relevant for simulation studies of thermal management and thermal runaway in lithium-ion batteries, in which the bulk properties are assumed, as a common approach, to be temperature independent.

Electrochemical binding and wiring in battery materials

Energy Technology Data Exchange (ETDEWEB)

Pejovnik, S. [National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana (Slovenia); Faculty of Chemistry and Chemical Technology, Askerceva 5, SI-1000 Ljubljana (Slovenia); Dominko, R.; Bele, M.; Gaberscek, M.; Jamnik, J. [National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana (Slovenia)

2008-10-01

Binders in battery electrodes not only provide mechanical cohesiveness during battery operation but can also affect the electrode properties via the surface modification. Using atomic force microscopy (AFM), we study the surface structuring of three binders: polyvinylidene fluoride (PVdF), carboxymethyl cellulose (CMC) and gelatin. We try to find correlation between the observed structures and the measured electrochemical charge-discharge characteristics. We further measure the binding ability of gelatin adsorbed from solutions of different pHs. While the best binding ability of gelatin is obtained at pH about 9, the least polarization is observed at pH 12. Both properties are explained based on the observed gelatin structuring as a function of pH. In the second part of this study, gelatin is used as a surface agent that dictates the organization of nanometre-sized carbon black particles around micrometre-sized cathodic active particles. Using microcontact impedance measurements on polished pellets we show that using gelatin-forced carbon black deposition the average electronic resistance around LiMn{sub 2}O{sub 4} particles is decreased by more than two orders of magnitude. We believe that it is this decrease in resistance that improves significantly the rate performance of various cathode materials, such as LiMn{sub 2}O{sub 4} and LiCoO{sub 2}. (author)

Modulating the Electrochemical Performances of Layered Cathode Materials for Sodium Ion Batteries through Tuning Coulombic Repulsion between Negatively Charged TMO2 Slabs.

Science.gov (United States)

Li, Zheng-Yao; Wang, Huibo; Yang, Wenyun; Yang, Jinbo; Zheng, Lirong; Chen, Dongfeng; Sun, Kai; Han, Songbai; Liu, Xiangfeng

2018-01-17

Exploiting advanced layered transition metal oxide cathode materials is of great importance to rechargeable sodium batteries. Layered oxides are composed of negatively charged TMO 2 slabs (TM = transition metal) separated by Na + diffusion layers. Herein, we propose a novel insight, for the first time, to control the electrochemical properties by tuning Coulombic repulsion between negatively charged TMO 2 slabs. Coulombic repulsion can finely tailor the d-spacing of Na ion layers and material structural stability, which can be achieved by employing Na + cations to serve as effective shielding layers between TMO 2 layers. A series of O3-type Na x Mn 1/3 Fe 1/3 Cu 1/6 Mg 1/6 O 2 (x = 1.0, 0.9, 0.8, and 0.7) have been prepared, and Na 0.7 Mn 1/3 Fe 1/3 Cu 1/6 Mg 1/6 O 2 shows the largest Coulombic repulsion between TMO 2 layers, the largest space for Na ion diffusion, the best structural stability, and also the longest Na-O chemical bond with weaker Coulombic attraction, thus leading to the best electrochemical performance. Meanwhile, the thermal stability depends on the Na concentration in pristine materials. Ex situ X-ray absorption (XAS) analysis indicates that Mn, Fe, and Cu ions are all electrochemically active components during insertion and extraction of sodium ion. This study enables some new insights to promote the development of advanced layered Na x TMO 2 materials for rechargeable sodium batteries in the future.

Solvothermal coating LiNi_0_._8Co_0_._1_5Al_0_._0_5O_2 microspheres with nanoscale Li_2TiO_3 shell for long lifespan Li-ion battery cathode materials

International Nuclear Information System (INIS)

Wu, Naiteng; Wu, Hao; Liu, Heng; Zhang, Yun

2016-01-01

LiNi_0_._8Co_0_._1_5Al_0_._0_5O_2 (NCA) microspheres covered by a nanoscale Li_2TiO_3-based shell were synthesized by a facile strategy based on a solvothermal pre-coating treatment combined with a post-sintering lithiation process. The morphology, structure and composition of the Li_2TiO_3-coated NCA samples were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning scanning electron microscope (SEM) with an energy-dispersive X-ray spectroscope (EDS), and transmission electron microscopy (TEM). Owing to the complete, uniform and nanoscale Li_2TiO_3 coating shell, the resultant surface-modified NCA microspheres used as Li-ion battery cathode materials manifest remarkably enhanced cycling performances, attaining 94% and 84% capacity retention after 200 and 400 cycles at 0.5 C, respectively, which is much better than the pristine NCA counterpart (60% retention, 200 cycles). More impressively, the surface-modified NCA also shows an intriguing storage stability. After being stored at 30 °C for 50 days, the coated NCA-based cells are subjected to be cycled both at room and elevated temperatures, in which the aged cells can still remain 84% capacity retention after 200 cycles at 25 °C and 77% capacity retention after 200 cycles at 55 °C, respectively. All these results demonstrate that the Li_2TiO_3-coated LiNi_0_._8Co_0_._1_5Al_0_._0_5O_2 microsphere is a promising cathode material for Li-ion batteries with long lifespan. - Graphical abstract: Nanoscale Li_2TiO_3-based shell encapsulated LiNi_0_._8Co_0_._1_5Al_0_._0_5O_2 (NCA) microspheres are fabricated through a solvothermal pre-coating treatment combined with post-lithiation process. The surface-coated NCA as cathode materials shows a remarkably enhanced cycling performance and storage stability for long lifespan Li-ion batteries. - Highlights: • Li_2TiO_3 is used as coating materials for layer structured LiNi_0_._8Co_0_._1_5Al_0_._0_5O_2 cathode. • Solvothermal coating

Structure-controlled synthesis and electrochemical properties of NH_4V_3O_8 as cathode material for Lithium ion batteries

International Nuclear Information System (INIS)

Cheng, Yayi; Huang, Jianfeng; Li, Jiayin; Cao, Liyun; Xu, Zhanwei; Wu, Jianpeng; Cao, Shanshan; Hu, Hailing

2016-01-01

NH_4V_3O_8 flower, nanobelt, lath and sheet were synthesized using a facile microwave hydrothermal method. The formation mechanism of NH_4V_3O_8 with various structures was proposed. As an cathode in Li-ion battery, the NH_4V_3O_8 nanobelt with one-dimensional structure as well as nanosized morphology, presents excellent cycling stability and enhanced rate capability when comparing with other NH_4V_3O_8 structures. Further study finds that the NH_4V_3O_8 nanobelt could provide high Li ion diffusion, excellent structural stability and good reversibility during the charge/discharge process, indicating a strong connection between the morphology and the electrochemical performance of NH_4V_3O_8 cathode.

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.

Spinel LiMn 2 O 4 Nanorods as Lithium Ion Battery Cathodes

KAUST Repository

Kim, Do Kyung

2008-11-12

Spinel LiMn 2O 4 is a low-cost, environmentally friendly, and highly abundant material for Li-ion battery cathodes. Here, we report the hydrothermal synthesis of single-crystalline β-MnO 2 nanorods and their chemical conversion into free-standing single-crystalline LiMn 2O 4 nanorods using a simple solid-state reaction. The LiMn 2O 4 nanorods have an average diameter of 130 nm and length of 1.2 μm. Galvanostatic battery testing showed that LiMn 2O 4 nanorods have a high charge storage capacity at high power rates compared with commercially available powders. More than 85% of the initial charge storage capacity was maintained for over 100 cycles. The structural transformation studies showed that the Li ions intercalated into the cubic phase of the LiMn 2O 4 with a small change of lattice parameter, followed by the coexistence of two nearly identical cubic phases in the potential range of 3.5 to 4.3V. © 2008 American Chemical Society.

Spinel LiMn 2 O 4 Nanorods as Lithium Ion Battery Cathodes

KAUST Repository

Kim, Do Kyung; Muralidharan, P.; Lee, Hyun-Wook; Ruffo, Riccardo; Yang, Yuan; Chan, Candace K.; Peng, Hailin; Huggins, Robert A.; Cui, Yi

2008-01-01

Spinel LiMn 2O 4 is a low-cost, environmentally friendly, and highly abundant material for Li-ion battery cathodes. Here, we report the hydrothermal synthesis of single-crystalline β-MnO 2 nanorods and their chemical conversion into free-standing single-crystalline LiMn 2O 4 nanorods using a simple solid-state reaction. The LiMn 2O 4 nanorods have an average diameter of 130 nm and length of 1.2 μm. Galvanostatic battery testing showed that LiMn 2O 4 nanorods have a high charge storage capacity at high power rates compared with commercially available powders. More than 85% of the initial charge storage capacity was maintained for over 100 cycles. The structural transformation studies showed that the Li ions intercalated into the cubic phase of the LiMn 2O 4 with a small change of lattice parameter, followed by the coexistence of two nearly identical cubic phases in the potential range of 3.5 to 4.3V. © 2008 American Chemical Society.

Effect of cathode component on the energy density of lithium-sulfur battery

International Nuclear Information System (INIS)

Choi, Yun Seok; Kim, Seok; Choi, Soo Seok; Han, Ji Sung; Kim, Jan Dee; Jeon, Sang Eun; Jung, Bok Hwan

2004-01-01

The effect of the carbon black types and the sulfur particle size on the discharge capacity or the utilization of sulfur was investigated for the cathode having high loading of sulfur. The DBP (dibutyl phthalate) absorption number of the used carbon black has a strong effect on the utilization while the specific surface area is not so critical to it. It was also found that the sulfur particle size is a factor having an effect on the utilization. We have improved the cathode component and achieved the utilization of about 50%. By using that cathode, the volumetric energy density of about 330 Wh/l was obtained for the full size Li-S battery (3.8 mm thickness, 35 mm width and 62 mm height)

Room-Temperature, Ambient-Pressure Chemical Synthesis of Amine-Functionalized Hierarchical Carbon-Sulfur Composites for Lithium-Sulfur Battery Cathodes.

Science.gov (United States)

Chae, Changju; Kim, Jinmin; Kim, Ju Young; Ji, Seulgi; Lee, Sun Sook; Kang, Yongku; Choi, Youngmin; Suk, Jungdon; Jeong, Sunho

2018-02-07

Recently, the achievement of newly designed carbon-sulfur composite materials has attracted a tremendous amount of attention as high-performance cathode materials for lithium-sulfur batteries. To date, sulfur materials have been generally synthesized by a sublimation technique in sealed containers. This is a well-developed technique for the synthesizing of well-ordered sulfur materials, but it is limited when used to scale up synthetic procedures for practical applications. In this study, we suggest an easily scalable, room-temperature/ambient-pressure chemical pathway for the synthesis of highly functioning cathode materials using electrostatically assembled, amine-terminated carbon materials. It is demonstrated that stable cycling performance outcomes are achievable with a capacity of 730 mAhg -1 at a current density of 1 C with good cycling stability by a virtue of the characteristic chemical/physical properties (a high conductivity for efficient charge conduction and the presence of a number of amine groups that can interact with sulfur atoms during electrochemical reactions) of composite materials. The critical roles of conductive carbon moieties and amine functional groups inside composite materials are clarified with combinatorial analyses by X-ray photoelectron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy.

Hollow Carbon Nanofiber-Encapsulated Sulfur Cathodes for High Specific Capacity Rechargeable Lithium Batteries

KAUST Repository

Zheng, Guangyuan; Yang, Yuan; Cha, Judy J.; Hong, Seung Sae; Cui, Yi

2011-01-01

Sulfur has a high specific capacity of 1673 mAh/g as lithium battery cathodes, but its rapid capacity fading due to polysulfides dissolution presents a significant challenge for practical applications. Here we report a hollow carbon nanofiber

Stabilized sulfur as cathodes for room temperature sodium-ion batteries.

Energy Technology Data Exchange (ETDEWEB)

Xu, Yunhua [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Liu, Yang [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States). Center for Integrated Nanotechnologies; Zhu, Yujie [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Zheng, Shiyou [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Liu, Yihang [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Luo, Chao [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Gaskell, Karen [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Eichhorn, Bryan [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Wang, Chunsheng [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering

2013-05-01

Sodium-sulfur batteries, offering high capacity and low cost, are promising alternative to lithium-ion batteries for large-scale energy storage applications. The conventional sodium-sulfur batteries, operating at a high temperature of 300–350°C in a molten state, could lead to severe safety problems. However, the room temperature sodium-sulfur batteries using common organic liuid electrolytes still face a significant challenge due to the dissolution of intermediate sodium polysulfides. For this study, we developed room temperatue sodium-sulfur batteries using a unique porous carbon/sulfur (C/S) composite cathode, which was synthesized by infusing sulfur vapor into porous carbon sphere particles at a high temperatrure of 600°C. The porous C/S composites delivered a reversible capacity of ~860 mAh/g and retained 83% after 300 cycles. The Coulombic efficiency of as high as 97% was observed over 300 cycles. The superior electrochemical performance is attrbuted to the super sulfur stability as evidenced by its lower sensitivity to probe beam irradiation in TEM, XPS and Raman charaterization and high evaperation temperature in TGA. The results make it promising for large-scale grid energy storage and electric vehicles.

Two-step carbon coating of lithium vanadium phosphate as high-rate cathode for lithium-ion batteries

Science.gov (United States)

Kuang, Quan; Zhao, Yanming

2012-10-01

Carbon-coated Li3V2(PO4)3 was firstly prepared at 850 °C via two-step reaction method combined sol-gel and conventional solid-state synthesis by using VPO4/carbon as an intermediate. Two different carbon sources, citric acid and glucose as carbon additives in sequence, ultimately deduced double carbon-coated Li3V2(PO4)3 as a high-rate cathode material. The Li3V2(PO4)3/carbon with 4.39% residual carbon has a splendid electronic conductivity of 4.76×10-2 S cm-1. Even in the voltage window of 2.5-4.8 V, the Li3V2(PO4)3/carbon cathode can retain outstanding rate ability (170.4 mAh g-1 at 1.2 C, 101.9 mAh g-1 at 17 C), and no degradation is found after 120 C current rate. These phenomena show that the two-step carbon-coated Li3V2(PO4)3 can act as a fast charge-discharge cathode material for high-power Li-ion batteries. Furthermore, it's believed that this synthesize method can be easily transplanted to prepare other lithiated vanadium-based phosphates.

Synthesis, Structure, and Sodium Mobility of Sodium Vanadium Nitridophosphate: A Zero-Strain and Safe High Voltage Cathode Material for Sodium-Ion Batteries

Directory of Open Access Journals (Sweden)

Huang Zhang

2017-06-01

Full Text Available Herein, the nitridophosphate Na3V(PO33N is synthesized by solid state method. X-ray diffraction (XRD and Rietveld refinement confirm the cubic symmetry with P213 space group. The material exhibits very good thermal stability and high operating voltage of 4.0 V vs. Na/Na+ due to V3+/V4+ redox couple. In situ X-ray diffraction studies confirm the two-phase (de-sodiation process to occur with very low volume changes. The refinement of the sodium occupancies reveal the low accessibility of sodium cations in the Na2 and Na3 sites as the main origin for the lower experimental capacity (0.38 eq. Na+, 28 mAh g−1 versus the theoretical one (1.0 eq. Na+, 74 mAh g−1. These observations provide valuable information for the further optimization of this materials class in order to access their theoretical electrochemical performance as a potentially interesting zero-strain and safe high-voltage cathode material for sodium-ion batteries.

Redox-Flow Batteries: From Metals to Organic Redox-Active Materials.

Science.gov (United States)

Winsberg, Jan; Hagemann, Tino; Janoschka, Tobias; Hager, Martin D; Schubert, Ulrich S

2017-01-16

Research on redox-flow batteries (RFBs) is currently experiencing a significant upturn, stimulated by the growing need to store increasing quantities of sustainably generated electrical energy. RFBs are promising candidates for the creation of smart grids, particularly when combined with photovoltaics and wind farms. To achieve the goal of "green", safe, and cost-efficient energy storage, research has shifted from metal-based materials to organic active materials in recent years. This Review presents an overview of various flow-battery systems. Relevant studies concerning their history are discussed as well as their development over the last few years from the classical inorganic, to organic/inorganic, to RFBs with organic redox-active cathode and anode materials. Available technologies are analyzed in terms of their technical, economic, and environmental aspects; the advantages and limitations of these systems are also discussed. Further technological challenges and prospective research possibilities are highlighted. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Towards deriving Ni-rich cathode and oxide-based anode materials from hydroxides by sharing a facile co-precipitation method.

Science.gov (United States)

Qiu, Haifa; Du, Tengfei; Wu, Junfeng; Wang, Yonglong; Liu, Jian; Ye, Shihai; Liu, Sheng

2018-05-22

Although intensive studies have been conducted on layered transition metal oxide(TMO)-based cathode materials and metal oxide-based anode materials for Li-ion batteries, their precursors generally follow different or even complex synthesis routes. To share one route for preparing precursors of the cathode and anode materials, herein, we demonstrate a facile co-precipitation method to fabricate Ni-rich hydroxide precursors of Ni0.8Co0.1Mn0.1(OH)2. Ni-rich layered oxide of LiNi0.8Co0.1Mn0.1O2 is obtained by lithiation of the precursor in air. An NiO-based anode material is prepared by calcining the precursor or multi-walled carbon nanotubes (MWCNTs) incorporated precursors. The pre-addition of ammonia solution can simplify the co-precipitation procedures and the use of an air atmosphere can also make the heat treatment facile. LiNi0.8Co0.1Mn0.1O2 as the cathode material delivers a reversible capacity of 194 mA h g-1 at 40 mA g-1 and a notable cycling retention of 88.8% after 100 cycles at 200 mA g-1. This noticeable performance of the cathode arises from a decent particle morphology and high crystallinity of the layered oxides. As the anode material, the MWCNTs-incorporated oxides deliver a much higher reversible capacity of 811.1 mA h g-1 after 200 cycles compared to the pristine oxides without MWCNTs. The improvement on electrochemical performance can be attributed to synergistic effects from MWCNTs incorporation, including reinforced electronic conductivity, rich meso-pores and an alleviated volume effect. This facile and sharing method may offer an integrated and economical approach for commercial production of Ni-rich electrode materials for Li-ion batteries.

Low-pressure chemical vapor deposition as a tool for deposition of thin film battery materials

NARCIS (Netherlands)

Oudenhoven, J.F.M.; Dongen, van T.; Niessen, R.A.H.; Croon, de M.H.J.M.; Notten, P.H.L.

2009-01-01

Low Pressure Chemical Vapor Deposition was utilized for the deposition of LiCoO2 cathode materials for all-solid-state thin-film micro-batteries. To obtain insight in the deposition process, the most important process parameters were optimized for the deposition of crystalline electrode films on

Atomic to Nanoscale Investigation of Functionalities of Al2O3 Coating Layer on Cathode for Enhanced Battery Performance

Energy Technology Data Exchange (ETDEWEB)

Yan, Pengfei; Zheng, Jianming; Zhang, Xiaofeng; Xu, Rui; Amine, Khalil; Xiao, Jie; Zhang, Jiguang; Wang, Chong M.

2016-01-06

Surface coating of cathode has been identified as an effective approach for enhancing the capacity retention of layered structure cathode. However, the underlying operating mechanism of such a thin layer of coating, in terms of surface chemical functionality and capacity retention, remains unclear. In this work, we use aberration corrected scanning transmission electron microscopy and high efficient spectroscopy to probe the delicate functioning mechanism of Al2O3 coating layer on Li1.2Ni0.2Mn0.6O2 cathode. We discovered that in terms of surface chemical function, the Al2O3 coating suppresses the side reaction between cathode and the electrolyte upon the battery cycling. At the same time, the Al2O3 coating layer also eliminates the chemical reduction of Mn from the cathode particle surface, therefore avoiding the dissolution of the reduced Mn into the electrolyte. In terms of structural stability, we found that the Al2O3 coating layer can mitigate the layer to spinel phase transformation, which otherwise will initiate from the particle surface and propagate towards the interior of the particle with the progression of the battery cycling. The atomic to nanoscale effects of the coating layer observed here provide insight for optimized design of coating layer on cathode to enhance the battery properties.

Highly ordered and ultra-long carbon nanotube arrays as air cathodes for high-energy-efficiency Li-oxygen batteries

Science.gov (United States)

Yu, Ruimin; Fan, Wugang; Guo, Xiangxin; Dong, Shaoming

2016-02-01

Carbonaceous air cathodes with rational architecture are vital for the nonaqueous Li-O2 batteries to achieve large energy density, high energy efficiency and long cycle life. In this work, we report the cathodes made of highly ordered and vertically aligned carbon nanotubes grown on permeable Ta foil substrates (VACNTs-Ta) via thermal chemical vapour deposition. The VACNTs-Ta, composed of uniform carbon nanotubes with approximately 240 μm in superficial height, has the super large surface area. Meanwhile, the oriented carbon nanotubes provide extremely outstanding passageways for Li ions and oxygen species. Electrochemistry tests of VACNTs-Ta air cathodes show enhancement in discharge capacity and cycle life compared to those made from short-range oriented and disordered carbon nanotubes. By further combining with the LiI redox mediator that is dissolved in the tetraethylene dimethyl glycol based electrolytes, the batteries exhibit more than 200 cycles at the current density of 200 mA g-1 with a cut-off discharge capacity of 1000 mAh g-1, and their energy efficiencies increase from 50% to 82%. The results here demonstrate the importance of cathode construction for high-energy-efficiency and long-life Li-O2 batteries.

Atomic Resolution Structural and Chemical Imaging Revealing the Sequential Migration of Ni, Co, and Mn upon the Battery Cycling of Layered Cathode

Energy Technology Data Exchange (ETDEWEB)

Yan, Pengfei; Zheng, Jianming; Zhang, Ji-Guang; Wang, Chongmin

2017-05-11

Layered lithium transition metal oxides (LTMO) are promising candidate cathode materials for next generation high energy density lithium ion battery. The challenge for using this category of cathode is the capacity and voltage fading, which is believed to be associated with the layered structure disordering, a process that is initiated from the surface or solid-electrolyte interface and facilitated by transition metal (TM) reduction and oxygen vacancy formation. However, the atomic level dynamic mechanism of such a layered structure disordering is still not fully clear. In this work, utilizing atomic resolution electron energy loss spectroscopy (EELS), we map, for the first time at atomic scale, the spatial evolution of Ni, Co and Mn in a cycled LiNi1/3M1/3Co1/3O2 layered cathode. In combination with atomic level structural imaging, we discovered the direct correlation of TM ions migration behavior with lattice disordering, featuring the residing of TM ions in the tetrahedral site and a sequential migration of Ni, Co, and Mn upon the increased lattice disordering of the layered structure. This work highlights that Ni ions, though acting as the dominant redox species in many LTMO, are labile to migrate to cause lattice disordering upon battery cycling; while the Mn ions are more stable as compared with Ni and Co and can act as pillar to stabilize layered structure. Direct visualization of the behavior of TM ions during the battery cycling provides insight for designing of cathode with structural stability and correspondingly a superior performance.

Synthesis and performances of Li-Rich@AlF3@Graphene as cathode of lithium ion battery

International Nuclear Information System (INIS)

Chen, Dongrui; Tu, Wenqiang; Chen, Min; Hong, Pengbo; Zhong, Xiaoxin; Zhu, Yunmin; Yu, Qipeng; Li, Weishan

2016-01-01

Highlights: • Li-Rich@AlF 3 @Graphene was developed as cathode of lithium ion battery. • Coating of 2 nm AlF 3 does not cause capacity loss but is beneficial to rate capability. • Concurrent AlF 3 coating and graphene wrapping significantly improve Li-Rich performance. - Abstract: A novel composite of layered lithium-rich oxide with AlF 3 and graphene, Li-Rich@AlF 3 @Graphene, is synthesized as high performance cathode of lithium ion battery in terms of rate capability and cyclic stability. Physical characterizations from X-ray diffraction, scanning electron microscope and transmission electron microscope, demonstrate that the layered lithium-rich oxide in Li-Rich@AlF 3 @Graphene is composed of uniform nanoparticles of 100 nm, which are coated with a layer of 2 nm AlF 3 and wrapped with graphene sheets. Charge/discharge tests indicate that the naked lithium-rich oxide exhibits poor cyclic stability and rate capability as cathode of lithium ion battery, which can be improved to some extent by the only contribution of AlF 3 but significantly by the concurrent contribution of AlF 3 and graphene.

Structural and thermal stabilities of layered Li(Ni 1/3Co 1/3Mn 1/3)O 2 materials in 18650 high power batteries

Science.gov (United States)

He, Yan-Bing; Ning, Feng; Yang, Quan-Hong; Song, Quan-Sheng; Li, Baohua; Su, Fangyuan; Du, Hongda; Tang, Zhi-Yuan; Kang, Feiyu

The structural and thermal stabilities of the layered Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathode materials under high rate cycling and abusive conditions are investigated using the commercial 18650 Li(Ni 1/3Co 1/3Mn 1/3)O 2/graphite high power batteries. The Li(Ni 1/3Co 1/3Mn 1/3)O 2 materials maintain their layered structure even when the power batteries are subjected to 200 cycles with 10 C discharge rate at temperatures of 25 and 50 °C, whereas their microstructure undergoes obvious distortion, which leads to the relatively poor cycling performance of power batteries at high charge/discharge rates and working temperature. Under abusive conditions, the increase in the battery temperature during overcharge is attributed to both the reactions of electrolyte solvents with overcharged graphite anode and Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathode and the Joule heat that results from the great increase in the total resistance (R cell) of batteries. The reactions of fully charged Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathodes and graphite anodes with electrolyte cannot be activated during short current test in the fully charged batteries. However, these reactions occur at around 140 °C in the fully charged batteries during oven test, which is much lower than the temperature of about 240 °C required for the reactions outside batteries.

Metalized, three-dimensional structured oxygen cathode materials for lithium/air batteries and method for making and using the same

Energy Technology Data Exchange (ETDEWEB)

Xing, Weibing; Buettner-Garrett, Josh

2017-04-18

This disclosure relates generally to cathode materials for electrochemical energy cells, more particularly to metal/air electrochemical energy cell cathode materials containing silver vanadium oxide and methods of making and using the same. The metal/air electrochemical energy cell can be a lithium/air electrochemical energy cell. Moreover the silver vanadium oxide can be a catalyst for one or more of oxidation and reduction processes of the electrochemical energy cell.

Novel lithium iron phosphate materials for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Popovic, Jelena

2011-06-15

Conventional energy sources are diminishing and non-renewable, take million years to form and cause environmental degradation. In the 21st century, we have to aim at achieving sustainable, environmentally friendly and cheap energy supply by employing renewable energy technologies associated with portable energy storage devices. Lithium-ion batteries can repeatedly generate clean energy from stored materials and convert reversely electric into chemical energy. The performance of lithium-ion batteries depends intimately on the properties of their materials. Presently used battery electrodes are expensive to be produced; they offer limited energy storage possibility and are unsafe to be used in larger dimensions restraining the diversity of application, especially in hybrid electric vehicles (HEVs) and electric vehicles (EVs). This thesis presents a major progress in the development of LiFePO4 as a cathode material for lithium-ion batteries. Using simple procedure, a completely novel morphology has been synthesized (mesocrystals of LiFePO4) and excellent electrochemical behavior was recorded (nanostructured LiFePO4). The newly developed reactions for synthesis of LiFePO4 are single-step processes and are taking place in an autoclave at significantly lower temperature (200 deg. C) compared to the conventional solid-state method (multi-step and up to 800 deg. C). The use of inexpensive environmentally benign precursors offers a green manufacturing approach for a large scale production. These newly developed experimental procedures can also be extended to other phospho-olivine materials, such as LiCoPO4 and LiMnPO4. The material with the best electrochemical behavior (nanostructured LiFePO4 with carbon coating) was able to deliver a stable 94% of the theoretically known capacity.

Anionic Redox Chemistry in Polysulfide Electrode Materials for Rechargeable Batteries.

Science.gov (United States)

Grayfer, Ekaterina D; Pazhetnov, Egor M; Kozlova, Mariia N; Artemkina, Sofya B; Fedorov, Vladimir E

2017-12-22

Classical Li-ion battery technology is based on the insertion of lithium ions into cathode materials involving metal (cationic) redox reactions. However, this vision is now being reconsidered, as many new-generation electrode materials with enhanced reversible capacities operate through combined cationic and anionic (non-metal) reversible redox processes or even exclusively through anionic redox transformations. Anionic participation in the redox reactions is observed in materials with more pronounced covalency, which is less typical for oxides, but quite common for phosphides or chalcogenides. In this Concept, we would like to draw the reader's attention to this new idea, especially, as it applies to transition-metal polychalcogenides, such as FeS 2 , VS 4 , TiS 3 , NbS 3 , TiS 4 , MoS 3 , etc., in which the key role is played by the (S-S) 2- /2 S 2- redox reaction. The exploration and better understanding of the anion-driven chemistry is important for designing advanced materials for battery and other energy-related applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and Exploration of Ladder-Structured Large Aromatic Dianhydrides as Organic Cathodes for Rechargeable Lithium-Ion Batteries.

Science.gov (United States)

Xie, Jian; Chen, Wangqiao; Wang, Zilong; Jie, Kenneth Choo Wei; Liu, Ming; Zhang, Qichun

2017-04-18

Compared to anode materials in Li-ion batteries, the research on cathode materials is far behind, and their capacities are much smaller. Thus, in order to address these issues, we believe that organic conjugated materials could be a solution. In this study, we synthesized two non-polymeric dianhydrides with large aromatic structures: NDA-4N (naphthalenetetracarboxylic dianhydride with four nitrogen atoms) and PDA-4N (perylenetetracarboxylic dianhydride with four nitrogen atoms). Their electrochemical properties have been investigated between 2.0 and 3.9 V (vs. Li + /Li). Benefiting from multi-electron reactions, NDA-4N and PDA-4N could reversibly achieve 79.7 % and 92.3 %, respectively, of their theoretical capacity. Further cycling reveals that the organic compound with a relatively larger aromatic building block could achieve a better stability, as an obvious 36.5 % improvement of the capacity retention was obtained when the backbone was switched from naphthalene to perylene. This study proposes an opportunity to attain promising small-molecule-based cathode materials through tailoring organic structures. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale surface modification of Li-rich layered oxides for high-capacity cathodes in Li-ion batteries

Science.gov (United States)

Lan, Xiwei; Xin, Yue; Wang, Libin; Hu, Xianluo

2018-03-01

Li-rich layered oxides (LLOs) have been developed as a high-capacity cathode material for Li-ion batteries, but the structural complexity and unique initial charging behavior lead to several problems including large initial capacity loss, capacity and voltage fading, poor cyclability, and inferior rate capability. Since the surface conditions are critical to electrochemical performance and the drawbacks, nanoscale surface modification for improving LLO's properties is a general strategy. This review mainly summarizes the surface modification of LLOs and classifies them into three types of surface pre-treatment, surface gradient doping, and surface coating. Surface pre-treatment usually introduces removal of Li2O for lower irreversible capacity while surface doping is aimed to stabilize the structure during electrochemical cycling. Surface coating layers with different properties, protective layers to suppress the interface side reaction, coating layers related to structural transformation, and electronic/ionic conductive layers for better rate capability, can avoid the shortcomings of LLOs. In addition to surface modification for performance enhancement, other strategies can also be investigated to achieve high-performance LLO-based cathode materials.

Investigation of hydrogen content in chemically delithiated lithium-ion battery cathodes using prompt gamma activation analysis

International Nuclear Information System (INIS)

Aghara, S.K.; Alvarez II, E.; Venkatraman, S.; Manthiram, A.

2005-01-01

Lithium-ion batteries are widely used as a power source for portable electronic devices. Currently, only 50-70% of the theoretical capacity of the layered oxide cathode (positive electrode) materials could be reversibly used. The reason for this limitation is not fully understood in the literature. Recent structural and chemical characterizations of chemically delithiated (charged) cathodes suggest that loss of oxygen from the lattice may play a role in this regard. However, during the chemical delithiation process any proton inserted from the solvent could adversely affect the oxygen content analysis data. The challenge in addressing this issue is to detect and determine precisely the proton content in the chemically delithiated samples. The prompt gamma-ray activation analysis (PGAA) facility at the Nuclear Engineering Teaching Laboratory (NETL) is used to determine the proton content in the layered oxide cathode LiNi 0.5 Mn 0.5 O 2 before and after chemical delithiation. The data are compared with those obtained with Fourier transform infrared (FTIR) spectroscopy, which can provide mainly qualitative analysis. The technique has proved to be promising for these compounds and will be applied to characterize several other chemically delithiated Li 1-x Co 1-y M y O 2 (M = Cr, Mn, Fe, Ni, Cu, Mg, and Al) cathodes. (author)

Facile Synthesis of Boron-Doped rGO as Cathode Material for High Energy Li–O ₂ Batteries

Energy Technology Data Exchange (ETDEWEB)

Wu, Feng [Beijing Key Laboratory; amp, Engineering, Beijing Institute of Technology, Beijing 100081, PR China; Collaborative Innovation Center; Xing, Yi [Beijing Key Laboratory; amp, Engineering, Beijing Institute of Technology, Beijing 100081, PR China; Li, Li [Beijing Key Laboratory; amp, Engineering, Beijing Institute of Technology, Beijing 100081, PR China; Collaborative Innovation Center; Qian, Ji [Beijing Key Laboratory; amp, Engineering, Beijing Institute of Technology, Beijing 100081, PR China; Qu, Wenjie [Beijing Key Laboratory; amp, Engineering, Beijing Institute of Technology, Beijing 100081, PR China; Wen, Jianguo [Electron Microscopy; Miller, Dean [Electron Microscopy; Ye, Yusheng [Beijing Key Laboratory; amp, Engineering, Beijing Institute of Technology, Beijing 100081, PR China; Chen, Renjie [Beijing Key Laboratory; amp, Engineering, Beijing Institute of Technology, Beijing 100081, PR China; Collaborative Innovation Center; Amine, Khalil [Chemical Science and Engineering Division, Argonne; Lu, Jun [Chemical Science and Engineering Division, Argonne

2016-08-29

To improve the electrochemical performance of the high energy Li–O2 batteries, it is important to design and construct a suitable and effective oxygen-breathing cathode. Herein, a three-dimensional (3D) porous boron-doped reduction graphite oxide (B-rGO) material with a hierarchical structure has been prepared by a facile freeze-drying method. In this design, boric acid as the boron source helps to form the 3D porous structure, owing to its cross-linking and pore-forming function. This architecture facilitates the rapid oxygen diffusion and electrolyte penetration in the electrode. Meanwhile, the boron–oxygen functional groups linking to the carbon surface or edge serve as additional reaction sites to activate the ORR process. It is vital that boron atoms have been doped into the carbon lattices to greatly activate the electrons in the carbon π system, which is beneficial for fast charge under large current densities. Density functional theory calculation demonstrates that B-rGO exhibits much stronger interactions with Li5O6 clusters, so that B-rGO more effectively activates Li–O bonds to decompose Li2O2 during charge than rGO does. With B-rGO as a catalytic substrate, the Li–O2 battery achieves a high discharge capacity and excellent rate capability. Moreover, catalysts could be added into the B-rGO substrate to further lower the overpotential and enhance the cycling performance in future.

Electrochemical impedance spectroscopy characterization of LiFePO4 cathode material with carboxymethylcellulose and poly-3,4-ethylendioxythiophene/polystyrene sulfonate

International Nuclear Information System (INIS)

Eliseeva, S.N.; Apraksin, R.V.; Tolstopjatova, E.G.; Kondratiev, V.V.

2017-01-01

Highlights: • New composition of perspective LiFePO 4 /PEDOT:PSS/CMC cathode material are explored. • Conducting polymer binder markedly reduce an interfacial resistance. • High rate performance due to enhanced ionic and electronic conductivity. • Comparison of kinetic parameters obtained from fitting of EIS data was performed. - Abstract: Novel cathode material compositions based on lithium iron phosphate (LFP) were prepared using conducting polymer dispersion poly-3,4-ethylenedioxythiopene/polystyrene sulfonate (PEDOT:PSS) and water-based carboxymethylcellulose (РЎРњРЎ) as a binder solely and in mixture PEDOT:PSS/РЎРњРЎ. The electrochemical properties of materials in lithium-ion batteries were investigated by galvanostatic charge-discharge curves and by electrochemical impedance spectroscopy and the results were compared with conventional PVDF-bound material. Our best materials consisting of 92 wt% of C-LiFePO 4 , 4 wt% of carbon black and 4 wt% of conducting polymer binder exhibited excellent rate capability with discharge capacity 148 mAh g −1 (at 0.2C, normalized by the electrode mass), 143 mAh g −1 at 1C and 128 mAh g −1 at 5C as well as good cycling stability at 1C (less than 1% decay after 100 cycles). Impedance spectra of batteries with different compositions were measured and analyzed. Comparison of kinetic parameters obtained for different electrodes revealed main factors responsible for significant improvement of electrochemical performance of LFP-based cathode materials modified with conducting polymer in comparison with conventional electrode. The transition from conventional PVDF-bound LFP-based cathode composition to modified by conducting polymer PEDOT:PSS/CMC was found very effective. The electrode with optimal composition showed substantial decrease of interfacial charge transfer resistance for 30 times, and decrease of Warburg diffusion resistance. The mechanism of positive influence of

In-situ Electrodeposition of Highly Active Silver Catalyst on Carbon Fiber Papers as Binder Free Cathodes for Aluminum-air Battery.

Science.gov (United States)

Hong, Qingshui; Lu, Huimin

2017-06-13

Carbon fiber papers supported Ag catalysts (Ag/CFP) with different coverage of electro-active site are prepared by electrochemical deposition and used as binder free cathodes in primary aluminum-air (Al-air) battery. Scanning Electron Microscopy and X-ray Diffraction studies are carried out to characterize the as-prepared Ag/CFP air cathodes. Oxygen reduction reaction (ORR) activities on these air cathodes in alkaline solutions are systematic studied. A newly designed aluminum-air cell is used to further determine the cathodes performance under real operation condition and during the test, the Ag/CFP electrodes show outstanding catalytic activity for ORR in concentrated alkaline electrolyte, and no obvious activity degradation is observed after long-time discharge. The electrochemical test results display the dependence of coverage of the electro-active Ag on the catalytic performance of the air cathodes. The resulting primary Al-air battery made from the best-performing cathode shows an impressive discharge peak power density, outperforming that of using commercial nano-manganese catalyst air electrodes.

An Approach Toward Replacing Vanadium: A Single Organic Molecule for the Anode and Cathode of an Aqueous Redox-Flow Battery.

Science.gov (United States)

Janoschka, Tobias; Friebe, Christian; Hager, Martin D; Martin, Norbert; Schubert, Ulrich S

2017-04-01

By combining a viologen unit and a 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) radical in one single combi-molecule, an artificial bipolar redox-active material, 1-(4-(((1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy)carbonyl)benzyl)-1'-methyl-[4,4'-bipyridine]-1,1'-diium-chloride ( VIOTEMP ), was created that can serve as both the anode (-0.49 V) and cathode (0.67 V vs. Ag/AgCl) in a water-based redox-flow battery. While it mimics the redox states of flow battery metals like vanadium, the novel aqueous electrolyte does not require strongly acidic media and is best operated at pH 4. The electrochemical properties of VIOTEMP were investigated by using cyclic voltammetry, rotating disc electrode experiments, and spectroelectrochemical methods. A redox-flow battery was built and the suitability of the material for both electrodes was demonstrated through a polarity-inversion experiment. Thus, an organic aqueous electrolyte system being safe in case of cross contamination is presented.

Building Honeycomb-Like Hollow Microsphere Architecture in a Bubble Template Reaction for High-Performance Lithium-Rich Layered Oxide Cathode Materials.

Science.gov (United States)

Chen, Zhaoyong; Yan, Xiaoyan; Xu, Ming; Cao, Kaifeng; Zhu, Huali; Li, Lingjun; Duan, Junfei

2017-09-13

In the family of high-performance cathode materials for lithium-ion batteries, lithium-rich layered oxides come out in front because of a high reversible capacity exceeding 250 mAh g -1 . However, the long-term energy retention and high energy densities for lithium-rich layered oxide cathode materials require a stable structure with large surface areas. Here we propose a "bubble template" reaction to build "honeycomb-like" hollow microsphere architecture for a Li 1.2 Mn 0.52 Ni 0.2 Co 0.08 O 2 cathode material. Our material is designed with ca. 8-μm-sized secondary particles with hollow and highly exposed porous structures that promise a large flexible volume to achieve superior structure stability and high rate capability. Our preliminary electrochemical experiments show a high capacity of 287 mAh g -1 at 0.1 C and a capacity retention of 96% after 100 cycles at 1.0 C. Furthermore, the rate capability is superior without any other modifications, reaching 197 mAh g -1 at 3.0 C with a capacity retention of 94% after 100 cycles. This approach may shed light on a new material engineering for high-performance cathode materials.

A three-dimensional cathode matrix with bi-confinement effect of polysulfide for lithium-sulfur battery

Science.gov (United States)

Song, Ren-Sheng; Wang, Bo; Ruan, Ting-Ting; Wang, Lei; Luo, Hao; Wang, Fei; Gao, Tian-Tian; Wang, Dian-Long

2018-01-01

Soluble polysulfide shuttling is still the main cause of restricting the development of lithium-sulfur (Li-S) battery. Here, we propose a novel three-dimensional reduced graphene oxide@sulfur/nitrogen-doped porous carbon polyhedron/carbon nanotubes (rGO@S/NCP/CNTs) composite with bi-confinement effect of polysulfide as an effective cathode material. In rGO@S/NCP/CNTs, NCP provides physical confinement for sulfur and soluble polysulfide by its abundant micropores and mesopores, while oxygen functional groups of rGO provide strong chemical confinement to soluble polysulfide. Additionally, CNTs with one-dimensional conductivity enable facile transport of electrons. Therefore, the resulting rGO@S/NCP/CNTs composite shows an obvious enhancement in cycling performance for Li-S battery, and reversible capacities up to 738 mAh g-1 and 660 mAh g-1 over 100 and 200 cycles are remained at 0.2 C rate.

Electrode nanomaterials for lithium-ion batteries

International Nuclear Information System (INIS)

Yaroslavtsev, A B; Kulova, T L; Skundin, A M

2015-01-01

The state-of-the-art in the field of cathode and anode nanomaterials for lithium-ion batteries is considered. The use of these nanomaterials provides higher charge and discharge rates, reduces the adverse effect of degradation processes caused by volume variations in electrode materials upon lithium intercalation and deintercalation and enhances the power and working capacity of lithium-ion batteries. In discussing the cathode materials, attention is focused on double phosphates and silicates of lithium and transition metals and also on vanadium oxides. The anode materials based on nanodispersions of carbon, silicon, certain metals, oxides and on nanocomposites are also described. The bibliography includes 714 references

Verifying the Rechargeability of Li-CO2 Batteries on Working Cathodes of Ni Nanoparticles Highly Dispersed on N-Doped Graphene.

Science.gov (United States)

Zhang, Zhang; Wang, Xin-Gai; Zhang, Xu; Xie, Zhaojun; Chen, Ya-Nan; Ma, Lipo; Peng, Zhangquan; Zhou, Zhen

2018-02-01

Li-CO 2 batteries could skillfully combine the reduction of "greenhouse effect" with energy storage systems. However, Li-CO 2 batteries still suffer from unsatisfactory electrochemical performances and their rechargeability is challenged. Here, it is reported that a composite of Ni nanoparticles highly dispersed on N-doped graphene (Ni-NG) with 3D porous structure, exhibits a superior discharge capacity of 17 625 mA h g -1 , as the air cathode for Li-CO 2 batteries. The batteries with these highly efficient cathodes could sustain 100 cycles at a cutoff capacity of 1000 mA h g -1 with low overpotentials at the current density of 100 mA g -1 . Particularly, the Ni-NG cathodes allow to observe the appearance/disappearance of agglomerated Li 2 CO 3 particles and carbon thin films directly upon discharge/charge processes. In addition, the recycle of CO 2 is detected through in situ differential electrochemical mass spectrometry. This is a critical step to verify the electrochemical rechargeability of Li-CO 2 batteries. Also, first-principles computations further prove that Ni nanoparticles are active sites for the reaction of Li and CO 2 , which could guide to design more advantageous catalysts for rechargeable Li-CO 2 batteries.

A Polysulfide-Infiltrated Carbon Cloth Cathode for High-Performance Flexible Lithium–Sulfur Batteries

Directory of Open Access Journals (Sweden)

Ji-Yoon Song

2018-02-01

Full Text Available For practical application of lithium–sulfur batteries (LSBs, it is crucial to develop sulfur cathodes with high areal capacity and cycle stability in a simple and inexpensive manner. In this study, a carbon cloth infiltrated with a sulfur-containing electrolyte solution (CC-S was utilized as an additive-free, flexible, high-sulfur-loading cathode. A freestanding carbon cloth performed double duty as a current collector and a sulfur-supporting/trapping material. The active material in the form of Li2S6 dissolved in a 1 M LiTFSI-DOL/DME solution was simply infiltrated into the carbon cloth (CC during cell fabrication, and its optimal loading amount was found to be in a range between 2 and 10 mg/cm2 via electrochemical characterization. It was found that the interwoven carbon microfibers retained structural integrity against volume expansion/contraction and that the embedded uniform micropores enabled a high loading and an efficient trapping of sulfur species during cycling. The LSB coin cell employing the CC-S electrode with an areal sulfur loading of 6 mg/cm2 exhibited a high areal capacity of 4.3 and 3.2 mAh/cm2 at C/10 for 145 cycles and C/3 for 200 cycles, respectively, with minor capacity loss (<0.03%/cycle. More importantly, such high performance could also be realized in flexible pouch cells with dimensions of 2 cm × 6 cm before and after 300 bending cycles. Simple and inexpensive preparation of sulfur cathodes using CC-S electrodes, therefore, has great potential for the manufacture of high-performance flexible LSBs.

In situ study of Li-ions diffusion and deformation in Li-rich cathode materials by using scanning probe microscopy techniques

Science.gov (United States)

Zeng, Kaiyang; Li, Tao; Tian, Tian

2017-08-01

In this paper, the scanning probe microscopy (SPM) based techniques, namely, conductive-AFM, electrochemical strain microscopy (ESM) and AM-FM (amplitude modulation-frequency modulation) techniques, are used to in situ characterize the changes in topography, conductivity and elastic properties of Li-rich layered oxide cathode (Li1.2Mn0.54Ni0.13Co0.13O2) materials, in the form of nanoparticles, when subject to the external electric field. Nanoparticles are the basic building blocks for composite cathode in a Li-ion rechargeable battery. Characterization of the structure and electrochemical properties of the nanoparticles is very important to understand the performance and reliability of the battery materials and devices. In this study, the conductivity, deformation and mechanical properties of the Li-rich oxide nanoparticles under different polarities of biases are studied using the above-mentioned SPM techniques. This information can be correlated with the Li+-ion diffusion and migration in the particles under external electrical field. The results also confirm that the SPM techniques are ideal tools to study the changes in various properties of electrode materials at nano- to micro-scales during or after the ‘simulated’ battery operation conditions. These techniques can also be used to in situ characterize the electrochemical performances of other energy storage materials, especially in the form of the nanoparticles.

The Science of Electrode Materials for Lithium Batteries

Energy Technology Data Exchange (ETDEWEB)

Fultz, Brent

2007-03-15

Rechargeable lithium batteries continue to play the central role in power systems for portable electronics, and could play a role of increasing importance for hybrid transportation systems that use either hydrogen or fossil fuels. For example, fuel cells provide a steady supply of power, whereas batteries are superior when bursts of power are needed. The National Research Council recently concluded that for dismounted soldiers "Among all possible energy sources, hybrid systems provide the most versatile solutions for meeting the diverse needs of the Future Force Warrior. The key advantage of hybrid systems is their ability to provide power over varying levels of energy use, by combining two power sources." The relative capacities of batteries versus fuel cells in a hybrid power system will depend on the capabilities of both. In the longer term, improvements in the cost and safety of lithium batteries should lead to a substantial role for electrochemical energy storage subsystems as components in fuel cell or hybrid vehicles. We have completed a basic research program for DOE BES on anode and cathode materials for lithium batteries, extending over 6 years with a 1 year phaseout period. The emphasis was on the thermodynamics and kinetics of the lithiation reaction, and how these pertain to basic electrochemical properties that we measure experimentally — voltage and capacity in particular. In the course of this work we also studied the kinetic processes of capacity fade after cycling, with unusual results for nanostructued Si and Ge materials, and the dynamics underlying electronic and ionic transport in LiFePO4. This document is the final report for this work.

Review of US Nanocorp - SNL Joint Development of Thermal-Sprayed Thin-Film Cathodes for Thermal Batteries

Energy Technology Data Exchange (ETDEWEB)

GUIDOTTI,RONALD A.; REINHARDT,FREDERICK W.; DAI,JINXIANG; XIAO,T. DANNY; REISNER,DAVID E.

2000-11-14

The use of plasma spray to deposit thin metal-sulfide cathode films is described in this paper. Conventional electroactive stack components in thermal batteries are constructed from pressed-powder parts that are difficult to fabricate in large diameters in thicknesses <0.010. Plasma-sprayed electrodes do not steer from this difficulty, allowing greater energy densities and specific energies to be realized. Various co-spraying agents have been found suitable for improving the mechanical as well as electrochemical properties of plasma-sprayed cathodes for thermal batteries. These electrodes generally show equal or improved performance over conventional pressed-powder electrodes. A number of areas for future growth and development of plasma-spray technology is discussed.

Formation and effect of orientation domains in layered oxide cathodes of lithium-ion batteries

International Nuclear Information System (INIS)

Jarvis, Karalee A.; Wang, Chih-Chieh; Knight, James C.; Rabenberg, Lew; Manthiram, Arumugam; Ferreira, Paulo J.

2016-01-01

We show that in layered oxides that are employed as cathodes in lithium-ion batteries, the cation layers can order on different {111} NaCl planes within a single particle, which makes the lithium layer discontinuous across a particle. The findings challenge previous assertions that lithium undergoes 2-D diffusion in layered oxides and the data provide new insights into the decrease in rate capabilities for some layered oxides. Therefore, it is critically important to understand how these discontinuities form and how the loss of 2-D diffusion impacts the overall performance of the layered oxide cathode materials. Employing X-ray diffraction (XRD) and aberration-corrected scanning transmission electron microscopy (STEM), we find that as the material transitions from a disordered to an ordered state, it forms four orientation variants corresponding to the four {111} NaCl planes. This transition is not intrinsic to all layered oxides and appears to be more strongly affected by nickel. Furthermore, with energy dispersive spectroscopy (EDS), we show that there is an increase in the nickel concentration at the interface between each orientation variant. This reduces the rate of lithium diffusion, negatively affects the rate capability, and could be contributing to the overall capacity fade.

Synchrotron radiation-based {sup 61}Ni Mössbauer spectroscopic study of Li(Ni{sub 1/3}Mn{sub 1/3}Co{sub 1/3})O{sub 2} cathode materials of lithium ion rechargeable battery

Energy Technology Data Exchange (ETDEWEB)

Segi, Takashi, E-mail: segi.takashi@kki.kobelco.com [Kobelco Research Institute, Inc. (Japan); Masuda, Ryo; Kobayashi, Yasuhiro [Kyoto University, Research Reactor Institute (Japan); Tsubota, Takayuki [Kobelco Research Institute, Inc. (Japan); Yoda, Yoshitaka [Japan Synchrotron Radiation Research Institute, Research and Utilization Division (Japan); Seto, Makoto [Kyoto University, Research Reactor Institute (Japan)

2016-12-15

Layered rocksalt type oxides, such as Li(Ni{sub 1/3}Mn{sub 1/3}Co{sub 1/3})O{sub 2}, are widely used as the cathode active materials of lithium-ion rechargeable batteries. Because the nickel ions are associated with the role of the charge compensation at discharge and charge, the {sup 61}Ni Mössbauer measurements at 6 K using synchrotron radiation were performed to reveal the role of Ni. The Ni ions of the active materials play two roles for the redox process between the charge and discharge states of lithium-ion batteries. Half of the total Ni ions change to the low-spin Ni {sup 3+} with Jahn-Teller distortion from the Ni {sup 2+} ions of the discharge state. The remainder exhibit low-spin state divalent Ni ions.

Nuclear Magnetic Resonance Imaging of Li-ion Battery

Directory of Open Access Journals (Sweden)

D. Ohno

2010-12-01

Full Text Available Nuclear magnetic resonance (NMR imaging has high sensitivity to proton (1H and lithium (7Li. It is a useful measurement for electrolyte in Li-ion battery. 1H NMR images of lithium ion battery which is composed of LiMn2O4 / LiClO4 + propylene carbonate (PC / Li-metal have been studied. 1H NMR images of electrolyte near cathode material (LiMn2O4 showed anomalous intensity distribution, which was quite inhomogeneous. From NMR images as a function of repetition time (TR, it was concluded that the anomalous intensity distribution was not due to change of relaxation time but an indirect (spatial para-magnetization effect from cathode material. The paramagnetization induced by high magnetic field distorts linearity of magnetic gradient field, leading to apparent intensity variance. This functional image is an easy diagnostic measurement for magnetization of cathode material, which allows the possibility to check uniformity of cathode material and change of magnetization under electrochemical process.

A Combined Thermodynamics & Computational Method to Assess Lithium Composition in Anode and Cathode of Lithium Ion Batteries

International Nuclear Information System (INIS)

Zhang, Wenyu; Jiang, Lianlian; Van Durmen, Pauline; Saadat, Somaye; Yazami, Rachid

2016-01-01

With aim to address the open question of accurate determination of lithium composition in anode and cathode at a defined state of charge (SOC) of lithium ion batteries (LIB), we developed a method combining electrochemical thermodynamic measurements (ETM) and computational data fitting protocol. It is a common knowledge that in a lithium ion battery the SOC of anode and cathode differ from the SOC of the full-cell. Differences are in large part due to irreversible lithium losses within cell and to electrode mass unbalance. This implies that the lithium composition range in anode and in cathode during full charge and discharge cycle in full-cell is different from the composition range achieved in lithium half-cells of anode and cathode over their respective full SOC ranges. To the authors knowledge there is no unequivocal and practical method to determine the actual lithium composition of electrodes in a LIB, hence their SOC. Yet, accurate lithium composition assessment is fundamental not only for understanding the physics of electrodes but also for optimizing cell performances, particularly energy density and cycle life.

Prelithiated Silicon Nanowires as an Anode for Lithium Ion Batteries

KAUST Repository

Liu, Nian; Hu, Liangbing; McDowell, Matthew T.; Jackson, Ariel; Cui, Yi

2011-01-01

Silicon is one of the most promising anode materials for the next-generation high-energy lithium ion battery (LIB), while sulfur and some other lithium-free materials have recently shown high promise as cathode materials. To make a full battery out

S-containing copolymer as cathode material in poly(ethylene oxide)-based all-solid-state Li-S batteries

Science.gov (United States)

Gracia, Ismael; Ben Youcef, Hicham; Judez, Xabier; Oteo, Uxue; Zhang, Heng; Li, Chunmei; Rodriguez-Martinez, Lide M.; Armand, Michel

2018-06-01

Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur and divinylbenzene (DVB) have been studied as cathode active materials in poly(ethylene oxide) (PEO)-based all-solid-state Li-S cells. The Li-S cell comprising the optimized p(S-DVB) cathode (80:20 w/w S/DVB ratio) and lithium bis(fluorosulfonyl)imide/PEO (LiFSI/PEO) electrolyte shows high specific capacity (ca. 800 mAh g-1) and high Coulombic efficiency for 50 cycles. Most importantly, polysulfide (PS) shuttle is highly mitigated due to the strong interactions of PS species with polymer backbone in p(S-DVB). This is demonstrated by the stable cycling of the p(S-DVB)-based cell using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/PEO electrolyte, where successful charging cannot be achieved even at the first cycle with plain elemental S-based cathode material due to the severe PS shuttle phenomenon. These results suggest that inverse vulcanization copolymers are promising alternatives to elemental sulfur for enhancing the electrochemical performance of PEO-based all-solid-state Li-S cells.

Electrolytic deposition of Sn-coated mesocarbon microbeads as anode material for lithium ion battery

International Nuclear Information System (INIS)

Deng, Min-Jen; Tsai, Du-Cheng; Ho, Wen-Hsien; Li, Ching-Fei; Shieu, Fuh-Sheng

2013-01-01

Deposited of crystalline tin (Sn) coatings on mesocarbon microbead (MCMB) powder as anodes of lithium ion (Li-ion) battery was conducted in the SnSO 4 solution by a cathodic electrochemical synthesis. The Sn-coated MCMB specimens were characterized by X-ray diffraction, scanning electron microscopy, and charge/discharge tests. The synthesis condition of Sn-coated MCMB was optimized by considering the agglomeration, size, and adhesion of the samples to the current collectors in the battery. The Sn-coated MCMB electrodes exhibit increased reversible capacity without sacrificing its cycling behavior, compared with bare MCMB electrodes. It is concluded that electrolysis-deposited Sn-coated MCMB electrodes may emerge as a practical and promising anode material for secondary Li-ion batteries.

Color-Coded Batteries - Electro-Photonic Inverse Opal Materials for Enhanced Electrochemical Energy Storage and Optically Encoded Diagnostics.

Science.gov (United States)

O'Dwyer, Colm

2016-07-01

For consumer electronic devices, long-life, stable, and reasonably fast charging Li-ion batteries with good stable capacities are a necessity. For exciting and important advances in the materials that drive innovations in electrochemical energy storage (EES), modular thin-film solar cells, and wearable, flexible technology of the future, real-time analysis and indication of battery performance and health is crucial. Here, developments in color-coded assessment of battery material performance and diagnostics are described, and a vision for using electro-photonic inverse opal materials and all-optical probes to assess, characterize, and monitor the processes non-destructively in real time are outlined. By structuring any cathode or anode material in the form of a photonic crystal or as a 3D macroporous inverse opal, color-coded "chameleon" battery-strip electrodes may provide an amenable way to distinguish the type of process, the voltage, material and chemical phase changes, remaining capacity, cycle health, and state of charge or discharge of either existing or new materials in Li-ion or emerging alternative battery types, simply by monitoring its color change. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and electrochemical performance of Li2FeSiO4/C/carbon nanosphere composite cathode materials for lithium ion batteries

International Nuclear Information System (INIS)

Yang, Jinlong; Kang, Xiaochun; Hu, Lin; Gong, Xue; He, Daping; Peng, Tao; Mu, Shichun

2013-01-01

Highlights: •The Li 2 FeSiO 4 /C/CNS was prepared by effective double-carbon composite route. •The CNS as the conductivity belt connects the Li 2 FeSiO 4 /C particles. •The samples have a high capacity and excellent cyclic and rate performance. -- Abstract: Li 2 FeSiO 4 /C/carbon nanosphere (CNS) composites as cathode materials for lithium-ion batteries were synthesized by a simple hydro-chemical method. The double-carbon structural design of glucose pyrolysis-carbon (C) and CNS improved electrochemical performance of the composite where the CNS can build conductivity belts to connect the Li 2 FeSiO 4 /C particles and to favor electronic transmission. The exchange current density and the diffusion coefficient of lithium ions with the composite were 0.208 mA cm −2 and 1.06E−11 cm 2 S −1 , respectively, which were much larger than that of conventional Li 2 FeSiO 4 /C composite cathode materials (i = 0.131 mA cm −2 , D Li = 4.69E−12 cm 2 S −1 ). The electrochemical test results showed that the discharge capacity of 164.7 mA h g −1 could be obtained, and especially, after 60 cycles, 98.4% of the initial discharge capacity remained at 0.1 C of galvanostatic discharge in the potential range of 1.5–4.8 V (vs. Li/Li + ). In addition, the discharge capacity of 92.4 mA h g −1 at 5 C was easily recovered to 159.8 mA h g −1 at 0.1 C

Probing the failure mechanism of nanoscale LiFePO4 for Li-ion batteries

International Nuclear Information System (INIS)

Gu, Meng; Yan, Pengfei; Wang, Chongmin; Shi, Wei; Zheng, Jianming; Zhang, Ji-guang

2015-01-01

LiFePO 4 is a high power rate cathode material for lithium ion battery and shows remarkable capacity retention, featuring a 91% capacity retention after 3300 cycles. In this work, we use high-resolution transmission electron microscopy and electron energy loss spectroscopy to study the gradual capacity fading mechanism of LiFePO 4 materials. We found that upon prolonged electrochemical cycling of the battery, the LiFePO 4 cathode shows surface amorphization and loss of oxygen species, which directly contribute to the gradual capacity fading of the battery. The finding can guide the design and improvement of LiFePO 4 cathode for high-energy and high-power rechargeable battery for electric transportation

Calcium cation enhanced cathode/electrolyte interface property of Li2FeSiO4/C cathode for lithium-ion batteries with long-cycling life

Science.gov (United States)

Qu, Long; Li, Mingtao; Tian, Xiaolu; Liu, Pei; Yi, Yikun; Yang, Bolun

2018-03-01

Currently, the cycle performance at low rate is one of the most critical factor for realizing practical applications of Li2FeSiO4/C as a cathode of the lithium-ion batteries. To meet this challenge, calcium (Ca)-doped Li2FeSiO4/C is prepared by using the sol-gel method with soluble Li, Fe, Si and Ca sources. X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy and X-ray photoelectron spectroscopy measurements are carried out to determine the crystal structures, morphologies, particle sizes and chemical valence states of the resulting products. Rietveld refinement confirms that Ca-doped Li2FeSiO4 has a monoclinic P21/n structure and that a Ca cation occupies the Fe site in the Li2FeSiO4 lattice. The grain size of Ca-doped Li2FeSiO4 is approximately 20 nm and the nanoparticles are interconnected tightly with amorphous carbon layer. As a cathode material for the lithium-ion batteries, Li2Fe0.97Ca0.03SiO4/C delivers a high discharge capacity of 186 mAh g-1 at a 0.5 C rate. Its capacity retention after the 100th cycle reaches 87%, which increases by 25 percentage points compared with Li2FeSiO4/C. The Li2Fe0.97Ca0.03SiO4/C cathode exhibits good rate performance, with corresponding discharge capacities of 170, 157, 144 and 117 mAh g-1 at 1 C, 2 C, 5 C and 10 C rates, respectively. In summary, the improvement of the electrochemical performance can be attributed to a coefficient of the strengthened crystal structure stability during Li+ deintercalation-intercalation and restrained side reactions between electrode and electrolyte.

Process for recycling mixed-cathode materials from spent lithium-ion batteries and kinetics of leaching.

Science.gov (United States)

Li, Li; Bian, Yifan; Zhang, Xiaoxiao; Guan, Yibiao; Fan, Ersha; Wu, Feng; Chen, Renjie

2018-01-01

A "grave-to-cradle" process for the recycling of spent mixed-cathode materials (LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , and LiMn 2 O 4 ) has been proposed. The process comprises an acid leaching followed by the resynthesis of a cathode material from the resulting leachate. Spent cathode materials were leached in citric acid (C 6 H 8 O 7 ) and hydrogen peroxide (H 2 O 2 ). Optimal leaching conditions were obtained at a leaching temperature of 90 °C, a H 2 O 2 concentration of 1.5 vol%, a leaching time of 60 min, a pulp density of 20 g L -1 , and a citric acid concentration of 0.5 M. The leaching efficiencies of Li, Co, Ni, and Mn exceeded 95%. The leachate was used to resynthesize new LiCo 1/3 Ni 1/3 Mn 1/3 O 2 material by using a sol-gel method. A comparison of the electrochemical properties of the resynthesized material (NCM-spent) with that synthesized directly from original chemicals (NCM-syn) indicated that the initial discharge capacity of NCM-spent at 0.2 C was 152.8 mA h g -1 , which was higher than the 149.8 mA h g -1 of NCM-syn. After 160 cycles, the discharge capacities of the NCM-spent and NCM-syn were 140.7 mA h g -1 and 121.2 mA h g -1 , respectively. After discharge at 1 C for 300 cycles, the NCM-spent material remained a higher capacity of 113.2 mA h g -1 than the NCM-syn (78.4 mA h g -1 ). The better performance of the NCM-spent resulted from trace Al doping. A new formulation based on the shrinking-core model was proposed to explain the kinetics of the leaching process. The activation energies of the Li, Co, Ni, and Mn leaching were calculated to be 66.86, 86.57, 49.46, and 45.23 kJ mol -1 , respectively, which indicates that the leaching was a chemical reaction-controlled process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Gradiently Polymerized Solid Electrolyte Meets with Micro/Nano-Structured Cathode Array.

Science.gov (United States)

Dong, Wei; Zeng, Xian-Xiang; Zhang, Xu-Dong; Li, Jin-Yi; Shi, Ji-Lei; Xiao, Yao; Shi, Yang; Wen, Rui; Yin, Ya-Xia; Wang, Tai-Shan; Wang, Chun-Ru; Guo, Yu-Guo

2018-05-02

The poor contact between the solid-state electrolyte and cathode materials leads to high interfacial resistance, severely limiting the rate capability of solid Li metal batteries. Herein, an integrative battery design is introduced with a gradiently polymerized solid electrolyte (GPSE), a micro-channel current collector array and nano-sized cathode particles. In-situ formed GPSE encapsulates cathode nanoparticles in the micro-channel with ductile inclusions to lower interfacial impedance, and the stiff surface layer of GPSE toward anode suppresses Li dendrites growth. Li metal batteries based on GPSE and Li-free hydrogenated V2O5 (V2O5-H) cathode exhibit an outstanding high-rate response of up to 5 C (the capacity ratio of 5 C / 1 C is 90.3%) and an ultralow capacity fade rate of 0.07% per cycle over 300 cycles. Other Li-containing cathodes as LiFePO4 and LiNi0.5Mn0.3Co0.2O2 can also operate effectively at 5 C and 2 C rate, respectively. Such an ingenious design may provide new insights into other solid metal batteries through interfacial engineering manipulation at micro and nano level.

Electrochemical performance of LiV3O8 micro-rod at various calcination temperatures as cathode materials for lithium ion batteries

Science.gov (United States)

Noerochim, Lukman; Ginanjar, Edith Setia; Susanti, Diah; Prihandoko, Bambang