Identification and quantification of gases emitted during abuse tests by overcharge of a commercial Li-ion battery

Science.gov (United States)

Fernandes, Y.; Bry, A.; de Persis, S.

2018-06-01

As hazardous situations can occur during the life of a Li-ion battery, it is of great importance to understand its behavior under abusive conditions (mechanical, thermal or electrical). In particular, the study of overcharge, which consists of forcing a current through the cell, can be very helpful in improving battery safety. Very few studies in the literature have focused on the chemical reaction mechanism responsible for failure during overcharge. This is, however, of great interest because a Li-ion battery can produce reactions in a sealed container and is thus a highly reactive system. Here, experimental approaches are employed to understand the reaction mechanisms that occur during overcharge testing. Experiments consist of studying the overcharge kinetics of a commercial battery at an initial state of charge of 100%. The battery is maintained in a known volume and gaseous samples are withdrawn both at the end of the test and continuously during the test. The main gaseous species are then identified and quantified by gas phase chromatography coupled with mass spectrometry and FTIR spectroscopy. This experimental study is completed by a numerical investigation to determine the combustion parameters of the exhaust gases using a detailed reaction mechanism associated with a numerical code.

Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)-Ion Batteries.

Science.gov (United States)

Xu, Jiantie; Dou, Yuhai; Wei, Zengxi; Ma, Jianmin; Deng, Yonghong; Li, Yutao; Liu, Huakun; Dou, Shixue

2017-10-01

Lithium-ion batteries (LIBs) with higher energy density are very necessary to meet the increasing demand for devices with better performance. With the commercial success of lithiated graphite, other graphite intercalation compounds (GICs) have also been intensively reported, not only for LIBs, but also for other metal (Na, K, Al) ion batteries. In this Progress Report, we briefly review the application of GICs as anodes and cathodes in metal (Li, Na, K, Al) ion batteries. After a brief introduction on the development history of GICs, the electrochemistry of cationic GICs and anionic GICs is summarized. We further briefly summarize the use of cationic GICs and anionic GICs in alkali ion batteries and the use of anionic GICs in aluminium-ion batteries. Finally, we reach some conclusions on the drawbacks, major progress, emerging challenges, and some perspectives on the development of GICs for metal (Li, Na, K, Al) ion batteries. Further development of GICs for metal (Li, Na, K, Al) ion batteries is not only a strong supplement to the commercialized success of lithiated-graphite for LIBs, but also an effective strategy to develop diverse high-energy batteries for stationary energy storage in the future.

Flexible probe for measuring local conductivity variations in Li-ion electrode films

Science.gov (United States)

Hardy, Emilee; Clement, Derek; Vogel, John; Wheeler, Dean; Mazzeo, Brian

2018-04-01

Li-ion battery performance is governed by electronic and ionic properties of the battery. A key metric that characterizes Li-ion battery cell performance is the electronic conductivity of the electrodes, which are metal foils with thin coatings of electrochemically active materials. To accurately measure the spatial variation of electronic conductivity of these electrodes, a micro-four-line probe (μ4LP) was designed and used to non-destructively measure the properties of commercial-quality Li-ion battery films. This previous research established that the electronic conductivity of film electrodes is not homogeneous throughout the entirety of the deposited film area. In this work, a micro-N-line probe (μNLP) and a flexible micro-flex-line probe (μFLP) were developed to improve the non-destructive micro-scale conductivity measurements that we can take. These devices were validated by comparing test results to that of the predecessor, the micro-four-line probe (μ4LP), on various commercial-quality Li-ion battery electrodes. Results show that there is significant variation in conductivity on a millimeter and even micrometer length scale through the electrode film. Compared to the μ4LP, the μNLP and μFLP also introduce additional measurement configuration possibilities, while providing a more robust design. Researchers and manufacturers can use these probes to identify heterogeneity in their electrodes during the fabrication process, which will lead to the development of better batteries.

Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)‐Ion Batteries

Science.gov (United States)

Xu, Jiantie; Dou, Yuhai; Wei, Zengxi; Li, Yutao; Liu, Huakun; Dou, Shixue

2017-01-01

Abstract Lithium‐ion batteries (LIBs) with higher energy density are very necessary to meet the increasing demand for devices with better performance. With the commercial success of lithiated graphite, other graphite intercalation compounds (GICs) have also been intensively reported, not only for LIBs, but also for other metal (Na, K, Al) ion batteries. In this Progress Report, we briefly review the application of GICs as anodes and cathodes in metal (Li, Na, K, Al) ion batteries. After a brief introduction on the development history of GICs, the electrochemistry of cationic GICs and anionic GICs is summarized. We further briefly summarize the use of cationic GICs and anionic GICs in alkali ion batteries and the use of anionic GICs in aluminium‐ion batteries. Finally, we reach some conclusions on the drawbacks, major progress, emerging challenges, and some perspectives on the development of GICs for metal (Li, Na, K, Al) ion batteries. Further development of GICs for metal (Li, Na, K, Al) ion batteries is not only a strong supplement to the commercialized success of lithiated‐graphite for LIBs, but also an effective strategy to develop diverse high‐energy batteries for stationary energy storage in the future. PMID:29051856

Neutron imaging of a commercial Li-ion battery during discharge: Application of monochromatic imaging and polychromatic dynamic tomography

International Nuclear Information System (INIS)

Butler, Leslie G.; Schillinger, Burkhard; Ham, Kyungmin; Dobbins, Tabbetha A.; Liu, Ping; Vajo, John J.

2011-01-01

A commercial lithium-ion polymer battery of prismatic construction was imaged in 2D by monochromatic neutron radiography at wavelengths around a LiC 6 spectral feature. Over the range of 3-4 A, the neutron attenuation spectra for charged and discharged batteries are distinctly different. In a real-time experiment, a battery was observed during discharge at wavelengths spanning the LiC 6 spectral feature and its disappearance monitored. No evidence of 'staging' was detected in this preliminary experiment. A similar battery was imaged in 3D with a new tomographic data acquisition scheme based on the Greek golden ratio; the scheme allows convenient post-processing to establish 'time windows' for 3D image reconstruction. The 3D images at 5% state of charge intervals are compromised by beam hardening, but still show some asymmetric battery volume change with discharge. Finally comments on the future of neutron imaging for battery experiments, whether at continuous sources at nuclear reactors or at pulsed spallation sources, are discussed.

Electrical safety of commercial Li-ion cells based on NMC and NCA technology compared to LFP technology

OpenAIRE

Brand, Martin; Gläser, Simon; Geder, Jan; Menacher, Stefan; Obpacher, Sebastian; Jossen, Andreas; Quinger, Daniel

2013-01-01

Since a laptop caught fire in 2006 at the latest, Li-ion cells were considered as more dangerous than other accumulators [1]. Recent incidents, such as the one involving a BYD e6 electric taxi [2] or the Boeing Dreamliner [3], give rise to questions concerning the safety of L#i-ion cells. This is a crucial point, since Li-ion cells are increasingly integrated in all kinds of (electric) vehicles. Therefore the economic success of hybrid electric vehicles (HEV) and battery electric vehicles (BE...

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.

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.

Polymethylmethacrylate/Polyacrylonitrile Membranes via Centrifugal Spinning as Separator in Li-Ion Batteries

Directory of Open Access Journals (Sweden)

Meltem Yanilmaz

2015-04-01

Full Text Available Electrospun nanofiber membranes have been extensively studied as separators in Li-ion batteries due to their large porosity, unique pore structure, and high electrolyte uptake. However, the electrospinning process has some serious drawbacks, such as low spinning rate and high production cost. The centrifugal spinning technique can be used as a fast, cost-effective and safe technique to fabricate high-performance fiber-based separators. In this work, polymethylmethacrylate (PMMA/polyacrylonitrile (PAN membranes with different blend ratios were produced via centrifugal spinning and characterized by using different electrochemical techniques for use as separators in Li-ion batteries. Compared with commercial microporous polyolefin membrane, centrifugally-spun PMMA/PAN membranes had larger ionic conductivity, higher electrochemical oxidation limit, and lower interfacial resistance with lithium. Centrifugally-spun PMMA/PAN membrane separators were assembled into Li/LiFePO4 cells and these cells delivered high capacities and exhibited good cycling performance at room temperature. In addition, cells using centrifugally-spun PMMA/PAN membrane separators showed superior C-rate performance compared to those using microporous polypropylene (PP membranes. It is, therefore, demonstrated that centrifugally-spun PMMA/PAN membranes are promising separator candidate for high-performance Li-ion batteries.

Diffusion of Li+ ion on graphene: A DFT study

International Nuclear Information System (INIS)

Zheng Jiming; Ren Zhaoyu; Guo Ping; Fang Li; Fan Jun

2011-01-01

Density functional theory investigations show that the Li + ion is stabilized at Center of hexagonal carbon ring with the distance of 1.84 Å from graphene surface. The potential barrier of Li + ion diffusion on the graphene surface, about 0.32 eV, is much lower than that of Li + ion penetrating the carbon ring which is 10.68 eV. When a vacancy of graphene exists, potential barrier about 10.25 eV for Li + ion penetrating the defect is still high, and the ability of the vacancy to sizing the Li + ion is also observed. Electronic densities of states show that the formation of a localized bond between Li atom and edge carbon of vacancy is the main reason for high potential barrier when Li + ion penetrate a vacancy. While Coulomb repulsion is the control factor for high potential barrier in case of Li + ion penetrating a carbon ring.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-03-07

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

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.

Association and Diffusion of Li(+) in Carboxymethylcellulose Solutions for Environmentally Friendly Li-ion Batteries.

Science.gov (United States)

Casalegno, Mosè; Castiglione, Franca; Passarello, Marco; Mele, Andrea; Passerini, Stefano; Raos, Guido

2016-07-21

Carboxymethylcellulose (CMC) has been proposed as a polymeric binder for electrodes in environmentally friendly Li-ion batteries. Its physical properties and interaction with Li(+) ions in water are interesting not only from the point of view of electrode preparation-processability in water is one of the main reasons for its environmental friendliness-but also for its possible application in aqueous Li-ion batteries. We combine molecular dynamics simulations and variable-time pulsed field gradient spin-echo (PFGSE) NMR spectroscopy to investigate Li(+) transport in CMC-based solutions. Both the simulations and experimental results show that, at concentrations at which Li-CMC has a gel-like consistency, the Li(+) diffusion coefficient is still very close to that in water. These Li(+) ions interact preferentially with the carboxylate groups of CMC, giving rise to a rich variety of coordination patterns. However, the diffusion of Li(+) in these systems is essentially unrestricted, with a fast, nanosecond-scale exchange of the ions between CMC and the aqueous environment. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene-enhanced hybrid phase change materials for thermal management of Li-ion batteries

Science.gov (United States)

Goli, Pradyumna; Legedza, Stanislav; Dhar, Aditya; Salgado, Ruben; Renteria, Jacqueline; Balandin, Alexander A.

2014-02-01

Li-ion batteries are crucial components for progress in mobile communications and transport technologies. However, Li-ion batteries suffer from strong self-heating, which limits their life-time and creates reliability and environmental problems. Here we show that thermal management and the reliability of Li-ion batteries can be drastically improved using hybrid phase change material with graphene fillers. Conventional thermal management of batteries relies on the latent heat stored in the phase change material as its phase changes over a small temperature range, thereby reducing the temperature rise inside the battery. Incorporation of graphene to the hydrocarbon-based phase change material allows one to increase its thermal conductivity by more than two orders of magnitude while preserving its latent heat storage ability. A combination of the sensible and latent heat storage together with the improved heat conduction outside of the battery pack leads to a significant decrease in the temperature rise inside a typical Li-ion battery pack. The described combined heat storage-heat conduction approach can lead to a transformative change in thermal management of Li-ion and other types of batteries.

Properties of large Li ion cells using a nickel based mixed oxide

Science.gov (United States)

Broussely, M.; Blanchard, Ph; Biensan, Ph; Planchat, J. P.; Nechev, K.; Staniewicz, R. J.

The possible use of LiNiO 2 similar to LiCoO 2, as a positive material in rechargeable lithium batteries was recognized 20 years ago and starting 10 years later, many research studies led to material improvement through substitution of some of the nickel ions by other metallic ions. These modifications improve the thermal stability at high charge level or overcharge, as well as cycling and storage properties. Commercial material is now available at large industrial scale, which allows its use in big "industrial" Li ion batteries. Using low cost raw material (Ni), it is expected to be cost competitive with the manganese based systems usually mentioned as low cost on the total cell $/Wh basis. Providing higher energy density, and demonstrating excellent behavior on storage and extended cycle life, LiNiO 2 has definite advantages over the manganese system. Thanks to their properties, these batteries have demonstrated their ability to be used in lot of applications, either for transportation or standby. Their light weight makes them attractive for powering satellites. Although safety improvements are always desirable for all non-aqueous batteries using flammable organic electrolytes, suitable battery designs allow the systems to reach the acceptable level of safety required by many users. Beside the largely distributed lead acid and nickel cadmium batteries, Li ion will found its place in the "industrial batteries" market, in a proportion directly linked to its future cost reduction.

Life Prediction Model for Grid-Connected Li-ion Battery Energy Storage System: Preprint

Energy Technology Data Exchange (ETDEWEB)

Smith, Kandler A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Saxon, Aron R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Keyser, Matthew A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Lundstrom, Blake R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Cao, Ziwei [SunPower Corporation; Roc, Albert [SunPower Corp.

2017-08-25

Life Prediction Model for Grid-Connected Li-ion Battery Energy Storage System: Preprint Lithium-ion (Li-ion) batteries are being deployed on the electrical grid for a variety of purposes, such as to smooth fluctuations in solar renewable power generation. The lifetime of these batteries will vary depending on their thermal environment and how they are charged and discharged. To optimal utilization of a battery over its lifetime requires characterization of its performance degradation under different storage and cycling conditions. Aging tests were conducted on commercial graphite/nickel-manganese-cobalt (NMC) Li-ion cells. A general lifetime prognostic model framework is applied to model changes in capacity and resistance as the battery degrades. Across 9 aging test conditions from 0oC to 55oC, the model predicts capacity fade with 1.4 percent RMS error and resistance growth with 15 percent RMS error. The model, recast in state variable form with 8 states representing separate fade mechanisms, is used to extrapolate lifetime for example applications of the energy storage system integrated with renewable photovoltaic (PV) power generation.

Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility.

Science.gov (United States)

Yang, Chongyin; Suo, Liumin; Borodin, Oleg; Wang, Fei; Sun, Wei; Gao, Tao; Fan, Xiulin; Hou, Singyuk; Ma, Zhaohui; Amine, Khalil; Xu, Kang; Wang, Chunsheng

2017-06-13

Leveraging the most recent success in expanding the electrochemical stability window of aqueous electrolytes, in this work we create a unique Li-ion/sulfur chemistry of both high energy density and safety. We show that in the superconcentrated aqueous electrolyte, lithiation of sulfur experiences phase change from a high-order polysulfide to low-order polysulfides through solid-liquid two-phase reaction pathway, where the liquid polysulfide phase in the sulfide electrode is thermodynamically phase-separated from the superconcentrated aqueous electrolyte. The sulfur with solid-liquid two-phase exhibits a reversible capacity of 1,327 mAh/(g of S), along with fast reaction kinetics and negligible polysulfide dissolution. By coupling a sulfur anode with different Li-ion cathode materials, the aqueous Li-ion/sulfur full cell delivers record-high energy densities up to 200 Wh/(kg of total electrode mass) for >1,000 cycles at ∼100% coulombic efficiency. These performances already approach that of commercial lithium-ion batteries (LIBs) using a nonaqueous electrolyte, along with intrinsic safety not possessed by the latter. The excellent performance of this aqueous battery chemistry significantly promotes the practical possibility of aqueous LIBs in large-format applications.

Characteristics and properties of nano-LiCoO2 synthesized by pre-organized single source precursors: Li-ion diffusivity, electrochemistry and biological assessment.

Science.gov (United States)

Brog, Jean-Pierre; Crochet, Aurélien; Seydoux, Joël; Clift, Martin J D; Baichette, Benoît; Maharajan, Sivarajakumar; Barosova, Hana; Brodard, Pierre; Spodaryk, Mariana; Züttel, Andreas; Rothen-Rutishauser, Barbara; Kwon, Nam Hee; Fromm, Katharina M

2017-08-22

LiCoO 2 is one of the most used cathode materials in Li-ion batteries. Its conventional synthesis requires high temperature (>800 °C) and long heating time (>24 h) to obtain the micronscale rhombohedral layered high-temperature phase of LiCoO 2 (HT-LCO). Nanoscale HT-LCO is of interest to improve the battery performance as the lithium (Li + ) ion pathway is expected to be shorter in nanoparticles as compared to micron sized ones. Since batteries typically get recycled, the exposure to nanoparticles during this process needs to be evaluated. Several new single source precursors containing lithium (Li + ) and cobalt (Co 2+ ) ions, based on alkoxides and aryloxides have been structurally characterized and were thermally transformed into nanoscale HT-LCO at 450 °C within few hours. The size of the nanoparticles depends on the precursor, determining the electrochemical performance. The Li-ion diffusion coefficients of our LiCoO 2 nanoparticles improved at least by a factor of 10 compared to commercial one, while showing good reversibility upon charging and discharging. The hazard of occupational exposure to nanoparticles during battery recycling was investigated with an in vitro multicellular lung model. Our heterobimetallic single source precursors allow to dramatically reduce the production temperature and time for HT-LCO. The obtained nanoparticles of LiCoO 2 have faster kinetics for Li + insertion/extraction compared to microparticles. Overall, nano-sized LiCoO 2 particles indicate a lower cytotoxic and (pro-)inflammogenic potential in vitro compared to their micron-sized counterparts. However, nanoparticles aggregate in air and behave partially like microparticles.

Modeling Li-ion conductivity in LiLa(PO3)4 powder

International Nuclear Information System (INIS)

Mounir, Ferhi; Karima, Horchani-Naifer; Khaled, Ben Saad; Mokhtar, Férid

2012-01-01

Polycrystalline powder and single-crystal of LiLa(PO 3 ) 4 are synthesized by solid state reaction and flux technique, respectively. A morphological description of the obtained product was made based on scanning electron microscopy micrographs. The obtained powder was characterized by X-ray powder diffraction, FTIR and Raman spectroscopies. Ionic conductivity of the LiLa(PO 3 ) 4 powder was measured and evaluated over a temperature range from 553 to 913 K. Single crystals of LiLa(PO 3 ) 4 are characterized by single-crystal X-ray diffraction. The LiLa(PO 3 ) 4 structure was found to be isotypic with LiNd(PO 3 ) 4 . It crystallizes in the monoclinic system with space group C2/c and cell parameters: a=16.635(6) Å, b=7.130(3) Å, c=9.913(3) Å, β=126.37(4)°, V=946.72(6) Å 3 and Z=4. The LiLa(PO 3 ) 4 structure was described as an alternation between spiraling chains (PO 3 ) n and (La 3+ , Li + ) cations along the b direction. The small Li + ions, coordinated to four oxygen atoms, were located in the large connected cavities created between the LaO 8 polyhedra and the polyphosphate chains. The jumping of Li + through tunnels of the crystalline network was investigated using complex impedance spectroscopy. The close value of the activation energies calculated through the analysis of conductivity data and loss spectra indicate that the transport in the investigated system is through hopping mechanism. The correlation between ionic conductivity of LiLa(PO 3 ) 4 and its crystallographic structure was investigated and the most probably transport pathway model was determined.

The Surface Coating of Commercial LiFePO4 by Utilizing ZIF-8 for High Electrochemical Performance Lithium Ion Battery

Science.gov (United States)

Xu, XiaoLong; Qi, CongYu; Hao, ZhenDong; Wang, Hao; Jiu, JinTing; Liu, JingBing; Yan, Hui; Suganuma, Katsuaki

2018-03-01

The requirement of energy-storage equipment needs to develop the lithium ion battery (LIB) with high electrochemical performance. The surface modification of commercial LiFePO4 (LFP) by utilizing zeolitic imidazolate frameworks-8 (ZIF-8) offers new possibilities for commercial LFP with high electrochemical performances. In this work, the carbonized ZIF-8 (CZIF-8) was coated on the surface of LFP particles by the in situ growth and carbonization of ZIF-8. Transmission electron microscopy indicates that there is an approximate 10 nm coating layer with metal zinc and graphite-like carbon on the surface of LFP/CZIF-8 sample. The N2 adsorption and desorption isotherm suggests that the coating layer has uniform and simple connecting mesopores. As cathode material, LFP/CZIF-8 cathode-active material delivers a discharge specific capacity of 159.3 mAh g-1 at 0.1C and a discharge specific energy of 141.7 mWh g-1 after 200 cycles at 5.0C (the retention rate is approximate 99%). These results are attributed to the synergy improvement of the conductivity, the lithium ion diffusion coefficient, and the degree of freedom for volume change of LFP/CZIF-8 cathode. This work will contribute to the improvement of the cathode materials of commercial LIB.[Figure not available: see fulltext.

Thin, Flexible Secondary Li-Ion Paper Batteries

KAUST Repository

Hu, Liangbing; Wu, Hui; La Mantia, Fabio; Yang, Yuan; Cui, Yi

2010-01-01

, flexible Li-ion batteries using paper as separators and free-standing carbon nanotube thin films as both current collectors. The current collectors and Li-ion battery materials are integrated onto a single sheet of paper through a lamination process

Thermal Stability of Li-Ion Cells

International Nuclear Information System (INIS)

ROTH, EMANUEL P.

1999-01-01

The thermal stability of Li-ion cells with intercalating carbon anodes and metal oxide cathodes was measured as a function of state of charge and temperature for two advanced cell chemistries. Cells of the 18650 design with Li(sub x)CoO(sub 2) cathodes (commercial SONY cells) and Li(sub x)Ni(sub 0.8)Co(sub 0.2)O(sub 2) cathodes were measured for thermal reactivity in the open circuit cell condition. Accelerating rate calorimetry (ARC) was used to measure cell thermal runaway as a function of state of charge (SOC). Microcalorimetry was used to measure the time dependence of heat generating side reactions also as a function of SOC. Components of cells were measured using differential scanning calorimetry (DSC) to study the thermal reactivity of the individual electrodes to determine the temperature regimes and conditions of the major thermal reactions. Thermal decomposition of the SEI layer at the anodes was identified as the initiating source for thermal runaway. The cells with Li(sub x)CoO(sub 2) cathodes showed greater sensitivity to SOC and higher accelerating heating rates than seen for the cells with Li(sub x)Ni(sub 0.8)Co(sub 0.2)O(sub 2)cathodes. Lower temperature reactions starting as low as 40 C were also observed that were SOC dependent but not accelerating. These reactions were also measured in the microcalorimeter and observed to decay over time with a power-law dependence and are believed to result in irreversible capacity loss in the cells

Facile synthesis of nanostructured transition metal oxides as electrodes for Li-ion batteries

Science.gov (United States)

Opra, Denis P.; Gnedenkov, Sergey V.; Sokolov, Alexander A.; Minaev, Alexander N.; Kuryavyi, Valery G.; Sinebryukhov, Sergey L.

2017-09-01

At all times, energy storage is one of the greatest scientific challenge. Recently, Li-ion batteries are under special attention due to high working voltage, long cycle life, low self-discharge, reliability, no-memory effect. However, commercial LIBs usage in medium- and large-scale energy storage are limited by the capacity of lithiated metal oxide cathode and unsafety of graphite anode at high-rate charge. In this way, new electrode materials with higher electrochemical performance should be designed to satisfy a requirement in both energy and power. As it known, nanostructured transition metal oxides are promising electrode materials because of their elevated specific capacity and high potential vs. Li/Li+. In this work, the perspective of an original facile technique of pulsed high-voltage plasma discharge in synthesis of nanostructured transition metal oxides as electrodes for lithium-ion batteries has been demonstrated.

Electrochemical behavior and stability of a commercial activated carbon in various organic electrolyte combinations containing Li-salts

International Nuclear Information System (INIS)

Zhang, Tong; Fuchs, Bettina; Secchiaroli, Marco; Wohlfahrt-Mehrens, Margret; Dsoke, Sonia

2016-01-01

Highlights: • 1 M LiPF 6 in PC displays the widest electrochemical stability window among others couples electrolyte/activated carbon. • Electrolytes based on EC-DMC show lower impedance than electrolytes containing PC. • 1 M LiPF 6 in PC has the highest cycling stability with 75% of capacitance retention after 20 000 cycles. - Abstract: The fast development of Li-ion capacitor (LIC) technologies requires the use of low resistance and stable electrolytes. An electrolyte for a LIC not only has to provide Li for the intercalation/deintercalation of the battery-type materials, but it also needs to be compatible with the supercapacitor material. Before designing a hybrid Li-ion capacitor device containing Li-insertion and double layer-type materials, it is necessary to understand and separate the contribution of each electrode material to the resistance, capacity and stability in the chosen electrolyte. Due to the intensive research on Li-ion batteries, the interactions of Li-salt containing electrolytes combined with Li insertion materials have been extensively investigated, and a lot of literature is available on this field. In contrast, there is only little knowledge about the exclusive interaction and compatibility of Li containing electrolytes with supercapacitor-type electrode materials (in absence of battery materials). With this purpose, this paper explores the electrochemical performance of electrodes based on commercial activated carbon (AC) in various lithium salt-containing electrolytes. A standard electrolyte for Li-ion batteries (1 M LiPF 6 in EC:DMC, 1:1) is evaluated and compared with an electrolyte prepared with the same salt dissolved in propylene carbonate (1 M LiPF 6 in PC) which is a solvent typically used in commercial supercapacitors. Furthermore, two new electrolyte solutions are proposed, based on a blend of salts 0.8 M LiPF 6 + 0.2 M NEt 4 BF 4 in EC:DMC (1:1) as well as in pure PC. The effect of the electrolyte composition is evaluated

Nb-based MXenes for Li-ion battery applications

KAUST Repository

Zhu, Jiajie

2015-11-16

Li-ion batteries depend critically on the stability and capacity of the electrodes. In this respect the recently synthesized two-dimensional MXenes are promising materials, as they combine an excellent Li-ion capacity with very high charging rates. We employ density functional theory to investigate the impact of Li adsorption on the structural and electronic properties of monolayer Nb2C and Nb2CX2. The Li ions are predicted to migrate easily on the pristine MXene due to a diffusion barrier of only 36 meV, whereas larger diffusion barriers are obtained for the functionalized MXenes.

Lifecycle comparison of selected Li-ion battery chemistries under grid and electric vehicle duty cycle combinations

Science.gov (United States)

Crawford, Alasdair J.; Huang, Qian; Kintner-Meyer, Michael C. W.; Zhang, Ji-Guang; Reed, David M.; Sprenkle, Vincent L.; Viswanathan, Vilayanur V.; Choi, Daiwon

2018-03-01

Li-ion batteries are expected to play a vital role in stabilizing the electrical grid as solar and wind generation capacity becomes increasingly integrated into the electric infrastructure. This article describes how two different commercial Li-ion batteries based on LiNi0.8Co0.15Al0.05O2 (NCA) and LiFePO4 (LFP) chemistries were tested under grid duty cycles recently developed for two specific grid services: (1) frequency regulation (FR) and (2) peak shaving (PS) with and without being subjected to electric vehicle (EV) drive cycles. The lifecycle comparison derived from the capacity, round-trip efficiency (RTE), resistance, charge/discharge energy, and total used energy of the two battery chemistries are discussed. The LFP chemistry shows better stability for the energy-intensive PS service, while the NCA chemistry is more conducive to the FR service under the operating regimes investigated. The results can be used as a guideline for selection, deployment, operation, and cost analyses of Li-ion batteries used for different applications.

Ion production from LiF-coated field emitter tips

International Nuclear Information System (INIS)

Pregenzer, A.L.; Bieg, K.W.; Olson, R.E.; Panitz, J.A.

1990-01-01

Ion emission has been obtained from a LiF-coated tungsten field-emitter tip. Ion formation is thought to be caused by the high electric field experienced by the LiF. At the time of emission the electric field at the surface of the LiF is calculated to be on the order of 100 MV/cm. Inside the LiF the field is on the order of 10 MV/cm. These fields exceed the value needed to produce bulk dielectric breakdown in LiF. The surface field is of sufficient magnitude to produce ion emission by field evaporation from the crystal surface. Even prior to dielectric breakdown, precursor processes can lead to ion formation. Electric-field-stress fragmentation of the LiF layer is thought to occur, followed by ionization of the fragments

Behavior of pellet injected Li ions into heliotron E plasmas

International Nuclear Information System (INIS)

Kondo, K.; Christou, C.; Ida, K.

1996-07-01

Li pellet injection has provided a complex plasma with a large fraction of Li ions, which is characterized by intense emissions from Li I and III. The spatial profiles of the fully ionized Li 3+ ions are measured by charge exchange recombination spectroscopy with a resolution of 13 mm, and the local decay time of the injected Li ion has been estimated. The spectral profile of the charge exchange recombination line of Li 2+ from n=5 to n=4 shows a complicated structure, which depends of Li 3+ density. The effects on other intrinsic impurities and recycled Li are also discussed. (author)

Effects of additives on thermal stability of Li ion cells

Science.gov (United States)

Doughty, Daniel H.; Roth, E. Peter; Crafts, Chris C.; Nagasubramanian, G.; Henriksen, Gary; Amine, Khalil

Li ion cells are being developed for high-power applications in hybrid electric vehicles, because these cells offer superior combination of power and energy density over current cell chemistries. Cells using this chemistry are proposed for battery systems in both internal combustion engine and fuel cell-powered hybrid electric vehicles. However, the safety of these cells needs to be understood and improved for eventual widespread commercial applications. The thermal-abuse response of Li ion cells has been improved by the incorporation of more stable anode carbons and electrolyte additives. Electrolyte solutions containing vinyl ethylene carbonate (VEC), triphenyl phosphate (TPP), tris(trifluoroethyl)phosphate (TFP) as well as some proprietary flame-retardant additives were evaluated. Test cells in the 18,650 configuration were built at Sandia National Laboratories using new stable electrode materials and electrolyte additives. A special test fixture was designed to allow determination of self-generated cell heating during a thermal ramp profile. The flammability of vented gas and expelled electrolyte was studied using a novel arrangement of a spark generator placed near the cell to ignite vent gas if a flammable gas mixture was present. Flammability of vent gas was somewhat reduced by the presence of certain additives. Accelerating rate calorimetry (ARC) was also used to characterize 18,650-size test cell heat and gas generation. Gas composition was analyzed by gas chromatography (GC) and was found to consist of CO 2, H 2, CO, methane, ethane, ethylene and small amounts of C1-C4 organic molecules.

Synthesis, Structure, and Li-Ion Conductivity of LiLa(BH4)3X, X = Cl, Br, I

DEFF Research Database (Denmark)

GharibDoust, Seyed Hosein Payandeh; Brighi, Matteo; Sadikin, Yolanda

2017-01-01

In this work, a new type of addition reaction between La(BH4)3 and LiX, X = Cl, Br, I, is used to synthesize LiLa(BH4)3Cl and two new compounds LiLa(BH4)3X, X = Br, I. This method increases the amounts of LiLa(BH4)3X and the sample purity. The highest Li-ion conductivity is observed for LiLa(BH4...... with increasing lattice parameter, that is, increasing size of the halide ion in the structure. Thus, we conclude that the sizes of both windows are important for the lithium ion conduction in LiLa(BH4)3X compounds. The lithium ion conductivity is measured over one to three heating cycles and with different...

Life Prediction Model for Grid-Connected Li-ion Battery Energy Storage System

Energy Technology Data Exchange (ETDEWEB)

Smith, Kandler A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Saxon, Aron R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Keyser, Matthew A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Lundstrom, Blake R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Cao, Ziwei [SunPower Corporation; Roc, Albert [SunPower Corporation

2017-09-06

Lithium-ion (Li-ion) batteries are being deployed on the electrical grid for a variety of purposes, such as to smooth fluctuations in solar renewable power generation. The lifetime of these batteries will vary depending on their thermal environment and how they are charged and discharged. To optimal utilization of a battery over its lifetime requires characterization of its performance degradation under different storage and cycling conditions. Aging tests were conducted on commercial graphite/nickel-manganese-cobalt (NMC) Li-ion cells. A general lifetime prognostic model framework is applied to model changes in capacity and resistance as the battery degrades. Across 9 aging test conditions from 0oC to 55oC, the model predicts capacity fade with 1.4% RMS error and resistance growth with 15% RMS error. The model, recast in state variable form with 8 states representing separate fade mechanisms, is used to extrapolate lifetime for example applications of the energy storage system integrated with renewable photovoltaic (PV) power generation.

Effects of electrode properties and fabricated pressure on Li ion diffusion and diffusion-induced stresses in cylindrical Li-ion batteries

International Nuclear Information System (INIS)

Zhang, Tao; Guo, Zhansheng

2014-01-01

The effects of electrode properties and fabricated pressure on Li ion diffusion and diffusion-induced stress in a cylindrical Li-ion battery are studied. It is found that hydrostatic pressure or elastic modulus variation in the active layer have little effect on the distribution of Li ions for a higher diffusivity coefficient, but both can facilitate Li ion diffusion for a lower diffusivity coefficient. The elastic modulus variation has a significant effect on the distribution of stress and hydrostatic pressure can reduce the surface stress for the lower diffusivity coefficient. A higher charging rate causes a more transient response in the stress history, but a linear charging history is observed for slow charging rates. A higher charging rate would not inflict extra damage on the electrode for the higher diffusivity coefficient and the stress history becomes highly transient and charging rate dependent for the lower diffusivity coefficient. The effect of fabricated pressure can be neglected. (paper)

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

Directory of Open Access Journals (Sweden)

R. Miyazaki

2014-05-01

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

Storage and Effective Migration of Li-Ion for Defected β-LiFePO4 Phase Nanocrystals.

Science.gov (United States)

Guo, Hua; Song, Xiaohe; Zhuo, Zengqing; Hu, Jiangtao; Liu, Tongchao; Duan, Yandong; Zheng, Jiaxin; Chen, Zonghai; Yang, Wanli; Amine, Khalil; Pan, Feng

2016-01-13

Lithium iron phosphate, a widely used cathode material, crystallizes typically in olivine-type phase, α-LiFePO4 (αLFP). However, the new phase β-LiFePO4 (βLFP), which can be transformed from αLFP under high temperature and pressure, is originally almost electrochemically inactive with no capacity for Li-ion battery, because the Li-ions are stored in the tetrahedral [LiO4] with very high activation barrier for migration and the one-dimensional (1D) migration channels for Li-ion diffusion in αLFP disappear, while the Fe ions in the β-phase are oriented similar to the 1D arrangement instead. In this work, using experimental studies combined with density functional theory calculations, we demonstrate that βLFP can be activated with creation of effective paths of Li-ion migration by optimized disordering. Thus, the new phase of βLFP cathode achieved a capacity of 128 mAh g(-1) at a rate of 0.1 C (1C = 170 mA g(-1)) with extraordinary cycling performance that 94.5% of the initial capacity retains after 1000 cycles at 1 C. The activation mechanism can be attributed to that the induced disorder (such as FeLiLiFe antisite defects, crystal distortion, and amorphous domains) creates new lithium migration passages, which free the captive stored lithium atoms and facilitate their intercalation/deintercalation from the cathode. Such materials activated by disorder are promising candidate cathodes for lithium batteries, and the related mechanism of storage and effective migration of Li-ions also provides new clues for future design of disordered-electrode materials with high capacity and high energy density.

Electrochemical behavior of LiV3O8 positive electrode in hybrid Li,Na-ion batteries

Science.gov (United States)

Maletti, S.; Sarapulova, A.; Tsirlin, A. A.; Oswald, S.; Fauth, F.; Giebeler, L.; Bramnik, N. N.; Ehrenberg, H.; Mikhailova, D.

2018-01-01

Vanadium(V)-containing oxides show superior intercalation properties for alkaline ions, although the performance of the material strongly depends on its surface morphology. In this work, intercalation activity of LiV3O8, prepared by a conventional solid state synthesis, is demonstrated for the first time in non-aqueous Li,Na-ion hybrid batteries with Na as negative electrode, and different Na/Li ratios in the electrolyte. In the pure Na-ion cell, one Na per formula unit of LiV3O8 can be reversibly inserted at room temperature via a two-step process, while further intercalation leads to gradual amorphisation of the material, with a specific capacity of 190 mAhg-1 after 10 cycles in the potential window of 0.8-3.4 V. Hybrid Li,Na-ion batteries feature simultaneous intercalation of Li+ and Na+ cations into LiV3O8, resulting in the formation of a second phase. Depending on the electrolyte composition, this second phase bears structural similarities either to Li0.7Na0.7V3O8 in Na-rich electrolytes, or to Li4V3O8 in Li-rich electrolytes. The chemical diffusion coefficients of Na+ and Li+ in crystalline LiV3O8 are very close, hence explaining the co-intercalation of these cations. As DFT calculations show, once formed, the Li0.7Na0.7V3O8-type structure favors intercalation of Na+, whereas the LiV3O8-type prefers to accommodate Li+ cations.

Re-entrant lithium local environments and defect driven electrochemistry of Li- and Mn-rich Li-ion battery cathodes.

Science.gov (United States)

Dogan, Fulya; Long, Brandon R; Croy, Jason R; Gallagher, Kevin G; Iddir, Hakim; Russell, John T; Balasubramanian, Mahalingam; Key, Baris

2015-02-18

Direct observations of structure-electrochemical activity relationships continue to be a key challenge in secondary battery research. (6)Li magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy is the only structural probe currently available that can quantitatively characterize local lithium environments on the subnanometer scale that dominates the free energy for site occupation in lithium-ion (Li-ion) intercalation materials. In the present study, we use this local probe to gain new insights into the complex electrochemical behavior of activated 0.5(6)Li2MnO3·0.5(6)LiMn(0.5)Ni(0.5)O2, lithium- and manganese-rich transition-metal (TM) oxide intercalation electrodes. We show direct evidence of path-dependent lithium site occupation, correlated to structural reorganization of the metal oxide and the electrochemical hysteresis, during lithium insertion and extraction. We report new (6)Li resonances centered at ∼1600 ppm that are assigned to LiMn6-TM(tet) sites, specifically, a hyperfine shift related to a small fraction of re-entrant tetrahedral TMs (Mn(tet)), located above or below lithium layers, coordinated to LiMn6 units. The intensity of the TM layer lithium sites correlated with tetrahedral TMs loses intensity after cycling, indicating limited reversibility of TM migrations upon cycling. These findings reveal that defect sites, even in dilute concentrations, can have a profound effect on the overall electrochemical behavior.

Local Electric Field Facilitates High-Performance Li-Ion Batteries.

Science.gov (United States)

Liu, Youwen; Zhou, Tengfei; Zheng, Yang; He, Zhihai; Xiao, Chong; Pang, Wei Kong; Tong, Wei; Zou, Youming; Pan, Bicai; Guo, Zaiping; Xie, Yi

2017-08-22

By scrutinizing the energy storage process in Li-ion batteries, tuning Li-ion migration behavior by atomic level tailoring will unlock great potential for pursuing higher electrochemical performance. Vacancy, which can effectively modulate the electrical ordering on the nanoscale, even in tiny concentrations, will provide tempting opportunities for manipulating Li-ion migratory behavior. Herein, taking CuGeO 3 as a model, oxygen vacancies obtained by reducing the thickness dimension down to the atomic scale are introduced in this work. As the Li-ion storage progresses, the imbalanced charge distribution emerging around the oxygen vacancies could induce a local built-in electric field, which will accelerate the ions' migration rate by Coulomb forces and thus have benefits for high-rate performance. Furthermore, the thus-obtained CuGeO 3 ultrathin nanosheets (CGOUNs)/graphene van der Waals heterojunctions are used as anodes in Li-ion batteries, which deliver a reversible specific capacity of 1295 mAh g -1 at 100 mA g -1 , with improved rate capability and cycling performance compared to their bulk counterpart. Our findings build a clear connection between the atomic/defect/electronic structure and intrinsic properties for designing high-efficiency electrode materials.

Capacity Fading Mechanism of the Commercial 18650 LiFePO4-Based Lithium-Ion Batteries: An in Situ Time-Resolved High-Energy Synchrotron XRD Study.

Science.gov (United States)

Liu, Qi; Liu, Yadong; Yang, Fan; He, Hao; Xiao, Xianghui; Ren, Yang; Lu, Wenquan; Stach, Eric; Xie, Jian

2018-02-07

In situ high-energy synchrotron XRD studies were carried out on commercial 18650 LiFePO 4 cells at different cycles to track and investigate the dynamic, chemical, and structural changes in the course of long-term cycling to elucidate the capacity fading mechanism. The results indicate that the crystalline structural deterioration of the LiFePO 4 cathode and the graphite anode is unlikely to happen before capacity fades below 80% of the initial capacity. Rather, the loss of the active lithium source is the primary cause for the capacity fade, which leads to the appearance of inactive FePO 4 that is proportional to the absence of the lithium source. Our in situ HESXRD studies further show that the lithium-ion insertion and deinsertion behavior of LiFePO 4 continuously changed with cycling. For a fresh cell, the LiFePO 4 experienced a dual-phase solid-solution behavior, whereas with increasing cycle numbers, the dynamic change, which is characteristic of the continuous decay of solid solution behavior, is obvious. The unpredicted dynamic change may result from the morphology evolution of LiFePO 4 particles and the loss of the lithium source, which may be the cause of the decreased rate capability of LiFePO 4 cells after long-term cycling.

Physics of electron and lithium-ion transport in electrode materials for Li-ion batteries

International Nuclear Information System (INIS)

Wu Musheng; Xu Bo; Ouyang Chuying

2016-01-01

The physics of ionic and electrical conduction at electrode materials of lithium-ion batteries (LIBs) are briefly summarized here, besides, we review the current research on ionic and electrical conduction in electrode material incorporating experimental and simulation studies. Commercial LIBs have been widely used in portable electronic devices and are now developed for large-scale applications in hybrid electric vehicles (HEV) and stationary distributed power stations. However, due to the physical limits of the materials, the overall performance of today’s LIBs does not meet all the requirements for future applications, and the transport problem has been one of the main barriers to further improvement. The electron and Li-ion transport behaviors are important in determining the rate capacity of LIBs. (topical review)

Enhanced electrochemical properties of LiFePO4 (LFP) cathode using the carboxymethyl cellulose lithium (CMC-Li) as novel binder in lithium-ion battery.

Science.gov (United States)

Qiu, Lei; Shao, Ziqiang; Wang, Daxiong; Wang, Wenjun; Wang, Feijun; Wang, Jianquan

2014-10-13

Novel water-based binder CMC-Li is synthesized using cotton as raw material. The mechanism of the CMC-Li as a binder is reported. Electrochemical properties of batteries cathodes based on commercially available lithium iron phosphate (LiFePO4, LFP) and CMC-Li as a water-soluble binder are investigated. CMC-Li is a novel lithium-ion binder. Compare with conventional poly(vinylidene fluoride) (PVDF) binder, and the battery with CMC-Li as the binder retained 97.8% of initial reversible capacity after 200 cycles at 176 mAh g(-1), which is beyond the theoretical specific capacity of LFP. Constant current charge-discharge test results demonstrate that the LFP electrode using CMC-Li as the binder has the highest rate capability, follow closely by that using PVDF binder. The batteries have good electrochemical property, outstanding pollution-free and excellent stability. Copyright © 2014 Elsevier Ltd. All rights reserved.

Nanostructured Materials for Li-Ion Batteries and Beyond

Directory of Open Access Journals (Sweden)

Xifei Li

2016-04-01

Full Text Available This Special Issue “Nanostructured Materials for Li-Ion Batteries and Beyond” of Nanomaterials is focused on advancements in the synthesis, optimization, and characterization of nanostructured materials, with an emphasis on the application of nanomaterials for building high performance Li-ion batteries (LIBs and future systems.[...

The influence of ion hydration on nucleation and growth of LiF crystals in aqueous solution.

Science.gov (United States)

Lanaro, G; Patey, G N

2018-01-14

Molecular dynamics (MD) simulations are employed to investigate crystal nucleation and growth in oversaturated aqueous LiF solutions. Results obtained for a range of temperatures provide evidence that the rate of crystal growth is determined by a substantial energy barrier (∼49 kJ mol -1 ) related to the loss of water from the ion hydration shells. Employing direct MD simulations, we do not observe spontaneous nucleation of LiF crystals at 300 K, but nucleation is easily observable in NVT simulations at 500 K. This contrasts with the NaCl case, where crystal nucleation is directly observed in similar simulations at 300 K. Based on these observations, together with a detailed analysis of ion clustering in metastable LiF solutions, we argue that the ion dehydration barrier also plays a key role in crystal nucleation. The hydration of the relatively small Li + and F - ions strongly influences the probability of forming large, crystal-like ion clusters, which are a necessary precursor to nucleation. This important factor is not accounted for in classical nucleation theory.

Single-crystalline LiFePO4 nanosheets for high-rate Li-ion batteries.

Science.gov (United States)

Zhao, Yu; Peng, Lele; Liu, Borui; Yu, Guihua

2014-05-14

The lithiation/delithiation in LiFePO4 is highly anisotropic with lithium-ion diffusion being mainly confined to channels along the b-axis. Controlling the orientation of LiFePO4 crystals therefore plays an important role for efficient mass transport within this material. We report here the preparation of single crystalline LiFePO4 nanosheets with a large percentage of highly oriented {010} facets, which provide the highest pore density for lithium-ion insertion/extraction. The LiFePO4 nanosheets show a high specific capacity at low charge/discharge rates and retain significant capacities at high C-rates, which may benefit the development of lithium batteries with both favorable energy and power density.

Modeling Li-ion conductivity in LiLa(PO{sub 3}){sub 4} powder

Energy Technology Data Exchange (ETDEWEB)

Mounir, Ferhi, E-mail: ferhi.mounir@gmail.com [Laboratoire de Physicochimie des Materiaux Mineraux et leurs Applications, Centre National des Recherches en Sciences des Materiaux, BP No. 73, 8027 Soliman (Tunisia); Karima, Horchani-Naifer [Laboratoire de Physicochimie des Materiaux Mineraux et leurs Applications, Centre National des Recherches en Sciences des Materiaux, BP No. 73, 8027 Soliman (Tunisia); Khaled, Ben Saad [Laboratoire de Photovoltaieque, Centre des Recherches et des Technologies de l' Energie, Technopole Borj Cedria, BP No. 95, 2050 Hammam Lif (Tunisia); Mokhtar, Ferid [Laboratoire de Physicochimie des Materiaux Mineraux et leurs Applications, Centre National des Recherches en Sciences des Materiaux, BP No. 73, 8027 Soliman (Tunisia)

2012-07-01

Polycrystalline powder and single-crystal of LiLa(PO{sub 3}){sub 4} are synthesized by solid state reaction and flux technique, respectively. A morphological description of the obtained product was made based on scanning electron microscopy micrographs. The obtained powder was characterized by X-ray powder diffraction, FTIR and Raman spectroscopies. Ionic conductivity of the LiLa(PO{sub 3}){sub 4} powder was measured and evaluated over a temperature range from 553 to 913 K. Single crystals of LiLa(PO{sub 3}){sub 4} are characterized by single-crystal X-ray diffraction. The LiLa(PO{sub 3}){sub 4} structure was found to be isotypic with LiNd(PO{sub 3}){sub 4}. It crystallizes in the monoclinic system with space group C2/c and cell parameters: a=16.635(6) A, b=7.130(3) A, c=9.913(3) A, {beta}=126.37(4) Degree-Sign , V=946.72(6) A{sup 3} and Z=4. The LiLa(PO{sub 3}){sub 4} structure was described as an alternation between spiraling chains (PO{sub 3}){sub n} and (La{sup 3+}, Li{sup +}) cations along the b direction. The small Li{sup +} ions, coordinated to four oxygen atoms, were located in the large connected cavities created between the LaO{sub 8} polyhedra and the polyphosphate chains. The jumping of Li{sup +} through tunnels of the crystalline network was investigated using complex impedance spectroscopy. The close value of the activation energies calculated through the analysis of conductivity data and loss spectra indicate that the transport in the investigated system is through hopping mechanism. The correlation between ionic conductivity of LiLa(PO{sub 3}){sub 4} and its crystallographic structure was investigated and the most probably transport pathway model was determined.

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.

Thermal Stability of LiPF6 Salt and Li-ion Battery Electrolytes Containing LiPF6

OpenAIRE

Yang, Hui; Zhuang, Guorong V.; Ross Jr., Philip N.

2006-01-01

The thermal stability of the neat LiPF6 salt and of 1 molal solutions of LiPF6 in prototypical Li-ion battery solvents was studied with thermogravimetric analysis (TGA) and on-line FTIR. Pure LiPF6 salt is thermally stable up to 380 oK in a dry inert atmosphere, and its decomposition path is a simple dissociation producing LiF as solid and PF5 as gaseous products. In the presence of water (300 ppm) in the carrier gas, its decomposition onset temperature is lowered as a result of direct t...

Attainable high capacity in Li-excess Li-Ni-Ru-O rock-salt cathode for lithium ion battery

Science.gov (United States)

Wang, Xingbo; Huang, Weifeng; Tao, Shi; Xie, Hui; Wu, Chuanqiang; Yu, Zhen; Su, Xiaozhi; Qi, Jiaxin; Rehman, Zia ur; Song, Li; Zhang, Guobin; Chu, Wangsheng; Wei, Shiqiang

2017-08-01

Peroxide structure O2n- has proven to appear after electrochemical process in many lithium-excess precious metal oxides, representing extra reversible capacity. We hereby report construction of a Li-excess rock-salt oxide Li1+xNi1/2-3x/2Ru1/2+x/2O2 electrode, with cost effective and eco-friendly 3d transition metal Ni partially substituting precious 4d transition metal Ru. It can be seen that O2n- is formed in pristine Li1.23Ni0.155Ru0.615O2, and stably exists in subsequent cycles, enabling discharge capacities to 295.3 and 198 mAh g-1 at the 1st/50th cycle, respectively. Combing ex-situ X-ray absorption near edge spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, high resolution transmission electron microscopy and electrochemical characterization, we demonstrate that the excellent electrochemical performance comes from both percolation network with disordered structure and cation/anion redox couples occurring in charge-discharge process. Li-excess and substitution of common element have been demonstrated to be a breakthrough for designing novel high performance commercial cathodes in rechargeable lithium ion battery field.

Zr4+ doping in Li4Ti5O12 anode for lithium-ion batteries: open Li+ diffusion paths through structural imperfection.

Science.gov (United States)

Kim, Jae-Geun; Park, Min-Sik; Hwang, Soo Min; Heo, Yoon-Uk; Liao, Ting; Sun, Ziqi; Park, Jong Hwan; Kim, Ki Jae; Jeong, Goojin; Kim, Young-Jun; Kim, Jung Ho; Dou, Shi Xue

2014-05-01

One-dimensional nanomaterials have short Li(+) diffusion paths and promising structural stability, which results in a long cycle life during Li(+) insertion and extraction processes in lithium rechargeable batteries. In this study, we fabricated one-dimensional spinel Li4Ti5O12 (LTO) nanofibers using an electrospinning technique and studied the Zr(4+) doping effect on the lattice, electronic structure, and resultant electrochemical properties of Li-ion batteries (LIBs). Accommodating a small fraction of Zr(4+) ions in the Ti(4+) sites of the LTO structure gave rise to enhanced LIB performance, which was due to structural distortion through an increase in the average lattice constant and thereby enlarged Li(+) diffusion paths rather than changes to the electronic structure. Insulating ZrO2 nanoparticles present between the LTO grains due to the low Zr(4+) solubility had a negative effect on the Li(+) extraction capacity, however. These results could provide key design elements for LTO anodes based on atomic level insights that can pave the way to an optimal protocol to achieve particular functionalities. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal stability of LiPF 6 salt and Li-ion battery electrolytes containing LiPF 6

Science.gov (United States)

Yang, Hui; Zhuang, Guorong V.; Ross, Philip N.

The thermal stability of the neat lithium hexafluorophosphate (LiPF 6) salt and of 1 molal (m) solutions of LiPF 6 in prototypical Li-ion battery solvents was studied with thermogravimetric analysis (TGA) and on-line Fourier transform infrared (FTIR). Pure LiPF 6 salt is thermally stable up to 107 °C in a dry inert atmosphere, and its decomposition path is a simple dissociation producing lithium fluoride (LiF) as solid and PF 5 as gaseous products. In the presence of water (300 ppm) in the carrier gas, its decomposition onset temperature is lowered as a result of direct thermal reaction between LiPF 6 and water vapor to form phosphorous oxyfluoride (POF 3) and hydrofluoric acid (HF). No new products were observed in 1 m solutions of LiPF 6 in ethylene carbonate (EC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) by on-line TGA-FTIR analysis. The storage of the same solutions in sealed containers at 85 °C for 300-420 h did not produce any significant quantity of new products as well. In particular, no alkylflurophosphates were found in the solutions after storage at elevated temperature. In the absence of either an impurity like alcohol or cathode active material that may (or may not) act as a catalyst, there is no evidence of thermally induced reaction between LiPF 6 and the prototypical Li-ion battery solvents EC, PC, DMC or EMC.

Developing New Electrolytes for Advanced Li-ion Batteries

Science.gov (United States)

McOwen, Dennis Wayne

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-11-15

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

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.

PEMODELAN KONDUKTIVITAS ION DALAM STRUKTUR Li2Sc3(PO43 (Modeling Ionic Conductivity in Li2Sc3(PO43 Structure

Directory of Open Access Journals (Sweden)

Akram La Kilo

2011-11-01

Full Text Available ABSTRAK Fasa Li2Sc3(PO43 merupakan material konduktor superionik yang dapat diaplikasikan sebagai baterai yang dapat diisi ulang (rechargeable. Ion Li+ dalam struktur Li2Sc3(PO4 dapat mengalami migrasi dari posisi terisi ke posisi kosong. Penelitian ini telah memodelkan migrasi ion Li+ dalam struktur Li2Sc3(PO4 dengan menggunakan metode bond valence sum (BVS. Metode ini dapat memprediksi bilangan oksidasi suatu atom berdasarkan jarak dengan atom-atom tetangga. Source code berbasis BVS yang digunakan adalah JUMPITER yang mensimulasi efek gaya listrik eksternal yang bertindak pada ion litium sehingga nilai BVS litium dapat dipetakan terhadap jarak. Hasil simulasi menunjukkan bahwa konduksi ion Li+ dapat terjadi pada arah [010], [101], dan [120]. Namun, lintasan konduksi ion Li+ lebih mudah terjadi pada arah [120] atau bidang ab dengan nilai maksimum BVS adalah 0,982. ABSTRACT g-phase of Li2Sc3(PO43 is a lithium super ionic conductor which can be applied as a rechargeable lithium battery. Lithium ions of g-Li2Sc3(PO43 can migrate from occupied site to vacant site. In this research, simulation of Li+ ions migration in the structure of g-Li2Sc3(PO43 carried out using bond valence sum (BVS to predict the oxidation state of Li+ion based on the distance of the ion to neighboring atoms. BVS-based code used JUMPITER to simulate the effect of external electrical force acting on the lithium ions to produce the lithium BVS value which can be mapped to the distance. The simulation results shows that Li+ ion conduction can be occurred on [010], [101], and [120] directions. However, the Li ion conduction pathway occur more easily in the direction of [120] or ab plane with the BVS maximum value is 0.982.

High voltage and high specific capacity dual intercalating electrode Li-ion batteries

Science.gov (United States)

West, William C. (Inventor); Blanco, Mario (Inventor)

2010-01-01

The present invention provides high capacity and high voltage Li-ion batteries that have a carbonaceous cathode and a nonaqueous electrolyte solution comprising LiF salt and an anion receptor that binds the fluoride ion. The batteries can comprise dual intercalating electrode Li ion batteries. Methods of the present invention use a cathode and electrode pair, wherein each of the electrodes reversibly intercalate ions provided by a LiF salt to make a high voltage and high specific capacity dual intercalating electrode Li-ion battery. The present methods and systems provide high-capacity batteries particularly useful in powering devices where minimizing battery mass is important.

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.

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.

Li-ion Battery Aging Datasets

Data.gov (United States)

National Aeronautics and Space Administration — This data set has been collected from a custom built battery prognostics testbed at the NASA Ames Prognostics Center of Excellence (PCoE). Li-ion batteries were run...

Nano-structured 3D Electrodes for Li-ion Micro-batteries

OpenAIRE

Perre, Emilie

2010-01-01

A new challenging application for Li-ion battery has arisen from the rapid development of micro-electronics. Powering Micro-ElectroMechanical Systems (MEMS) such as autonomous smart-dust nodes using conventional Li-ion batteries is not possible. It is not only new batteries based on new materials but there is also a need of modifying the actual battery design. In this context, the conception of 3D nano-architectured Li-ion batteries is explored. There are several micro-battery concepts that a...

Enhanced Li-Ion Battery

Directory of Open Access Journals (Sweden)

Natasha Ross

2015-01-01

Full Text Available Au with Pd nanoparticles were synthesized and coated onto the spinel LiMn2O4 via a coprecipitation calcination method with the objective to improve the microstructure, conductivity, and electrochemical activities of pristine LiMn2O4. The novel LiPdAuxMn2-xO4 composite cathode had high phase purity, well crystallized particles, and more regular morphological structures with narrow size distributions. At enlarged cycling potential ranges the LiPdAuxMn2-xO4 sample delivered 90 mAh g−1 discharge capacity compared to LiMn2O4 (45 mAh g−1. It was concluded that even a small amount of the Pd and Au enhanced both the lithium diffusivity and electrochemical conductivity of the host sample due to the beneficial properties of their synergy.

The application of phase contrast X-ray techniques for imaging Li-ion battery electrodes

Science.gov (United States)

Eastwood, D. S.; Bradley, R. S.; Tariq, F.; Cooper, S. J.; Taiwo, O. O.; Gelb, J.; Merkle, A.; Brett, D. J. L.; Brandon, N. P.; Withers, P. J.; Lee, P. D.; Shearing, P. R.

2014-04-01

In order to accelerate the commercialization of fuel cells and batteries across a range of applications, an understanding of the mechanisms by which they age and degrade at the microstructural level is required. Here, the most widely commercialized Li-ion batteries based on porous graphite based electrodes which de/intercalate Li+ ions during charge/discharge are studied by two phase contrast enhanced X-ray imaging modes, namely in-line phase contrast and Zernike phase contrast at the micro (synchrotron) and nano (laboratory X-ray microscope) level, respectively. The rate of charge cycling is directly dependent on the nature of the electrode microstructure, which are typically complex multi-scale 3D geometries with significant microstructural heterogeneities. We have been able to characterise the porosity and the tortuosity by micro-CT as well as the morphology of 5 individual graphite particles by nano-tomography finding that while their volume varied significantly their sphericity was surprisingly similar. The volume specific surface areas of the individual grains measured by nano-CT are significantly larger than the total volume specific surface area of the electrode from the micro-CT imaging, which can be attributed to the greater particle surface area visible at higher resolution.

The application of phase contrast X-ray techniques for imaging Li-ion battery electrodes

International Nuclear Information System (INIS)

Eastwood, D.S.; Bradley, R.S.; Tariq, F.; Cooper, S.J.; Taiwo, O.O.; Gelb, J.; Merkle, A.; Brett, D.J.L.; Brandon, N.P.; Withers, P.J.; Lee, P.D.; Shearing, P.R.

2014-01-01

In order to accelerate the commercialization of fuel cells and batteries across a range of applications, an understanding of the mechanisms by which they age and degrade at the microstructural level is required. Here, the most widely commercialized Li-ion batteries based on porous graphite based electrodes which de/intercalate Li + ions during charge/discharge are studied by two phase contrast enhanced X-ray imaging modes, namely in-line phase contrast and Zernike phase contrast at the micro (synchrotron) and nano (laboratory X-ray microscope) level, respectively. The rate of charge cycling is directly dependent on the nature of the electrode microstructure, which are typically complex multi-scale 3D geometries with significant microstructural heterogeneities. We have been able to characterise the porosity and the tortuosity by micro-CT as well as the morphology of 5 individual graphite particles by nano-tomography finding that while their volume varied significantly their sphericity was surprisingly similar. The volume specific surface areas of the individual grains measured by nano-CT are significantly larger than the total volume specific surface area of the electrode from the micro-CT imaging, which can be attributed to the greater particle surface area visible at higher resolution

Battery Energy Storage Market: Commercial Scale, Lithium-ion Projects in the U.S.

Energy Technology Data Exchange (ETDEWEB)

McLaren, Joyce; Gagnon, Pieter; Anderson, Kate; Elgqvist, Emma; Fu, Ran; Remo, Tim

2016-10-01

This slide deck presents current market data on the commercial scale li-ion battery storage projects in the U.S. It includes existing project locations, cost data and project cost breakdown, a map of demand charges across the U.S. and information about how the ITC and MACRS apply to energy storage projects that are paired with solar PV technology.

Fluoro-Carbonate Solvents for Li-Ion Cells

International Nuclear Information System (INIS)

NAGASUBRAMANIAN, GANESAN

1999-01-01

A number of fluoro-carbonate solvents were evaluated as electrolytes for Li-ion cells. These solvents are fluorine analogs of the conventional electrolyte solvents such as dimethyl carbonate, ethylene carbonate, diethyl carbonate in Li-ion cells. Conductivity of single and mixed fluoro carbonate electrolytes containing 1 M LiPF(sub 6) was measured at different temperatures. These electrolytes did not freeze at -40 C. We are evaluating currently, the irreversible 1st cycle capacity loss in carbon anode in these electrolytes and the capacity loss will be compared to that in the conventional electrolytes. Voltage stability windows of the electrolytes were measured at room temperature and compared with that of the conventional electrolytes. The fluoro-carbon electrolytes appear to be more stable than the conventional electrolytes near Li voltage. Few preliminary electrochemical data of the fluoro-carbonate solvents in full cells are reported in the literature. For example, some of the fluorocarbonate solvents appear to have a wider voltage window than the conventional electrolyte solvents. For example, methyl 2,2,2 trifluoro ethyl carbonate containing 1 M LiPF(sub 6) electrolyte has a decomposition voltage exceeding 6 V vs. Li compared to and lt;5 V for conventional electrolytes. The solvent also appears to be stable in contact with lithium at room temperature

Nanostructural evolution and behavior of H and Li in ion-implanted γ-LiAlO 2

Energy Technology Data Exchange (ETDEWEB)

Jiang, Weilin; Zhang, Jiandong; Edwards, Danny J.; Overman, Nicole R.; Zhu, Zihua; Price, Lloyd; Gigax, Jonathan; Castanon, Elizabeth; Shao, Lin; Senor, David J.

2017-10-01

In-situ He+ ion irradiation is performed under a helium ion microscope to study nanostructural evolution in polycrystalline gamma-LiAlO2 pellets. Various locations within a grain, across grain boundaries and at a cavity are selected. The results exhibit He bubble formation, grain-boundary cracking, nanoparticle agglomeration, increasing surface brightness with dose, and material loss from the surface. Similar brightening effects at grain boundaries are also observed under a scanning electron microscope. Li diffusion and loss from polycrystalline gamma-LiAlO2 is faster than its monocrystalline counterpart during H2+ ion implantation at elevated temperatures. There is also more significant H diffusion and release from polycrystalline pellets during thermal annealing of 300 K implanted samples. Grain boundaries and cavities could provide a faster pathway for H and Li diffusion. H release is slightly faster from the 573 K implanted monocrystalline gamma-LiAlO2 during annealing at 773 K. Metal hydrides could be formed preferentially along the grain boundaries to immobilize hydrogen.

Microstructural Analysis of the Effects of Thermal Runaway on Li-Ion and Na-Ion Battery Electrodes

Energy Technology Data Exchange (ETDEWEB)

Finegan, Donal [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Robinson, James B. [University College London; Heenan, Thomas M. M. [University College London; Smith, Katherine [Sharp Laboratories of Europe; Kendrick, Emma [Sharp Laboratories of Europe; University College London; Brett, Daniel J. L. [University College London; Shearing, Paul R. [University College London

2017-12-06

Thermal runaway is a phenomenon that occurs due to self-sustaining reactions within batteries at elevated temperatures resulting in catastrophic failure. Here, the thermal runaway process is studied for a Li-ion and Na-ion pouch cells of similar energy density (10.5 Wh, 12 Wh, respectively) using accelerating rate calorimetry (ARC). Both cells were constructed with a z-fold configuration, with a standard shutdown separator in the Li-ion and a low-cost polypropylene (PP) separator in the Na-ion. Even with the shutdown separator, it is shown that the self-heating rate and rate of thermal runaway in Na-ion cells is significantly slower than that observed in Li-ion systems. The thermal runaway event initiates at a higher temperature in Na-ion cells. The effect of thermal runaway on the architecture of the cells is examined using X-ray microcomputed tomography, and scanning electron microscopy (SEM) is used to examine the failed electrodes of both cells. Finally, from examination of the respective electrodes, likely due to the carbonate solvent containing electrolyte, it is suggested that thermal runaway in Na-ion batteries (NIBs) occurs via a similar mechanism to that reported for Li-ion cells.

Li14P2O3N6 and Li7PN4: Computational study of two nitrogen rich crystalline LiPON electrolyte materials

Science.gov (United States)

Al-Qawasmeh, Ahmad; Holzwarth, N. A. W.

2017-10-01

Two lithium oxonitridophosphate materials are computationally examined and found to be promising solid electrolytes for possible use in all solid-state batteries having metallic Li anodes - Li14P2O3N6 and Li7PN4. The first principles simulations are in good agreement with the structural analyses reported in the literature for these materials and the computed total energies indicate that both materials are stable with respect to decomposition into binary and ternary products. The computational results suggest that both materials are likely to form metastable interfaces with Li metal. The simulations also find both materials to have Li ion migration activation energies comparable or smaller than those of related Li ion electrolyte materials. Specifically, for Li7PN4, the experimentally measured activation energy can be explained by the migration of a Li ion vacancy stabilized by a small number of O2- ions substituting for N3- ions. For Li14P2O3N6, the activation energy for Li ion migration has not yet been experimentally measured, but simulations predict it to be smaller than that measured for Li7PN4.

Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling.

Science.gov (United States)

Zhang, Xiaoyu; van Hulzen, Martijn; Singh, Deepak P; Brownrigg, Alex; Wright, Jonathan P; van Dijk, Niels H; Wagemaker, Marnix

2015-09-23

Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is hindering fundamental understanding and progress. Here we use synchrotron microbeam diffraction to disclose the cycling rate-dependent phase transition mechanism within individual particles of LiFePO4, a key Li-ion electrode material. At low (dis)charge rates well-defined nanometer thin plate-shaped domains co-exist and transform much slower and concurrent as compared with the commonly assumed mosaic transformation mechanism. As the (dis)charge rate increases phase boundaries become diffuse speeding up the transformation rates of individual grains. Direct observation of the transformation of individual grains reveals that local current densities significantly differ from what has previously been assumed, giving new insights in the working of Li-ion battery electrodes and their potential improvements.

Li-ion batteries from LiFePO{sub 4} cathode and anatase/graphene composite anode for stationary energy storage

Energy Technology Data Exchange (ETDEWEB)

Choi, Daiwon; Wang, Donghai; Viswanathan, Vish V.; Wang, Wei; Nie, Zimin; Zhang, Ji-Guang; Graff, Gordon L.; Liu, Jun; Yang, Zhenguo [Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, Richland, WA 99352 (United States); Bae, In-Tae [Small Scale Systems Integration and Packaging Center, State University of New York at Binghamton, P.O. Box 6000, Binghamton, NY 13902 (United States); Duong, Tien [US Departments of Energy, 1000 Independence Ave., Washington, DC 20858 (United States)

2010-03-15

Li-ion batteries made from LiFePO{sub 4} cathode and anatase TiO{sub 2}/graphene composite anode were investigated for potential application in stationary energy storage. Fine-structured LiFePO{sub 4} was synthesized by a novel molten surfactant approach whereas anatase TiO{sub 2}/graphene nanocomposite was prepared via self-assembly method. The full cell that operated at 1.6 V demonstrated negligible fade even after more than 700 cycles at measured 1 C rate. While with relative lower energy density than traditional Li-ion chemistries interested for vehicle applications, the Li-ion batteries based on LiFePO{sub 4}/TiO{sub 2} combination potentially offers long life and low cost, along with safety, all which are critical to the stationary applications. (author)

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.

Considerations for application of Si(Li) detectors in analyses of sub-keV, ion-induced x rays

International Nuclear Information System (INIS)

Musket, R.G.

1985-01-01

Spectroscopy of ion-induced x rays is commonly performed using lithium-drifted, silicon detectors, Si(Li), with beryllium windows. Strong absorption of x rays with energies below 1 keV occurs in even the thinnest commercially available beryllium windows and precludes useful analysis of sub-keV x rays. Access to the sub-keV x ray region can be achieved using windowless (WL) and ultra-thin-windowed (UTW) Si(Li) detectors. These detectors have been shown to be useful for spectroscopy of x rays with energies above approximately 200 eV. The properties of such detectors are reviewed with regard to analysis of ion-induced x rays. In particular, considerations of detection efficiency, output linearity, energy resolution, peak shapes, and vacuum requirements are presented. The use of ion excitation for determination of many detector properties serves to demonstrate the usefulness of WL and UTW detectors for the spectroscopy of sub-keV, ion-induced x rays. 23 refs., 4 figs

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

International Nuclear Information System (INIS)

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

2016-01-01

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

Confined Li ion migration in the silicon-graphene complex system: An ab initio investigation

Science.gov (United States)

Wang, Guoqing; Xu, Bo; Shi, Jing; Lei, Xueling; Ouyang, Chuying

2018-04-01

Silicon-Carbon complex systems play an important role in enhancing the performance of Si-based anode materials for Li ion batteries. In this work, the Li migration property of the Silicon-Graphene (Si-Gr) complex systems are investigated by using first-principles calculations. Especially, the effects of graphene coating on the migration of Li ions are discussed in detail. The distance between Si surface and graphene in the Si-Gr system significantly affects the lateral migration of Li ions. With the decrease of the distance from 4.715 to 3.844 Å, the energy barrier of Li ion migration also decreases from 0.115 to 0.067 eV, which are all lower than that of the case without graphene d(0.135 eV). However, smaller distance (3.586 Å) brings the high energy barrier (0.237 eV). Through AIMD calculations, it is found that the graphene coating in the Si-Gr complex system would result in the larger intercalation depths, more uniform distributions, and higher migration coefficients of Li ions. Further calculations of migration coefficients of Li ions at different temperature are used to obtained the activation energy for Li ions migration in the Si-Gr system, which is as low as 0.028 eV. This low activation energy shows that it is easy for Li ions migrating in the Si-Gr system. Our study provided the basically information to understand the migration mechanism of Li ions in Si-C system.

Surface studies of Li-ion and Mg battery electrodes

Science.gov (United States)

Esbenshade, Jennifer

This dissertation focuses on studies of the surfaces of both Li-ion and Mg-ion battery electrodes. A fundamental understanding of processes occurring at the electrode surface is vital to the development of advanced battery systems. Additionally, modifications to the electrode surfaces are made and further characterized for improved performance. LiMn2O4 Cathodes for Li-ion Batteries: Effect of Mn in electrolyte on anode and Au coating to minimize dissolution: LiMn2O4 (LMO) is known to dissolve Mn ions with cycling. This section focuses on both the effect of the dissolution of Mn2+ into the electrolyte as well as Au coating on the LMO to improve electrochemical performance. Electrochemical quartz crystal microbalance (EQCM) was used to monitor changes in mass on the anode, SEM and AES were used to observe changes in surface morphology and chemical composition, and potentiostatic voltammetry was used to monitor charge and discharge capacity. The effect of Cu2+ addition in place of Mn2+ was also studied, as Cu is known to form an underpotential deposition (UPD) monolayer on Au electrodes. Following this, LMO particles were coated with a Au shell by a simple and scalable electroless deposition for use as Li-ion battery cathodes. The Au shell was intended to limit the capacity fade commonly seen with LMO cathodes by reducing the dissolution of Mn. Characterization by SEM, TEM, EELS, and AFM showed that the Au shell was approximately 3 nm thick. The Au shell prevented much of the Mn from dissolving in the electrolyte with 82% and 88% less dissolved Mn in the electrolyte at room temperature and 65 ºC, respectively, as compared to the uncoated LMO. Electrochemical performance studies with half cells showed that the Au shell maintained a higher discharge capacity over 400 cycles by nearly 30% with 110 mA hr g-1 for the 400th cycle as compared to a commercial LMO at 85 mA hr g-1. Similarly, the capacity fade was reduced in full cells: the coated LMO had 47% greater capacity

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

International Nuclear Information System (INIS)

Huang Qizhao; Wang Qing

2016-01-01

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

The effect of Li2CO3 substitution on synthesis of LiBOB compounds as salt of electrolyte battery lithium ion

Science.gov (United States)

Lestariningsih, Titik; Wigayati, Etty Marty; Sabrina, Qolby; Prihandoko, Bambang; Priyono, Slamet

2018-04-01

Development of the synthesis of LiB(C2O4)2 compounds continues to evolve along with the need for electrolyte salts to support the research of the manufacture of lithium ion batteries. A study had been conducted on the effect of Li2CO3 substitution on the synthesis of LiB(C2O4)2 or LiBOB compounds. LiBOB was a major candidate to replace LiPF6 as a highly toxic lithium battery electrolyte and harmful to human health. Synthesis of Lithium bis(oxalato) borate used powder metallurgy method. The raw materials used are H2C2O4.2H2O, Li2CO3 or LiOH and H2BO3 from Merck Germany products. The materials are mixed with 2: 1: 1 mol ratio until homogeneous. The synthesis of LiBOB refers to previous research, where the heating process was done gradually. The first stage heating is carried out at 120°C for 4 hours, then the next stage heating is carried out at 240°C for 7 hours. The sample variation in this study was to distinguish the lithium source from Li2CO3 and LiOH. Characterization was done by XRD to know the phase formed, FTIR to confirm that functional group of LiB(C2O4)2 compound, SEM to know the morphological structure, and TG/DTA to know the thermal properties. The results of the analysis shows that LiBOB synthesis using Lithium source from Li2CO3 has succeeded to form LiBOB compound with more LiBOB phase composition is 59.1% and 40.9% LiBOB hydrate phase, SEM morphology shows powder consist of elongated round particle porous and similar to LiBOB commercial and show higher thermal stability.

Electrolytes and interphasial chemistry in Li ion devices

Energy Technology Data Exchange (ETDEWEB)

Xu, K. [Electrochemistry Branch, Sensors and Electron Devices Directorate, U. S. Army Research Laboratory, Adelphi, Maryland, 20783-1197 (United States)

2010-07-01

Since its appearance in 1991, the Li ion battery has been the major power source driving the rapid digitalisation of our daily life; however, much of the processes and mechanisms underpinning this newest battery chemistry remains poorly understood. As in any electrochemical device, the major challenge comes from the electrolyte/electrode interfaces, where the discontinuity in charge distribution and extreme disequality in electric forces induce diversified processes that eventually determine the kinetics of Li{sup +} intercalation chemistry. This article will summarize the most recent efforts on the fundamental understanding of the interphases in Li ion devices. Emphasis will be placed on the formation chemistry of the so-called 'SEI' on graphitic anode, the effect of solvation sheath structure of Li{sup +} on the intercalation energy barrier, and the feasibility of tailoring a desired interphase. Biologically inspired approaches to an ideal interphase will also be briefly discussed. (author)

Electrolytes and Interphasial Chemistry in Li Ion Devices

Directory of Open Access Journals (Sweden)

Kang Xu

2010-01-01

Full Text Available Since its appearance in 1991, the Li ion battery has been the major power source driving the rapid digitalization of our daily life; however, much of the processes and mechanisms underpinning this newest battery chemistry remains poorly understood. As in any electrochemical device, the major challenge comes from the electrolyte/electrode interfaces, where the discontinuity in charge distribution and extreme disequality in electric forces induce diversified processes that eventually determine the kinetics of Li+ intercalation chemistry. This article will summarize the most recent efforts on the fundamental understanding of the interphases in Li ion devices. Emphasis will be placed on the formation chemistry of the so-called “SEI” on graphitic anode, the effect of solvation sheath structure of Li+ on the intercalation energy barrier, and the feasibility of tailoring a desired interphase. Biologically inspired approaches to an ideal interphase will also be briefly discussed.

Exploring Lithium-Cobalt-Nickel Oxide Spinel Electrodes for ≥3.5 V Li-Ion Cells

Energy Technology Data Exchange (ETDEWEB)

Lee, Eungje; Blauwkamp, Joel; Castro, Fernando C.; Wu, Jinsong; Dravid, Vinayak P.; Yan, Pengfei; Wang, Chongmin; Kim, Soo; Wolverton, Christopher; Benedek, Roy; Dogan, Fulya; Park, Joong Sun; Croy, Jason R.; Thackeray, Michael M.

2016-10-19

Recent reports have indicated that a manganese oxide spinel component, when embedded in a relatively small concentration in layered xLi2MnO3(1-x)LiMO2 (M=Ni, Mn, Co) electrode systems, can act as a stabilizer that increases their capacity, rate capability, cycle life, and first-cycle efficiency. These findings prompted us to explore the possibility of exploiting lithiated cobalt oxide spinel stabilizers by taking advantage of (1) the low mobility of cobalt ions relative to manganese and nickel ions in close-packed oxides and (2) their higher potential (~3.6 V vs. Li0) relative to manganese oxide spinels (~2.9 V vs. Li0) for the spinel-to-lithiated spinel electrochemical reaction. In particular, we have revisited the structural and electrochemical properties of lithiated spinels in the LiCo1-xNixO2 (0x0.2) system, first reported almost 25 years ago, by means of high-resolution (synchrotron) X-ray diffraction, transmission electron microscopy, nuclear magnetic resonance spectroscopy, electrochemical cell tests, and theoretical calculations. The results provide a deeper understanding of the complexity of intergrown layered/lithiated spinel LiCo1-xNixO2 structures, when prepared in air between 400 and 800 C, and the impact of structural variations on their electrochemical behavior. These structures, when used in low concentration, offer the possibility of improving the cycling stability, energy, and power of high energy (≥3.5 V) lithium-ion cells.

The application of phase contrast X-ray techniques for imaging Li-ion battery electrodes

Energy Technology Data Exchange (ETDEWEB)

Eastwood, D.S. [Manchester X-ray Imaging Facility, School of Materials, University of Manchester, Manchester M13 9PL (United Kingdom); Research Complex at Harwell, Didcot, Oxon OX11 0FA (United Kingdom); Bradley, R.S. [Manchester X-ray Imaging Facility, School of Materials, University of Manchester, Manchester M13 9PL (United Kingdom); Tariq, F.; Cooper, S.J. [Dept. Earth Science and Engineering, Imperial College London, London SW7 2AZ (United Kingdom); Taiwo, O.O. [Dept. Chemical Engineering, University College London, London WC1E 7JE (United Kingdom); Gelb, J.; Merkle, A. [Carl Zeiss X-ray Microscopy Inc., Pleasanton, CA 94588 (United States); Brett, D.J.L. [Dept. Chemical Engineering, University College London, London WC1E 7JE (United Kingdom); Brandon, N.P. [Dept. Earth Science and Engineering, Imperial College London, London SW7 2AZ (United Kingdom); Withers, P.J.; Lee, P.D. [Manchester X-ray Imaging Facility, School of Materials, University of Manchester, Manchester M13 9PL (United Kingdom); Research Complex at Harwell, Didcot, Oxon OX11 0FA (United Kingdom); Shearing, P.R., E-mail: p.shearing@ucl.ac.uk [Dept. Chemical Engineering, University College London, London WC1E 7JE (United Kingdom)

2014-04-01

In order to accelerate the commercialization of fuel cells and batteries across a range of applications, an understanding of the mechanisms by which they age and degrade at the microstructural level is required. Here, the most widely commercialized Li-ion batteries based on porous graphite based electrodes which de/intercalate Li{sup +} ions during charge/discharge are studied by two phase contrast enhanced X-ray imaging modes, namely in-line phase contrast and Zernike phase contrast at the micro (synchrotron) and nano (laboratory X-ray microscope) level, respectively. The rate of charge cycling is directly dependent on the nature of the electrode microstructure, which are typically complex multi-scale 3D geometries with significant microstructural heterogeneities. We have been able to characterise the porosity and the tortuosity by micro-CT as well as the morphology of 5 individual graphite particles by nano-tomography finding that while their volume varied significantly their sphericity was surprisingly similar. The volume specific surface areas of the individual grains measured by nano-CT are significantly larger than the total volume specific surface area of the electrode from the micro-CT imaging, which can be attributed to the greater particle surface area visible at higher resolution.

Modeling all-solid-state Li-ion batteries

NARCIS (Netherlands)

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

2011-01-01

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

Cracking in Si-based anodes for Li-ion batteries

NARCIS (Netherlands)

Aifantis, KE; Dempsey, JP; Hackney, SA

2005-01-01

In attempts to increase the anode capacity of rechargeable Li-ion batteries, composite materials with micro- and nano-scale domains of Li active material surrounded by Li inactive material are being investigated. Materials such as Si, Al and Sn that provide capacities between 900 and 4000 mAh g(-1)

Si clusters/defective graphene composites as Li-ion batteries anode materials: A density functional study

International Nuclear Information System (INIS)

Li, Meng; Liu, Yue-Jie; Zhao, Jing-xiang; Wang, Xiao-guang

2015-01-01

Highlights: • We study the interaction between Si clusters with pristine and defective graphene. • We find that the binding strength of Si clusters on graphene can be enhanced to different degrees after introducing various defects. • It is found that both graphene and Si cluster in the Si/graphene composites can preserve their Li uptake ability. - Abstract: Recently, the Si/graphene hybrid composites have attracted considerable attention due to their potential application for Li-ion batteries. How to effectively anchor Si clusters to graphene substrates to ensure their stability is an important factor to determine their performance for Li-ion batteries. In the present work, we have performed comprehensive density functional theory (DFT) calculations to investigate the geometric structures, stability, and electronic properties of the deposited Si clusters on defective graphenes as well as their potential applications for Li-ion batteries. The results indicate that the interfacial bonding between these Si clusters with the pristine graphene is quietly weak with a small adsorption energy (<−0.21 eV). Due to the presence of vacancy site, the binding strength of Si clusters on defective graphene is much stronger than that of pristine one, accompanying with a certain amount of charge transfer from Si clusters to graphene substrates. Moreover, the ability of Si/graphene hybrids for Li uptake is studied by calculating the adsorption of Li atoms. We find that both graphenes and Si clusters in the Si/graphene composites preserve their Li uptake ability, indicating that graphenes not only server as buffer materials for accommodating the expansion of Si cluster, but also provide additional intercalation sites for Li

In situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates for superior Li-ion battery cathodes.

Science.gov (United States)

Ma, Zhipeng; Fan, Yuqian; Shao, Guangjie; Wang, Guiling; Song, Jianjun; Liu, Tingting

2015-02-04

The low electronic conductivity and one-dimensional diffusion channel along the b axis for Li ions are two major obstacles to achieving high power density of LiFePO4 material. Coating carbon with excellent conductivity on the tailored LiFePO4 nanoparticles therefore plays an important role for efficient charge and mass transport within this material. We report here the in situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates with highly oriented (010) facets by introducing ferrocene as a catalyst during thermal treatment. The as-obtained material exhibits superior performances for Li-ion batteries at high rate (100 C) and low temperature (-20 °C), mainly because of fast electron transport through the graphitic carbon layer and efficient Li(+)-ion diffusion through the thin nanoplates.

Improvement of the cycling performance of LiCoO2 with assistance of cross-linked PAN for lithium ion batteries

International Nuclear Information System (INIS)

Yang, Xinhe; Shen, Lanyao; Wu, Bin; Zuo, Zicheng; Mu, Daobin; Wu, Borong; Zhou, Henghui

2015-01-01

Highlights: • Cross-linked PAN coating was prepared without damaging the surface of LiCoO 2 . • The coating layer owns good electronic conductivity and mechanical strength. • The cross-linked PAN coating layer is more sufficient than Al 2 O 3 coating. • It shows much improved cyclability than that of bare and Al 2 O 3 coated LiCoO 2 . - Abstract: LiCoO 2 has been widely used in lithium ion batteries for digital electronic products. However, the limited cycling performance under high cut-off voltage hinders its commercial application. Many metal oxides and/or phosphorus coating have been reported to improve the cycling performance of LiCoO 2 . In this paper, we report on cross-linked PAN coated LiCoO 2 composite as a cathode material for lithium ion batteries. The coating layer was obtained by intermolecular crosslinking of PAN polymer chain by heat treatment at high temperature in air. The air heating process avoids the possible damage arising from the carbon thermal reduction to the surface structure of LiCoO 2 . Electrochemical test indicates that the LiCoO 2 with the cross-linked PAN coating layer shows much improved cycle performance compared with that of bare and Al 2 O 3 coated LiCoO 2 . These findings might also open new avenues to explore polymer coating for other cathode materials of lithium ion batteries

Relating the 3D electrode morphology to Li-ion battery performance; a case for LiFePO4

Science.gov (United States)

Liu, Zhao; Verhallen, Tomas W.; Singh, Deepak P.; Wang, Hongqian; Wagemaker, Marnix; Barnett, Scott

2016-08-01

One of the main goals in lithium ion battery electrode design is to increase the power density. This requires insight in the relation between the complex heterogeneous microstructure existing of active material, conductive additive and electrolyte providing the required electronic and Li-ion transport. FIB-SEM is used to determine the three phase 3D morphology, and Li-ion concentration profiles obtained with Neutron Depth Profiling (NDP) are compared for two cases, conventional LiFePO4 electrodes and better performing carbonate templated LiFePO4 electrodes. This provides detailed understanding of the impact of key parameters such as the tortuosity for electron and Li-ion transport though the electrodes. The created hierarchical pore network of the templated electrodes, containing micron sized pores, appears to be effective only at high rate charge where electrolyte depletion is hindering fast discharge. Surprisingly the carbonate templating method results in a better electronic conductive CB network, enhancing the activity of LiFePO4 near the electrolyte-electrode interface as directly observed with NDP, which in a large part is responsible for the improved rate performance both during charge and discharge. The results demonstrate that standard electrodes have a far from optimal charge transport network and that significantly improved electrode performance should be possible by engineering the microstructure.

Metal-Organic Frameworks Triggered High-Efficiency Li storage in Fe-Based Polyhedral Nanorods for Lithium-ion Batteries

International Nuclear Information System (INIS)

Shen, Lisha; Song, Huawei; Wang, Chengxin

2017-01-01

Recently, metal organic framework (MOF) nanostructures have been frequently reported in the field of energy storage, specifically for Li-ion or Na-ion storage. By inter-separating the active sites of metal cluster and organic ligands, MOF nanostructures are exceptionally promising for realizing fast ion exchange and high-efficiency transportation and addressing the intricate issues that the energy-intensive Li-ion batteries have faced over many years. The related ion-storage mechanism remains to be explored. Is the traditional redox reaction mechanism operative for these nanostructure, as it is for transitional metal oxide? Herein, taking [Fe_3O(BDC)_3(H_2O)_2(NO_3)]n (Fe-MIL-88B) as an example, an Fe-based metal organic polyhedral nanorods of MIL–88 B structure was designed as an anode for Li-ion storage. When tested at 60 mA g"−"1, the nanoporous Fe-MIL–88 B polyhedral nanorods retained a reversible capacity of 744.5 mAh g"−"1 for more than 400 cycles. Ex situ characterizations of the post-cycled electrodes revealed that both the transition metal ions and the organic ligands contributed to the high reversible specific capacity. The polyhedral nanorods electrodes held the metal-organic skeleton together throughout the battery operation, although in a somewhat different manner than the pristine ones. This further substantiated that some MOF nanostructures are more appropriate than others for stable lithiation/delithiation processes. State-of-the-art CR2032 full cells showed that a high capacity of 86.8 mAh g"−"1 that was retained after 100 cycles (herein, the capacity for the full cell was calculated based on both the weight of the anode and the cathode, and the charge-discharge rate was 0.25C), when commercial LiFePO_4 powders were used as the cathode.

Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling

NARCIS (Netherlands)

Zhang, X.; Van Hulzen, M.; Singh, D.P.; Brownrigg, A.W.; Wright, J.P.; Van Dijk, N.H.; Wagemaker, M.

2015-01-01

Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is

Equivalent circuit model parameters of a high-power Li-ion battery: Thermal and state of charge effects

Science.gov (United States)

Gomez, Jamie; Nelson, Ruben; Kalu, Egwu E.; Weatherspoon, Mark H.; Zheng, Jim P.

2011-05-01

Equivalent circuit model (EMC) of a high-power Li-ion battery that accounts for both temperature and state of charge (SOC) effects known to influence battery performance is presented. Electrochemical impedance measurements of a commercial high power Li-ion battery obtained in the temperature range 20 to 50 °C at various SOC values was used to develop a simple EMC which was used in combination with a non-linear least squares fitting procedure that used thirteen parameters for the analysis of the Li-ion cell. The experimental results show that the solution and charge transfer resistances decreased with increase in cell operating temperature and decreasing SOC. On the other hand, the Warburg admittance increased with increasing temperature and decreasing SOC. The developed model correlations that are capable of being used in process control algorithms are presented for the observed impedance behavior with respect to temperature and SOC effects. The predicted model parameters for the impedance elements Rs, Rct and Y013 show low variance of 5% when compared to the experimental data and therefore indicates a good statistical agreement of correlation model to the actual experimental values.

Carbon coated Li4Ti5O12 nanorods as superior anode material for high rate lithium ion batteries

International Nuclear Information System (INIS)

Luo, Hongjun; Shen, Laifa; Rui, Kun; Li, Hongsen; Zhang, Xiaogang

2013-01-01

Highlights: •A novel approach has been developed to fabricate 1D Li 4 Ti 5 O 12 /C nanorods by a wet-chemical route. •Carbon coating layer effectively restrict the particle growth and enhance electronic conductivity. •The Li 4 Ti 5 O 12 /C nanorods exhibit remarkable rate capability and long cycle life. -- Abstract: We describe a novel approach for the synthesis of carbon coated Li 4 Ti 5 O 12 (Li 4 Ti 5 O 12 /C) nanorods for high rate lithium ion batteries. The carbon coated TiO 2 nanotubes using the glucose as carbon source are first synthesized by hydrothermal treatment. The commercial anatase TiO 2 powder is immersed in KOH sulotion and subsequently transforms into Li 4 Ti 5 O 12 /C in LiOH solution under hydrothermal condition. Field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, nitrogen adsorption/desorption and Raman spectra are performed to characterize their morphologies and structures. Compared with the pristine Li 4 Ti 5 O 12 , one-dimensional (1D) Li 4 Ti 5 O 12 /C nanostructures show much better rate capability and cycling stability. The 1D Li 4 Ti 5 O 12 /C architectures effectively restrict the particle growth and enhance their electronic conductivity, enabling fast ion and electron transport

Synthesis, Structure, and Li-Ion Conductivity of LiLa(BH4)3X, X = Cl, Br, I

DEFF Research Database (Denmark)

Payandeh GharibDoust, SeyedHosein; Brighi, Matteo; Sadikin, Yolanda

2017-01-01

In this work, a new type of addition reaction between La(BH4)3 and LiX, X = Cl, Br, I, is used to synthesize LiLa(BH4)3Cl and two new compounds LiLa(BH4)3X, X = Br, I. This method increases the amounts of LiLa(BH4)3X and the sample purity. The highest Li-ion conductivity is observed for LiLa(BH4)...

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-12-06

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

LiFePO4/polymer/natural graphite: low cost Li-ion batteries

International Nuclear Information System (INIS)

Zaghib, K.; Striebel, K.; Guerfi, A.; Shim, J.; Armand, M.; Gauthier, M

2004-01-01

The aging and performance of natural graphite/PEO-based gel electrolyte/LiFePO 4 cells are reported. The gel polymer electrolytes were produced by electron-beam irradiation and then soaked in a liquid electrolyte. The natural graphite anode in gel electrolyte containing LiBF4-EC/GBL exhibited high reversible capacity (345 mAh/g) and high coulombic efficiency (91%). The LiFePO 4 cathode in the same gel-polymer exhibited a reversible capacity of 160 mAh/g and 93% coulombic efficiency. Better performance was obtained at high-rate discharge with 6% carbon additive in the cathode, however the graphite anode performance suffers at high rate. The Li-ion gel polymer battery shows a capacity fade of 13% after 180 cycles and has poor performance at low temperature due to low diffusion of the lithium to the graphite in the GBL system. The LiFePO 4 /gel/Li system has an excellent rate capacity. LiFePO 4 cathode material is suitable for HEV application

Mesoporous Spinel Li4Ti5O12 Nanoparticles for High Rate Lithium-ion Battery Anodes

International Nuclear Information System (INIS)

Liu, Weijian; Shao, Dan; Luo, Guoen; Gao, Qiongzhi; Yan, Guangjie; He, Jiarong; Chen, Dongyang; Yu, Xiaoyuan; Fang, Yueping

2014-01-01

Graphical abstract: - Highlights: • Mesoporous Li 4 Ti 5 O 12 nanoparticles were prepared by a simple hydrothermal method. • The mesoporous Li 4 Ti 5 O 12 nanoparticles exhibited a diameter of 40 ± 5 nm and a pore-size distribution of 6 - 8 nm. • Cells with the mesoporous Li 4 Ti 5 O 12 anode showed excellent high rate electrochemical properties. - Abstract: Mesoporous spinel lithium titanate (Li 4 Ti 5 O 12 ) nanoparticles with the diameter of 40 ± 5 nm and the pore-size distribution of 6 - 8 nm were prepared by a simple hydrothermal method. As an anode material for lithium-ion batteries, these spinel Li 4 Ti 5 O 12 mesoporous nanoparticles exhibited desirable lithium storage properties with an initial discharge capacity of 176 mAh g −1 at 1 C rate and a capacity of approximately 145 mAh g −1 after 200 cycles at a high rate of 20 C. These excellent electrochemical properties at high charge/discharge rates are due to the mesoporous nano-scale structures with small size particles, uniform mesopores and larger electrode/electrolyte contact area, which shortens the diffusion path for both electrons and Li + ions, and offers more active sites for Li + insertion-extraction process

Li ion transport in sputter deposited LiCoO{sub 2} thin films and glassy borate membranes

Energy Technology Data Exchange (ETDEWEB)

Stockhoff, Tobias; Gallasch, Tobias; Schmitz, Guido [Westfaelische Wilhelms-Universitaet Muenster, Institut fuer Materialphysik, Muenster (Germany)

2010-07-01

LiCoO{sub 2} membranes are key components of current battery technology. We investigate sputter-deposited thin films of these materials aiming at the application in all-solid-state thin film batteries. For this, LiCoO{sub 2} films (10-200 nm) were deposited onto ITO-coated glass substrates by ion beam sputtering. In addition, a part of these films are coated by an ion-conductive membrane of Li{sub 2}O-B{sub 2}O{sub 3} glasses in the thickness range of 50 to 300 nm. Structural, chemical and electrical properties of the layers are studied by means of TEM(EELS) and various electrical methods (cyclic voltammetry, chrono-amperometry/-potentiometry). Since the color of the LiCoO{sub 2} films changes from red-brown to grey during de-intercalation of Li and the substrate as well as the glassy membrane deposited on top are optical transparent, reversible Li de- and intercalation can be directly demonstrated and quantified by a measurement of light transmission through the layered system. Samples coated with an ion-conductive membrane reveal a characteristic delay in switching optical transparency which is due to the slower transport across the membrane. Varying the thickness of the glassy membrane, the d.c. ion-conductivity and permeation through the membrane is determined quantitatively. Using thin membranes in the range of a few tens of nanometers the critical current densities are way sufficient for battery applications.

Li2 NH-LiBH4 : a Complex Hydride with Near Ambient Hydrogen Adsorption and Fast Lithium Ion Conduction.

Science.gov (United States)

Wang, Han; Cao, Hujun; Zhang, Weijin; Chen, Jian; Wu, Hui; Pistidda, Claudio; Ju, Xiaohua; Zhou, Wei; Wu, Guotao; Etter, Martin; Klassen, Thomas; Dornheim, Martin; Chen, Ping

2018-01-26

Complex hydrides have played important roles in energy storage area. Here a complex hydride made of Li 2 NH and LiBH 4 was synthesized, which has a structure tentatively indexed using an orthorhombic cell with a space group of Pna2 1 and lattice parameters of a=10.121, b=6.997, and c=11.457 Å. The Li 2 NH-LiBH 4 sample (in a molar ratio of 1:1) shows excellent hydrogenation kinetics, starting to absorb H 2 at 310 K, which is more than 100 K lower than that of pristine Li 2 NH. Furthermore, the Li + ion conductivity of the Li 2 NH-LiBH 4 sample is about 1.0×10 -5  S cm -1 at room temperature, and is higher than that of either Li 2 NH or LiBH 4 at 373 K. Those unique properties of the Li 2 NH-LiBH 4 complex render it a promising candidate for hydrogen storage and Li ion conduction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

First-principles investigation of the electronic and Li-ion diffusion properties of LiFePO4 by sulfur surface modification

International Nuclear Information System (INIS)

Xu, Guigui; Zhong, Kehua; Zhang, Jian-Min; Huang, Zhigao

2014-01-01

We present a first-principles calculation for the electronic and Li-ion diffusion properties of the LiFePO 4 (010) surface modified by sulfur. The calculated formation energy indicates that the sulfur adsorption on the (010) surface of the LiFePO 4 is energetically favored. Sulfur is found to form Fe-S bond with iron. A much narrower band gap (0.67 eV) of the sulfur surface-modified LiFePO 4 [S-LiFePO 4 (010)] is obtained, indicating the better electronic conductive properties. By the nudged elastic band method, our calculations show that the activation energy of Li ions diffusion along the one-dimensional channel on the surface can be effectively reduced by sulfur surface modification. In addition, the surface diffusion coefficient of S-LiFePO 4 (010) is estimated to be about 10 −11 (cm 2 /s) at room temperature, which implies that sulfur modification will give rise to a higher Li ion carrier mobility and enhanced electrochemical performance

SAFT Li-ion Technology for High Rate Applications

National Research Council Canada - National Science Library

Nechev, Kamen; Deveney, Bridget; Guseynov, Teymur; Erbacher, John; Vukson, Stephen

2006-01-01

SAFT will present an update of its state-of-the art Very High Power (VHP) Lithium-ion (Li-ion) technology. The VHP cells are currently being qualified for use in military aircraft applications as well as in future military hybrid vehicles...

Thermal abuse performance of high-power 18650 Li-ion cells

Science.gov (United States)

Roth, E. P.; Doughty, D. H.

High-power 18650 Li-ion cells have been developed for hybrid electric vehicle applications as part of the DOE Advanced Technology Development (ATD) program. The thermal abuse response of two advanced chemistries (Gen1 and Gen2) were measured and compared with commercial Sony 18650 cells. Gen1 cells consisted of an MCMB graphite based anode and a LiNi 0.85Co 0.15O 2 cathode material while the Gen2 cells consisted of a MAG10 anode graphite and a LiNi 0.80Co 0.15 Al 0.05O 2 cathode. Accelerating rate calorimetry (ARC) and differential scanning calorimetry (DSC) were used to measure the thermal response and properties of the cells and cell materials up to 400 °C. The MCMB graphite was found to result in increased thermal stability of the cells due to more effective solid electrolyte interface (SEI) formation. The Al stabilized cathodes were seen to have higher peak reaction temperatures that also gave improved cell thermal response. The effects of accelerated aging on cell properties were also determined. Aging resulted in improved cell thermal stability with the anodes showing a rapid reduction in exothermic reactions while the cathodes only showed reduced reactions after more extended aging.

Surface Modification Technique of Cathode Materials for LI-ION Battery

Science.gov (United States)

Jia, Yongzhong; Han, Jinduo; Jing, Yan; Jin, Shan; Qi, Taiyuan

Cathode materials for Li-ion battery LiMn2O4 and LiCo0.1Mn1.9O4 were prepared by soft chemical method. Carbon, which was made by decomposing organic compounds, was used as modifying agent. Cathode material matrix was mixed with water solution that had contained organic compound such as cane sugar, soluble amylum, levulose et al. These mixture were reacted at 150 200 °C for 0.5 4 h in a Teflon-lined autoclave to get a series of homogeneously C-coated cathode materials. The new products were analyzed by X-ray diffraction (XRD) and infrared (IR). Morphology of cathode materials was characterized by scanning electron microscope (SEM) and transition electron microscope (TEM). The new homogeneously C-coated products that were used as cathode materials of lithium-ion battery had good electrochemical stability and cycle performance. This technique has free-pollution, low cost, simpleness and easiness to realize the industrialization of the cathode materials for Li-ion battery.

A comprehensive study on Li-ion battery nail penetrations and the possible solutions

International Nuclear Information System (INIS)

Zhao, Rui; Liu, Jie; Gu, Junjie

2017-01-01

Li-ion batteries are the state-of-the-art power sources for portable electronics, electric vehicles, and aerospace applications. The safety issues regarding Li-ion batteries arouse particular attentions after several accidents reported in recent years. Among various abuse conditions, nail penetration is one of the most dangerous for Li-ion batteries due to the accumulated heat generation, which could give rise to the thermal runaway and could damage entire energy storage system. In this paper, an electrochemical-thermal coupling model is developed to study the nail penetration process of Li-ion batteries. By introducing joule heating at the nail location, the model shows good agreement with the testing results. With this verified model, a comprehensive parametric study is carried out to investigate the effects of battery capacity, internal resistance, and nail diameter on the electrochemical and thermal behaviors of Li-ion batteries during the penetration processes. Furthermore, three possible solutions to prevent the thermal runaway, which includes decreasing the state of charge, improving heat dissipation, and increasing contact resistance, are compared and discussed in detail based on a series of simulations. - Highlights: • A coupling model is developed to simulate Li-ion battery nail penetrations. • A contact resistance – contact area curve is plotted based on experiments. • Simulation results show good agreements with nail tests. • The behaviors of Li-ion batteries in different penetration scenarios are studied. • Possible strategies to prevent thermal runaway are investigated and discussed.

Spatial atomic layer deposition for coating flexible porous Li-ion battery electrodes

Energy Technology Data Exchange (ETDEWEB)

Yersak, Alexander S.; Sharma, Kashish; Wallas, Jasmine M.; Dameron, Arrelaine A.; Li, Xuemin; Yang, Yongan; Hurst, Katherine E.; Ban, Chunmei; Tenent, Robert C.; George, Steven M. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309 and Department of Mechanical Engineering, University of Colorado, Boulder, Colorado 80309

2018-01-01

Ultrathin atomic layer deposition (ALD) coatings on the electrodes of Li-ion batteries can enhance the capacity stability of the Li-ion batteries. To commercialize ALD for Li-ion battery production, spatial ALD is needed to decrease coating times and provide a coating process compatible with continuous roll-to-roll (R2R) processing. The porous electrodes of Li-ion batteries provide a special challenge because higher reactant exposures are needed for spatial ALD in porous substrates. This work utilized a modular rotating cylinder spatial ALD reactor operating at rotation speeds up to 200 revolutions/min (RPM) and substrate speeds up to 200 m/min. The conditions for spatial ALD were adjusted to coat flexible porous substrates. The reactor was initially used to characterize spatial Al2O3 and ZnO ALD on flat, flexible metalized polyethylene terephthalate foils. These studies showed that slower rotation speeds and spacers between the precursor module and the two adjacent pumping modules could significantly increase the reactant exposure. The modular rotating cylinder reactor was then used to coat flexible, model porous anodic aluminum oxide (AAO) membranes. The uniformity of the ZnO ALD coatings on the porous AAO membranes was dependent on the aspect ratio of the pores and the reactant exposures. Larger reactant exposures led to better uniformity in the pores with higher aspect ratios. The reactant exposures were increased by adding spacers between the precursor module and the two adjacent pumping modules. The modular rotating cylinder reactor was also employed for Al2O3 ALD on porous LiCoO2 (LCO) battery electrodes. Uniform Al coverages were obtained using spacers between the precursor module and the two adjacent pumping modules at rotation speeds of 25 and 50 RPM. The LCO electrodes had a thickness of ~49 um and pores with aspect ratios of ~12-25. Coin cells were then constructed using the ALD-coated LCO electrodes and were tested to determine their battery

Lithium metal microreference electrodes and their applications to Li-ion batteries

NARCIS (Netherlands)

Zhou, J.

2007-01-01

Li-ion batteries are nowadays widely used as power sources for a wide variety of electronic devices by virtue of their high cell voltage, high energy density and excellent cyclability. Though the performance of Li-ion batteries has been greatly improved during the last decade, it is still, to some

Electrochemical behavior of LiCoO2 as aqueous lithium-ion battery electrodes

KAUST Repository

Ruffo, Riccardo

2009-02-01

Despite the large number of studies on the behavior of LiCoO2 in organic electrolytes and its recent application as a positive electrode in rechargeable water battery prototypes, a little information is available about the lithium intercalation reaction in this layered compound in aqueous electrolytes. This work shows that LiCoO2 electrodes can be reversibly cycled in LiNO3 aqueous electrolytes for tens of cycles at remarkably high rates with impressive values specific capacity higher than 100 mAh/g, and with a coulomb efficiency greater than 99.7%. Stable and reproducible cycling measurements have been made using a simple cell design that can be easily applied to the study of other intercalation materials, assuming that they are stable in water and that their intercalation potential range matches the electrochemical stability window of the aqueous electrolyte. The experimental arrangement uses a three-electrode flooded cell in which another insertion compound acts as a reversible source and sink of lithium ions, i.e., as the counter electrode. A commercial reference electrode is also present. Both the working and the counter electrodes have been prepared as thin layers on a metallic substrate using the procedures typical for the study of electrodes for lithium-ion batteries in organic solvent electrolytes. © 2008 Elsevier B.V. All rights reserved.

Activated graphene as a cathode material for Li-ion hybrid supercapacitors.

Science.gov (United States)

Stoller, Meryl D; Murali, Shanthi; Quarles, Neil; Zhu, Yanwu; Potts, Jeffrey R; Zhu, Xianjun; Ha, Hyung-Wook; Ruoff, Rodney S

2012-03-14

Chemically activated graphene ('activated microwave expanded graphite oxide', a-MEGO) was used as a cathode material for Li-ion hybrid supercapacitors. The performance of a-MEGO was first verified with Li-ion electrolyte in a symmetrical supercapacitor cell. Hybrid supercapacitors were then constructed with a-MEGO as the cathode and with either graphite or Li(4)Ti(5)O(12) (LTO) for the anode materials. The results show that the activated graphene material works well in a symmetrical cell with the Li-ion electrolyte with specific capacitances as high as 182 F g(-1). In a full a-MEGO/graphite hybrid cell, specific capacitances as high as 266 F g(-1) for the active materials at operating potentials of 4 V yielded gravimetric energy densities for a packaged cell of 53.2 W h kg(-1).

Comparison of electrochemical performances of olivine NaFePO4 in sodium-ion batteries and olivine LiFePO4 in lithium-ion batteries.

Science.gov (United States)

Zhu, Yujie; Xu, Yunhua; Liu, Yihang; Luo, Chao; Wang, Chunsheng

2013-01-21

Carbon-coated olivine NaFePO(4) (C-NaFePO(4)) spherical particles with a uniform diameter of ∼80 nm are obtained by chemical delithiation and subsequent electrochemical sodiation of carbon-coated olivine LiFePO(4) (C-LiFePO(4)), which is synthesized by a solvothermal method. The C-NaFePO(4) electrodes are identical (particle size, particle size distribution, surface coating, and active material loading, etc.) to C-LiFePO(4) except that Li ions in C-LiFePO(4) are replaced by Na ions, making them ideal for comparison of thermodynamics and kinetics between C-NaFePO(4) cathode in sodium-ion (Na-ion) batteries and C-LiFePO(4) in lithium-ion (Li-ion) batteries. In this paper, the equilibrium potentials, reaction resistances, and diffusion coefficient of Na in C-NaFePO(4) are systematically investigated by using the galvanostatic intermittent titration technique (GITT), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV), and compared to those of the well-known LiFePO(4) cathodes in Li-ion batteries. Due to the lower diffusion coefficient of Na-ion and higher contact and charge transfer resistances in NaFePO(4) cathodes, the rate performance of C-NaFePO(4) in Na-ion batteries is much worse than that of C-LiFePO(4) in Li-ion batteries. However, the cycling stability of C-NaFePO(4) is almost comparable to C-LiFePO(4) by retaining 90% of its capacity even after 100 charge-discharge cycles at a charge-discharge rate of 0.1 C.

Direction-dependent RBS channelling studies in ion implanted LiNbO{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Wendler, E., E-mail: elke.wendler@uni-jena.de; Becker, G.; Rensberg, J.; Schmidt, E.; Wolf, S.; Wesch, W.

2016-07-15

Damage formation in ion implanted LiNbO{sub 3} was studied by Rutherford backscattering spectrometry (RBS) along various directions of the LiNbO{sub 3} crystal. From the results obtained it can be unambiguously concluded that Nb atoms being displaced during ion implantation preferably occupy the free octahedron sites of the LiNbO{sub 3} lattice structure and most likely also form Nb{sub Li} antisite defects.

Formation of positive cluster ions Li(n) Br (n = 2-7) and ionization energies studied by thermal ionization mass spectrometry.

Science.gov (United States)

Veličković, S R; Đustebek, J B; Veljković, F M; Veljković, M V

2012-05-01

Clusters of the type Li(n)X (X = halides) can be considered as potential building blocks of cluster-assembly materials. In this work, Li(n)Br (n = 2-7) clusters were obtained by a thermal ionization source of modified design and selected by a magnetic sector mass spectrometer. Positive ions of the Li(n)Br (n = 4-7) cluster were detected for the first time. The order of ion intensities was Li(2)Br(+) > Li(4)Br(+) > Li(5)Br(+) > Li(6)Br(+) > Li(3)Br(+). The ionization energies (IEs) were measured and found to be 3.95 ± 0.20 eV for Li(2)Br, 3.92 ± 0.20 eV for Li(3)Br, 3.93 ± 0.20 eV for Li(4)Br, 4.08 ± 0.20 eV for Li(5)Br, 4.14 ± 0.20 eV for Li(6)Br and 4.19 ± 0.20 eV for Li(7)Br. All of these clusters have a much lower ionization potential than that of the lithium atom, so they belong to the superalkali class. The IEs of Li(n)Br (n = 2-4) are slightly lower than those in the corresponding small Li(n) or Li(n)H clusters, whereas the IEs of Li(n)Br are very similar to those of Li(n) or Li(n)H for n = 5 and 6. The thermal ionization source of modified design is an important means for simultaneously obtaining and measuring the IEs of Li(n)Br (n = 2-7) clusters (because their ions are hermodynamically stable with respect to the loss of lithium atoms in the gas phase) and increasingly contributes toward the development of clusters for practical applications. Copyright © 2012 John Wiley & Sons, Ltd.

Li-Ion Batteries for Forensic Neutron Dosimetry

Science.gov (United States)

2016-03-01

Li-Ion Batteries for Forensic Neutron Dosimetry Distribution Statement A. Approved for public release, distribution is unlimited. March...ion batteries are the common technology for powering portable electronics. The nuclear reactions within the batteries are sensitive to neutrons. By...and chemical changes within the battery . These changes can be determined by mass spectrometry or gamma and beta spectroscopy of long-lived

Li-adsorption on doped Mo2C monolayer: A novel electrode material for Li-ion batteries

Science.gov (United States)

Mehta, Veenu; Tankeshwar, K.; Saini, Hardev S.

2018-04-01

A first principle calculation has been used to study the electronic and magnetic properties of pristine and N/Mn-doped Mo2C with and without Li-adsorption. The pseudopotential method implemented in SIESTA code based on density functional theory with generalized gradient approximation (GGA) as exchange-correlation (XC) potential has been employed. Our calculated results revealed that the Li gets favorably adsorbed on the hexagonal centre in pristine Mo2C and at the top of C-atom in case of N/Mn-doped Mo2C. The doping of Mn and N atom increases the adsorption of Li in Mo2C monolayer which may results in enhancement of storage capacity in Li-ion batteries. The metallic nature of Li-adsorbed pristine and N/Mn-doped Mo2C monolayer implies a good electronic conduction which is crucial for anode materials for its applications in rechargeable batteries. Also, the open circuit voltage for single Li-adsorption in doped Mo2C monolayer comes in the range of 0.4-1.0 eV which is the optimal range for any material to be used as an anode material. Our result emphasized the enhanced performance of doped Mo2C as an anode material in Li-ion batteries.

Temperature-dependent electrochemical heat generation in a commercial lithium-ion battery

Science.gov (United States)

Bandhauer, Todd M.; Garimella, Srinivas; Fuller, Thomas F.

2014-02-01

Lithium-ion batteries suffer from inherent thermal limitations (i.e., capacity fade and thermal runaway); thus, it is critical to understand heat generation experienced in the batteries under normal operation. In the current study, reversible and irreversible electrochemical heat generation rates were measured experimentally on a small commercially available C/LiFePO4 lithium-ion battery designed for high-rate applications. The battery was tested over a wide range of temperatures (10-60 °C) and discharge and charge rates (∼C/4-5C) to elucidate their effects. Two samples were tested in a specially designed wind tunnel to maintain constant battery surface temperature within a maximum variation of ±0.88 °C. A data normalization technique was employed to account for the observed capacity fade, which was largest at the highest rates. The heat rate was shown to increase with both increasing rate and decreasing temperature, and the reversible heat rate was shown to be significant even at the highest rate and temperature (7.4% at 5C and 55 °C). Results from cycling the battery using a dynamic power profile also showed that constant-current data predict the dynamic performance data well. In addition, the reversible heat rate in the dynamic simulation was shown to be significant, especially for charge-depleting HEV applications.

Lithium ion conduction in sol-gel synthesized LiZr2(PO4)3 polymorphs

Science.gov (United States)

Kumar, Milind; Yadav, Arun Kumar; Anita, Sen, Somaditya; Kumar, Sunil

2018-04-01

Safety issue associated with the high flammability and volatility of organic electrolytes used in commercial rechargeable lithium ion batteries has led to significant attention to ceramic-based solid electrolytes. In the present study, lithium ion conduction in two polymorphs of LiZr2(PO4)3 synthesized via the sol-gel route has been investigated. Rietveld refinement of room temperature X-ray diffraction data of LiZr2(PO4)3 powders calcined at 900 °C and 1300 °C confirmed these to be the monoclinic phase with P21/n structure and rhombohedral phase with R3¯c structure, respectively. Increase in calcination temperature and resultant phase transformation improved the room temperature conductivity from 2.27×10-6 ohm-1m-1 for the monoclinic phase to 1.41×10-4 ohm-1m-1 for rhombohedral phase. Temperature dependence of conductivity was modeled using Arrhenius law and activation energy of ˜ 0.59 eV (for monoclinic phase) and ˜0.50 eV (for rhombohedral phase) were obtained.

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.

Charge-discharge mechanisms of Li3V2(PO4)3 cathode materials in Li-batteries - studied by operando PXD

DEFF Research Database (Denmark)

Sørensen, Daniel Risskov; Mathiesen, Jette Katja; Henriksen, Christian

Rechargeable Li-ion batteries are widely recognized as an enabling technology for electrochemical energy storage in applications ranging from small portable electronics over electric vehicles to grid-scale electricity storage1. However, Li-ion batteries still face challenges in terms...

Li+ solvation and kinetics of Li+-BF4-/PF6- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

Science.gov (United States)

Chang, Tsun-Mei; Dang, Liem X.

2017-10-01

Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li+ and the dissociation kinetics of ion pairs Li+-[BF4] and Li+-[PF6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li+ ions varied from 60 to 450 ps, depending on the correction method used. We found that the relaxation times changed significantly from Li+-[BF4] to Li+-[PF6] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.

Chemical recycling of cell phone Li-ion batteries: Application in environmental remediation.

Science.gov (United States)

Gonçalves, Mariana C Abreu; Garcia, Eric M; Taroco, Hosane A; Gorgulho, Honória F; Melo, Júlio O F; Silva, Rafael R A; Souza, Amauri G

2015-06-01

This paper presents, for the first time, the recycling and use of spent Li-ion battery cathode tape as a catalyst in the degradation of an organic dye. In our proposal, two major environmental problems can be solved: the secure disposal of cell phone batteries and the treatment of effluents with potentially toxic organic dyes. The spent Li-ion battery cathode investigated in this paper corresponds to 29% of the mass of Li-ion batteries and is made up of 83% LiCoO2, 14.5% C and less than 2.5% Al, Al2O3 and Co3O4. The use of spent Li-ion battery cathode tape increased the degradation velocity constant of methylene blue in the absence of light by about 200 times in relation to pure H2O2. This increase can be explained by a reduction in the activation energy from 83 kJ mol(-1) to 26 kJ mol(-1). The mechanism of degradation promoted by LiCoO2 is probably related to the generation of superoxide radical (O2(-)). The rupture of the aromatic rings of methylene blue was analyzed by ESI-MS. Copyright © 2015. Published by Elsevier Ltd.

Nanoconfined LiBH4 as a Fast Lithium Ion Conductor

DEFF Research Database (Denmark)

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

2015-01-01

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

Diode-Pumped Mode-Locked LiSAF Laser; FINAL

International Nuclear Information System (INIS)

None

1996-01-01

Under this contract we have developed Cr(sup 3+):LiSrAlF(sub 6) (Cr:LiSAF, LiSAF) mode-locked lasers suitable for generation of polarized electrons for CEBAF. As 670 nm is an excellent wavelength for optical pumping of Cr:LiSAF, we have used a LIGHTWAVE developed 670 nm diode pump module that combines the output of ten diode lasers and yields approximately 2 Watts of optical power. By the use of a diffraction limited pump beam however, it is possible to maintain a small mode size through the length of the crystal and hence extract more power from Cr:LiSAF laser. For this purpose we have developed a 1 Watt, red 660nm laser (LIGHTWAVE model 240R) which serves as an ideal pump for Cr:LiSAF and is a potential replacement of costly and less robust krypton laser. This new system is to compliment LIGHTWAVE Series 240, and is currently being considered for commercialization. Partially developed under this contract is LIGHTWAVEs product model 240 which has already been in our production lines for a few months and is commercially available. This laser produces 2 Watts of output at 532 nm using some of the same technology developed for production of the 660nm red system. It is a potential replacement for argon ion lasers and has better current and cooling requirements and is an excellent pump source for Ti:Al(sub 2)O(sub 3). Also, as a direct result of this contract we now have the capability of commercially developing a mode-locked 100MHz Cr:LiSAF system. Such a laser could be added to our 100 MHz LIGHTWAVE Series 131. The Series 131 lasers provide pico second pulses and were originally developed under another DOE SBIR. Both models of LIGHTWAVE Series 240 lasers, the fiber coupled pump module and the 100MHz LiSAF laser of Series 131 have been partially developed under this contract, and are commercially competitive products

Lithium-ion battery electrolyte emissions analyzed by coupled thermogravimetric/Fourier-transform infrared spectroscopy

Science.gov (United States)

Bertilsson, Simon; Larsson, Fredrik; Furlani, Maurizio; Albinsson, Ingvar; Mellander, Bengt-Erik

2017-10-01

In the last few years the use of Li-ion batteries has increased rapidly, powering small as well as large applications, from electronic devices to power storage facilities. The Li-ion battery has, however, several safety issues regarding occasional overheating and subsequent thermal runaway. During such episodes, gas emissions from the electrolyte are of special concern because of their toxicity, flammability and the risk for gas explosion. In this work, the emissions from heated typical electrolyte components as well as from commonly used electrolytes are characterized using FT-IR spectroscopy and FT-IR coupled with thermogravimetric (TG) analysis, when heating up to 650 °C. The study includes the solvents EC, PC, DEC, DMC and EA in various single, binary and ternary mixtures with and without the LiPF6 salt, a commercially available electrolyte, (LP71), containing EC, DEC, DMC and LiPF6 as well as extracted electrolyte from a commercial 6.8 Ah Li-ion cell. Upon thermal heating, emissions of organic compounds and of the toxic decomposition products hydrogen fluoride (HF) and phosphoryl fluoride (POF3) were detected. The electrolyte and its components have also been extensively analyzed by means of infrared spectroscopy for identification purposes.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-03-07

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

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

Thin-film type Li-ion battery, using a polyethylene separator grafted with glycidyl methacrylate

International Nuclear Information System (INIS)

Ko, J.M.; Min, B.G.; Kim, D.-W.; Ryu, K.S.; Kim, K.M.; Lee, Y.G.; Chang, S.H.

2004-01-01

For the improvement of organic electrolyte holding ability, the hydrophobic surface of a porous polyethylene (PE)-membrane separator was modified by grafting a hydrophilic monomer, glycidyl methacrylate (GMA), PE-g-GMA, by using electron beam technology, and applied to a thin film type Li-ion battery to elucidate the effect of a surface modification of a PE membrane separator on the cyclic life of Li-ion batteries. The Li-ion battery using the PE-g-GMA membrane separator showed a better cycle life than that of the unmodified PE membrane separator, indicating that the surface hydrophilicity of the PE membrane separator improved the electrolyte holding capability between the electrodes in the Li-ion cell and prevented the electrolyte leakage

Li2SnO3 derived secondary Li-Sn alloy electrode for lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, D.W.; Zhang, S.Q.; Jin, Y.; Yi, T.H.; Xie, S.; Chen, C.H.

2006-01-01

As a possible high-capacity Li-ion battery anode material, Li 2 SnO 3 was prepared via a solid-state reaction route and a sol-gel route, separately. Its electrochemical performance was tested in coin-type cells with metallic Li as the counter electrode. The results show that the sol-gel derived Li 2 SnO 3 has uniform nano-sized particles (200-300 nm) and can deliver a better reversible capacity (380 mAh/g after 50 cycles in the voltage window of 0-1 V) than that from the solid-state reaction route. The characterizations by means of galvanostatic cycling, cyclic voltammetry and ex situ X-ray diffraction indicate that the electrochemical process of the Li 2 SnO 3 lithiation proceeds with an initial structural reduction of the composite oxide into Sn-metal and Li 2 O followed by a reversible Li-Sn alloy formation in the Li 2 O matrix. Due to the buffer role of the Li 2 O matrix, the reversibility of the secondary Li-Sn alloy electrode is largely secured

Peapod-like Li3 VO4 /N-Doped Carbon Nanowires with Pseudocapacitive Properties as Advanced Materials for High-Energy Lithium-Ion Capacitors.

Science.gov (United States)

Shen, Laifa; Lv, Haifeng; Chen, Shuangqiang; Kopold, Peter; van Aken, Peter A; Wu, Xiaojun; Maier, Joachim; Yu, Yan

2017-07-01

Lithium ion capacitors are new energy storage devices combining the complementary features of both electric double-layer capacitors and lithium ion batteries. A key limitation to this technology is the kinetic imbalance between the Faradaic insertion electrode and capacitive electrode. Here, we demonstrate that the Li 3 VO 4 with low Li-ion insertion voltage and fast kinetics can be favorably used for lithium ion capacitors. N-doped carbon-encapsulated Li 3 VO 4 nanowires are synthesized through a morphology-inheritance route, displaying a low insertion voltage between 0.2 and 1.0 V, a high reversible capacity of ≈400 mAh g -1 at 0.1 A g -1 , excellent rate capability, and long-term cycling stability. Benefiting from the small nanoparticles, low energy diffusion barrier and highly localized charge-transfer, the Li 3 VO 4 /N-doped carbon nanowires exhibit a high-rate pseudocapacitive behavior. A lithium ion capacitor device based on these Li 3 VO 4 /N-doped carbon nanowires delivers a high energy density of 136.4 Wh kg -1 at a power density of 532 W kg -1 , revealing the potential for application in high-performance and long life energy storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrothermal preparation of zeolite Li-A and ion exchange properties of Cs and Sr in salt waste

International Nuclear Information System (INIS)

Lee, S. H.; Kim, J. G.; Lee, J. H.; Kim, J. H.

2005-01-01

An advanced spent fuel management process that were based on Li reduction of the oxide spent fuel to a metallic form will generate a LiCl waste. Zeolite A has been reported as a promising immobilization medium for waste salt with CsCl and SrCl 2 . However, Sodium is accumulated as an ionic form (Na + -ion) in molten salt during ion exchange step between Na + -ion in zeolite A and Li + -ion in the molten salt. Therefore, zeolite Na-A need to be replaced by the Li-type zeolite for recycling the salt waste by removing the Cs and Sr ions. In this study, the hydrothermal preparation of zeolite Li-A was performed in 350ml pressure vessel by P. Norby method. The preparation characteristics of zeolite Li-A was investigated. And the ion exchange properties of Cs and Sr in molten LiCl salt were investigated under the condition of 923K using zeolite 4A and prepared zeolite Li-A

Calendar aging of a 250 kW/500 kWh Li-ion battery deployed for the grid storage application

Science.gov (United States)

Kubiak, Pierre; Cen, Zhaohui; López, Carmen M.; Belharouak, Ilias

2017-12-01

The introduction of Li-ion batteries for grid applications has become evidence as the cost per kWh is continuously decreasing. Although the Li-ion battery is a mature technology for automotive applications and portable electronics, its use for stationary applications needs more validation. The Li-ion technology is considered safe enough for grid storage application, but its lifetime is generally evaluated to be around 10 years. Higher market penetration will be achieved if a longer lifespan could be demonstrated. Therefore, aging evaluation of the batteries becomes crucial. In this paper we investigated the effects of aging after a three years' standby field deployment of a 250 kW/500 kWh Li-ion battery integrated with the grid and solar farm under the harsh climate conditions of Qatar. The development of tools for acquisition and analysis of data from the battery management system (BMS) allows the assessment of the battery performance at the battery stack, string and cell levels. The analysis of the residual capacity after aging showed that the stack suffered from a low decrease of capacity, whereas some inconsistencies have been found between the strings. These inconsistencies are caused by misalignment of a small number of cells that underwent self-discharge during standby at high state of charge.

Review—Multifunctional Materials for Enhanced Li-Ion Batteries Durability: A Brief Review of Practical Options

Energy Technology Data Exchange (ETDEWEB)

Banerjee, Anjan; Shilina, Yuliya; Ziv, Baruch; Ziegelbauer, Joseph M.; Luski, Shalom; Aurbach, Doron; Halalay, Ion C.

2017-01-01

Transition metal (TM) ions dissolution from positive electrodes, migration to and deposition on negative electrodes, followed by Mn-catalyzed reactions of solvents and anions, with loss of Li+ ions, is a major degradation (DMDCR) mechanism in Li-ion batteries (LIBs) with spinel positive electrode materials. While the details of the DMDCR mechanism are still under debate, it is clear that HF and other acid species’ attack is the main cause in solutions with LiPF6 electrolyte. We first review the work on various mitigation measures for the DMDCR mechanism, now spanning more than two decades. We then discuss recent progress on our understanding of Mn species in electrolyte solutions and the extension of a mitigation measure first proposed by Tarascon and coworkers in 1999, namely chelation of TM cations, to Mn cation trapping, HF scavenging, and alkali metal ions dispensing multi-functional materials. We focus on practicable, drop-in technical solutions, based on placing such materials in the inter-electrode space, with significant benefits for LIBs performance: increased capacity retention during operation at room and above-ambient temperatures as well as robust (both maximally ionically conducting and electronically insulating) solid-electrolyte interfaces, having reduced charge transfer and film resistances at both negative and positive electrodes. We illustrate the multifunctional materials approach with both new and previously published data. We also discuss and offer our evaluation regarding the merits and drawbacks of the various mitigation measures, with an eye for practically relevant technical solutions capable to meet both the performance requirements and cost constraints for commercial LIBs, and end with recommendations for future work.

A dynamic capacity degradation model and its applications considering varying load for a large format Li-ion battery

International Nuclear Information System (INIS)

Ouyang, Minggao; Feng, Xuning; Han, Xuebing; Lu, Languang; Li, Zhe; He, Xiangming

2016-01-01

Highlights: • A dynamic capacity degradation model for large format Li-ion battery is proposed. • The change of the model parameters directly link with the degradation mechanisms. • The model can simulate the fading behavior of Li-ion battery under varying loads. • The model can help evaluate the longevity of a battery system under specific load. • The model can help predict the evolution of cell variations within a battery pack. - Abstract: The capacity degradation of the lithium ion battery should be well predicted during battery system design. Therefore, high-fidelity capacity degradation models that are suitable for the task of capacity prediction are required. This paper proposes a novel capacity degradation model that can simulate the degradation dynamics under varying working conditions for large-format lithium ion batteries. The degradation model is built based on a mechanistic and prognostic model (MPM) whose parameters are closely linked with the degradation mechanisms of lithium ion batteries. Chemical kinetics was set to drive the parameters of the MPM to change as capacity degradation continues. With the dynamic parameters of the MPM, the capacity predicted by the degradation model decreases as the cycle continues. Accelerated aging tests were conducted on three types of commercial lithium ion batteries to calibrate the capacity degradation model. The good fit with the experimental data indicates that the model can capture the degradation mechanisms well for different types of commercial lithium ion batteries. Furthermore, the calibrated model can be used to (1) evaluate the longevity of a battery system under a specific working load and (2) predict the evolution of cell variations within a battery pack when different cell works at different conditions. Correlated applications are discussed using the calibrated degradation model.

Probing the failure mechanism of nanoscale LiFePO₄ for Li-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Gu, Meng [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Shi, Wei [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environmental Directorate; Beijing Jiaotong University (China). School of Electrical Engineering, National Active Distribution Network Technology Research Center; Zheng, Jianming [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environmental Directorate; Yan, Pengfei [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Zhang, Ji-guang [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environmental Directorate; Wang, Chongmin [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

2015-05-18

LiFePO₄ 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 (HRTEM), energy dispersive x-ray spectroscopy (EDS), and electron energy loss spectroscopy (EELS) to study the gradual capacity fading mechanism of LiFePO₄ materials. We found that upon prolonged electrochemical cycling of the battery, the LiFePO₄ cathode shows surface amorphization and loss of oxygen species, which directly contribute to the gradual capacity fading of the battery. The finding is of great importance for the design and improvement of new LiFePO₄ cathode for high-energy and high-power rechargeable battery for electric transportation.

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

International Nuclear Information System (INIS)

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

2016-01-01

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

Li+ alumino-silicate ion source development for the Neutralized Drift Compression Experiment (NDCX)

Energy Technology Data Exchange (ETDEWEB)

Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.; Seidl, Peter A.; Waldron, William L.; Wu, James K.

2010-10-01

We report results on lithium alumino-silicate ion source development in preparation for warmdense-matter heating experiments on the new Neutralized Drift Compression Experiment (NDCXII). The practical limit to the current density for a lithium alumino-silicate source is determined by the maximum operating temperature that the ion source can withstand before running into problems of heat transfer, melting of the alumino-silicate material, and emission lifetime. Using small prototype emitters, at a temperature of ~;;1275 oC, a space-charge-limited Li+ beam current density of J ~;;1 mA/cm2 was obtained. The lifetime of the ion source was ~;;50 hours while pulsing at a rate of 0.033 Hz with a pulse duration of 5-6 mu s.

Li+ alumino-silicate ion source development for the Neutralized Drift Compression Experiment (NDCX)

International Nuclear Information System (INIS)

Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.; Seidl, Peter A.; Waldron, William L.; Wu, James K.

2010-01-01

We report results on lithium alumino-silicate ion source development in preparation for warm-dense-matter heating experiments on the new Neutralized Drift Compression Experiment (NDCX-II). The practical limit to the current density for a lithium alumino-silicate source is determined by the maximum operating temperature that the ion source can withstand before running into problems of heat transfer, melting of the alumino-silicate material, and emission lifetime. Using small prototype emitters, at a temperature of ∼1275 C, a space-charge-limited Li + beam current density of J ∼1 mA/cm 2 was obtained. The lifetime of the ion source was ∼50 hours while pulsing at a rate of 0.033 Hz with a pulse duration of 5-6 (micro) s.

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.

Application of silicene, germanene and stanene for Na or Li ion storage: A theoretical investigation

International Nuclear Information System (INIS)

Mortazavi, Bohayra; Dianat, Arezoo; Cuniberti, Gianaurelio; Rabczuk, Timon

2016-01-01

Silicene, germanene and stanene likely to graphene are atomic thick material with interesting properties. We employed first-principles density functional theory (DFT) calculations to investigate and compare the interaction of Na or Li ions on these films. We first identified the most stable binding sites and their corresponding binding energies for a single Na or Li adatom on the considered membranes. Then we gradually increased the ions concentration until the full saturation of the surfaces is achieved. Our Bader charge analysis confirmed complete charge transfer between Li or Na ions with the studied 2D sheets. We then utilized nudged elastic band method to analyze and compare the energy barriers for Li or Na ions diffusions along the surface and through the films thicknesses. Our investigation findings can be useful for the potential application of silicene, germanene and stanene for Na or Li ion batteries.

Li-Ion, Ultra-capacitor Based Hybrid Energy Module

National Research Council Canada - National Science Library

Daboussi, Zaher; Paryani, Anil; Khalil, Gus; Catherino, Henry; Gargies, Sonya

2007-01-01

.... To determine the optimum utilization of ultra-capacitors in applications where high power density and high energy density are required, an optimized Li-Ion/Ultra-capacitor Hybrid Energy Module (HEM...

The real potential continuous ambiguity for 90 MeV Li ions

International Nuclear Information System (INIS)

Cook, J.; Barnwell, J.M.; Clarke, N.M.; Griffiths, R.J.

1980-01-01

The features of discrete and continuous ambiguities in the real phenomenological optical potential are clarified. The continuous ambiguity in the real potential for the scattering of 90 MeV 6 Li and 7 Li ions from 27 Al is investigated. For 6 Li the ambiguity is of Igo (Phys. Rev. Lett.; 1: 72 (1958) and Phys. Rev.; 115: 1665 (1959)) type but for 7 Li it is of Vrsup(n) = constant type. The implications of this are that 7 Li is less strongly absorbed than 6 Li. (author)

Li interactions with the B40 fullerene and its application in Li-ion batteries: DFT studies

Science.gov (United States)

Moradi, Morteza; Bagheri, Zargham; Bodaghi, Ali

2017-05-01

The interaction of Li and Li+ with a B40 all-boron fullerene was theoretically investigated at the B3LYP, and Minnesota 2006 levels of theory. It was found that, unexpectedly, the interaction Li+ cation with the electron deficient B40 fullerene is stronger than the Li atom. It indicates that the B40 fullerene does not act as a conventional Lewis acid because of its highly correlated structure. Frontier molecular orbitals, partial density of states, and natural bond orbital analyses were used to discuss this unusual behavior. Our calculations indicate that this behavior makes the B40 fullerene more appropriate for application in the Li-ion batteries as anode material. The calculated cell voltage is about 530 mV. Also, it was found that Hartree Fock (HF) exchange percentage of density functionals has a reverse effect on the adsorption energies of Li and Li+. This energy is increased and decreased, respectively, for Li+ and Li adsorptions by increasing %HF exchange. Finally, a potential energy surface for Li and Li+ penetration into B40 fullerene was predicted.

Flexible Aqueous Li-Ion Battery with High Energy and Power Densities.

Science.gov (United States)

Yang, Chongyin; Ji, Xiao; Fan, Xiulin; Gao, Tao; Suo, Liumin; Wang, Fei; Sun, Wei; Chen, Ji; Chen, Long; Han, Fudong; Miao, Ling; Xu, Kang; Gerasopoulos, Konstantinos; Wang, Chunsheng

2017-11-01

A flexible and wearable aqueous symmetrical lithium-ion battery is developed using a single LiVPO 4 F material as both cathode and anode in a "water-in-salt" gel polymer electrolyte. The symmetric lithium-ion chemistry exhibits high energy and power density and long cycle life, due to the formation of a robust solid electrolyte interphase consisting of Li 2 CO 3 -LiF, which enables fast Li-ion transport. Energy densities of 141 Wh kg -1 , power densities of 20 600 W kg -1 , and output voltage of 2.4 V can be delivered during >4000 cycles, which is far superior to reported aqueous energy storage devices at the same power level. Moreover, the full cell shows unprecedented tolerance to mechanical stress such as bending and cutting, where it not only does not catastrophically fail, as most nonaqueous cells would, but also maintains cell performance and continues to operate in ambient environment, a unique feature apparently derived from the high stability of the "water-in-salt" gel polymer electrolyte. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of PVA blended LiClO4 as electrolyte material for battery Li-ion

Science.gov (United States)

Gunawan, I.; Deswita; Sugeng, B.; Sudaryanto

2017-07-01

It have been synthesized the materials for Li ion battery electrolytes, namely PVA with the addition of LiClO4 salt were varied 0, 5, 10, 15 and 20% by weight respectively. The objective of this study is to control the ionic conductivity in traditional polymer electrolytes, to improve ionic conductivity with the addition of lithium perchlorat (LiClO4). These electrolyte materials prepared by PVA powder was dissolved into distilled water and added LiClO4 salt were varied. After drying the solution, PVA sheet blended LiClO4 salt as electrolyte material for Li ion battery obtained. PVA blended LiClO4 salt crystallite form was confirmed using X-Ray Difraction (XRD) equipment. Observation of the morphology done by using Scanning Electron Microscope (SEM). While the electrical conductivity of the material is measured using LCR meter. The results of XRD pattern of LiClO4 shows intense peaks at angles 2θ = 23.2, 32.99, and 36.58°, which represent the crystalline nature of the salt. Particles morphology of the sample revealed by scanning electron microscopy are irregular in shape and agglomerated, with mean size 200-300 nm. It can be concluded that polycrystalline particles are composed of large number of crystallites. The study of conductivity by using LCR meter shows that all the graphs represent the DC and AC conductivity phenomena.

Novel Organic-Inorganic Hybrid Electrolyte to Enable LiFePO4 Quasi-Solid-State Li-Ion Batteries Performed Highly around Room Temperature.

Science.gov (United States)

Tan, Rui; Gao, Rongtan; Zhao, Yan; Zhang, Mingjian; Xu, Junyi; Yang, Jinlong; Pan, Feng

2016-11-16

A novel type of organic-inorganic hybrid polymer electrolytes with high electrochemical performances around room temperature is formed by hybrid of nanofillers, Y-type oligomer, polyoxyethylene and Li-salt (PBA-Li), of which the T g and T m are significantly lowered by blended heterogeneous polyethers and embedded nanofillers with benefit of the dipole modification to achieve the high Li-ion migration due to more free-volume space. The quasi-solid-state Li-ion batteries based on the LiFePO 4 /15PBA-Li/Li-metal cells present remarkable reversible capacities (133 and 165 mAh g -1 @0.2 C at 30 and 45 °C, respectively), good rate ability and stable cycle performance (141.9 mAh g -1 @0.2 C at 30 °C after 150 cycles).

Novel Nanocomposite Materials for Advanced Li-Ion Rechargeable Batteries

Directory of Open Access Journals (Sweden)

Chuan Cai

2009-09-01

Full Text Available Nanostructured materials lie at the heart of fundamental advances in efficient energy storage and/or conversion, in which surface processes and transport kinetics play determining roles. Nanocomposite materials will have a further enhancement in properties compared to their constituent phases. This Review describes some recent developments of nanocomposite materials for high-performance Li-ion rechargeable batteries, including carbon-oxide nanocomposites, polymer-oxide nanocomposites, metal-oxide nanocomposites, and silicon-based nanocomposites, etc. The major goal of this Review is to highlight some new progress in using these nanocomposite materials as electrodes to develop Li-ion rechargeable batteries with high energy density, high rate capability, and excellent cycling stability.

Large-scale production of paper-based Li-ion cells

CERN Document Server

Zolin, Lorenzo

2017-01-01

This book describes in detail the use of natural cellulose fibers for the production of innovative, low-cost, and easily recyclable lithium-ion (Li-ion) cells by means of fast and reliable papermaking procedures that employ water as a solvent. In addition, it proposes specific methods to optimize the safety features of these paper-based cells and to improve the electronic conductivity of the electrodes by means of a carbonization process– an interesting novel technology that enables higher current rate capabilities to be achieved. The in-depth descriptions of materials, methods, and techniques are complemented by the inclusion of a general overview of electrochemical devices and, in particular, of different Li-ion battery configurations. Presenting the outcomes of this important research, the work is of wide interest to electrochemical engineers in both research institutions and industry.

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

KAUST Repository

Ming, Jun

2018-01-04

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

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

Science.gov (United States)

West, William; Whitacre, Jay; Lim, James

2008-01-01

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

Li3V2(PO4)3/LiFePO4 composite hollow microspheres for wide voltage lithium ion batteries

International Nuclear Information System (INIS)

He, Wen; Wei, Chuanliang; Zhang, Xudong; Wang, Yaoyao; Liu, Qinze; Shen, Jianxing; Wang, Lianzhou; Yue, Yuanzheng

2016-01-01

Highlights: • Using yeast cells to control the in-situ growth of crystal particle. • Heterogeneous isomorphism nanocomposite hollow microspheres are synthesized. • The cathode exhibits a higher discharge capacity and energy density. - Abstract: Li 3 V 2 (PO 4 ) 3 (LVP)/LiFePO 4 (LVP) composite hollow microspheres (LVP/LFP-CHMs) for lithium-ion batteries have been synthesized by a combination method, using yeast cells as both structure templates and biocarbon source. The stable heterogeneous isomorphism solid solution with superlattice structure is formed in the joint of LVP and LFP particles. A detailed analysis of the formation mechanism of solid solution with superlattice structure and the influences of different Fe:V mole ratios on the structure and electrochemical properties of composites are presented. When the LVP/LFP-CHMs with a Fe:V mole ratio of 1:3 were used as cathode material in coin cells with metallic Li as anode, the cell exhibits a discharge capacity of 221.5 mAh g −1 for 5 cycles and discharge specific energy of 682 Wh kg −1 at 0.1C in a wide voltage range (1.5–4.3 V). Its capacity is far higher than the capacity of unsubstituted LFP and LVP in the same wide voltage range. The energy density of this cell is about 4 times higher than that of modern commercial lithium-ion batteries (157 Wh kg −1 ). The wide voltage range not only increases the discharge capacity and energy density of cathode materials, but also could expand the range of its applications in electronic equipment.

A hybrid electrochemical device based on a synergetic inner combination of Li ion battery and Li ion capacitor for energy storage.

Science.gov (United States)

Zheng, Jun-Sheng; Zhang, Lei; Shellikeri, Annadanesh; Cao, Wanjun; Wu, Qiang; Zheng, Jim P

2017-02-07

Li ion battery (LIB) and electrochemical capacitor (EC) are considered as the most widely used energy storage systems (ESSs) because they can produce a high energy density or a high power density, but it is a huge challenge to achieve both the demands of a high energy density as well as a high power density on their own. A new hybrid Li ion capacitor (HyLIC), which combines the advantages of LIB and Li ion capacitor (LIC), is proposed. This device can successfully realize a potential match between LIB and LIC and can avoid the excessive depletion of electrolyte during the charge process. The galvanostatic charge-discharge cycling tests reveal that at low current, the HyLIC exhibits a high energy density, while at high current, it demonstrates a high power density. Ragone plot confirms that this device can make a synergetic balance between energy and power and achieve a highest energy density in the power density range of 80 to 300 W kg -1 . The cycle life test proves that HyLIC exhibits a good cycle life and an excellent coulombic efficiency. The present study shows that HyLIC, which is capable of achieving a high energy density, a long cycle life and an excellent power density, has the potential to achieve the winning combination of a high energy and power density.

Synthesis of hollandite-type LixMnO2 by Li+ ion-exchange in molten salt and lithium insertion characteristics

International Nuclear Information System (INIS)

Kadoma, Yoshihiro; Oshitari, Satoru; Ui, Koichi; Kumagai, Naoaki

2007-01-01

The Li + ion-exchange reaction of K + -type α-K 0.14 MnO 1.93 .nH 2 O containing different amounts of water molecules (n = 0-0.15) with a large (2 x 2) tunnel structure has been investigated in a LiNO 3 -LiCl molten salt at 300 deg. C. The Li + ion-exchanged products were examined by chemical analysis, X-ray diffraction, and transmission electron microscopy measurements. The K + ions and the hydrogens of the water molecules in the (2 x 2) tunnels of α-MnO 2 were exchanged by Li + ions in the molten salt, resulting in the Li + -type α-MnO 2 containing different amounts of Li + ions and lithium oxide (Li 2 O) in the (2 x 2) tunnels with maintaining the original hollandite structure. The electrochemical properties and structural variation with initial discharge and charge-discharge cycling of the Li + ion-exchanged α-MnO 2 samples have been investigated as insertion compounds in the search for new cathode materials for rechargeable lithium batteries. The Li + ion-exchanged α-MnO 2 samples provided higher capacities and higher Li + ion diffusivity than the parent K + -type materials on initial discharge and charge-discharge cyclings, probably due to the structural stabilization with the existence of Li 2 O in the (2 x 2) tunnels

New hydrogen titanium phosphate sulfate electrodes for Li-ion and Na-ion batteries

Science.gov (United States)

Zhao, Ran; Mieritz, Daniel; Seo, Dong-Kyun; Chan, Candace K.

2017-03-01

NASICON-type materials with general formula AxM2(PO4)3 (A = Li or Na, M = Ti, V, and Fe) are promising candidates for Li- and Na-ion batteries due to their open three-dimensional framework structure. Here we report the electrochemical properties of hydrogen titanium phosphate sulfate, H0.4Ti2(PO4)2.4(SO4)0.6 (HTPS), a new mixed polyanion material with NASICON structure. Micron-sized HTPS aggregates with crystallite grain size of ca. 23 nm are synthesized using a sol-gel synthesis in an acidic medium. The properties of the as-synthesized HTPS, ball-milled HTPS, and samples prepared as carbon composites using an in-situ glucose decomposition reaction are investigated. A capacity of 148 mAh g-1 corresponding to insertion of 2 Li+ per formula unit is observed in the ball-milled HTPS over the potential window of 1.5-3.4 V vs. Li/Li+. Lithiation at ca. 2.8 and 2.5 V is determined to occur through filling of the M1 and M2 sites, respectively. Powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) are used characterize the HTPS before and after cycling. Evaluation of the HTPS in a Na-ion cell is also performed. A discharge capacity of 93 mAh g-1 with sodiation at ca. 2.9 and 2.2 V vs. Na/Na+ is observed.

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

International Nuclear Information System (INIS)

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

2011-01-01

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

Advanced Electrodes for High Power Li-ion Batteries

Directory of Open Access Journals (Sweden)

Christian M. Julien

2013-03-01

Full Text Available While little success has been obtained over the past few years in attempts to increase the capacity of Li-ion batteries, significant improvement in the power density has been achieved, opening the route to new applications, from hybrid electric vehicles to high-power electronics and regulation of the intermittency problem of electric energy supply on smart grids. This success has been achieved not only by decreasing the size of the active particles of the electrodes to few tens of nanometers, but also by surface modification and the synthesis of new multi-composite particles. It is the aim of this work to review the different approaches that have been successful to obtain Li-ion batteries with improved high-rate performance and to discuss how these results prefigure further improvement in the near future.

Correlating capacity and Li content in layered material for Li-ion battery using XRD and particle size distribution measurements

Science.gov (United States)

Al-Tabbakh, A. A. A.; Al-Zubaidi, A. B.; Kamarulzaman, N.

2016-03-01

A lithiated transition-metal oxide material was successfully synthesized by a combustion method for Li-ion battery. The material was characterized using thermogravimetric and particle size analyzers, scanning electron microscope and X-ray diffractometer. The calcined powders of the material exhibited a finite size distribution and a single phase of pure layered structure of space group Roverline{3} m . An innovative method was developed to calculate the material electrochemical capacity based on considerations of the crystal structure and contributions of Li ions from specified unit cells at the surfaces and in the interiors of the material particles. Results suggested that most of the Li ions contributing to the electrochemical current originated from the surface region of the material particles. It was possible to estimate the thickness of the most delithiated region near the particle surfaces at any delithiation depth accurately. Furthermore, results suggested that the core region of the particles remained electrochemically inaccessible in the conventional applied voltages. This result was justified by direct quantitative comparison of specific capacity values calculated from the particle size distribution with those measured experimentally. The present analysis is believed to be of some value for estimation of the failure mechanism in cathode compounds, thus assisting the development of Li-ion batteries.

A study on specific heat capacities of Li-ion cell components and their influence on thermal management

Science.gov (United States)

Loges, André; Herberger, Sabrina; Seegert, Philipp; Wetzel, Thomas

2016-12-01

Thermal models of Li-ion cells on various geometrical scales and with various complexity have been developed in the past to account for the temperature dependent behaviour of Li-ion cells. These models require accurate data on thermal material properties to offer reliable validation and interpretation of the results. In this context a thorough study on the specific heat capacities of Li-ion cells starting from raw materials and electrode coatings to representative unit cells of jelly rolls/electrode stacks with lumped values was conducted. The specific heat capacity is reported as a function of temperature and state of charge (SOC). Seven Li-ion cells from different manufactures with different cell chemistry, application and design were considered and generally applicable correlations were developed. A 2D thermal model of an automotive Li-ion cell for plug-in hybrid electric vehicle (PHEV) application illustrates the influence of specific heat capacity on the effectivity of cooling concepts and the temperature development of Li-ion cells.

Insight into effects of graphene in Li4Ti5O12/carbon composite with high rate capability as anode materials for lithium ion batteries

International Nuclear Information System (INIS)

Ding, Y.; Li, G.R.; Xiao, C.W.; Gao, X.P.

2013-01-01

Li 4 Ti 5 O 12 /carbon composites have shown promising high rate capability as anode materials for lithium ion batteries. In this paper, unique effects of graphene in Li 4 Ti 5 O 12 /carbon composites on electrochemical performances are focused by means of comparing Li 4 Ti 5 O 12 /graphene with Li 4 Ti 5 O 12 /conductive carbon black (CCB) and Li 4 Ti 5 O 12 . The investigated anode materials are synthesized by a facile hydrothermal method. The amount of graphene or CCB in the Li 4 Ti 5 O 12 /carbon composites is about 3 wt% measured by thermogravimetric (TG) analysis. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that Li 4 Ti 5 O 12 /graphene consists of small sized Li 4 Ti 5 O 12 nanocrystals supported on graphene nanosheets, while Li 4 Ti 5 O 12 /CCB comprises Li 4 Ti 5 O 12 nanocrystal aggregates coated nearly by graphited carbon. The electrochemical performances of these samples as anode materials for lithium ion batteries are investigated by galvanostatic charge–discharge method. Li 4 Ti 5 O 12 /graphene provides a superior rate capability. At the high current density of 1600 mA g −1 , the reversible capacity after 200 cycles is still more than 120 mAh g −1 , which is about 40% higher than that of Li 4 Ti 5 O 12 /CCB. Cyclic voltammetry (CV) demonstrates that stronger pseudocapacitive effect occurs on Li 4 Ti 5 O 12 /graphene than on Li 4 Ti 5 O 12 /CCB. This derived from the structure features that graphene-supported small Li 4 Ti 5 O 12 nanocrystals provide more surface active sites for the lithium ion insertion/extraction. The strong pseudocapacitive effect is responsible for the improvements of capacity and high-rate capability. Further, electrochemical impedance spectra (EIS) show that Li 4 Ti 5 O 12 /graphene electrode have lower charge transfer resistance and smaller diffusion impedance, indicating the obvious advantages in electrode kinetics over Li 4 Ti 5 O 12 and Li 4 Ti 5 O 12

Self-assembled LiFePO4 nanowires with high rate capability for Li-ion batteries.

Science.gov (United States)

Peng, Lele; Zhao, Yu; Ding, Yu; Yu, Guihua

2014-08-28

Controlling the dimensions in the nanometer scale of olivine-type LiFePO4 has been regarded as one of the most effective strategies to improve its electrochemical performance for Li-ion batteries. In this communication, we demonstrate a novel LiFePO4 nanoarchitecture, which is composed of self-assembled single-crystalline nanowires and exhibits good rate capability with a reversible capacity of ∼110 mA h g(-1) at a current rate of 30 C, and a stable capacity retention of ∼86% after 1000 cycles at a current rate of 10 C.

Insight into the Gassing Problem of Li-ion Battery

International Nuclear Information System (INIS)

Zhang, Sheng S.

2014-01-01

Gas generation (namely, the volume swelling of battery, or called the gassing) is a common phenomenon of the degradation of battery performance, which is generally a result of the electrolyte decomposition occurring during the entire lifespan of Li-ion batteries no matter whether the battery is in service or not. Abuse conditions such as overcharging and overheating make the gassing worse or even result in disastrous accidents. In overcharging, the gassing occurs mainly through the electrochemical oxidation of electrolyte solvents on the cathode with the Li + ions from the electrolyte being reduced into metallic Li on the anode. In overheating, the gassing takes place through not only the redox decomposition but also the chemical decomposition of the electrolyte solvents on both the anode and cathode besides the vapor expansion of volatile electrolyte solvents. In this opinion article, only the gas generation occurring under the normal operation and storage conditions will be addressed.

Carbon coated Li{sub 4}Ti{sub 5}O{sub 12} nanorods as superior anode material for high rate lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Luo, Hongjun; Shen, Laifa; Rui, Kun; Li, Hongsen; Zhang, Xiaogang, E-mail: azhangxg@nuaa.edu.cn

2013-09-25

Highlights: •A novel approach has been developed to fabricate 1D Li{sub 4}Ti{sub 5}O{sub 12}/C nanorods by a wet-chemical route. •Carbon coating layer effectively restrict the particle growth and enhance electronic conductivity. •The Li{sub 4}Ti{sub 5}O{sub 12}/C nanorods exhibit remarkable rate capability and long cycle life. -- Abstract: We describe a novel approach for the synthesis of carbon coated Li{sub 4}Ti{sub 5}O{sub 12} (Li{sub 4}Ti{sub 5}O{sub 12}/C) nanorods for high rate lithium ion batteries. The carbon coated TiO{sub 2} nanotubes using the glucose as carbon source are first synthesized by hydrothermal treatment. The commercial anatase TiO{sub 2} powder is immersed in KOH sulotion and subsequently transforms into Li{sub 4}Ti{sub 5}O{sub 12}/C in LiOH solution under hydrothermal condition. Field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, nitrogen adsorption/desorption and Raman spectra are performed to characterize their morphologies and structures. Compared with the pristine Li{sub 4}Ti{sub 5}O{sub 12}, one-dimensional (1D) Li{sub 4}Ti{sub 5}O{sub 12}/C nanostructures show much better rate capability and cycling stability. The 1D Li{sub 4}Ti{sub 5}O{sub 12}/C architectures effectively restrict the particle growth and enhance their electronic conductivity, enabling fast ion and electron transport.

Probing the failure mechanism of nanoscale LiFePO{sub 4} for Li-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Gu, Meng; Yan, Pengfei; Wang, Chongmin, E-mail: chongmin.wang@pnnl.gov [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States); Shi, Wei [Energy and Environmental Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352 (United States); National Active Distribution Network Technology Research Center, School of Electrical Engineering, Beijing Jiaotong University, 3 Shangyuancun Street, Haidian District, Beijing 100044 (China); Zheng, Jianming; Zhang, Ji-guang [Energy and Environmental Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352 (United States)

2015-05-18

LiFePO{sub 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{sub 4} materials. We found that upon prolonged electrochemical cycling of the battery, the LiFePO{sub 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{sub 4} cathode for high-energy and high-power rechargeable battery for electric transportation.

Cubic Crystal-Structured SnTe for Superior Li- and Na-Ion Battery Anodes.

Science.gov (United States)

Park, Ah-Ram; Park, Cheol-Min

2017-06-27

A cubic crystal-structured Sn-based compound, SnTe, was easily synthesized using a solid-state synthetic process to produce a better rechargeable battery, and its possible application as a Sn-based high-capacity anode material for Li-ion batteries (LIBs) and Na-ion batteries (NIBs) was investigated. The electrochemically driven phase change mechanisms of the SnTe electrodes during Li and Na insertion/extraction were thoroughly examined utilizing various ex situ analytical techniques. During Li insertion, SnTe was converted to Li 4.25 Sn and Li 2 Te; meanwhile, during Na insertion, SnTe experienced a sequential topotactic transition to Na x SnTe (x ≤ 1.5) and conversion to Na 3.75 Sn and Na 2 Te, which recombined into the original SnTe phase after full Li and Na extraction. The distinctive phase change mechanisms provided remarkable electrochemical Li- and Na-ion storage performances, such as large reversible capacities with high Coulombic efficiencies and stable cyclabilities with fast C-rate characteristics, by preparing amorphous-C-decorated nanostructured SnTe-based composites. Therefore, SnTe, with its interesting phase change mechanisms, will be a promising alternative for the oncoming generation of anode materials for LIBs and NIBs.

Sputtering from swift-ion trails in LiF: A hybrid PIC/MD simulation

Energy Technology Data Exchange (ETDEWEB)

Cherednikov, Yaroslav; Sun, Si Neng; Urbassek, Herbert M., E-mail: urbassek@rhrk.uni-kl.de

2013-11-15

We model the sputtering of a LiF crystal induced by swift-ion impact. The impinging ion creates a trail of doubly ionized F{sup +} ions, while simultaneously the corresponding electrons are set free. Ions move according to molecular dynamics, while excited electrons are treated by a particle-in-cell scheme. We treat the recombination time of electrons as a free parameter in our model. We find that the energy distribution of sputtered ions consists of 2 groups: a low-energy group centered at <1 eV, and a high-energy group at 7–8 eV. Fast ions (mainly Li{sup +}) are emitted early; these charge the surface negatively. Later, larger cluster ions and also neutral LiF molecules are emitted. Emission occurs at low angles to the surface normal. A jet along the normal direction can be observed, which is due to the electric field building up at the track surface. With increasing recombination time, processes are colder; sputtering decreases and the non-thermal jet structure becomes stronger.

Annihilation of antiferromagnetic order in LiCoO2 by excess Li

International Nuclear Information System (INIS)

Sugiyama, Jun; Ikedo, Yutaka; Nozaki, Hiroshi; Mukai, Kazuhiko; Andreica, Daniel; Amato, Alex; Menetrier, Michel; Carlier, Dany; Delmas, Claude

2009-01-01

In order to elucidate the origin of antiferromagnetic (AF) order below 30 K in LiCoO 2 , in which all the Co 3+ ions are in a low-spin state with S=0, the magnetic nature of the Li-excess sample Li 1.04 Co 0.96 O 1.96 was studied by muon-spin spectroscopy in the temperature range between 1.8 and 100 K. Although disordered localized moments appeared below 25 K, static AF order was not detected even at 1.8 K. Moreover, a small amount of excess Li ions (4%) and oxygen vacancies (2%) was found to change ∼50% of the sample into a magnetically disordered phase at 1.8 K. The stoichiometric LiCoO 2 , which was prepared from the same starting materials to those for the Li-excess sample, showed an AF transition at 30 K, while the volume fraction of the AF phase was 10% even at 1.8 K. This therefore excludes the possible role of the excess Li + on the formation of static AF order.

The different Li/Na ion storage mechanisms of nano Sb2O3 anchored on graphene

Science.gov (United States)

Li, Hai; Qian, Kun; Qin, Xianying; Liu, Dongqing; Shi, Ruiying; Ran, Aihua; Han, Cuiping; He, Yan-Bing; Kang, Feiyu; Li, Baohua

2018-05-01

The antimony oxide/reduced graphene oxide (Sb2O3/rGO) nanocomposites are used as anode of Li-ion and Na-ion batteries (LIBs and NIBs). However, it is unclear about Li-ion and Na-ion storage mechanism in Sb2O3/rGO nanocomposites. Herein, the conversion-alloying mechanisms of Sb2O3/rGO anodes for Na-ion and Li-ion storage are comparatively studied with a combined in-situ XRD and quasi in-situ XPS method. The distinct behaviours are monitored during (de)lithiation and (de)sodiation with respect to crystal structure and chemical composition evolution. It is evidenced that the Na-ion can be easily transported to the inner part of the Sb2O3, where the Li-ion almost cannot reach, leading to a fully transformation during sodiation. In addition, the conversion reaction product of amorphous Na2O display their better chemical stability than amorphous Li2O during electrochemical cycles, which contribute to a stable and long cycling life of NIBs. This work gain insight into the high-capacity anodes with conversation-alloying mechanism for NIBs.

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

Science.gov (United States)

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

2018-05-01

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

Li-Ion, Ultra-capacitor Based Hybrid Energy Module

National Research Council Canada - National Science Library

Daboussi, Zaher; Paryani, Anil; Khalil, Gus; Catherino, Henry; Gargies, Sonya

2007-01-01

.... Combining their superb specific power of 2-5kW/kg, high efficiency and very long cycle life with the high energy density of Li-Ion batteries, practical solutions to a variety of applications can be foreseen...

Critical Review of Commercial Secondary Lithium-Ion Battery Safety Standards

Science.gov (United States)

Jones, Harry P.; Chapin, Thomas, J.; Tabaddor, Mahmod

2010-09-01

The development of Li-ion cells with greater energy density has lead to safety concerns that must be carefully assessed as Li-ion cells power a wide range of products from consumer electronics to electric vehicles to space applications. Documented field failures and product recalls for Li-ion cells, mostly for consumer electronic products, highlight the risk of fire, smoke, and even explosion. These failures have been attributed to the occurrence of internal short circuits and the subsequent thermal runaway that can lead to fire and explosion. As packaging for some applications include a large number of cells, the risk of failure is likely to be magnified. To address concerns about the safety of battery powered products, safety standards have been developed. This paper provides a review of various international safety standards specific to lithium-ion cells. This paper shows that though the standards are harmonized on a host of abuse conditions, most lack a test simulating internal short circuits. This paper describes some efforts to introduce internal short circuit tests into safety standards.

3D inverse-opal structured Li4Ti5O12 Anode for fast Li-Ion storage capabilities

Science.gov (United States)

Kim, Dahye; Quang, Nguyen Duc; Hien, Truong Thi; Chinh, Nguyen Duc; Kim, Chunjoong; Kim, Dojin

2017-11-01

Since the demand for high power Li-ion batteries (LIBs) is increasing, spinel-structured lithium titanate, Li4Ti5O12 (LTO), as the anode material has attracted great attention because of its excellent cycle retention, good thermal stability, high rate capability, and so on. However, LTO shows relatively low conductivity due to empty 3 d orbital of Ti4+ state. Nanoscale architectures can shorten electron conduction path, thus such low electronic conductivity can be overcome while Li+ can be easily accessed due to large surface area. Herein, three dimensional bicontinuous LTO electrodes were prepared via close-packed self-assembly with polystyrene (PS) spheres followed by removal of them, which leads to no blockage of Li+ ion transportation pathways as well as fast electron conduction. 3D bicontinuous LTO electrodes showed high-rate lithium storage capability (103 mAh/g at 20 C), which is promising as the power sources that require rapid electrochemical response.[Figure not available: see fulltext.

LiFePO4 mesocrystals for lithium-ion batteries.

Science.gov (United States)

Popovic, Jelena; Demir-Cakan, Rezan; Tornow, Julian; Morcrette, Mathieu; Su, Dang Sheng; Schlögl, Robert; Antonietti, Markus; Titirici, Maria-Magdalena

2011-04-18

Olivine LiFePO(4) is considered one of the most promising cathode materials for Li-ion batteries. A simple one-step, template-free, low-temperature solvothermal method is developed for the synthesis of urchinlike hierarchical mesocrystals of pristine LiFePO(4) as well as carbon-coated LiFePO(4) composites. Each urchinlike mesocrystal consists of LiFePO(4) sheets self-assembled via a dipolar field in spheres during a solvothermal process under the influence of Cl(-) anions. The obtained primary sheets of LiFePO(4) are single crystalline in nature and can be coated in situ with an amorphous nitrogen-doped carbonaceous layer several nanometers in thickness. To increase the conductivity of the carbon coating, the materials are subjected to further temperature treatment (700 °C) under an inert atmosphere. The lithium storage performance of the pure LiFePO(4) is compared with that of its carbon-coated counterparts. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Raman effects in γ-LiAlO2 induced by low-energy Ga ion implantation

Science.gov (United States)

Zhang, Jing; Song, Hong-Lian; Qiao, Mei; Wang, Tie-Jun; Yu, Xiao-Fei; Wang, Xue-Lin

2017-10-01

The tetragonal γ-LiAlO2 crystal, known as a promising solid breeding material in future fusion reactors, has attracted much attention for its irradiation effects. This work focused on the Raman effects in ion-implanted γ-LiAlO2. Ga ions of 30, 80 and 150 keV were implanted on the z-cut γ-LiAlO2 sample surfaces at a fluence of 1 × 1014 ions/cm2 or 1 × 1015 ions/cm2. The average ion range varied from 230 to 910 Å. The Raman spectra were collected from the implanted surfaces before and after the implantation. Evident changes were reflected in the Raman modes intensities, with abnormal increments for the most detected modes. According to the assignments of Raman modes, the Al-O vibration was enhanced to a greater extent than the Li-Al-O vibration, and the LiO4-AlO4 vibration gained a lesser enhancement. The discussion, including the factors of roughness, crystalline disorder and influence by Ga ions, attempts to explain the increments of Raman intensity.

Unique reduced graphene oxide as efficient anode material in Li ion ...

Indian Academy of Sciences (India)

2018-03-29

Mar 29, 2018 ... as an electrode material in dye-sensitized solar cell [1], super- capacitor [2] and Li ion battery ... Ar-filled glove box. In each of the coin cell, ... Li reacts with suitable materials' defects at low potential and as they charge, bonds ...

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.

Tuning Li2MO3 phase abundance and suppressing migration of transition metal ions to improve the overall performance of Li- and Mn-rich layered oxide cathode

Science.gov (United States)

Zhang, Shiming; Tang, Tian; Ma, Zhihua; Gu, Haitao; Du, Wubing; Gao, Mingxia; Liu, Yongfeng; Jian, Dechao; Pan, Hongge

2018-03-01

The poor cycling stability of Li- and Mn-rich layered oxide cathodes used in lithium-ion batteries (LIBs) has severely limited their practical application. Unfortunately, current strategies to improve their lifecycle sacrifice initial capacity. In this paper, we firstly report the synergistic improvement of the electrochemical performance of a Li1.2Ni0.13Co0.13Mn0.54O2 (LNCMO) cathode material, including gains for capacity, cycling stability, and rate capability, by the partial substitution of Li+ ions by Mg2+ ions. Electrochemical performance is evaluated by a galvanostatic charge and discharge test and electrochemical impedance spectroscopy (EIS). Structure and morphology are characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Compared with the substitution of transition metal (TM) ions with Mg2+ ions reported previously, the substitution of Li+ ions by Mg2+ ions not only drastically ameliorates the capacity retention and rate performance challenges of LNCMO cathodes but also markedly suppresses their voltage fading, due to the inhibition of the migration of TM ions during cycling, while also increasing the capacity of the cathode due to an increased abundance of the Li2MO3 phase.

Ionic conduction studies in Li3+ ion irradiated P(VDF-HFP)-(PC + DEC)-LiCF3SO3 gel polymer electrolyte

International Nuclear Information System (INIS)

Saikia, D.; Hussain, A.M.P.; Kumar, A.; Singh, F.; Avasthi, D.K.

2006-01-01

In an attempt to increase the Li ion diffusivity in gel polymer electrolytes, the effects of Li 3+ ion irradiation in P(VDF-HFP)-(PC + DEC)-LiCF 3 SO 3 electrolyte system, with five different fluences, is studied. Irradiation with swift heavy ions shows enhancement in conductivity at low fluences and decreased in conductivity at higher fluences with respect to pristine polymer electrolyte films. Maximum room temperature ionic conductivity after irradiation is found to be 2.6 x 10 -3 S/cm. This interesting result could be attributed to the fact that, higher fluence provides critical activation energy for cross-linking and crystallization to occur, which results in decrease in ionic conductivity. XRD results show decrease in the degree of crystallinity upon ion irradiation at low fluences (≤10 11 ions/cm 2 ) and increase in crystallinity at high fluences (>10 11 ions/cm 2 ). In FTIR spectra the absorption band intensities around 3025 cm -1 and 2985 cm -1 decrease upon irradiation with a fluence of 5 x 10 1 ions/cm 2 suggesting chain scission and increase upon irradiation with a fluence of 5 x 10 12 ions/cm 2 indicating cross-linking. FTIR analyses corroborate the conductivity and XRD results

Degradation Studies on LiFePO₄ cathode

DEFF Research Database (Denmark)

Scipioni, Roberto; Jørgensen, Peter Stanley; Hjelm, Johan

2014-01-01

Lithium-ion batteries are a promising technology for automotive application, but limited performance and lifetime is still a big issue. The aim of this work is to study and address degradation processes which affect LiFePO4 (LFP) cathodes - one of the most common cathodes in commercial Li...

S-functionalized MXenes as electrode materials for Li-ion batteries

KAUST Repository

Zhu, Jiajie

2016-09-03

MXenes are promising electrode materials for Li-ion batteries because of their high Li capacities and cycling rates. We use density functional theory to investigate the structural and energy storage properties of Li decorated Zr2C and Zr2CX2 (X = F, O and S). We find for Zr2C and Zr2CS2 high Li specific capacities and low diffusion barriers. To overcome the critical drawbacks of the OH, F, and O groups introduced during the synthesis we propose substitution by S groups and demonstrate that an exchange reaction is indeed possible. Zr2CS2 shows a similar Li specific capacity as Zr2CO2 but a substantially reduced diffusion barrier. © 2016 Elsevier Ltd

Adaptive thermal modeling of Li-ion batteries

International Nuclear Information System (INIS)

Shadman Rad, M.; Danilov, D.L.; Baghalha, M.; Kazemeini, M.; Notten, P.H.L.

2013-01-01

Highlights: • A simple, accurate and adaptive thermal model is proposed for Li-ion batteries. • Equilibrium voltages, overpotentials and entropy changes are quantified from experimental results. • Entropy changes are highly dependent on the battery State-of-Charge. • Good agreement between simulated and measured heat development is obtained under all conditions. • Radiation contributes to about 50% of heat dissipation at elevated temperatures. -- Abstract: An accurate thermal model to predict the heat generation in rechargeable batteries is an essential tool for advanced thermal management in high power applications, such as electric vehicles. For such applications, the battery materials’ details and cell design are normally not provided. In this work a simple, though accurate, thermal model for batteries has been developed, considering the temperature- and current-dependent overpotential heat generation and State-of-Charge dependent entropy contributions. High power rechargeable Li-ion (7.5 Ah) batteries have been experimentally investigated and the results are used for model verification. It is shown that the State-of-Charge dependent entropy is a significant heat source and is therefore essential to correctly predict the thermal behavior of Li-ion batteries under a wide variety of operating conditions. An adaptive model is introduced to obtain these entropy values. A temperature-dependent equation for heat transfer to the environment is also taken into account. Good agreement between the simulations and measurements is obtained in all cases. The parameters for both the heat generation and heat transfer processes can be applied to the thermal design of advanced battery packs. The proposed methodology is generic and independent on the cell chemistry and battery design. The parameters for the adaptive model can be determined by performing simple cell potential/current and temperature measurements for a limited number of charge/discharge cycles

First-principles density functional calculation of electrochemical stability of fast Li ion conducting garnet-type oxides.

Science.gov (United States)

Nakayama, Masanobu; Kotobuki, Masashi; Munakata, Hirokazu; Nogami, Masayuki; Kanamura, Kiyoshi

2012-07-28

The research and development of rechargeable all-ceramic lithium batteries are vital to realize their considerable advantages over existing commercial lithium ion batteries in terms of size, energy density, and safety. A key part of such effort is the development of solid-state electrolyte materials with high Li(+) conductivity and good electrochemical stability; lithium-containing oxides with a garnet-type structure are known to satisfy the requirements to achieve both features. Using first-principles density functional theory (DFT), we investigated the electrochemical stability of garnet-type Li(x)La(3)M(2)O(12) (M = Ti, Zr, Nb, Ta, Sb, Bi; x = 5 or 7) materials against Li metal. We found that the electrochemical stability of such materials depends on their composition and structure. The electrochemical stability against Li metal was improved when a cation M was chosen with a low effective nuclear charge, that is, with a high screening constant for an unoccupied orbital. In fact, both our computational and experimental results show that Li(7)La(3)Zr(2)O(12) and Li(5)La(3)Ta(2)O(12) are inert to Li metal. In addition, the linkage of MO(6) octahedra in the crystal structure affects the electrochemical stability. For example, perovskite-type La(1/3)TaO(3) was found, both experimentally and computationally, to react with Li metal owing to the corner-sharing MO(6) octahedral network of La(1/3)TaO(3), even though it has the same constituent elements as garnet-type Li(5)La(3)Ta(2)O(12) (which is inert to Li metal and features isolated TaO(6) octahedra).

Excess Li-Ion Storage on Reconstructed Surfaces of Nanocrystals To Boost Battery Performance

Energy Technology Data Exchange (ETDEWEB)

Duan, Yandong; Zhang, Bingkai; Zheng, Jiaxin; Hu, Jiangtao; Wen, Jianguo; Miller, Dean; Yan, Pengfei; Liu, Tongchao; Guo, Hua; Li, Wen; Song, Xiaohe; Zhou, Zengquing; Liu, Chaokun; Tang, Hanting; Tan, Rui; Chen, Zonghai; Ren, Yang; Lin, Yuan; Yang, Wanli; Wang, Chongmin; Wang, Lin-Wang; Lu, Jun; Amine, Khalil; Pan, Feng

2017-08-03

Abstract. Due to the enhanced kinetic properties, nanocrystallites have received much attention as potential electrode materials for energy storage. However, because of the large specific surface areas of nanocrystallites, they usually suffer from decreased energy density, reduced cycling stability and total electrode capacity. In this work, we report a size-dependent excess capacity beyond the theoretical value of 170 mAhg-1 in a special carbon coated LiFePO4 composite cathode material, which delivers capacities of 191.2 and 213.5 mAhg-1 with the mean particle sizes of 83 nm and 42 nm, respectively. Moreover, this LiFePO4 composite also shows excellent cycling stability and high rate performance. Our further experimental tests and ab initio calculations reveal that the excess capacity comes from the charge passivation for which the C-O-Fe bonds would lead to charge redistribution on the surface of LiFePO4 and hence to enhance the bonding interaction between surface O atoms and Li-ions. The surface reconstruction for excess Li-ion storage makes full use of the large specific surface area for the nanocrystallites, which can maintain the fast Li-ion transport and enhance the capacity greatly that the nanocrystallites usually suffers.

LiCoO/sub 2/ structures by spray pyrolysis technique for rechargeable Li-ion battery

International Nuclear Information System (INIS)

Yilmaz, M.; Turgut, G.; Aydin, S.; Ertugrul, M.

2012-01-01

As the lithium-ion batteries have high energy density, Lithium-batteries have become a very attractive field of study for the researchers. Batteries' high energy density is up to the anode and cathode materials used in the batteries and the technique which is chosen for getting these materials. In this study, LiCoO/sub 2/, used for cathode active material in lithium ion batteries, has been prepared with spraying on a glass base by spray pyrolysis technique. LiCoO/sub 2 /was annealed at 600 deg. C for 3h in an air atmosphere; and crystal structures of the obtained samples were examined with XRD, the surface morphology of them was examined with SEM. Effect of annealing on crystallization has been investigated in prepared samples. (author)

Atomic layer deposition for nanostructured Li-ion batteries

NARCIS (Netherlands)

Knoops, H.C.M.; Donders, M.E.; Sanden, van de M.C.M.; Notten, P.H.L.; Kessels, W.M.M.

2012-01-01

Nanostructuring is targeted as a solution to achieve the improvements required for implementing Li-ion batteries in a wide range of applications. These applications range in size from electrical vehicles down to microsystems. Atomic layer deposition (ALD) could be an enabling technology for

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

Effects of specific adsorption of copper (II) ion on charge transfer reaction at the thin film LiMn2O4 electrode/aqueous electrolyte interface

International Nuclear Information System (INIS)

Nakayama, N.; Yamada, I.; Huang, Y.; Nozawa, T.; Iriyama, Y.; Abe, T.; Ogumi, Z.

2009-01-01

This study investigated the effect of a specific adsorption ion, copper (II) ion, on the kinetics of the charge transfer reaction at a LiMn 2 O 4 thin film electrode/aqueous solution (1 mol dm -3 LiNO 3 ) interface. The zeta potential of LiMn 2 O 4 particles showed a negative value in 1 x 10 -2 mol dm -3 LiNO 3 aqueous solution, while it was measured as positive in the presence of 1 x 10 -2 mol dm -3 Cu(NO 3 ) 2 in the solution. The presence of copper (II) ions in the solution increased the charge transfer resistance, and CV measurement revealed that the lithium insertion/extraction reaction was retarded by the presence of small amount of copper (II) ions. The activation energy for the charge transfer reaction in the solution with Cu(NO 3 ) 2 was estimated to be 35 kJ mol -1 , which was ca. 10 kJ mol -1 larger than that observed in the solution without Cu(NO 3 ) 2 . These results suggest that the interaction between the lithium ion and electrode surface is a factor in the kinetics of charge transfer reaction

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.

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

Science.gov (United States)

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

2018-03-01

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

Rate theory of solvent exchange and kinetics of Li(+) - BF4 (-)/PF6 (-) ion pairs in acetonitrile.

Science.gov (United States)

Dang, Liem X; Chang, Tsun-Mei

2016-09-07

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li(+) and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li(+) in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li(+)-[BF4] and Li(+)-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li(+). We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li(+)-[BF4] and Li(+)-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

High Rate and Stable Li-Ion Insertion in Oxygen-Deficient LiV3O8 Nanosheets as a Cathode Material for Lithium-Ion Battery.

Science.gov (United States)

Song, Huanqiao; Luo, Mingsheng; Wang, Aimei

2017-01-25

Low performance of cathode materials has become one of the major obstacles to the application of lithium-ion battery (LIB) in advanced portable electronic devices, hybrid electric vehicles, and electric vehicles. The present work reports a versatile oxygen-deficient LiV 3 O 8 (D-LVO) nanosheet that was synthesized successfully via a facile oxygen-deficient hydrothermal reaction followed by thermal annealing in Ar. When used as a cathode material for LIB, the prepared D-LVO nanosheets display remarkable capacity properties at various current densities (a capacity of 335, 317, 278, 246, 209, 167, and 133 mA h g -1 at 50, 100, 200, 500, 1000, 2000, and 4000 mA g -1 , respectively) and excellent lithium-ion storage stability, maintaining more than 88% of the initial reversible capacity after 200 cycles at 1000 mA g -1 . The outstanding electrochemical properties are believed to arise largely from the introduction of tetravalent V (∼15% V 4+ ) and the attendant oxygen vacancies into LiV 3 O 8 nanosheets, leading to intrinsic electrical conductivity more than 1 order of magnitude higher and lithium-ion diffusion coefficient nearly 2 orders of magnitude higher than those of LiV 3 O 8 without detectable V 4+ (N-LVO) and thus contributing to the easy lithium-ion diffusion, rapid phase transition, and the excellent electrochemical reversibility. Furthermore, the more uniform nanostructure, as well as the larger specific surface area of D-LVO than N-LVO nanosheets may also improve the electrolyte penetration and provide more reaction sites for fast lithium-ion diffusion during the discharge/charge processes.

Degradation reactions in SONY-type Li-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Roth, E.P.; Nagasubramanian, G.

2000-07-01

Thermal instabilities were identified in SONY-type lithium-ion cells and correlated with interactions of cell constituents and reaction products. Three temperature regions of interaction were identified and associated with the state of charge (degree of Li intercalation) of the cell. Anodes were shown to undergo exothermic reactions as low as 100 C involving the solid electrolyte interface (SEI) layer and the LiPF{sub 6} salt in the electrolyte (EC:PC:DEC/LiPF{sub 6}). These reactions could account for the thermal runaway observed in these cells beginning at 100 C. Exothermic reactions were also observed in the 200 C--300 C region between the intercalated lithium anodes, the LiPF{sub 6} salt, and the PVDF. These reactions were followed by a high-temperature reaction region, 300 C--400 C, also involving the PVDF binder and the intercalated lithium anodes. The solvent was not directly involved in these reactions but served as a moderator and transport medium. Cathode exothermic reactions with the PVDF binder were observed above 200 C and increased with the state of charge (decreasing Li content). This offers an explanation for the observed lower thermal runaway temperatures for charged cells.

The progress of the electrode materials development for lithium ion battery

International Nuclear Information System (INIS)

Kang Kai; Dai Shouhui; Wan Yuhua

2001-01-01

The structure and the charge-discharge principle of Li-ion battery are briefly discussed; the progress of electrode materials for Li-ion battery is reviewed in detail. Graphite has found wide applications in commercial Li-ion batteries, however, the hard carbon, especially the carbon with hydrogen is the most promising anode material for Li-ion battery owing to its high capacity, which has now become hot spot of investigation. Following the LiCoO 2 , LiMn 2 O 4 spinel compound becomes the most powerful contestant. On the basis of the authors' results, the synthesis methods of LiMn 2 O 4 and its characterizations are compared. Moreover, the structural properties of intercalation electrode materials that are related to the rechargeable capacity and stability during cycling of lithium ions are also discussed

Location of rare-earth dopants on LiCAF and LiSAF laser hosts via XRD, EXAFS and computer modeling technique

International Nuclear Information System (INIS)

Valerio, Mario Ernesto Giroldo; Amaral, Jomar Batista de; Baldochi, Sonia Licia Vera; Mazzocchi, L.; Sasaki, Jose Marcos; Jackson, Robert A.

2004-01-01

Full text: Cr-doped LiCaAlF 6 (LiCAF) and LiSrAlF 6 (LiSAF) were used as laser operating in the near infrared region. Ce-doped LiCAF and LiSAF have been reported as leading candidates for tunable all-solid-state lasers in the UV region. Spectroscopic properties of LiCaAlF 6 : Nd suggest that this crystal can be used as selective optical filter and refractive element for 157 nm photolithography. The question of whether the RE dopant will prefer the Li + , the M 2+ site or the Al 3+ site is not yet known. Nevertheless most of the optical properties of these hosts including their laser action depend on the local symmetry, charge compensation mechanism and possible deformation of the lattice. In the present work, Powder X-ray Diffraction (XRD), X-ray Absorption Spectroscopy (XAS), Spectro fluorimetry, combined with computer modeling, were used to study the local structure around the dopant and determine the site occupied by them and also the distance and nature of the co-ordinating atoms. The compounds were prepared from commercially available CaF2 and SrF2 powders of high purity; LiF previously purified by the zone melting method, and AlF3 and RE dopants obtained from the hydro fluorination of commercial Al 2 O 3 . The synthesis of 2 mol % RE doped LiCAF and LiSAF samples were performed in a platinum reactor. The compositions were 2 mol % LiF and AlF3 enriched to compensate for their high vaporization. Powder XRD measurements were performed at room temperature in a Rigaku DMAX diffractometer in step scan mode using Cu K radiation. The Rietveld method (DBWS-9807a software) was employed in the analysis of the patterns. It was found that in the doped samples the concentration of the LiCAF or LiSAF phases are 84-95% and a small amount of AlF 3 and α - Li 3 AlF 6 were formed. The XAS experiments were performed on and above the L III absorption edge of the Er, Ho and Nd ions in fluorescence and transmission mode at room temperature in the XAS station at the LNLS, Campinas

Three-dimensional sandwich-structured NiMn2O4@reduced graphene oxide nanocomposites for highly reversible Li-ion battery anodes

Science.gov (United States)

Huang, Jiarui; Wang, Wei; Lin, Xirong; Gu, Cuiping; Liu, Jinyun

2018-02-01

A sandwich-structured NiMn2O4@reduced graphene oxide (NiMn2O4@rGO) nanocomposite consisting of ultrathin NiMn2O4 sheets uniformly anchored on both sides of a three-dimensional (3D) porous rGO is presented. The NiMn2O4@rGO nanocomposites prepared through a dipping process combining with a hydrothermal method show a good electrochemical performance including a high reversible capability of 1384 mAh g-1 at 1000 mA g-1 over 1620 cycles, and an superior rate performance. Thus, a full cell consisting of a commercial LiCoO2 cathode and the NiMn2O4@rGO anode delivers a stable capacity of about 1046 mAh g-1 (anode basis) after cycling at 50 mA g-1 for 60 times. It is demonstrated that the 3D porous composite structure accommodates the volume change during the Li+ insertion/extraction process and facilitates the rapid transport of ions and electrons. The high performance would enable the presented NiMn2O4@rGO nanocomposite a promising anode candidate for practical applications in Li-ion batteries.

Li4Ti5O12 thin-film electrodes by in-situ synthesis of lithium alkoxide for Li-ion microbatteries

International Nuclear Information System (INIS)

Mosa, J.; Aparicio, M.; Tadanaga, K.; Hayashi, A.; Tatsumisago, M.

2014-01-01

Rechargeable thin-film batteries have recently become the topic of widespread research for use as efficient energy storage devices. Spinel Li 4 Ti 5 O 12 has been considered as one of the most prospective anode materials for Li-ion batteries because of its excellent reversibility and long cycle life. We report here the sol–gel synthesis and coating preparation of spinel thin-film Li 4 Ti 5 O 12 electrodes for Li-ion microbatteries using lithium ethoxide produced in situ that reacts with titanium alkoxide to produce the precursor solution without particle precipitation. This synthesis procedure reduces the thermal treatment to obtain a pure phase at only 700 °C and 15 minutes. The physical and structural characterization of the 300 nm Li 4 Ti 5 O 12 coatings shows a very homogeneous distribution of elements and a pure spinel phase. Galvanostatic discharge-charge tests indicate maximum discharge capacities of 152 mA h g −1 when the material is treated at 700 °C for 15 minutes

The Li-ion rechargeable battery: a perspective.

Science.gov (United States)

Goodenough, John B; Park, Kyu-Sung

2013-01-30

Each cell of a battery stores electrical energy as chemical energy in two electrodes, a reductant (anode) and an oxidant (cathode), separated by an electrolyte that transfers the ionic component of the chemical reaction inside the cell and forces the electronic component outside the battery. The output on discharge is an external electronic current I at a voltage V for a time Δt. The chemical reaction of a rechargeable battery must be reversible on the application of a charging I and V. Critical parameters of a rechargeable battery are safety, density of energy that can be stored at a specific power input and retrieved at a specific power output, cycle and shelf life, storage efficiency, and cost of fabrication. Conventional ambient-temperature rechargeable batteries have solid electrodes and a liquid electrolyte. The positive electrode (cathode) consists of a host framework into which the mobile (working) cation is inserted reversibly over a finite solid-solution range. The solid-solution range, which is reduced at higher current by the rate of transfer of the working ion across electrode/electrolyte interfaces and within a host, limits the amount of charge per electrode formula unit that can be transferred over the time Δt = Δt(I). Moreover, the difference between energies of the LUMO and the HOMO of the electrolyte, i.e., electrolyte window, determines the maximum voltage for a long shelf and cycle life. The maximum stable voltage with an aqueous electrolyte is 1.5 V; the Li-ion rechargeable battery uses an organic electrolyte with a larger window, which increase the density of stored energy for a given Δt. Anode or cathode electrochemical potentials outside the electrolyte window can increase V, but they require formation of a passivating surface layer that must be permeable to Li(+) and capable of adapting rapidly to the changing electrode surface area as the electrode changes volume during cycling. A passivating surface layer adds to the impedance of the

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.

Graphite as negative electrode in Li-ion batteries; Le graphite comme electrode negative dans les accumulateurs Li-ion

Energy Technology Data Exchange (ETDEWEB)

Fischer, F.; Monnier, A. [Timcal SA (France)

1996-12-31

The last developments in lithium batteries design have demonstrated the advantages of graphite: competitive cost, flat output curve, high capacity thanks to the obtention of a final compound close to LiC{sub 6}, good behaviour during cycling and a high mass energy. However, these advantages are slightly tarnished by parasite secondary reactions during the evolution of the element. Two different cases are encountered: the formation of a passivation layer (loss of Li ions and formation of irreversible bounds) and the formation of a passivation layer with a reaction between graphite and the solvent (partial destruction of the graphite crystal lattice). In the first case, the theoretical graphite insertion capacity remains at 372 mAh/g while in the second case the insertion capacity is greatly reduced. Abstract only. (J.S.)

Graphite as negative electrode in Li-ion batteries; Le graphite comme electrode negative dans les accumulateurs Li-ion

Energy Technology Data Exchange (ETDEWEB)

Fischer, F; Monnier, A [Timcal SA (France)

1997-12-31

The last developments in lithium batteries design have demonstrated the advantages of graphite: competitive cost, flat output curve, high capacity thanks to the obtention of a final compound close to LiC{sub 6}, good behaviour during cycling and a high mass energy. However, these advantages are slightly tarnished by parasite secondary reactions during the evolution of the element. Two different cases are encountered: the formation of a passivation layer (loss of Li ions and formation of irreversible bounds) and the formation of a passivation layer with a reaction between graphite and the solvent (partial destruction of the graphite crystal lattice). In the first case, the theoretical graphite insertion capacity remains at 372 mAh/g while in the second case the insertion capacity is greatly reduced. Abstract only. (J.S.)

Further development of pyrometallurgical IME recycling process for Li-ion batteries from electric vehicles

International Nuclear Information System (INIS)

Vest, Matthias

2016-01-01

Li-ion batteries are increasingly used in hybrid electric vehicles (HEV), electric vehicles (EV) and stationary storage applications. Those applications are significantly different in terms of storage capacity, life cycles and charging times from consumer type batteries such as mobile phones and handheld tools. Naturally, those HEV and EV Li-ion batteries also differ significantly in chemical composition and size. Coherently, a recycling concept has been developed for HEV, EV and stationary storage Li-ion batteries. This concept is based on the existing IME-ACCUREC recycling process for consumer type batteries. This work describes the whole process development including slag design, test series in a lab-scale electric arc furnace and a 1 t scale trial in a top blown rotary converter.

Production and characterization of thin 7Li targets fabricated by ion implantation

International Nuclear Information System (INIS)

Cruz, J.; Fonseca, M.; Luis, H.; Mateus, R.; Marques, H.; Jesus, A.P.; Ribeiro, J.P.; Teodoro, O.M.N.D.; Rolfs, C.

2009-01-01

Very high fluence implantation of 7 Li + ions was used to promote the formation of a thin and high density 7 Li target in the surface region of Al samples. The implanted volume was characterized by particle induced gamma-ray emission, Rutherford backscattering spectrometry, X-ray photoelectron spectroscopy and nuclear reaction analysis, revealing that the implanted surface is a combination of Li 2 CO 3 , metallic lithium, LiOH and C, with almost no Al present. Radiation damage effects by proton beams were studied by observing the evolution of the 7 Li(p, α) 4 He nuclear reaction yield with the accumulated charge, at different proton energies, revealing high stability of the produced Li target.

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.

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.

Controlling Factors of Cell Design on Large-format Li-ion Battery Safety During Nail Penetration

Directory of Open Access Journals (Sweden)

Qing eWang

2015-08-01

Full Text Available In this paper we investigate the controlling design parameters of large-format Li-ion batteries on safety while undergoing nail penetration. We have identified three critical design parameters that control the safety during the nail penetration process: nail diameter, single sheet foil area, and cell capacity.Using commercial AutoLion software, we have investigated two typical design problems related to the selection of cell thickness and aspect ratio, namely: (1 the safety ramifications of increasing cell capacity via greater cell thickness for a fixed footprint, and (2 the effect of aspect ratio, or single sheet foil size, on safety at a given capacity. For a fixed footprint, our results indicate that the safety of the cell can be predicted by (Qcell Dnail^-0.5. For a given cell capacity, our results indicate that typically a larger single sheet foil area leads to a greater likelihood for thermal runaway due to its effect of making the heating more local in nature; however, for small cells (~ 5Ah and large nails (~ 20mm, the greater aspect ratio can lead to a safer cell, as the greater surface area strongly cools the global heating of the cell.

In situ methods for Li-ion battery research: A review of recent developments

Science.gov (United States)

Harks, P. P. R. M. L.; Mulder, F. M.; Notten, P. H. L.

2015-08-01

A considerable amount of research is being directed towards improving lithium-ion batteries in order to meet today's market demands. In particular in situ investigations of Li-ion batteries have proven extremely insightful, but require the electrochemical cell to be fully compatible with the conditions of the testing method and are therefore often challenging to execute. Advantageously, in the past few years significant progress has been made with new, more advanced, in situ techniques. Herein, a comprehensive overview of in situ methods for studying Li-ion batteries is given, with the emphasis on new developments and reported experimental highlights.

Synthesis of hollandite-type Li yMn 1- xCo xO 2 (x = 0-0.15) by Li + ion-exchange in molten salt and the electrochemical property for rechargeable lithium battery electrodes

Science.gov (United States)

Kumagai, Naoaki; Oshitari, Satoru; Komaba, Shinichi; Kadoma, Yoshihiro

The Li + ion-exchange reaction of K +-type α-K 0.14MnO 1.93·0.18H 2O and its Co-doped α-K 0.14(Mn 0.85Co 0.15)O 1.96·0.21H 2O with a large (2 × 2) tunnel structure has been investigated in a LiNO 3/LiCl molten salt at 300 °C. The Li + ion-exchanged products were examined by chemical analysis, X-ray diffraction, and scanning and transmission electron microscopic measurements. Almost all the K + ions and the hydrogens of water molecules in the (2 × 2) tunnel of α-MnO 2 and its Co-doped one were exchanged by Li + ions in the molten salt, resulting in Li +-type α-MnO 2 and its Co-doped one containing Li + ions as well as Li 2O (lithium oxide) in the (2 × 2) tunnel with maintaining the original hollandite structure. The electrochemical properties including charge-discharge cycling of the Li + ion-exchanged α-MnO 2 and its Co-doped samples have been investigated as insertion compounds in the search for new cathode materials for rechargeable lithium batteries. The Li + ion-exchanged α-MnO 2 and its Co-doped samples provided higher capacities than the K +-type parent materials on initial discharge and charge-discharge cyclings, probably due to the structural stabilization with the existence of Li 2O in the (2 × 2) tunnels.

Effective regeneration of anode material recycled from scrapped Li-ion batteries

Science.gov (United States)

Zhang, Jin; Li, Xuelei; Song, Dawei; Miao, Yanli; Song, Jishun; Zhang, Lianqi

2018-06-01

Recycling high-valuable metal elements (such as Li, Ni, Co, Al and Cu elements) from scrapped lithium ion batteries can bring significant economic benefits. However, recycling and reusing anode material has not yet attracted wide attention up to now, due to the lower added-value than the above valuable metal materials and the difficulties in regenerating process. In this paper, a novel regeneration process with significant green advance is proposed to regenerate anode material recycled from scrapped Li-ion batteries for the first time. After regenerated, most acetylene black (AB) and all the styrene butadiene rubber (SBR), carboxymethylcellulose sodium (CMC) in recycled anode material are removed, and the surface of anode material is coated with pyrolytic carbon from phenolic resin again. Finally, the regenerated anode material (graphite with coating layer, residual AB and a little CMC pyrolysis product) is obtained. As expected, all the technical indexs of regenerated anode material exceed that of a midrange graphite with the same type, and partial technical indexs are even closed to that of the unused graphite. The results indicate the effective regeneration of anode material recycled from scrapped Li-ion batteries is really achieved.

Electrochemical and diffusional insights of combustion synthesized SrLi2Ti6O14 negative insertion material for Li-ion Batteries

Science.gov (United States)

Dayamani, Allumolu; Shinde, Ganesh S.; Chaupatnaik, Anshuman; Rao, R. Prasada; Adams, Stefan; Barpanda, Prabeer

2018-05-01

Solvothermal synthetic routes can provide energy-savvy platforms to fabricate battery anode materials involving relatively milder annealing steps vis-à-vis the conventional solid-state synthesis. These energy efficient routes in turn restrict aggressive grain growth to form nanoscale particles favouring efficient Li+ diffusion. Here, we report an economic solution combustion synthesis of SrLi2Ti6O14 anode involving nitrate-urea complexation with a short annealing duration of only 2 h (900 °C). Rietveld refinement confirms the phase purity of target product assuming an orthorhombic framework (Cmca symmetry). It delivers reversible capacity of ∼125 mAh.g-1 at a rate of C/20 involving a 1.38 V Ti4+/Ti3+ redox activity with excellent rate kinetics and cycling stability. Bond valence site energy (BVSE) calculations gauge SrLi2Ti6O14 to be an anisotropic 3D Li+ ion conductor with the highest ionic conductivity along the c direction. The electrochemical and diffusional pathways have been elucidated for combustion prepared SrLi2Ti6O14 as an efficient and safe negative electrode candidate for Li-ion batteries.

Ferric chloride-graphite intercalation compounds as anode materials for Li-ion batteries.

Science.gov (United States)

Wang, Lili; Zhu, Yongchun; Guo, Cong; Zhu, Xiaobo; Liang, Jianwen; Qian, Yitai

2014-01-01

Ferric chloride-graphite intercalation compounds (FeCl3 -GICs) with stage 1 and stage 2 structures were synthesized by reacting FeCl3 and expanded graphite (EG) in air in a stainless-steel autoclave. As rechargeable Li-ion batteries, these FeCl3 -GICs exhibit high capacity, excellent cycling stability, and superior rate capability, which could be attributed to their unique intercalation features. This work may enable new possibilities for the fabrication of Li-ion batteries. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface and interface sciences of Li-ion batteries. -Research progress in electrode-electrolyte interface-

Science.gov (United States)

Minato, Taketoshi; Abe, Takeshi

2017-12-01

The application potential of Li-ion batteries is growing as demand increases in different fields at various stages in energy systems, in addition to their conventional role as power sources for portable devices. In particular, applications in electric vehicles and renewable energy storage are increasing for Li-ion batteries. For these applications, improvements in battery performance are necessary. The Li-ion battery produces and stores electric power from the electrochemical redox reactions between the electrode materials. The interface between the electrodes and electrolyte strongly affects the battery performance because the charge transfer causing the electrode redox reaction begins at this interface. Understanding of the surface structure, electronic structure, and chemical reactions at the electrode-electrolyte interface is necessary to improve battery performance. However, the interface is located between the electrode and electrolyte materials, hindering the experimental analysis of the interface; thus, the physical properties and chemical processes have remained poorly understood until recently. Investigations of the physical properties and chemical processes at the interface have been performed using advanced surface science techniques. In this review, current knowledge and future research prospects regarding the electrode-electrolyte interface are described for the further development of Li-ion batteries.

Etched colloidal LiFePO4 nanoplatelets toward high-rate capable Li-ion battery electrodes.

Science.gov (United States)

Paolella, Andrea; Bertoni, Giovanni; Marras, Sergio; Dilena, Enrico; Colombo, Massimo; Prato, Mirko; Riedinger, Andreas; Povia, Mauro; Ansaldo, Alberto; Zaghib, Karim; Manna, Liberato; George, Chandramohan

2014-12-10

LiFePO4 has been intensively investigated as a cathode material in Li-ion batteries, as it can in principle enable the development of high power electrodes. LiFePO4, on the other hand, is inherently "plagued" by poor electronic and ionic conductivity. While the problems with low electron conductivity are partially solved by carbon coating and further by doping or by downsizing the active particles to nanoscale dimensions, poor ionic conductivity is still an issue. To develop colloidally synthesized LiFePO4 nanocrystals (NCs) optimized for high rate applications, we propose here a surface treatment of the NCs. The particles as delivered from the synthesis have a surface passivated with long chain organic surfactants, and therefore can be dispersed only in aprotic solvents such as chloroform or toluene. Glucose that is commonly used as carbon source for carbon-coating procedure is not soluble in these solvents, but it can be dissolved in water. In order to make the NCs hydrophilic, we treated them with lithium hexafluorophosphate (LiPF6), which removes the surfactant ligand shell while preserving the structural and morphological properties of the NCs. Only a roughening of the edges of NCs was observed due to a partial etching of their surface. Electrodes prepared from these platelet NCs (after carbon coating) delivered a capacity of ∼ 155 mAh/g, ∼ 135 mAh/g, and ∼ 125 mAh/g, at 1 C, 5 C, and 10 C, respectively, with significant capacity retention and remarkable rate capability. For example, at 61 C (10.3 A/g), a capacity of ∼ 70 mAh/g was obtained, and at 122 C (20.7 A/g), the capacity was ∼ 30 mAh/g. The rate capability and the ease of scalability in the preparation of these surface-treated nanoplatelets make them highly suitable as electrodes in Li-ion batteries.

Continuous flame aerosol synthesis of carbon-coated nano-LiFePO4 for Li-ion batteries

Science.gov (United States)

Waser, Oliver; Büchel, Robert; Hintennach, Andreas; Novák, Petr; Pratsinis, Sotiris E.

2013-01-01

Core-shell, nanosized LiFePO4-carbon particles were made in one step by scalable flame aerosol technology at 7 g/h. Core LiFePO4 particles were made in an enclosed flame spray pyrolysis (FSP) unit and were coated in-situ downstream by auto thermal carbonization (pyrolysis) of swirl-fed C2H2 in an O2-controlled atmosphere. The formation of acetylene carbon black (ACB) shell was investigated as a function of the process fuel-oxidant equivalence ratio (EQR). The core-shell morphology was obtained at slightly fuel-rich conditions (1.0 < EQR < 1.07) whereas segregated ACB and LiFePO4 particles were formed at fuel-lean conditions (0.8 < EQR < 1). Post-annealing of core-shell particles in reducing environment (5 vol% H2 in argon) at 700 °C for up to 4 hours established phase pure, monocrystalline LiFePO4 with a crystal size of 65 nm and 30 wt% ACB content. Uncoated LiFePO4 or segregated LiFePO4-ACB grew to 250 nm at these conditions. Annealing at 800 °C induced carbothermal reduction of LiFePO4 to Fe2P by ACB shell consumption that resulted in cavities between carbon shell and core LiFePO4 and even slight LiFePO4 crystal growth but better electrochemical performance. The present carbon-coated LiFePO4 showed superior cycle stability and higher rate capability than the benchmark, commercially available LiFePO4. PMID:23407817

Ion beam analysis of zeolites type Li-ABW synthesized by hydrothermal method

Energy Technology Data Exchange (ETDEWEB)

Andrade, E.; De Lucio, O. G.; Solis, C.; Zavala, E. P.; Cruz, J. [UNAM, Instituto de Fisica, Circuito Exterior, Ciudad Universitaria, 04510 Mexico D. F. (Mexico); Alfaro, S.; Rodriguez, C.; Valenzuela, M. A. [IPN, Escuela Superior de Ingenieria Quimica e Industrias Extractivas, Laboratorio de Catalisis y Materiales, Zacantenco, 07738 Mexico D. F. (Mexico); Rocha, M. F. [IPN, Escuela Superior de Ingenieria Mecanica y Electrica, Av. Instituto Politecnico Nacional s/n, Col. Lindavista, 07738 Mexico D. F. (Mexico); Murillo, G.; Policroniades, R. [ININ, Carretera Mexico-Toluca s/n, Ocoyoacac 52750, Estado de Mexico (Mexico)

2010-02-15

This work reports a method to synthesize and characterize Li-ABW zeolites by a hydrothermal method. These materials are good candidates for CO{sub 2} capture because of the high reactivity between the Li{sup +} with CO{sub 2} to form Li{sub 2}CO{sub 3}. We performed and elemental profile concentration using ion beam analysis. The elastic backscattered proton energy spectra from the Al, Si, O and Li nuclei, in combination with the {alpha} particles from the {sup 7}Li ({rho}, {alpha}){sup 4}He nuclear reaction energy spectra, were employed for this task. X-ray diffraction was also applied to determine the crystalline structure. (Author)

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

HNbO3 and HTaO3: new cubic perovskites prepared from LiNbO3 and LiTaO3 via ion exchange

International Nuclear Information System (INIS)

Rice, C.E.; Jackel, J.L.

1982-01-01

The synthesis of HNbO 3 and HTaO 3 from LiNbO 3 via ion exchange in hot aqueous acid solutions is reported. This reaction is accompanied by a topotactic structural transformation from the rhombohedral LiNbO 3 structure to the cubic perovskite structure; cell constants are a = 3.822(1) angstrom for HNbO 3 and 3.810(2) angstrom for HTaO 3 . These new compounds have been characterized by powder X-ray diffraction, thermogravimetric analysis, and solid-state NMR. They are electronic insulators and have low ionic conductivity. Evidence of partially proton-exchange phases Li/sub 1-x/H/sub x/MO 3 was also seen. The possible significance of this ion exchange reaction for devices using LiNbO 3 or LiTaO 3 is discussed

Nanostructured lithium titanates (Li4Ti5O12) for lithium-ion batteries

CSIR Research Space (South Africa)

Wen, L

2016-07-01

Full Text Available Nanostructured lithium titanates (Li(sub4)Ti(sub5)O(sub12)) have been intensively investigated as anode materials of Li-ion batteries due to their many advantages, such as excellent performance, outstanding safety, and excellent cycle life...

Li Storage of Calcium Niobates for Lithium Ion Batteries.

Science.gov (United States)

Yim, Haena; Yu, Seung-Ho; Yoo, So Yeon; Sung, Yung-Eun; Choi, Ji-Won

2015-10-01

New types of niobates negative electrode were studied for using in lithium-ion batteries in order to alternate metallic lithium anodes. The potassium intercalated compound KCa2Nb3O10 and proton intercalated compound HCa2Nb3O10 were studied, and the electrochemical results showed a reversible cyclic voltammetry profile with acceptable discharge capacity. The as-prepared KCa2Nb3O10 negative electrode had a low discharge capacity caused by high overpotential, but the reversible intercalation and deintercalation reaction of lithium ions was activated after exchanging H+ ions for intercalated K+ ions. The initial discharge capacity of HCa2Nb3O10 was 54.2 mAh/g with 92.1% of coulombic efficiency, compared with 10.4 mAh/g with 70.2% of coulombic efficiency for KCa2Nb3O10 at 1 C rate. The improved electrochemical performance of the HCa2Nb3O10 was related to the lower bonding energy between proton cation and perovskite layer, which facilitate Li+ ions intercalating into the cation site, unlike potassium cation and perovskite layer. Also, this negative material can be easily exfoliated to Ca2Nb3O10 layer by using cation exchange process. Then, obtained two-dimensional nanosheets layer, which recently expected to be an advanced electrode material because of its flexibility, chemical stable, and thin film fabricable, can allow Li+ ions to diffuse between the each perovskite layer. Therefore, this new type layered perovskite niobates can be used not only bulk-type lithium ion batteries but also thin film batteries as a negative material.

Scalable integration of Li5FeO4 towards robust, high-performance lithium-ion hybrid capacitors.

Science.gov (United States)

Park, Min-Sik; Lim, Young-Geun; Hwang, Soo Min; Kim, Jung Ho; Kim, Jeom-Soo; Dou, Shi Xue; Cho, Jaephil; Kim, Young-Jun

2014-11-01

Lithium-ion hybrid capacitors have attracted great interest due to their high specific energy relative to conventional electrical double-layer capacitors. Nevertheless, the safety issue still remains a drawback for lithium-ion capacitors in practical operational environments because of the use of metallic lithium. Herein, single-phase Li5FeO4 with an antifluorite structure that acts as an alternative lithium source (instead of metallic lithium) is employed and its potential use for lithium-ion capacitors is verified. Abundant Li(+) amounts can be extracted from Li5FeO4 incorporated in the positive electrode and efficiently doped into the negative electrode during the first electrochemical charging. After the first Li(+) extraction, Li(+) does not return to the Li5FeO4 host structure and is steadily involved in the electrochemical reactions of the negative electrode during subsequent cycling. Various electrochemical and structural analyses support its superior characteristics for use as a promising lithium source. This versatile approach can yield a sufficient Li(+)-doping efficiency of >90% and improved safety as a result of the removal of metallic lithium from the cell. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cr-substituted LiCoPO4 core with a conductive carbon layer towards high-voltage lithium-ion batteries

Science.gov (United States)

Wang, Yue; Chen, Junhong; Qiu, Jingyi; Yu, Zhongbao; Ming, Hai; Li, Meng; Zhang, Songtong; Yang, Yusheng

2018-02-01

Electrical and ionic conductivity are two major limiting factors for LiCoPO4 cathode material. To overcome these shortcomings, a Cr-substituted LiCoPO4 core with a conductive carbon layer cathode material is synthesized using the sol-gel method. The physical chemistry properties of these materials are systematically investigated by using various characterization methods. For instance, the XRD and Rietveld refinement results reveal that Cr successfully substitutes the Co within the LiCoPO4 core to form LiCo1-1.5xCrxPO4/C (x = 0, 0.02, 0.04, 0.06) without changing the olivine structure but exhibits a decrease in the unit cell volume with increasing Cr substitution. SEM and TEM images indicate that Cr substitution does not lead to changes in the basic morphology of LiCo1-1.5xCrxPO4/C (x = 0, 0.02, 0.04, 0.06) material, which is composed of agglomerated nanoparticles with an 8 nm carbon layer on the surface. The EDS and XPS results confirm that Cr is uniformly distributed on the surface and that the oxidation state of Cr is +3. FTIR spectra indicate that the antisite defect concentration decreases with increasing Cr substitution. Furthermore, Cr substitution significantly improves the electrochemical performances of LiCo1-1.5xCrxPO4/C (x = 0.02, 0.04, 0.06) cathode. Notably, the LiCo0.94Cr0.04PO4/C delivers an initial discharge capacity of 144 mA h g-1 at 0.1 C and shows a capacity retention of 71% after 100 cycles between 3.0 and 5.0 V. The CV and EIS results indicate that the polarization is reduced and that the electronic and ionic conductivities are improved by Cr substitution. The good electrochemical performances for Cr-substituted LiCoPO4/C electrodes are attributed to the lower antisite defect concentration, as the reduction of polarization, the improvement of electronic and ion conductivity and the uniform carbon layer. These features will accelerate the commercial application of LiCoPO4 towards the start-art of the high voltage lithium-ion batteries.

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

Science.gov (United States)

Knight, Brandon M.

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

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.

Contribution of Li-ion batteries to the environmental impact of electric vehicles.

Science.gov (United States)

Notter, Dominic A; Gauch, Marcel; Widmer, Rolf; Wäger, Patrick; Stamp, Anna; Zah, Rainer; Althaus, Hans-Jörg

2010-09-01

Battery-powered electric cars (BEVs) play a key role in future mobility scenarios. However, little is known about the environmental impacts of the production, use and disposal of the lithium ion (Li-ion) battery. This makes it difficult to compare the environmental impacts of BEVs with those of internal combustion engine cars (ICEVs). Consequently, a detailed lifecycle inventory of a Li-ion battery and a rough LCA of BEV based mobility were compiled. The study shows that the environmental burdens of mobility are dominated by the operation phase regardless of whether a gasoline-fueled ICEV or a European electricity fueled BEV is used. The share of the total environmental impact of E-mobility caused by the battery (measured in Ecoindicator 99 points) is 15%. The impact caused by the extraction of lithium for the components of the Li-ion battery is less than 2.3% (Ecoindicator 99 points). The major contributor to the environmental burden caused by the battery is the supply of copper and aluminum for the production of the anode and the cathode, plus the required cables or the battery management system. This study provides a sound basis for more detailed environmental assessments of battery based E-mobility.

Ab initio study of isomerism in molecular Li2AB+ ions with 12 and 14 valence electrons

International Nuclear Information System (INIS)

Charkin, O.P.; Klimenko, N.M.; Mak-Ki, M.L.; Shlojer, P.R.

1997-01-01

Ab initio calculations of potential energy surfaces (PES) of molecular ions Li 2 AB + with 12 and 14 valence electrons have been made in the framework of approximations MP2/6-31G*//HF/6-31G*+ZPE(HF/6-31G*) and MP4SDTQ/6-31*//MP2/6-31G*+ZPE(MP2/6-31G*). The following most favourable structures have been found: a double-terminal linear for LiNO + (a triplet); a plane bicyclic one for Li 2 OF + , Li 2 SCl + , Li 2 NO + (a singlet) and Li 2 PS + (a singlet), where both cations are coordinated to A-B bond; rectangular (T-shaped) for Li 2 OCl + and SFLi + , as well as for LiNS + and POLi 2 + ions in singlet and triplet states; in the form of a half-opened butterfly for Li 2 PS + (a triplet) and Li 2 SCl +

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-01-01

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

Environmental characteristics comparison of Li-ion batteries and Ni–MH batteries under the uncertainty of cycle performance

International Nuclear Information System (INIS)

Yu, Yajuan; Wang, Xiang; Wang, Dong; Huang, Kai; Wang, Lijing; Bao, Liying; Wu, Feng

2012-01-01

An environmental impact assessment model for secondary batteries under uncertainty is proposed, which is a combination of the life cycle assessment (LCA), Eco-indicator 99 system and Monte Carlo simulation (MCS). The LCA can describe the environmental impact mechanism of secondary batteries, whereas the cycle performance was simulated through MCS. The composite LCA–MCS model was then carried out to estimate the environmental impact of two kinds of experimental batteries. Under this kind of standard assessment system, a comparison between different batteries could be accomplished. The following results were found: (1) among the two selected batteries, the environmental impact of the Li-ion battery is lower than the nickel–metal hydride (Ni–MH) battery, especially with regards to resource consumption and (2) the lithium ion (Li-ion) battery is less sensitive to cycle uncertainty, its environmental impact fluctuations are small when compared with the selected Ni–MH battery and it is more environmentally friendly. The assessment methodology and model proposed in this paper can also be used for any other secondary batteries and they can be helpful in the development of environmentally friendly secondary batteries.

An omnipotent Li-ion battery charger with multimode control and polarity reversible techniques

Science.gov (United States)

Chen, Jiann-Jong; Ku, Yi-Tsen; Yang, Hong-Yi; Hwang, Yuh-Shyan; Yu, Cheng-Chieh

2016-07-01

The omnipotent Li-ion battery charger with multimode control and polarity reversible techniques is presented in this article. The proposed chip is fabricated with TSMC 0.35μm 2P4M complementary metal-oxide- semiconductor processes, and the chip area including pads is 1.5 × 1.5 mm2. The structure of the omnipotent charger combines three charging modes and polarity reversible techniques, which adapt to any Li-ion batteries. The three reversible Li-ion battery charging modes, including trickle-current charging, large-current charging and constant-voltage charging, can charge in matching polarities or opposite polarities. The proposed circuit has a maximum charging current of 300 mA and the input voltage of the proposed circuit is set to 4.5 V. The maximum efficiency of the proposed charger is about 91% and its average efficiency is 74.8%. The omnipotent charger can precisely provide the charging current to the battery.

High speed pulsed laser cutting of LiCoO2 Li-ion battery electrodes

Science.gov (United States)

Lutey, Adrian H. A.; Fortunato, Alessandro; Carmignato, Simone; Fiorini, Maurizio

2017-09-01

Laser cutting of Li-ion battery electrodes represents an alternative to mechanical blanking that avoids complications associated with tool wear and allows assembly of different cell geometries with a single device. In this study, laser cutting of LiCoO2 Li-ion battery electrodes is performed at up to 5m /s with a 1064nm wavelength nanosecond pulsed fiber laser with a maximum average power of 500W and a repetition rate of up to 2MHz . Minimum average cutting power for cathode and anode multi-layer films is established for 12 parameter groups with velocities over the range 1 - 5m /s , varying laser pulse fluence and overlap. Within the tested parameter range, minimum energy per unit cut length is found to decrease with increasing repetition rate and velocity. SEM analysis of the resulting cut edges reveals visible clearance widths in the range 20 - 50 μm , with cut quality found to improve with velocity due to a reduction in lateral heat conduction losses. Raman line map spectra reveal changes in the cathode at 60 μm from the cut edge, where bands at 486cm-1 and 595cm-1 , corresponding to the Eg and A1g modes of LiCoO2 , are replaced with a single wide band centered at 544cm-1 , and evidence of carbon black is no longer present. No changes in Raman spectra are observed in the anode. The obtained results suggest that further improvements in cutting efficiency and quality could be achieved by increasing the repetition rate above 2MHz , thereby improving ablation efficiency of the metallic conductor layers. The laser source utilized in the present study nonetheless represents an immediately available solution for repeatability and throughput that are superior to mechanical blanking.

A High Efficiency Li-Ion Battery LDO-Based Charger for Portable Application

Directory of Open Access Journals (Sweden)

Youssef Ziadi

2015-01-01

Full Text Available This paper presents a high efficiency Li-ion battery LDO-based charger IC which adopted a three-mode control: trickle constant current, fast constant current, and constant voltage modes. The criteria of the proposed Li-ion battery charger, including high accuracy, high efficiency, and low size area, are of high importance. The simulation results provide the trickle current of 116 mA, maximum charging current of 448 mA, and charging voltage of 4.21 V at the power supply of 4.8–5 V, using 0.18 μm CMOS technology.

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.

Electrospun hierarchical LiV3O8 nanofibers assembled from nanosheets with exposed {100} facets and their enhanced performance in aqueous lithium-ion batteries.

Science.gov (United States)

Liang, Lin; Zhou, Min; Xie, Yi

2012-03-05

Hierarchical LiV(3)O(8) nanofibers, assembled from nanosheets that have exposed {100} facets, have been fabricated by using electrospinning combined with calcination. The formation mechanism of hierarchical nanofibers was investigated by X-ray diffraction and scanning electron microscopy. Poly(vinyl alcohol) (PVA) played a dual role in the formation of the nanofibers: besides acting as the template for forming the fibers, it effectively prevented the aggregation of LiV(3)O(8) nanoparticles, thereby allowing them to grow into small nanosheets with exposed {100} facets owing to the self-limitation property of LiV(3)O(8). This nanostructure is beneficial for the insertion/extraction of lithium ions. Meanwhile, the {100} facets have fewer and smaller channels, which may effectively alleviate proton co-intercalation into the electrode materials. Hence, the hierarchical LiV(3)O(8) nanofibers exhibit higher discharge capacities and better cycling stabilities as the anode electrode material for aqueous lithium-ion batteries than those reported previously. We demonstrate that these hierarchical nanofibers have promising potential applications in aqueous lithium-ion batteries. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion exchange and electrochemical evaluation of the microporous phosphate Li9Fe7(PO4)10

International Nuclear Information System (INIS)

Becht, Gregory A.; Vaughey, John T.; Britt, Robin L.; Eagle, Cassandra T.; Hwu, Shiou-Jyh

2008-01-01

A new lithium iron(III) phosphate, Li 9 Fe 7 (PO 4 ) 10 , has been synthesized and is currently under electrochemical evaluation as an anode material for rechargeable lithium-ion battery applications. The sample was prepared via the ion exchange reaction of Cs 5 K 4 Fe 7 (PO 4 ) 10 1 in the 1 M LiNO 3 solution under hydrothermal conditions at 200 deg. C. The fully Li + -exchanged sample Li 9 Fe 7 (PO 4 ) 10 2 cannot yet be synthesized by conventional high-temperature, solid-state methods. The parent compound 1 is a member of the Cs 9-x K x Fe 7 (PO 4 ) 10 series that was previously isolated from a high-temperature (750 deg. C) reaction employing the eutectic CsCl/KCl molten salt. The polycrystalline solid 1 was first prepared in a stoichiometric reaction via conventional solid-state method then followed by ion exchange giving rise to 2. Both compounds adopt three-dimensional structures that consist of orthogonally interconnected channels where electropositive ions reside. It has been demonstrated that the Cs 9-x K x Fe 7 (PO 4 ) 10 series possesses versatile ion exchange capabilities with all the monovalent alkali metal and silver cations due to its facile pathways for ion transport. 1 and 2 were subject to electrochemical analysis and preliminary results suggest that the latter can be considered as an anode material. Electrochemical results indicate that Li 9 Fe 7 (PO 4 ) 10 is reduced below 1 V (vs. Li) to most likely form a Fe(0)/Li 3 PO 4 composite material, which can subsequently be cycled reversibly at relatively low potential. An initial capacity of 250 mAh/g was measured, which is equivalent to the insertion of thirteen Li atoms per Li 9+x Fe 7 (PO 4 ) 10 (x = 13) during the charge/discharge process (Fe 2+ + 2e → Fe 0 ). Furthermore, 2 shows a lower reduction potential (0.9 V), by approximately 200 mV, and much better electrochemical reversibility than iron(III) phosphate, FePO 4 , highlighting the value of improving the ionic conductivity of the sample

NASA Aerospace Flight Battery Program: Generic Safety, Handling and Qualification Guidelines for Lithium-Ion (Li-Ion) Batteries; Availability of Source Materials for Lithium-Ion (Li-Ion) Batteries; Maintaining Technical Communications Related to Aerospace Batteries (NASA Aerospace Battery Workshop). Volume 1, Part 1

Science.gov (United States)

Manzo, Michelle A.; Brewer, Jeffrey C.; Bugga, Ratnakumar V.; Darcy, Eric C.; Jeevarajan, Judith A.; McKissock, Barbara I.; Schmitz, Paul C.

2010-01-01

This NASA Aerospace Flight Battery Systems Working Group was chartered within the NASA Engineering and Safety Center (NESC). The Battery Working Group was tasked to complete tasks and to propose proactive work to address battery related, agency-wide issues on an annual basis. In its first year of operation, this proactive program addressed various aspects of the validation and verification of aerospace battery systems for NASA missions. Studies were performed, issues were discussed and in many cases, test programs were executed to generate recommendations and guidelines to reduce risk associated with various aspects of implementing battery technology in the aerospace industry. This document contains Part 1 - Volume I: Generic Safety, Handling and Qualification Guidelines for Lithium-Ion (Li-Ion) Batteries, Availability of Source Materials for Lithium-Ion (Li-Ion) Batteries, and Maintaining Technical Communications Related to Aerospace Batteries (NASA Aerospace Battery Workshop).

Synthesis of ultrasmall Li-Mn spinel oxides exhibiting unusual ion exchange, electrochemical, and catalytic properties

Science.gov (United States)

Miyamoto, Yumi; Kuroda, Yoshiyuki; Uematsu, Tsubasa; Oshikawa, Hiroyuki; Shibata, Naoya; Ikuhara, Yuichi; Suzuki, Kosuke; Hibino, Mitsuhiro; Yamaguchi, Kazuya; Mizuno, Noritaka

2015-10-01

The efficient surface reaction and rapid ion diffusion of nanocrystalline metal oxides have prompted considerable research interest for the development of high functional materials. Herein, we present a novel low-temperature method to synthesize ultrasmall nanocrystalline spinel oxides by controlling the hydration of coexisting metal cations in an organic solvent. This method selectively led to Li-Mn spinel oxides by tuning the hydration of Li+ ions under mild reaction conditions (i.e., low temperature and short reaction time). These particles exhibited an ultrasmall crystallite size of 2.3 nm and a large specific surface area of 371 ± 15 m2 g-1. They exhibited unique properties such as unusual topotactic Li+/H+ ion exchange, high-rate discharge ability, and high catalytic performance for several aerobic oxidation reactions, by creating surface phenomena throughout the particles. These properties differed significantly from those of Li-Mn spinel oxides obtained by conventional solid-state methods.

Primary frequency regulation with Li-ion battery energy storage system: A case study for Denmark

DEFF Research Database (Denmark)

Swierczynski, Maciej Jozef; Stroe, Daniel Ioan; Stan, Ana-Irina

2013-01-01

Meeting ambitious goals of transition to distributed and environmentally-friendly renewable energy generation can be difficult to achieve without energy storage systems due to technical and economical challenges. Moreover, energy storage systems have a high potential of not only smoothing and imp...... electricity market. Moreover, in this paper a possible improvement of the Li-ion BESS energy management strategy is shown, which allows for obtaining the higher NPV....... lifetime, which introduces significant risk into the business model. This paper deals with the investigation of the lifetime of LiFeP04/C battery systems when they are used to provide primary frequency regulation service. A semi-empirical lifetime model for these battery cells was developed based...... on the results obtained from accelerated lifetime testing. The developed Li­-ion battery lifetime model is later a base for the analyses of the economic profitability of the investment in the Li-ion battery energy storage system (BESS), which delivers the primary frequency regulation service on the Danish...

Comparison of comprehensive properties of Ni-MH (nickel-metal hydride) and Li-ion (lithium-ion) batteries in terms of energy efficiency

International Nuclear Information System (INIS)

Kang, Jianqiang; Yan, Fuwu; Zhang, Pei; Du, Changqing

2014-01-01

In this work, we successfully proposed a method to compare the comprehensive properties of different battery systems in terms of a parameter, energy efficiency. The quantitative relationship of OCV (open circuit voltage) and SOC (state of charge) for Ni-MH batteries is firstly established to calculate the energy efficiency. Then a comprehensive comparison of the energy efficiency for Ni-MH and Li-ion batteries is systemically analyzed under different operating conditions. The results suggest that the energy efficiency is larger for Li-ion batteries than for Ni-MH batteries under charge and charge–discharge cycles, but lesser under a large current rate discharge. The outcome indicates that Ni-MH batteries are more favorable in the case of large current rates discharge than Li-ion batteries. Under plus current rates, two factors, SOC and current rates are analyzed with respect to energy efficiency. For both the batteries, the energy efficiency is varied slightly with SOC, but declines greatly with increased current rates. - Highlights: • A method to compare the comprehensive property for different battery systems. • The relationship of OCV and SOC for Ni-MH batteries established. • An analysis of energy efficiency for Ni-MH and Li-ion batteries. • Ni-MH batteries are more favorable under large current rates discharge

Lithium ion mobility in lithium phosphidosilicates: Crystal structure, {sup 7}Li, {sup 29}Si, and {sup 31}P MAS NMR spectroscopy, and impedance spectroscopy of Li{sub 8}SiP{sub 4} and Li{sub 2}SiP{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Toffoletti, Lorenzo; Landesfeind, Johannes; Klein, Wilhelm; Gasteiger, Hubert A.; Faessler, Thomas F. [Department of Chemistry, Technische Universitaet Muenchen, Lichtenbergstrasse 4, 85747, Garching bei Muenchen (Germany); Kirchhain, Holger; Wuellen, Leo van [Department of Physics, University of Augsburg, Universitaetsstrasse 1, 86159, Augsburg (Germany)

2016-12-05

The need to improve electrodes and Li-ion conducting materials for rechargeable all-solid-state batteries has drawn enhanced attention to the investigation of lithium-rich compounds. The study of the ternary system Li-Si-P revealed a series of new compounds, two of which, Li{sub 8}SiP{sub 4} and Li{sub 2}SiP{sub 2}, are presented. Both phases represent members of a new family of Li ion conductors that display Li ion conductivity in the range from 1.15(7) x 10{sup -6} Scm{sup -1} at 0 C to 1.2(2) x 10{sup -4} Scm{sup -1} at 75 C (Li{sub 8}SiP{sub 4}) and from 6.1(7) x 10{sup -8} Scm{sup -1} at 0 C to 6(1) x 10{sup -6} Scm{sup -1} at 75 C (Li{sub 2}SiP{sub 2}), as determined by impedance measurements. Temperature-dependent solid-state {sup 7}Li NMR spectroscopy revealed low activation energies of about 36 kJ mol{sup -1} for Li{sub 8}SiP{sub 4} and about 47 kJ mol{sup -1} for Li{sub 2}SiP{sub 2}. Both compounds were structurally characterized by X-ray diffraction analysis (single crystal and powder methods) and by {sup 7}Li, {sup 29}Si, and {sup 31}P MAS NMR spectroscopy. Both phases consist of tetrahedral SiP{sub 4} anions and Li counterions. Li{sub 8}SiP{sub 4} contains isolated SiP{sub 4} units surrounded by Li atoms, while Li{sub 2}SiP{sub 2} comprises a three-dimensional network based on corner-sharing SiP{sub 4} tetrahedra, with the Li ions located in cavities and channels. (copyright 2016 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

High Performance Li4Ti5O12/Si Composite Anodes for Li-Ion Batteries

Directory of Open Access Journals (Sweden)

Chunhui Chen

2015-08-01

Full Text Available Improving the energy capacity of spinel Li4Ti5O12 (LTO is very important to utilize it as a high-performance Li-ion battery (LIB electrode. In this work, LTO/Si composites with different weight ratios were prepared and tested as anodes. The anodic and cathodic peaks from both LTO and silicon were apparent in the composites, indicating that each component was active upon Li+ insertion and extraction. The composites with higher Si contents (LTO:Si = 35:35 exhibited superior specific capacity (1004 mAh·g−1 at lower current densities (0.22 A·g−1 but the capacity deteriorated at higher current densities. On the other hand, the electrodes with moderate Si contents (LTO:Si = 50:20 were able to deliver stable capacity (100 mAh·g−1 with good cycling performance, even at a very high current density of 7 A·g−1. The improvement in specific capacity and rate performance was a direct result of the synergy between LTO and Si; the former can alleviate the stresses from volumetric changes in Si upon cycling, while Si can add to the capacity of the composite. Therefore, it has been demonstrated that the addition of Si and concentration optimization is an easy yet an effective way to produce high performance LTO-based electrodes for lithium-ion batteries.

ESTABLISHING SUSTAINABLE US HEV/PHEV MANUFACTURING BASE: STABILIZED LITHIUM METAL POWDER, ENABLING MATERIAL AND REVOLUTIONARY TECHNOLOGY FOR HIGH ENERGY LI-ION BATTERIES

Energy Technology Data Exchange (ETDEWEB)

Yakovleva, Marina

2012-12-31

FMC Lithium Division has successfully completed the project “Establishing Sustainable US PHEV/EV Manufacturing Base: Stabilized Lithium Metal Powder, Enabling Material and Revolutionary Technology for High Energy Li-ion Batteries”. The project included design, acquisition and process development for the production scale units to 1) produce stabilized lithium dispersions in oil medium, 2) to produce dry stabilized lithium metal powders, 3) to evaluate, design and acquire pilot-scale unit for alternative production technology to further decrease the cost, and 4) to demonstrate concepts for integrating SLMP technology into the Li- ion batteries to increase energy density. It is very difficult to satisfy safety, cost and performance requirements for the PHEV and EV applications. As the initial step in SLMP Technology introduction, industry can use commercially available LiMn2O4 or LiFePO4, for example, that are the only proven safer and cheaper lithium providing cathodes available on the market. Unfortunately, these cathodes alone are inferior to the energy density of the conventional LiCoO2 cathode and, even when paired with the advanced anode materials, such as silicon composite material, the resulting cell will still not meet the energy density requirements. We have demonstrated, however, if SLMP Technology is used to compensate for the irreversible capacity in the anode, the efficiency of the cathode utilization will be improved and the cost of the cell, based on the materials, will decrease.

Synthesis and structure of novel lithium-ion conductor Li{sub 7}Ge{sub 3}PS{sub 12}

Energy Technology Data Exchange (ETDEWEB)

Inoue, Yuki [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8502 (Japan); Suzuki, Kota [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8502 (Japan); Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8502 (Japan); Matsui, Naoki [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8502 (Japan); Hirayama, Masaaki [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8502 (Japan); Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8502 (Japan); Kanno, Ryoji, E-mail: kanno@echem.titech.ac.jp [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8502 (Japan); Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8502 (Japan)

2017-02-15

The novel lithium-ion conductor Li{sub 7}Ge{sub 3}PS{sub 12} was synthesized by slow cooling from the ternary Li{sub 2}S–GeS{sub 2}–P{sub 2}S{sub 5} system, and was shown to exhibit a cubic argyrodite-type structure. The phase composition was determined by varying the ratio of starting materials; the observed monophasic properties were close to those for the Li{sub 7}Ge{sub 3}PS{sub 12} composition. The lattice parameter (a =9.80192(3) Å) of Li{sub 7}Ge{sub 3}PS{sub 12} was slightly smaller than that of Li{sub 7}PS{sub 6} (a =9.993 Å), indicating that substitution of a Li cation by the smaller Ge cation contracted the cubic lattice. In addition, the novel structure consisted of a framework composed of four isolated (Ge/P)S{sub 4} tetrahedra. Li{sup +} ions occupied tetrahedral sites within the framework, forming a three-dimensional conduction pathway. Finally, Li{sub 7}Ge{sub 3}PS{sub 12} exhibited a high ionic conductivity of 1.1×10{sup −4} S cm{sup −1} at 25 °C and an activation energy of 25 kJ mol{sup −1}. - Graphical abstract: A novel Li{sub 7}Ge{sub 3}PS{sub 12} solid lithium ion conductor, with cubic argyrodite strucuture, shows high ion conductivity of 1.1×10{sup –4} S cm{sup –1} with an activation energy of 25 kJ mol{sup –1}. The argyrodite structure consists of (Ge/P)S{sub 4} tetrahedra units along with partial occupation of lithium and germanium at 48 h site. - Highlights: • A novel lithium-ion conductor Li{sub 7}Ge{sub 3}PS{sub 12} was detected. • This was achieved through slow cooling of the ternary Li{sub 2}S–GeS{sub 2}–P{sub 2}S{sub 5} system. • This novel conductor revealed a cubic argyrodite-type structure. • Li{sub 7}Ge{sub 3}PS{sub 12} exhibited a high ionic conductivity of 1.1×10{sup −4} S cm{sup −1} at 25 °C. • These properties will aid in the design of superior lithium-ion conductors.

Ultralong Lifespan and Ultrafast Li Storage: Single-Crystal LiFePO4 Nanomeshes.

Science.gov (United States)

Zhang, Yan; Zhang, Hui Juan; Feng, Yang Yang; Fang, Ling; Wang, Yu

2016-01-27

A novel LiFePO4 material, in the shape of a nanomesh, has been rationally designed and synthesized based on the low crystal-mismatch strategy. The LiFePO4 nanomesh possesses several advantages in morphology and crystal structure, including a mesoporous structure, its crystal orientation that is along the [010] direction, and a shortened Li-ion diffusion path. These properties are favorable for their application as cathode in Li-ion batteries, as these will accelerate the Li-ion diffusion rate, improve the Li-ion exchange between the LiFePO4 nanomesh and the electrolyte, and reduce the Li-ion capacitive behavior during Li intercalation. So the LiFePO4 nanomesh exhibits a high specific capacity, enhanced rate capability, and strengthened cyclability. The method developed here can also be extended to other similar systems, for instance, LiMnPO4 , LiCoPO4 , and LiNiPO4 , and may find more applications in the designed synthesis of functional materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab initio study of isomerism of Li2AB2 molecules and Li2AB2+ ions with 16 valent electrons

International Nuclear Information System (INIS)

Charkin, O.P.; Klimenko, N.M.; MakKi, M.L.

2000-01-01

In the framework of MP2(6-31*//HF/6-31G + ZPE(HF/6-31G*) and MP4SDTQ/6-31G*//MP2/6-31G* + ZPE(MP2/6-31G*) approximations ab initio calculations of surfaces of potential energy of molecules of lithium salts of Li 2 AB 2 (Li 2 BeO 2 , L 2 MgO 2 , Li 2 BeS 2 , Li 2 MgS 2 , Li 2 CN 2 , Li 2 SiN 2 , Li 2 CP 2 ) type and ions of Li 2 AB 2 + (Li 2 BO 2 + , Li 2 AlO 2 + , Li 2 BS 2 + , Li 2 AlS 2 + , Li 2 N 3 + , Li 2 PN 2 + , Li 2 P 3 + ) type with 16 valent electrons are done. For oxide and nitride systems global minimum corresponds to symmetric linear structure D ∞h and for their sulfide and phosphorus analogues curved plane or unplane (C 2 ) structure with bond angle φ(LBA)=90-110 Deg are preferable. Equilibrium geometric parameters, relative energies and energies of isomer decomposition, frequencies and IR-intensities of normal vibrations are determined [ru

Electronic Properties of LiFePO4 and Li doped LiFePO4

International Nuclear Information System (INIS)

Zhuang, G.V.; Allen, J.L.; Ross, P.N.; Guo, J.-H.; Jow, T.R.

2005-01-01

The potential use of different iron phosphates as cathode materials in lithium-ion batteries has recently been investigated.1 One of the promising candidates is LiFePO4. This compound has several advantages in comparison to the state-of-the-art cathode material in commercial rechargeable lithium batteries. Firstly, it has a high theoretical capacity (170 mAh/g). Secondly, it occurs as mineral triphylite in nature and is inexpensive, thermally stable, non-toxic and non-hygroscopic. However, its low electronic conductivity (∼10-9 S/cm) results in low power capability. There has been intense worldwide research activity to find methods to increase the electronic conductivity of LiFePO4, including supervalent ion doping,2 introducing non-carbonaceous network conduction3 and carbon coating, and the optimization of the carbon coating on LiFePO4 particle surfaces.4 Recently, the Li doped LiFePO4 (Li1+xFe1-xPO4) synthesized at ARL has yield electronic conductivity increase up to 106.5 We studied electronic structure of LiFePO4 and Li doped LiFePO4 by synchrotron based soft X-ray emission (XES) and X-ray absorption (XAS) spectroscopies. XAS probes the unoccupied partial density of states, while XES the occupied partial density of states. By combining XAS and XES measurements, we obtained information on band gap and orbital character of both LiFePO4 and Li doped LiFePO4. The occupied and unoccupied oxygen partial density of states (DOS) of LiFePO4 and 5 percent Li doped LiFePO4 are presented in Fig. 1. Our experimental results clearly indicate that LiFePO4 has wideband gap (∼ 4 eV). This value is much larger than what is predicted by DFT calculation. For 5 percent Li doped LiFePO4, a new doping state was created closer to the Fermi level, imparting p-type conductivity, consistent with thermopower measurement. Such observation substantiates the suggestion that high electronic conductivity in Li1.05Fe0.95 PO4 is due to available number of charge carriers in the material

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.

Implications of the formation of small polarons in Li2O2 for Li-air batteries

Science.gov (United States)

Kang, Joongoo; Jung, Yoon Seok; Wei, Su-Huai; Dillon, Anne C.

2012-01-01

Lithium-air batteries (LABs) are an intriguing next-generation technology due to their high theoretical energy density of ˜11 kWh/kg. However, LABs are hindered by both poor rate capability and significant polarization in cell voltage, primarily due to the formation of Li2O2 in the air cathode. Here, by employing hybrid density functional theory, we show that the formation of small polarons in Li2O2 limits electron transport. Consequently, the low electron mobility μ = 10-10-10-9 cm2/V s contributes to both the poor rate capability and the polarization that limit the LAB power and energy densities. The self-trapping of electrons in the small polarons arises from the molecular nature of the conduction band states of Li2O2 and the strong spin polarization of the O 2p state. Our understanding of the polaronic electron transport in Li2O2 suggests that designing alternative carrier conduction paths for the cathode reaction could significantly improve the performance of LABs at high current densities.

The Application of the EIS in Li-ion Batteries Measurement

Science.gov (United States)

Zhai, N. S.; Li, M. W.; Wang, W. L.; Zhang, D. L.; Xu, D. G.

2006-10-01

The measurement and determination of the lithium ion battery's electrochemical impedance spectroscopy (EIS) and the application of EIS to battery classification are researched in this paper. The lithium ion battery gets extensive applications due to its inherent advantages over other batteries. For proper and sustainable performance, it is very necessary to check the uniformity of the lithium ion batteries. In this paper, the equivalent circuit of the lithium ion battery is analyzed; the design of hardware circuit based on DSP and software that calculates the EIS of the lithium ion battery is critically done and evaluated. The parameters of the lithium ion equivalent circuit are determined, the parameter values of li-ion equivalent circuit are achieved by least square method, and the application of Principal Component Analysis (CPA) to the battery classification is analyzed.

The Application of the EIS in Li-ion Batteries Measurement

International Nuclear Information System (INIS)

Zhai, N S; Li, M W; Wang, W L; Zhang, D L; Xu, D G

2006-01-01

The measurement and determination of the lithium ion battery's electrochemical impedance spectroscopy (EIS) and the application of EIS to battery classification are researched in this paper. The lithium ion battery gets extensive applications due to its inherent advantages over other batteries. For proper and sustainable performance, it is very necessary to check the uniformity of the lithium ion batteries. In this paper, the equivalent circuit of the lithium ion battery is analyzed; the design of hardware circuit based on DSP and software that calculates the EIS of the lithium ion battery is critically done and evaluated. The parameters of the lithium ion equivalent circuit are determined, the parameter values of li-ion equivalent circuit are achieved by least square method, and the application of Principal Component Analysis (CPA) to the battery classification is analyzed

Fragmentation of copper current collectors in Li-ion batteries during spherical indentation

International Nuclear Information System (INIS)

Wang, Hsin; Watkins, Thomas R.; Simunovic, Srdjan; Bingham, Philip R.; Allu, Srikanth; Turner, John A.

2017-01-01

Large, areal, brittle fracture of copper current collector foils was observed by 3D x-ray computed tomography (XCT) of a spherically indented Li-ion cell. This fracture was hidden and non-catastrophic to a degree because the graphite layers deformed plastically, and held the materials together so that the cracks in the foils could not be seen under optical and electron microscopy. 3D XCT on the indented cell showed “mud cracks” within the copper layer. The cracking of copper foils could not be immediately confirmed when the cell was opened for post-mortem examination. However, an X-ray radiograph on a single foil of the Cu anode showed clearly that the copper foil had broken into multiple pieces similar to the brittle cracking of a ceramic under indentation. This new failure mode of anodes on Li-ion cell has very important implications on the behavior of Li-ion cells under mechanical abuse conditions. Furthermore, the fragmentation of current collectors in the anode must be taken into consideration for the electrochemical responses which may lead to capacity loss and affect thermal runaway behavior of the cells.

Li-Ion Electrolytes with Improved Safety and Tolerance to High-Voltage Systems

Science.gov (United States)

Smart, Marshall C.; Bugga, Ratnakumar V.; Prakash, Surya; Krause, Frederick C.

2013-01-01

Given that lithium-ion (Li-ion) technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. Therefore, extensive effort has been devoted to developing nonflammable electrolytes to reduce the flammability of the cells/battery. A number of promising electrolytes have been developed incorporating flame-retardant additives, and have been shown to have good performance in a number of systems. However, these electrolyte formulations did not perform well when utilizing carbonaceous anodes with the high-voltage materials. Thus, further development was required to improve the compatibility. A number of Li-ion battery electrolyte formulations containing a flame-retardant additive [i.e., triphenyl phosphate (TPP)] were developed and demonstrated in high-voltage systems. These electrolytes include: (1) formulations that incorporate varying concentrations of the flame-retardant additive (from 5 to 15%), (2) the use of mono-fluoroethylene carbonate (FEC) as a co-solvent, and (3) the use of LiBOB as an electrolyte additive intended to improve the compatibility with high-voltage systems. Thus, improved safety has been provided without loss of performance in the high-voltage, high-energy system.

Measurement of air cooling characteristics for the several surface types of Li-ion battery

International Nuclear Information System (INIS)

Byelyayev, Andrey A.; Fedorchenko, Dmitrij V.; Khazhmuradov, Manap A.; Lukhanin, Olekdandr A.; Lukhanin, Oleksiy A.; Martynov, Sergey O.; Rudychev, Yegor V.; Sporov, Eugen O.; Rohatgi, Upendra S.

2013-01-01

The system of air cooling for Li-Ion batteries is considered. Experimental setup included thermal chamber and Li-Ion battery cell simulators with temperature sensors. We investigated static and dynamic cooling regimes for several types of cooling surfaces, for different gaps between the simulators and flow rates. Experimental results are compared to the data of computer modelling using SolidWorks Flow Simulation software. The cooling efficiencies of the various surfaces for static and transient heat emission modes are compared.

Li+ ions diffusion into sol-gel V2O5 thin films: electrochromic properties

Science.gov (United States)

Benmoussa, M.; Outzourhit, A.; Bennouna, A.; Ihlal, A.

2009-10-01

V{2}O{5} thin films were prepared by the sol-gel spin coating process. The Li+ ions insertion effect on optical and electrochromic properties of those films was studied. The diffusion coefficient was calculated using both cyclic voltammograms and chronoamperometric curves. The amount x of Li+ ions in LixV{2}O{5} was also calculated. Finally, the electrochromic performance evolution characteristics such as the reversibility, coloration efficiency, coloration memory stability and response time were studied.

A Novel Methodology for Estimating State-Of-Charge of Li-Ion Batteries Using Advanced Parameters Estimation

Directory of Open Access Journals (Sweden)

Ibrahim M. Safwat

2017-11-01

Full Text Available State-of-charge (SOC estimations of Li-ion batteries have been the focus of many research studies in previous years. Many articles discussed the dynamic model’s parameters estimation of the Li-ion battery, where the fixed forgetting factor recursive least square estimation methodology is employed. However, the change rate of each parameter to reach the true value is not taken into consideration, which may tend to poor estimation. This article discusses this issue, and proposes two solutions to solve it. The first solution is the usage of a variable forgetting factor instead of a fixed one, while the second solution is defining a vector of forgetting factors, which means one factor for each parameter. After parameters estimation, a new idea is proposed to estimate state-of-charge (SOC of the Li-ion battery based on Newton’s method. Also, the error percentage and computational cost are discussed and compared with that of nonlinear Kalman filters. This methodology is applied on a 36 V 30 A Li-ion pack to validate this idea.

In-situ measurement of the lithium distribution in Li-ion batteries using micro-IBA techniques

International Nuclear Information System (INIS)

Yamazaki, A.; Orikasa, Y.; Chen, K.; Uchimoto, Y.; Kamiya, T.; Koka, M.; Satoh, T.; Mima, K.; Kato, Y.; Fujita, K.

2016-01-01

Direct observation of lithium concentration distribution in lithium-ion battery composite electrodes has been performed for the first time. Lithium-ion battery model cells for particle induced X-ray emission (PIXE) and particle induced gamma ray emission (PIGE) measurements were designed and fabricated. Two dimensional images of lithium concentration in LiFePO_4 composite electrodes were obtained with PIXE and PIGE by scanning the proton microbeam for various charged states of the electrodes. Lithium concentration in LiFePO_4 composite electrodes was decreased from the contact interface between LiFePO_4 electrode and liquid electrolyte during the charge reaction.

Synthesis and characterisation of copper doped Ca–Li hydroxyapatite

International Nuclear Information System (INIS)

Pogosova, M.A.; Kazin, P.E.; Tretyakov, Y.D.

2012-01-01

Hydroxyapapites M 10 (PO 4 ) 6 (OH) 2 (MHAP), where M is an alkaline earth metal, colored by incorporation of copper ions substituting protons, were discovered recently . Now this kind of apatite-type materials can be used as inorganic pigments. Until now blue (BaHAP), violet (SrHAP) and wine-red (CaHAP) colors were achieved by the copper ions introduction . The task of the present work was to study possibility of further M-ion substitution to affect the color and shift it toward the red–orange tint. Polycrystalline hydroxyapatites Ca 10−x Li x+y Cu z (PO 4 ) 6 O 2 H 2−y−z−σ (Ca–LiHAP) were synthesized by solid state reaction at 1150 °C (ceramic method) and studied by X-ray powder diffraction (XRD), infrared absorption and diffuse-reflectance spectroscopy. Refinement of the X-ray diffraction patterns by the Rietveld method shows that CaHAP unit cell parameters are a little bigger, than Ca–LiHAP ones. Small difference between unit cell parameters could be caused by two ways of the Li + ions introduction: (1) at the Ca 2+ sites (Ca–Li substitution); (2) into hexagonal channels (H–Li substitution). The Li ions doping changes the color of the copper doped CaHAP from wine-red to pink and red.

TL response of Eu activated LiF nanocubes irradiated by 85 MeV carbon ions

Energy Technology Data Exchange (ETDEWEB)

Salah, Numan, E-mail: nsalah@kau.edu.sa [Center of Nanotechnology, King Abdulaziz University, Jeddah 21589 (Saudi Arabia); Alharbi, Najlaa D. [Sciences Faculty for Girls, King Abdulaziz University, Jeddah 21589 (Saudi Arabia); Habib, Sami S. [Center of Nanotechnology, King Abdulaziz University, Jeddah 21589 (Saudi Arabia); Lochab, S.P. [Inter-University Accelerator Centre, Aruna Asaf Ali Marg, New Delhi 110067 (India)

2015-09-01

Carbon ions were found to be effective for cancer treatment. These heavy ions have a high relative biological effectiveness compared to those of photons. They have higher linear energy transfer and sharper Bragg peak with a very excellent local tumor control. However, the dose of these swift heavy ions needs to be measured with great accuracy. Lithium fluoride (LiF) is a highly sensitive phosphor widely used for radiation dosimetry. In this work Eu activated LiF nanocubes were exposed to 85 MeV C{sup 6+} ion beam and evaluated for their thermoluminescence (TL) response. Pellet forms of this nanomaterial were exposed to these ions in the fluence range 10{sup 9}–10{sup 13} ions/cm{sup 2}. The obtained result shows a prominent TL glow peak at around 320 °C, which is different than that induced by gamma rays. This glow peak exhibits a linear response in the range 10{sup 9}–10{sup 12} ions/cm{sup 2}, corresponding to the equivalent absorbed doses 0.273–273 kGy. The absorbed doses, penetration depths and main energy loss were calculated using TRIM code based on the Monte Carlo simulation. The supralinearity function and stopping power in this nanomaterial were also studied. The modification induced in the glow curve structure as a result of changing irradiation type might be utilized to use LiF:Eu nanocubes as a dosimeter for mixed filed radiations. Moreover, the wide linear response of LiF:Eu nanocubes along with the low fading are another imperative results suggesting that this nanomaterial might be a good candidate for carbon ions dosimetry.

TL response of Eu activated LiF nanocubes irradiated by 85 MeV carbon ions

International Nuclear Information System (INIS)

Salah, Numan; Alharbi, Najlaa D.; Habib, Sami S.; Lochab, S.P.

2015-01-01

Carbon ions were found to be effective for cancer treatment. These heavy ions have a high relative biological effectiveness compared to those of photons. They have higher linear energy transfer and sharper Bragg peak with a very excellent local tumor control. However, the dose of these swift heavy ions needs to be measured with great accuracy. Lithium fluoride (LiF) is a highly sensitive phosphor widely used for radiation dosimetry. In this work Eu activated LiF nanocubes were exposed to 85 MeV C 6+ ion beam and evaluated for their thermoluminescence (TL) response. Pellet forms of this nanomaterial were exposed to these ions in the fluence range 10 9 –10 13 ions/cm 2 . The obtained result shows a prominent TL glow peak at around 320 °C, which is different than that induced by gamma rays. This glow peak exhibits a linear response in the range 10 9 –10 12 ions/cm 2 , corresponding to the equivalent absorbed doses 0.273–273 kGy. The absorbed doses, penetration depths and main energy loss were calculated using TRIM code based on the Monte Carlo simulation. The supralinearity function and stopping power in this nanomaterial were also studied. The modification induced in the glow curve structure as a result of changing irradiation type might be utilized to use LiF:Eu nanocubes as a dosimeter for mixed filed radiations. Moreover, the wide linear response of LiF:Eu nanocubes along with the low fading are another imperative results suggesting that this nanomaterial might be a good candidate for carbon ions dosimetry

Nano-Engineered Materials for Rapid Rechargeable Space Rated Advanced Li-Ion Batteries, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — Lithium-ion (Li-ion) batteries are attractive candidates for use as power sources in aerospace applications because they have high specific energy, energy density...

Nano-Engineered Materials for Rapid Rechargeable Space Rated Advanced Li-Ion Batteries, Phase II

Data.gov (United States)

National Aeronautics and Space Administration — Lithium-ion (Li-ion) batteries are attractive candidates for use as power sources in aerospace applications because they have high specific energy, energy density...

PHEV/EV Li-Ion Battery Second-Use Project (Presentation)

Energy Technology Data Exchange (ETDEWEB)

Neubauer, J.; Pesaran, A.

2010-04-01

Accelerated development and market penetration of plug-in hybrid electric vehicles (PHEVs) and electric vehicles (Evs) are restricted at present by the high cost of lithium-ion (Li-ion) batteries. One way to address this problem is to recover a fraction of the battery cost via reuse in other applications after the battery is retired from service in the vehicle, if the battery can still meet the performance requirements of other energy storage applications. In several current and emerging applications, the secondary use of PHEV and EV batteries may be beneficial; these applications range from utility peak load reduction to home energy storage appliances. However, neither the full scope of possible opportunities nor the feasibility or profitability of secondary use battery opportunities have been quantified. Therefore, with support from the Energy Storage activity of the U.S. Department of Energy's Vehicle Technologies Program, the National Renewable Energy Laboratory (NREL) is addressing this issue. NREL will bring to bear its expertise and capabilities in energy storage for transportation and in distributed grids, advanced vehicles, utilities, solar energy, wind energy, and grid interfaces as well as its understanding of stakeholder dynamics. This presentation introduces NREL's PHEV/EV Li-ion Battery Secondary-Use project.

Atomic Layer Deposition of SnO2 on MXene for Li-Ion Battery Anodes

KAUST Repository

Ahmed, Bilal

2017-02-24

In this report, we show that oxide battery anodes can be grown on two-dimensional titanium carbide sheets (MXenes) by atomic layer deposition. Using this approach, we have fabricated a composite SnO2/MXene anode for Li-ion battery applications. The SnO2/MXene anode exploits the high Li-ion capacity offered by SnO2, while maintaining the structural and mechanical integrity by the conductive MXene platform. The atomic layer deposition (ALD) conditions used to deposit SnO2 on MXene terminated with oxygen, fluorine, and hydroxyl-groups were found to be critical for preventing MXene degradation during ALD. We demonstrate that SnO2/MXene electrodes exhibit excellent electrochemical performance as Li-ion battery anodes, where conductive MXene sheets act to buffer the volume changes associated with lithiation and delithiation of SnO2. The cyclic performance of the anodes is further improved by depositing a very thin passivation layer of HfO2, in the same ALD reactor, on the SnO2/MXene anode. This is shown by high-resolution transmission electron microscopy to also improve the structural integrity of SnO2 anode during cycling. The HfO2 coated SnO2/MXene electrodes demonstrate a stable specific capacity of 843 mAh/g when used as Li-ion battery anodes.

Enhanced electrochemical performance of LiMnPO4 by Li+-conductive Li3VO4 surface coatings

International Nuclear Information System (INIS)

Dong, Youzhong; Zhao, Yanming; Duan, He; Liang, Zhiyong

2014-01-01

By a simple wet ball-milling method, Li 3 VO 4 -coated LiMnPO 4 samples were prepared successfully for the first time. The thin Li 3 VO 4 coating layer with a three-dimensional Li + -ion transport path and high mobility of Li + -ion strongly adhered to the LiMnPO 4 material reduces Mn dissolution and increases the Li + flux through the surface of the LiMnPO 4 itself by preventing formation of phases on the surface that would normally block Li + as well as Li + -ion permeation into the surface of the LiMnPO 4 electrode and therefore improve the rate capability as well as the cycling stability of LiMnPO 4 materials. The electrochemical testing shows that the 5% Li 3 VO 4 -coated LiMnPO 4 sample shows a clear voltage plateau in the charge curves and a much higher reversible capacity at different discharge rates compared with the pristine LiMnPO 4 . EIS results also show that the surface charge transfer resistance and Warburg impedance of the Li 3 VO 4 -coated LiMnPO 4 samples significantly decreased. The surface charge transfer resistance and Warburg impedance for the pristine LiMnPO 4 are 955.1 Ω and 400.3 Ω, respectively. While, for the 5% Li 3 VO 4 -coated LiMnPO 4 , the value are only 400.2 Ω and 283.6 Ω, respectively. The surface charge transfer resistance decreases more than half. All of the improved performance will be favorable for application of the LiMnPO 4 in high-power lithium ion batteries

LiFePO4/C nanocomposites for lithium-ion batteries

Science.gov (United States)

Eftekhari, Ali

2017-03-01

LiFePO4, as the most famous member of the family of olivine-type lithium transition metal phosphates, is one of the promising candidates for the cathodes of lithium-ion batteries. However, its battery performance is limited by its low electrical conductivity and slow Li solid-state diffusion. Various methods have been attempted to improve the battery performance of lithium iron phosphate. Among them, compositing the LiFePO4 with carbon nanomaterials seems to be the most promising, as it is facile and efficient. Carbon nanomaterials usually serve as a conductive agent to improve the electrical conductivity while increasing the material porosity in which the solid-state diffusion distances are significantly shortened. Owing to the popularity of various carbonaceous nanomaterials, there is no straightforward line of research for comparing the LiFePO4/C nanocomposites. This review aims to provide a general perspective based on the research achievements reported in the literature. While surveying the research findings reported in the literature, controversial issues are also discussed. The possible contribution of pseudocapacitance as a result of functionalized carbon or LiFePO4 lattice defects is described, since from a practical perspective, a LiFePO4/C electrode can be considered as a supercapacitor at high C rates (with a specific capacitance as large as 200 F g-1). The Li diffusion in LiFePO4 has not been well understood yet; while the Li diffusion within the LiFePO4 lattice seems to be quite fast, the peculiar interfacial electrochemistry of LiFePO4 slows down the diffusion within the entire electrode by a few orders of magnitude.

Controlling Factors of Cell Design on Large-Format Li-Ion Battery Safety during Nail Penetration

Energy Technology Data Exchange (ETDEWEB)

Wang, Qing; Shaffer, Christian Edward, E-mail: ceshaffer@ecpowergroup.com; Sinha, Puneet K. [EC Power, State College, PA (United States)

2015-08-21

In this paper, we investigate the controlling design parameters of large-format Li-ion batteries on safety while undergoing nail penetration. We have identified three critical design parameters that control the safety during the nail penetration process: nail diameter (D{sub nail}), single sheet foil area (A{sub foil}), and cell capacity (Q{sub cell}).Using commercial AutoLion™ software, we have investigated two typical design problems related to the selection of cell thickness and aspect ratio, namely, (1) the safety ramifications of increasing cell capacity via greater cell thickness for a fixed footprint and (2) the effect of aspect ratio, or single sheet foil size, on safety at a given capacity. For a fixed footprint, our results indicate that the safety of the cell can be predicted by (Q{sub cell} D{sub nail}{sup -0.5}). For a given cell capacity, our results indicate that typically a larger single sheet foil area leads to a greater likelihood for thermal runaway due to its effect of making the heating more local in nature; however, for small cells (~5 Ah) and large nails (~20 mm), the greater aspect ratio can lead to a safer cell, as the greater surface area strongly cools the global heating of the cell.

The Application of the EIS in Li-ion Batteries Measurement

Energy Technology Data Exchange (ETDEWEB)

Zhai, N S [Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen (China); Li, M W [Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen (China); Wang, W L [Shenzhen BPL instrument Ltd., Shenzhen (China); Zhang, D L [Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen (China); Xu, D G [Electrical Engineering and Automation School, Harbin Institute of Technology, Harbin (China)

2006-10-15

The measurement and determination of the lithium ion battery's electrochemical impedance spectroscopy (EIS) and the application of EIS to battery classification are researched in this paper. The lithium ion battery gets extensive applications due to its inherent advantages over other batteries. For proper and sustainable performance, it is very necessary to check the uniformity of the lithium ion batteries. In this paper, the equivalent circuit of the lithium ion battery is analyzed; the design of hardware circuit based on DSP and software that calculates the EIS of the lithium ion battery is critically done and evaluated. The parameters of the lithium ion equivalent circuit are determined, the parameter values of li-ion equivalent circuit are achieved by least square method, and the application of Principal Component Analysis (CPA) to the battery classification is analyzed.

Rate theory of solvent exchange and kinetics of Li+ − BF4−/PF6− ion pairs in acetonitrile

International Nuclear Information System (INIS)

Dang, Liem X.; Chang, Tsun-Mei

2016-01-01

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li + and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li + in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li + -[BF 4 ] and Li + -[PF 6 ] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li + . We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li + -[BF 4 ] and Li + -[PF 6 ] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

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.

Pseudocapacitive Behaviors of Li2FeTiO4/C Hybrid Porous Nanotubes for Novel Lithium-Ion Battery Anodes with Superior Performances.

Science.gov (United States)

Tang, Yakun; Liu, Lang; Zhao, Hongyang; Zhang, Yue; Kong, Ling Bing; Gao, Shasha; Li, Xiaohui; Wang, Lei; Jia, Dianzeng

2018-06-20

Hybrid nanotubes of cation disordered rock salt structured Li 2 FeTiO 4 nanoparticles embedded in porous CNTs were developed. Such unique hybrids with continuous 3D electron transportation paths and isolated small particles have been shown to be an ideal architecture that brought out enhanced electrochemical performances. Meanwhile, they exhibited improved extrinsic capacitive characteristics. In addition, we demonstrate a successful example to use cathode active material as anode for lithium-ion batteries (LIBs). More importantly, our hybrids had much superior electrochemical performances than most of the reported Li 4 Ti 5 O 12 -based nanocomposites. Therefore, it is concluded that Li 2 FeTiO 4 can be a prospective anode material for LIBs.

In-situ measurement of the lithium distribution in Li-ion batteries using micro-IBA techniques

Energy Technology Data Exchange (ETDEWEB)

Yamazaki, A., E-mail: yamazaki@tac.tsukuba.ac.jp [Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 (Japan); Orikasa, Y.; Chen, K.; Uchimoto, Y. [Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-nihonmatsucho, Sakyo-ku, Kyoto 606-8501 (Japan); Kamiya, T.; Koka, M.; Satoh, T. [Takasaki Advanced Radiation Research Institute, Japan Atomic Energy Agency (JAEA), 1233, Watanuki-machi, Takasaki, Gunma 370-1292 (Japan); Mima, K.; Kato, Y.; Fujita, K. [The Graduate School for the Creation of New Photonics Industries, 1955-1, Kurematsu, NIshi-ku, Hamamatsu, Shizuoka 431-1202 (Japan)

2016-03-15

Direct observation of lithium concentration distribution in lithium-ion battery composite electrodes has been performed for the first time. Lithium-ion battery model cells for particle induced X-ray emission (PIXE) and particle induced gamma ray emission (PIGE) measurements were designed and fabricated. Two dimensional images of lithium concentration in LiFePO{sub 4} composite electrodes were obtained with PIXE and PIGE by scanning the proton microbeam for various charged states of the electrodes. Lithium concentration in LiFePO{sub 4} composite electrodes was decreased from the contact interface between LiFePO{sub 4} electrode and liquid electrolyte during the charge reaction.

In-situ generation of Li2FeSiO4/C nanocomposite as cathode material for lithium ion battery

International Nuclear Information System (INIS)

Yi, Jin; Hou, Meng-yan; Bao, Hong-liang; Wang, Cong-xiao; Wang, Jian-qiang; Xia, Yong-yao

2014-01-01

Highlights: • A Li 2 FeSiO 4 /C nanocomposite is prepared via thermal vapor deposition technology. • The Li 2 FeSiO 4 /C nanocomposite is free from impurity and coated with carbon layer. • The Li 2 FeSiO 4 /C nanocomposite exhibits good rate capability and cycling stability. • Lithium benzoate serves as both lithium and carbon sources. - Abstract: A Li 2 FeSiO 4 /C nanocomposite is prepared via solvothermal method in combination with carbon coating technology. The as-prepared Li 2 FeSiO 4 /C nanocomposite is a single phase Li 2 FeSiO 4 with nano-tickness coated carbon layer and connected by the mutual cross-linked carbon conductive matrix. As cathode material for lithium ion battery, the composite delivers a discharge capacity of 154 mAh g −1 at 1 C and exhibits good rate capability with a discharge capacity of 106 mAh g −1 at the rate of 10 C, which is ascribed to the small particle size and enhanced electronic conductivity using carbon coating technology. The as-prepared Li 2 FeSiO 4 /C nanocomposite also behaves a good cycling stability with capacity retention of over 100 cycles

Enhanced electrochemical properties of F-doped Li2MnSiO4/C for lithium ion batteries

Science.gov (United States)

Wang, Chao; Xu, Youlong; Sun, Xiaofei; Zhang, Baofeng; Chen, Yanjun; He, Shengnan

2018-02-01

The Li2MnSiO4 as a novel cathode material for lithium ion batteries, performs high specific capacity, high thermal stability, low cost and etc. However, it suffers from relatively low electronic conductivity and lithium ion diffusion rate. Herein, we successfully introduce fluorine to Li2MnSiO4 (Li2MnSiO4-xFx, x = 0.00, 0.01, 0.03 and 0.05) to overcome these obstacles. The results show that F doping not only enlarges the lattice parameters but also decreases the particle size, synergistically improving the lithium ion diffusion of Li2MnSiO4. Moreover, F doping increase electronic conductivity of Li2MnSiO4/C by inhibiting the formation of C-O bonds in the carbon layers. Meanwhile, F doping improves the crystallinity and stabilizes the crystal structure of Li2MnSiO4. Finally, the Li2MnSiO3.97F0.03/C with the best electrochemical performances delivers the initial specific discharge capacity of 279 mA h g-1 at 25mA g-1 current density from 1.5 V to 4.8 V. Also, it maintains a higher capacity (201 mA h g-1) than F-free Li2MnSiO4 (145 mA h g-1) after 50 cycles.

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

Development of Large Li-Ion Batteries for Aircraft and Spacecraft Applications

National Research Council Canada - National Science Library

Bruce, Gregg

1998-01-01

.... Concurrent was a chemical direction which changed the emphasis of the program from the rechargeable Li/SO2 chemistry to that of the family of cell chemistries which are collectively referred to as lithium ion...

Explaining key properties of lithiation in TiO2-anatase Li-ion battery electrodes using phase-field modeling

NARCIS (Netherlands)

de Klerk, N.J.J.; Vasileiadis, A.; Smith, Raymond B.; Bazant, Martin Z.; Wagemaker, M.

2017-01-01

The improvement of Li-ion battery performance requires development of models that capture the essential physics and chemistry in Li-ion battery electrode materials. Phase-field modeling has recently been shown to have this ability, providing new opportunities to gain understanding of these complex

Facile Solution Route to Synthesize Nanostructure Li4Ti5O12 for High Rate Li-Ion Battery

Directory of Open Access Journals (Sweden)

M. V. Tran

2016-01-01

Full Text Available High rate Li-ion batteries have been given great attention during the last decade as a power source for hybrid electric vehicles (HEVs, EVs, etc. due to the highest energy and power density. These lithium batteries required a new design of material structure as well as innovative electrode materials. Among the promising candidates, spinel Li4Ti5O12 has been proposed as a high rate anode to replace graphite anode because of high capacity and a negligible structure change during intercalation of lithium. In this work, we synthesized a spinel Li4Ti5O12 in nanosize by a solution route using LiOH and Ti(OBu4 as precursor. An evaluation of structure and morphology by XRD and SEM exhibited pure spinel phase Li4Ti5O12 and homogenous nanoparticles around 100 nm. In the charge-discharge test, nanospinel Li4Ti5O12 presents excellent discharge capacity 160 mAh/g at rate C/10, as well as good specific capacities of 120, 110, and 100 mAh/g at high rates C, 5C and 10C, respectively.

CuLi2Sn and Cu2LiSn: Characterization by single crystal XRD and structural discussion towards new anode materials for Li-ion batteries.

Science.gov (United States)

Fürtauer, Siegfried; Effenberger, Herta S; Flandorfer, Hans

2014-12-01

The stannides CuLi 2 Sn (CSD-427095) and Cu 2 LiSn (CSD-427096) were synthesized by induction melting of the pure elements and annealing at 400 °C. The phases were reinvestigated by X-ray powder and single-crystal X-ray diffractometry. Within both crystal structures the ordered CuSn and Cu 2 Sn lattices form channels which host Cu and Li atoms at partly mixed occupied positions exhibiting extensive vacancies. For CuLi 2 Sn, the space group F-43m. was verified (structure type CuHg 2 Ti; a =6.295(2) Å; wR 2 ( F ²)=0.0355 for 78 unique reflections). The 4( c ) and 4( d ) positions are occupied by Cu atoms and Cu+Li atoms, respectively. For Cu 2 LiSn, the space group P 6 3 / mmc was confirmed (structure type InPt 2 Gd; a =4.3022(15) Å, c =7.618(3) Å; wR 2 ( F ²)=0.060 for 199 unique reflections). The Cu and Li atoms exhibit extensive disorder; they are distributed over the partly occupied positions 2( a ), 2( b ) and 4( e ). Both phases seem to be interesting in terms of application of Cu-Sn alloys as anode materials for Li-ion batteries.

Effective tuning of the ratio of red to green emission of Ho"3"+ ions in single LiLuF_4 microparticle via codoping Ce"3"+ ions

International Nuclear Information System (INIS)

Gao, Wei; Dong, Jun; Liu, Jihong; Yan, Xuewen

2016-01-01

Yb"3"+/Ho"3"+ codoped LiLuF_4 microparticles have been successfully prepared via a facile hydrothermal method. The crystal phase and morphology of LiLuF_4 microparticles were inspected by x-ray diffraction and scanning electron microscope, respectively. The upconversion emission of single LiLuF_4: Yb"3"+/Ho"3"+ microparticle was carefully studied by a confocal microscopy setup under NIR 980 nm excitation. With the increase of Ce"3"+ ion concentrations of 12%, the ratio of red to green emission of the Ho"3"+ ions of single LiLuF_4 microparticle was boosted about 17-fold, and the output colors were tuned from green to red, which is due to the two efficient cross-relaxation between Ho"3"+ and Ce"3"+ ions enhances the red and suppresses the green in the emission processes. To investigate the optical properties of the single microparticle or nanoparticle through the confocal microscopy setup can effectively avoid the influence of surrounding particle or environment, and could provide more precise information for better exploring the emission mechanisms of rare earth ions. The tunable upconversion emission of Ho"3"+ in single LiLuF_4 microparticle in this work will have great potential applications in the micro optoelectronic devices and color display applications. - Highlights: • The optical properties of the single LiLuF4: Yb3+/Ho3+/Ce3+ microparticle were studied. • The output colors of single LiLuF4 microparticle were tuned from green to red. • The upconversion mechanisms between Ho3+ and Ce3+ ions were discussed based on emission spectrum.

Polypyrrole-coated α-LiFeO2 nanocomposite with enhanced electrochemical properties for lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, Zhi-jia; Wang, Jia-Zhao; Chou, Shu-Lei; Liu, Hua-Kun; Ozawa, Kiyoshi; Li, Hui-jun

2013-01-01

A conducting α-LiFeO 2 -polypyrrole (α-LiFeO 2 -PPy) nanocomposite material was prepared by the chemical polymerization method as a cathode material for lithium-ion batteries. The porous α-LiFeO 2 was prepared via the microwave hydrothermal method and a post-annealing. The X-ray diffraction, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy measurements showed that the α-LiFeO 2 nanoparticles were coated with PPy. The polypyrrole coating improves the reversible capacity and cycling stability (104 mAh g −1 at 0.1C after 100 cycles) for lithium-ion batteries. Even at the high rate of 10C, the electrode showed more than 40% of the capacity at low rate (0.1C)

Studi Electrochemical Impedance Spectroscopy dari Lembaran Polyvinyl Alcohol dengan Penambahan Liclo4 sebagai Bahan Elektolit Baterai Li-ion

OpenAIRE

Gunawan, Indra; Wahyudianingsih, Wahyudianingsih; Sudaryanto, Sudaryanto

2016-01-01

ELECTROCHEMICALIMPEDANCE SPECTROSCOPY STUDY OF POLYVINYL ALCOHOL SHEETWITHADDITION OFLiClO4AS ELECTROLYTE MATERIAL OF Li-ION BATTERAY. Solid polymer electrolyte materials for Li ion battery have been prepared using polyvinyl alcohol (PVA) added by lithium perchlorate (LiClO4) salt with various concentration. Electrochemical Impedance Spectroscopy (EIS) study of the material was done by making a Nyquist plot of the measurement with a LCR meter. These electrolyte materials prepared by using PVA...

Spinel-structured surface layers for facile Li ion transport and improved chemical stability of lithium manganese oxide spinel

Energy Technology Data Exchange (ETDEWEB)

Lee, Hae Ri [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Seo, Hyo Ree; Lee, Boeun; Cho, Byung Won [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Lee, Kwan-Young [Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Oh, Si Hyoung, E-mail: sho74@kist.re.kr [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)

2017-01-15

Graphical abstract: Strategically-designed spinel-structured nano-scale surface layer, LiM{sub x}Mn{sup IV}{sub 1−x}O{sub 4}, featuring a high Li{sup +} ion conductivity and a good chemical stability was applied on Al-doped LiMn{sub 2}O{sub 4} spinel for the drastic improvement of the electrochemical performance at the elevated temperature as a promising cathode material for lithium rechargeable batteries. - Highlights: • Spinel-structured surface layer with a high Li-ion conductivity and a good chemical stability was prepared. • Simple wet process was developed to apply nano-scale surface layer on aluminum doped lithium manganese oxide spinel. • The properties of nano-scale surface layer were characterized by analytical tools including GITT, HR-TEM and XAS. • Materials with surface coating layer exhibit an excellent electrochemical performance at the elevated temperature. - Abstract: Li-ion conducting spinel-structured oxide layer with a manganese oxidation state close to being tetravalent was prepared on aluminum-doped lithium manganese oxide spinel for improving the electrochemical performances at the elevated temperatures. This nanoscale surface layer provides a good ionic conduction path for lithium ion transport to the core and also serves as an excellent chemical barrier for protecting the high-capacity core material from manganese dissolution into the electrolyte. In this work, a simple wet process was employed to prepare thin LiAlMnO{sub 4} and LiMg{sub 0.5}Mn{sub 1.5}O{sub 4} layers on the surface of LiAl{sub 0.1}Mn{sub 1.9}O{sub 4}. X-ray absorption studies revealed an oxidation state close to tetravalent manganese on the surface layer of coated materials. Materials with these surface coating layers exhibited excellent capacity retentions superior to the bare material, without undermining the lithium ion transport characteristics and the high rate performances.

Li diffusion and the effect of local structure on Li mobility in Li2O-SiO2 glasses.

Science.gov (United States)

Bauer, Ute; Welsch, Anna-Maria; Behrens, Harald; Rahn, Johanna; Schmidt, Harald; Horn, Ingo

2013-12-05

Aimed to improve the understanding of lithium migration mechanisms in ion conductors, this study focuses on Li dynamics in binary Li silicate glasses. Isotope exchange experiments and conductivity measurements were carried out to determine self-diffusion coefficients and activation energies for Li migration in Li2Si3O7 and Li2Si6O13 glasses. Samples of identical composition but different isotope content were combined for diffusion experiments in couples or triples. Diffusion profiles developed between 511 and 664 K were analyzed by femtosecond laser ablation combined with multiple collector inductively coupled plasma mass spectrometry (fs LA-MC-ICP-MS) and secondary ion mass spectrometry (SIMS). Analyses of diffusion profiles and comparison of diffusion data reveal that the isotope effect of lithium diffusion in silicate glasses is rather small, consistent with classical diffusion behavior. Ionic conductivity of glasses was measured between 312 and 675 K. The experimentally obtained self-diffusion coefficient, D(IE), and ionic diffusion coefficient, D(σ), derived from specific DC conductivity provided information about correlation effects during Li diffusion. The D(IE)/D(σ) is higher for the trisilicate (0.27 ± 0.05) than that for the hexasilicate (0.17 ± 0.02), implying that increasing silica content reduces the efficiency of Li jumps in terms of long-range movement. This trend can be rationalized by structural concepts based on nuclear magnetic resonance (NMR) and Raman spectroscopy as well as molecular dynamic simulations, that is, lithium is percolating in low-dimensional, alkali-rich regions separated by a silica-rich matrix.

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

International Nuclear Information System (INIS)

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

2011-01-01

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

LiFePO4 nanoparticles encapsulated in graphene nanoshells for high-performance lithium-ion battery cathodes.

Science.gov (United States)

Fei, Huilong; Peng, Zhiwei; Yang, Yang; Li, Lei; Raji, Abdul-Rahman O; Samuel, Errol L G; Tour, James M

2014-07-11

LiFePO4 encapsulated in graphene nanoshells (LiFePO4@GNS) nanoparticles were synthesized by solid state reaction between graphene-coated Fe nanoparticles and LiH2PO4. The resulting nanocomposite was demonstrated to be a superior lithium-ion battery cathode with improved cycle and rate performances.

A mesoporous WO3−X/graphene composite as a high-performance Li-ion battery anode

International Nuclear Information System (INIS)

Liu, Fei; Kim, Jong Gu; Lee, Chul Wee; Im, Ji Sun

2014-01-01

Graphical abstract: The highly flexible and conductive graphene layer can enhance electron transfer, protect metal oxides against disintegration and aggregation and buffer the strain induced by volume expansion during cycles. The mesoporous surface layer provides an open network for Li+ diffusion. - Highlights: • Novel cocktail effects of 2D mesoporous WO 3−X /graphene for lithium ion battery. • New approach for lithium ion battery by easy and unique synthesis method. • Mechanism study with proper data for understanding a reaction on anode surface. - Abstract: A novel mesoporous WO 3−X /graphene composite was developed. This material allowed rapid electron and Li + ion diffusion when used as a Li-ion battery (LIB) anode material. Remarkably, the graphene support protected WO 3−X from changing volume during the electrochemical cycling process; this process generally induces capacity loss. The current work describes a high-performance anode material for LIB that has highly dense WO 3−X , as well as high capacity, rate capability and stability

Enhanced Lithium Ion Transport by Superionic Pathways Formed on the Surface of Two-dimensional Structured Li0.85Na0.15V3O8 for High-Performance Lithium Ion Batteries

International Nuclear Information System (INIS)

Lu, Xuena; Shang, Yu; Zhang, Sen; Deng, Chao

2015-01-01

Highlights: • Li 0.85 Na 0.15 V 3 O 8 nanosheet with superionic conductive layer was constructed. • Li x V 2 O 5 surface layer provides facile pathways for lithium migration. • Li x V 2 O 5 -Li 0.85 Na 0.15 V 3 O 8 composite displays good high rate capability. - Abstract: Poor ion transport and rate capability are the main challenges for LiV 3 O 8 as cathode material for lithium ion batteries. Here we report a novel strategy for enhancing lithium ion transport by building superionic pathways on the surface of Li 0.85 Na 0.15 V 3 O 8 nanosheet. The two-dimensional Li 0.85 Na 0.15 V 3 O 8 nanoparticle with an ion conductive layer of Li x V 2 O 5 on its surface is constructed by a modified sol–gel strategy with carefully controlled sodium incorporation and elements stoichiometry. Ultrathin Li x V 2 O 5 surface layer not only provides facile pathways for lithium migration, but also increases the structure stability during cycling. The Li x V 2 O 5 -Li 0.85 Na 0.15 V 3 O 8 composite displays good high rate capability of 172.3 mAh g −1 at 5C and excellent cycling stability of 98.9% over fifty cycles. This superior electrochemical property is attributed to the occupation of lithium site by Na + in LiV 3 O 8 host crystals and the surface superionic pathways of Li x V 2 O 5 phase. Therefore, the advantages of both high ion transport and the structure stabilization in present study put forward a new strategy for achieving high-performance LiV 3 O 8 electrode material with tailored nanoarchitecture

Maleic anhydride as an additive to γ-butyrolactone solutions for Li-ion batteries

International Nuclear Information System (INIS)

Ufheil, Joachim; Baertsch, Martin C.; Wuersig, Andreas; Novak, Petr

2005-01-01

The effect of maleic anhydride (MA) as a new film-forming additive in γ-butyrolactone (GBL)-based electrolytes for use in Li-ion batteries has been studied to advance the understanding of the solid electrolyte interphase (SEI) formation on graphite electrodes. Cyclic voltammetry measurements showed that even small amounts of MA (up to 4 wt.%) improved the lithium intercalation into graphite. The effect of MA was also verified by electrochemical impedance spectroscopy. In situ subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS) and differential electrochemical mass spectrometry (DEMS) allowed identification of gas formation and decomposition products during the SEI formation. GBL-based electrolytes with MA showed both, higher cycling efficiency and cycle life of graphite electrodes

Borophane as a Benchmate of Graphene: A Potential 2D Material for Anode of Li and Na-Ion Batteries.

Science.gov (United States)

Jena, Naresh K; Araujo, Rafael B; Shukla, Vivekanand; Ahuja, Rajeev

2017-05-17

Borophene, single atomic-layer sheet of boron ( Science 2015 , 350 , 1513 ), is a rather new entrant into the burgeoning class of 2D materials. Borophene exhibits anisotropic metallic properties whereas its hydrogenated counterpart borophane is reported to be a gapless Dirac material lying on the same bench with the celebrated graphene. Interestingly, this transition of borophane also rendered stability to it considering the fact that borophene was synthesized under ultrahigh vacuum conditions on a metallic (Ag) substrate. On the basis of first-principles density functional theory computations, we have investigated the possibilities of borophane as a potential Li/Na-ion battery anode material. We obtained a binding energy of -2.58 (-1.08 eV) eV for Li (Na)-adatom on borophane and Bader charge analysis revealed that Li(Na) atom exists in Li + (Na + ) state. Further, on binding with Li/Na, borophane exhibited metallic properties as evidenced by the electronic band structure. We found that diffusion pathways for Li/Na on the borophane surface are anisotropic with x direction being the favorable one with a barrier of 0.27 and 0.09 eV, respectively. While assessing the Li-ion anode performance, we estimated that the maximum Li content is Li 0.445 B 2 H 2 , which gives rises to a material with a maximum theoretical specific capacity of 504 mAh/g together with an average voltage of 0.43 V versus Li/Li + . Likewise, for Na-ion the maximum theoretical capacity and average voltage were estimated to be 504 mAh/g and 0.03 V versus Na/Na + , respectively. These findings unambiguously suggest that borophane can be a potential addition to the map of Li and Na-ion anode materials and can rival some of the recently reported 2D materials including graphene.

Nano-glass ceramic cathodes for Li+/Na+ mixed-ion batteries

DEFF Research Database (Denmark)

He, Wen; Zhang, Xudong; Jin, Chao

2017-01-01

reactions, and the influences of molar ratio of Fe/V on the structure and electrochemical properties of NGCs. This nanoscale design offers a new possibility improved the electrochemical performances of Li+/Na+ mixed-ion batteries (LNMIBs). The NGCs-3 electrode exhibits a higher discharge capacity (145 mAh g...

A flexible Li-ion battery with design towards electrodes electrical insulation

Science.gov (United States)

Vieira, E. M. F.; Ribeiro, J. F.; Sousa, R.; Correia, J. H.; Goncalves, L. M.

2016-08-01

The application of micro electromechanical systems (MEMS) technology in several consumer electronics leads to the development of micro/nano power sources with high power and MEMS integration possibility. This work presents the fabrication of a flexible solid-state Li-ion battery (LIB) (~2.1 μm thick) with a design towards electrodes electrical insulation, using conventional, low cost and compatible MEMS fabrication processes. Kapton® substrate provides flexibility to the battery. E-beam deposited 300 nm thick Ge anode was coupled with LiCoO2/LiPON (cathode/solid-state electrolyte) in a battery system. LiCoO2 and LiPON films were deposited by RF-sputtering with a power source of 120 W and 100 W, respectively. LiCoO2 film was annealed at 400 °C after deposition. The new design includes Si3N4 and LiPO thin-films, providing electrode electrical insulation and a battery chemical stability safeguard, respectively. Microstructure and battery performance were investigated by scanning electron microscopy, electric resistivity and electrochemical measurements (open circuit potential, charge/discharge cycles and electrochemical impedance spectroscopy). A rechargeable thin-film and lightweight flexible LIB using MEMS processing compatible materials and techniques is reported.

A phenomenological force model of Li-ion battery packs for enhanced performance and health management

Science.gov (United States)

Oh, Ki-Yong; Epureanu, Bogdan I.

2017-10-01

A 1-D phenomenological force model of a Li-ion battery pack is proposed to enhance the control performance of Li-ion battery cells in pack conditions for efficient performance and health management. The force model accounts for multiple swelling sources under the operational environment of electric vehicles to predict swelling-induced forces in pack conditions, i.e. mechanically constrained. The proposed force model not only incorporates structural nonlinearities due to Li-ion intercalation swelling, but also separates the overall range of states of charge into three ranges to account for phase transitions. Moreover, an approach to study cell-to-cell variations in pack conditions is proposed with serial and parallel combinations of linear and nonlinear stiffness, which account for battery cells and other components in the battery pack. The model is shown not only to accurately estimate the reaction force caused by swelling as a function of the state of charge, battery temperature and environmental temperature, but also to account for cell-to-cell variations due to temperature variations, SOC differences, and local degradation in a wide range of operational conditions of electric vehicles. Considering that the force model of Li-ion battery packs can account for many possible situations in actual operation, the proposed approach and model offer potential utility for the enhancement of current battery management systems and power management strategies.

Hollow-Cuboid Li3VO4/C as High-Performance Anodes for Lithium-Ion Batteries.

Science.gov (United States)

Zhang, Changkun; Liu, Chaofeng; Nan, Xihui; Song, Huanqiao; Liu, Yaguang; Zhang, Cuiping; Cao, Guozhong

2016-01-13

Li3VO4 has been demonstrated to be a promising anode material for lithium-ion batteries with a low, safe voltage and large capacity. However, its poor electronic conductivity hinders its practical application particularly at a high rate. This work reports that Li3VO4 coated with carbon was synthesized by a one-pot, two-step method with F127 ((PEO)100-(PPO)65-(PEO)100) as both template and carbon source, yielding a microcuboid structure. The resulting Li3VO4/C cuboid shows a stable capacity of 415 mAh g(-1) at 0.5 C and excellent capacity stability at high rates (e.g., 92% capacity retention after 1000 cycles at 10 C = 4 A g(-1)). The lithiation/delithiation process of Li3VO4/C was studied by ex situ X-ray diffraction and Raman spectroscopy, which confirmed that Li3VO4/C underwent a reversible intercalation reaction during discharge/charge processes. The excellent electrochemical performance is attributed largely to the unique microhollow structure. The voids inside hollow structure can not only provide more space to accommodate volume change during discharge/charge processes but also allow the lithium ions insertion and extraction from both outside and inside the hollow structure with a much larger surface area or more reaction sites and shorten the lithium ions diffusion distance, which leads to smaller overpotential and faster reaction kinetics. Carbon derived from F127 through pyrolysis coats Li3VO4 conformably and thus offers good electrical conduction. The results in this work provide convincing evidence that the significant potential of hollow-cuboid Li3VO4/C for high-power batteries.

High Voltage Surface Degradation on Carbon Blacks in Lithium Ion Batteries

DEFF Research Database (Denmark)

Younesi, Reza

In order to increase the power density of Li-ion batteries, much research is focused on developing cathode materials that can operate at high voltages above 4.5 V with a high capacity, high cycling stability, and rate capability. However, at high voltages all the components of positive electrodes...... including carbon black (CB) additives have a potential risk of degradation. Though the weight percentage of CB in commercial batteries is generally very small, the volumetric amount and thus the surface area of CB compose a rather large part of a cathode due to its small particle size (≈ 50 nm) and high...

Thermal modelling of Li-ion polymer battery for electric vehicle drive cycles

Science.gov (United States)

Chacko, Salvio; Chung, Yongmann M.

2012-09-01

Time-dependent, thermal behaviour of a lithium-ion (Li-ion) polymer cell has been modelled for electric vehicle (EV) drive cycles with a view to developing an effective battery thermal management system. The fully coupled, three-dimensional transient electro-thermal model has been implemented based on a finite volume method. To support the numerical study, a high energy density Li-ion polymer pouch cell was tested in a climatic chamber for electric load cycles consisting of various charge and discharge rates, and a good agreement was found between the model predictions and the experimental data. The cell-level thermal behaviour under stressful conditions such as high power draw and high ambient temperature was predicted with the model. A significant temperature increase was observed in the stressful condition, corresponding to a repeated acceleration and deceleration, indicating that an effective battery thermal management system would be required to maintain the optimal cell performance and also to achieve a full battery lifesapn.

A chemically activated graphene-encapsulated LiFePO4 composite for high-performance lithium ion batteries.

Science.gov (United States)

Ha, Jeonghyun; Park, Seung-Keun; Yu, Seung-Ho; Jin, Aihua; Jang, Byungchul; Bong, Sungyool; Kim, In; Sung, Yung-Eun; Piao, Yuanzhe

2013-09-21

A composite of modified graphene and LiFePO4 has been developed to improve the speed of charging-discharging and the cycling stability of lithium ion batteries using LiFePO4 as a cathode material. Chemically activated graphene (CA-graphene) has been successfully synthesized via activation by KOH. The as-prepared CA-graphene was mixed with LiFePO4 to prepare the composite. Microscopic observation and nitrogen sorption analysis have revealed the surface morphologies of CA-graphene and the CA-graphene/LiFePO4 composite. Electrochemical properties have also been investigated after assembling coin cells with the CA-graphene/LiFePO4 composite as a cathode active material. Interestingly, the CA-graphene/LiFePO4 composite has exhibited better electrochemical properties than the conventional graphene/LiFePO4 composite as well as bare LiFePO4, including exceptional speed of charging-discharging and excellent cycle stability. That is because the CA-graphene in the composite provides abundant porous channels for the diffusion of lithium ions. Moreover, it acts as a conducting network for easy charge transfer and as a divider, preventing the aggregation of LiFePO4 particles. Owing to these properties of CA-graphene, LiFePO4 could demonstrate enhanced and stably long-lasting electrochemical performance.

On fabrication procedures of Li-ion conducting garnets

Energy Technology Data Exchange (ETDEWEB)

Hanc, Emil [The Mineral and Energy Economy Research Institute, Polish Academy of Sciences, ul. Wybickiego 7, 31-261 Kraków (Poland); Zając, Wojciech, E-mail: wojciech.zajac@agh.edu.pl [AGH University of Science and Technology, Faculty of Energy and Fuels, al. Mickiewicza 30, 30-059 Kraków (Poland); Lu, Li; Yan, Binggong; Kotobuki, Masashi [Materials Science Group, Department of Mechanical Engineering, National University of Singapore (Singapore); Ziąbka, Magdalena [AGH University of Science and Technology, Faculty of Materials Science and Ceramics, al. Mickiewicza 30, 30-059 Kraków (Poland); Molenda, Janina [AGH University of Science and Technology, Faculty of Energy and Fuels, al. Mickiewicza 30, 30-059 Kraków (Poland)

2017-04-15

Ceramic oxides exhibiting high lithium-ion mobility at room temperature receive broad attention as candidate electrolytes for lithium batteries. Lithium-stuffed garnets from the Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} group seem to be especially promising because of their high ionic conductivity at room temperature and their electrochemical stability. In this work, we discuss factors that affect formation of the garnet in its bulk form or in the form of thick and thin films. We demonstrate that zinc oxide can be applied as a sintering aid that facilitate the formation of the highly conducting cubic Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} garnet phase in a single-step sintering procedure. Based on our experience with the single-step sintering experiments, we successfully fabricated a thick-film membrane consisting of a garnet solid electrolyte using the tape casting technique. In order to reduce the thickness of the electrolyte even further we investigated the fabrication of a thin-film Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} electrolyte by means of the pulsed laser deposition technique.

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

Twin boundary-assisted lithium-ion transport

KAUST Repository

Nie, Anmin

2015-01-14

With the increased need for high-rate Li-ion batteries, it has become apparent that new electrode materials with enhanced Li-ion transport should be designed. Interfaces, such as twin boundaries (TBs), offer new opportunities to navigate the ionic transport within nanoscale materials. Here, we demonstrate the effects of TBs on the Li-ion transport properties in single crystalline SnO2 nanowires. It is shown that the TB-assisted lithiation pathways are remarkably different from the previously reported lithiation behavior in SnO2 nanowires without TBs. Our in situ transmission electron microscopy study combined with direct atomic-scale imaging of the initial lithiation stage of the TB-SnO2 nanowires prove that the lithium ions prefer to intercalate in the vicinity of the (101¯) TB, which acts as conduit for lithium-ion diffusion inside the nanowires. The density functional theory modeling shows that it is energetically preferred for lithium ions to accumulate near the TB compared to perfect neighboring lattice area. These findings may lead to the design of new electrode materials that incorporate TBs as efficient lithium pathways, and eventually, the development of next generation rechargeable batteries that surpass the rate performance of the current commercial Li-ion batteries.

Oxygen Vacancies and Stacking Faults Introduced by Low-Temperature Reduction Improve the Electrochemical Properties of Li2MnO3 Nanobelts as Lithium-Ion Battery Cathodes.

Science.gov (United States)

Sun, Ya; Cong, Hengjiang; Zan, Ling; Zhang, Youxiang

2017-11-08

Among the Li-rich layered oxides Li 2 MnO 3 has significant theoretical capacity as a cathode material for Li-ion batteries. Pristine Li 2 MnO 3 generally has to be electrochemically activated in the first charge-discharge cycle which causes very low Coulombic efficiency and thus deteriorates its electrochemical properties. In this work, we show that low-temperature reduction can produce a large amount of structural defects such as oxygen vacancies, stacking faults, and orthorhombic LiMnO 2 in Li 2 MnO 3 . The Rietveld refinement analysis shows that, after a reduction reaction with stearic acid at 340 °C for 8 h, pristine Li 2 MnO 3 changes into a Li 2 MnO 3 -LiMnO 2 (0.71/0.29) composite, and the monoclinic Li 2 MnO 3 changes from Li 2.04 Mn 0.96 O 3 in the pristine Li 2 MnO 3 (P-Li 2 MnO 3 ) to Li 2.1 Mn 0.9 O 2.79 in the reduced Li 2 MnO 3 (R-Li 2 MnO 3 ), indicating the production of a large amount of oxygen vacancies in the R-Li 2 MnO 3 . High-resolution transmission electron microscope images show that a high density of stacking faults is also introduced by the low-temperature reduction. When measured as a cathode material for Li-ion batteries, R-Li 2 MnO 3 shows much better electrochemical properties than P-Li 2 MnO 3 . For example, when charged-discharged galvanostatically at 20 mA·g -1 in a voltage window of 2.0-4.8 V, R-Li 2 MnO 3 has Coulombic efficiency of 77.1% in the first charge-discharge cycle, with discharge capacities of 213.8 and 200.5 mA·h·g -1 in the 20th and 30th cycles, respectively. In contrast, under the same charge-discharge conditions, P-Li 2 MnO 3 has Coulombic efficiency of 33.6% in the first charge-discharge cycle, with small discharge capacities of 80.5 and 69.8 mA·h·g -1 in the 20th and 30th cycles, respectively. These materials characterizations, and electrochemical measurements show that low-temperature reduction is one of the effective ways to enhance the performances of Li 2 MnO 3 as a cathode material for Li-ion batteries.

Analysis of multi-wall carbon nanotube based porous Li battery electrodes’ using TOF-SIMS ion imaging

International Nuclear Information System (INIS)

Karar, N.; Singh, B.P.; Elizabeth, Indu

2015-01-01

Highlights: • Usage of MWCNT material for Li battery electrode. • LiPF 6 as electrolyte material. • Charging and discharging cycles of the battery and their effect on the electrode and electrolyte material. • TOF-SIMS ion imaging based analysis of the effects of the charging discharging cycles on the materials. • Effects of multi-atomic molecules. - Abstract: Li ion batteries and its accessories are now under increased focus of research due to enhanced energy storage and recycling requirements and the need for clean environments. In this context, observations on Li battery electrodes prepared using multi-wall carbon nanotubes (MWCNT) coated on stainless steel as observed by time of flight secondary ion mass spectrometry (TOF-SIMS) analysis and their relevance in understanding and improving the electrochemical properties of such battery systems are discussed. Porosity issues due to MWCNT, and accumulation of chemical residues with operational cycles were observed, their possible causes were also analyzed and discussed. Issues on change in electrode performance due to usage of tin oxide coatings on the MWCNT were also compared and analyzed

Influence of a Counterion on the Ion Atmosphere of an Anion: A Molecular Dynamics Study of LiX and CsX (X = F(-), Cl(-), I(-)) in Methanol.

Science.gov (United States)

Kumar, Parveen; Kulkarni, Anant D; Yashonath, S

2015-08-27

We report molecular dynamics (MD) simulations to explore the influence of a counterion on the structure and dynamics of cationic and anionic solvation shells for various ions in methanol at 298 K. We show that the variation in ionic size of either the cation or the anion in an ion pair influences the solvation structure of the other ion as well as the diffusivity in an electrolyte solution of methanol. The extent of ionic association between the cation and its counteranion of different ionic sizes has been investigated by analyzing the radial distribution functions (RDFs) and the orientation of methanol molecules in the first solvation shell (FSS) of ions. It is shown that the methanol in the FSS of the anion as well the cation exhibit quite different radial and orientational structures as compared to methanol which lie in the FSS of either the anion or the cation but not both. We find that the coordination number (CN) of F(-), Cl(-), and I(-) ions decreases with increasing size of the anion which is contrary to the trend reported for the anions in H2O. The mean residence time (MRT) of methanol molecules in the FSS of ions has been calculated using the stable states picture (SSP) approach. It is seen that the ion-counterion interaction has a considerable influence on the MRT of methanol molecules in the FSS of ions. We also discuss the stability order of the ion-counterion using the potentials of mean force (PMFs) for ion pairs with ions of different sizes. The PMF plots reveal that the Li(+)-F(-) pair (small-small) is highly stable and the Li(+)-I(-) pair is least stable (small-large) in electrolyte solutions.

Ion-exchange synthesis and improved Li insertion property of lithiated H2Ti12O25 as a negative electrode material for lithium-ion batteries

Directory of Open Access Journals (Sweden)

Kunimitsu Kataoka

2016-03-01

Full Text Available We successfully prepared the lithiated H2Ti12O25 sample by the H+/Li+ ion exchange synthetic technique in the molten LiNO3 at 270 °C using H2Ti12O25 as a starting compound. Chemical composition of the obtained lithiated H2Ti12O25 sample was determined to be H1.05Li0.35Ti12O25-δ having δ = 0.3 by ICP-AES and DTA-TG analyses. The H+/Li+ ion exchange was also confirmed by powder XRD, 1H-MAS NMR, and 7Li-MAS NMR measurements. Electrochemical Li insertion and extraction measurements revealed that the initial coulombic efficiency was improved from 88% in H2Ti12O25 to 93% in the lithiated H2Ti12O25 sample. In addition, superior capacity retention properties for the charge and discharge cycling performance and good charge rate capability of the present lithiated H2Ti12O25 were confirmed in the electrochemical measurements. Accordingly, the lithiated H2Ti12O25 is suggested to be one of the promising high-voltage and high-capacity oxide negative electrodes in advanced lithium-ion batteries.

Coupled electrochemical thermal modelling of a novel Li-ion battery pack thermal management system

International Nuclear Information System (INIS)

Basu, Suman; Hariharan, Krishnan S.; Kolake, Subramanya Mayya; Song, Taewon; Sohn, Dong Kee; Yeo, Taejung

2016-01-01

Highlights: • Three-dimensional electrochemical thermal model of Li-ion battery pack using computational fluid dynamics (CFD). • Novel pack design for compact liquid cooling based thermal management system. • Simple temperature estimation algorithm for the cells in the pack using the results from the model. • Sensitivity of the thermal performance to contact resistance has been investigated. - Abstract: Thermal management system is of critical importance for a Li-ion battery pack, as high performance and long battery pack life can be simultaneously achieved when operated within a narrow range of temperature around the room temperature. An efficient thermal management system is required to keep the battery temperature in this range, despite widely varying operating conditions. A novel liquid coolant based thermal management system, for 18,650 battery pack has been introduced herein. This system is designed to be compact and economical without compromising safety. A coupled three-dimensional (3D) electrochemical thermal model is constructed for the proposed Li-ion battery pack. The model is used to evaluate the effects of different operating conditions like coolant flow-rate and discharge current on the pack temperature. Contact resistance is found to have the strongest impact on the thermal performance of the pack. From the numerical solution, a simple and novel temperature correlation of predicting the temperatures of all the individual cells given the temperature measurement of one cell is devised and validated with experimental results. Such coefficients have great potential of reducing the sensor requirement and complexity in a large Li-ion battery pack, typical of an electric vehicle.

Phase I Advanced Battery Materials For Rechargeable Advanced Space-Rated Li-Ion Batteries, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — Lithium-ion (Li-ion) batteries are attractive candidates for use as power sources in aerospace applications because they have high specific energy (up to 200 Wh/kg),...

Effect of 50 MeV Li3+ ion irradiation on electrical characteristics of high speed NPN power transistor

International Nuclear Information System (INIS)

Dinesh, C.M.; Ramani; Radhakrishna, M.C.; Dutt, R.N.; Khan, S.A.; Kanjilal, D.

2008-01-01

Silicon NPN overlay RF power high speed commercial bipolar junction transistors (BJTs) find applications in military, space and communication equipments. Here we report the effect of 50 MeV Li 3+ ion irradiation in the fluence range 1 x 10 11 -1.8 x 10 12 ions cm -2 on NPN power transistor. The range (R), electronic energy loss (S e ), nuclear energy loss (S n ), total ionizing dose (TID) and total displacement damage (D d ) in the silicon target are calculated from TRIM Monte Carlo Code. Output resistance is 3.568 x 10 4 Ω for unirradiated device and it increases to 6 x 10 7 Ω as the fluence is increased from 1 x 10 11 to 1.8 x 10 12 ions cm -2 . The capacitance of the emitter-base junction of the transistor decreases and dielectric loss of the emitter-base junction increases with increase in ion fluence. The built in voltage of the unirradiated sample is 0.5 V and it shifts to 0.4 V after irradiation at fluence of 1.8 x 10 12 ions cm -2 and the corresponding doping density reduced to 5.758 x 10 16 cm -3 . The charge carrier removal rate varies linearly with the increase in ion fluence

Dynamic dipole polarizabilities of the Li atom and the Be+ ion

International Nuclear Information System (INIS)

Tang Liyan; Yan Zongchao; Shi Tingyun; Mitroy, J.

2010-01-01

The dynamic dipole polarizabilities for Li atoms and Be + ions in the 2 2 S and 2 2 P states are calculated using the variational method with a Hylleraas basis. The present polarizabilities represent the definitive values in the nonrelativistic limit. Corrections due to relativistic effects are also estimated. Analytic representations of the polarizabilities for frequency ranges encompassing the n=3 excitations are presented. The recommended polarizabilities for 7 Li and 9 Be + are 164.11±0.03 a 0 3 and 24.489±0.004 a 0 3 , respectively.

Salt-Zeolite Ion Exchange Equilibrium Studies for Complete Set of Fission Products in Molten LiCl-KCl

International Nuclear Information System (INIS)

Yoo, Tae-Sic; Frank, Steven M.; Simpson, Michael F.; Hahn, Paula A.; Battisti, Terry J.; Phongikaroon, Supathorn

2010-01-01

This paper presents results on LiCl-KCl based molten salts/zeolite-A contact experiments and the associated equilibrium ion exchange model. Experiments examine the contact behaviors of various ternary salts (LiCl-KCl-YCl3, LiCl-KCl-LaCl3, and LiCl-KCl-PrCl3) and quaternary salts (LiCl-KCl-CsCl-NdCl3 and LiCl-KCl-CsCl-SrCl2) with the zeolite-A. The developed equilibrium model assumes that there are ion exchange and occlusion sites, both of which are in equilibrium with the molten salt phase. A systematic approach in estimating total occlusion capacity of the zeolite-A is developed. The parameters of the model, including the total occlusion capacity of the zeolite-A, were determined from fitting experimental data collected via multiple independent studies including the ones reported in this paper. Experiments involving ternary salts were used for estimating the parameters of the model, while those involving quaternary salts were used to validate the model.

Electrochemical properties and lithium ion diffusion in Li4FeSbO6 studied by first principle

Science.gov (United States)

Jia, Mingzhen; Wang, Hongyan; Wang, Hui; Chen, Yuanzheng; Guo, Chunsheng; Gan, Liyong

2017-10-01

Due to the high capacity, Li-rich materials Li2MO3 (M = transition metal) have attracted considerable attention as the next generation of Li-ion batteries. Li4FeSbO6 is a new Li-rich layered oxide material with antiferromagnet honeycomb structure. In this work, the electrochemical behavior, charging process and oxygen stability of LixFeSbO6 (0 ≤ xextracted, the charge compensation is mainly contributed by the oxygen atoms through analyzing the Bader charges of each element. In addition, oxygen evolution reactions will occur in LixFeSbO6 (x ≤ 1.5), which will decay the capacities during cycling process. Finally, we calculated that the lithium ion can diffuse in a three-dimensional pathway with the activation barriers from 0.36 eV to 0.67 eV.

Luminescent properties of Eu2+ and Ce3+ ions in strontium litho-silicate Li2SrSiO4

International Nuclear Information System (INIS)

Dotsenko, V.P.; Levshov, S.M.; Berezovskaya, I.V.; Stryganyuk, G.B.; Voloshinovskii, A.S.; Efryushina, N.P.

2011-01-01

The luminescent properties of Eu 2+ and Ce 3+ ions in Li 2 SrSiO 4 have been studied upon excitation in the 2-20 eV region. Based on the results of luminescent measurements, values of the crystal field splitting and the centroid shift of the Ce 3+ 5d configuration in Li 2 SrSiO 4 were found and compared with those of Ce 3+ ions in some other inorganic compounds. The Eu 2+ ions in Li 2 SrSiO 4 exhibit a broad band emission with a maximum at 576 nm, which is due to the 4f 6 5d→4f 7 transition. It was shown that the long-wavelength position of the Eu 2+ emission in Li 2 SrSiO 4 is caused by the large crystal-field splitting of the Eu 2+ 4f 6 5d configuration and relatively high degree of covalency of the Eu-O bond. The stabilization of Eu 2+ ions in Li 2 SrSiO 4 during the synthesis process requires a strong reducing agent. Two phenomenological approaches to explain the low stability of Eu 2+ in Li 2 SrSiO 4 are also discussed.

Non-Destructive Monitoring of Charge-Discharge Cycles on Lithium Ion Batteries using 7Li Stray-Field Imaging

Science.gov (United States)

Tang, Joel A.; Dugar, Sneha; Zhong, Guiming; Dalal, Naresh S.; Zheng, Jim P.; Yang, Yong; Fu, Riqiang

2013-01-01

Magnetic resonance imaging provides a noninvasive method for in situ monitoring of electrochemical processes involved in charge/discharge cycling of batteries. Determining how the electrochemical processes become irreversible, ultimately resulting in degraded battery performance, will aid in developing new battery materials and designing better batteries. Here we introduce the use of an alternative in situ diagnostic tool to monitor the electrochemical processes. Utilizing a very large field-gradient in the fringe field of a magnet, stray-field-imaging (STRAFI) technique significantly improves the image resolution. These STRAFI images enable the real time monitoring of the electrodes at a micron level. It is demonstrated by two prototype half-cells, graphite∥Li and LiFePO4∥Li, that the high-resolution 7Li STRAFI profiles allow one to visualize in situ Li-ions transfer between the electrodes during charge/discharge cyclings as well as the formation and changes of irreversible microstructures of the Li components, and particularly reveal a non-uniform Li-ion distribution in the graphite. PMID:24005580

Evaluation of Ce3+ and alkali metal ions Co-doped LiSrAlF6 crystalline scintillators

International Nuclear Information System (INIS)

Wakahara, Shingo; Yanagida, Takayuki; Fujimoto, Yutaka; Yokota, Yuui; Pejchal, Jan; Kurosawa, Shunsuke; Suzuki, Shotaro; Kawaguchi, Noriaki; Fukuda, Kentaro; Yoshikawa, Akira

2013-01-01

High scintillation efficiency of Eu-doped LiSrAlF 6 (LiSAF) and LiCaAlF 6 (LiCAF) codoped with alkali metal ions has been reported in our recent studies. Thus in this paper, we demonstrated the scintillation properties of 1% Ce-doped LiSAF crystals with 1% alkali metal ions co-doping to increase the light yield and understand the scintillation mechanism. The crystals showed intense emission band corresponding to the 5d-4f transition of Ce 3+ , and their light yields under thermal neutron excitation were higher than that of the Ce only doped crystal. Especially, the light yield of Ce–Na co-doped crystal exceeded about two times that of Ce only doped one. -- Highlights: ► Ce-doped and alkali metal co-doped LiSAF crystals were grown by μ-PD method. ► Alkali metal co-doped crystals showed higher light yield than Ce only doped crystal. ► Decay time of alkali metal co-doped LiSAF were longer than that of Ce only doped one

Effect of doping rare earths on magnetostriction characteristics of CoFe2O4 prepared from spent Li-ion batteries

Science.gov (United States)

Xi, Guoxi; Zhao, Tingting; Wang, Lu; Dun, Changwei; Zhang, Ye

2018-04-01

Recovering spent Li-ion batteries is beneficial to the economy and environment. Therefore, this study synthesized nanoparticles of cobalt ferrite doped with different rare earth ions (Nd, Ce, and Pr) by a sol-gel auto-combustion method using spent Li-ion batteries. The effect of the different doping elements on grain sizes, structure, magnetic and magnetostrictive properties, and strain derivative were confirmed by X-ray diffraction, scanning election microscopy, vibrating sample magnetometer, and a magnetostrictive coefficient measuring system. Substitution of a small amount of Fe3+ with RE3+ in CoRExFe2-xO4 (x = 0.025, 0.05, and 0.1) had a large effect on magnetostrictive properties and strain derivative, which was improved compared with pure cobalt ferrite at low magnetic field. The maximum strain derivative (dλ/dH = -1.49 × 10-9 A-1 m at 18 kA m-1) was obtained for Nd, x = 0.05. Changes in the magnetostriction coefficients and strain derivatives were correlated with changes in cation distribution, microstructure, and magnetic anisotropy, which depended strongly on RE3+ substitution and distribution in the spinel structure.

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.

Lithium-ions diffusion kinetic in LiFePO4/carbon nanoparticles synthesized by microwave plasma chemical vapor deposition for lithium-ion batteries

Science.gov (United States)

Gao, Chao; Zhou, Jian; Liu, Guizhen; Wang, Lin

2018-03-01

Olivine structure LiFePO4/carbon nanoparticles are synthesized successfully using a microwave plasma chemical vapor deposition (MPCVD) method. Microwave is an effective method to synthesize nanomaterials, the LiFePO4/carbon nanoparticles with high crystallinity can shorten diffusion routes for ionic transfer and electron tunneling. Meanwhile, a high quality, complete and homogenous carbon layer with appropriate thickness coating on the surface of LiFePO4 particles during in situ chemical vapor deposition process, which can ensure that electrons are able to transfer fast enough from all sides. Electrochemical impedance spectroscopy (EIS) is carried out to collect information about the kinetic behavior of lithium diffusion in LiFePO4/carbon nanoparticles during the charging and discharging processes. The chemical diffusion coefficients of lithium ions, DLi, are calculated in the range of 10-15-10-9 cm2s-1. Nanoscale LiFePO4/carbon particles show the longer regions of the faster solid-solution diffusion, and corresponding to the narrower region of the slower two-phase diffusion during the insertion/exaction of lithium ions. The CV and galvanostatic charge-discharge measurements show that the LiFePO4/carbon nanoparticles perform an excellent electrochemical performance, especially the high rate capacity and cycle life.

The mobility of Li+ and K+ ions in helium and argon at 294 and 80 K and derived interaction potentials

International Nuclear Information System (INIS)

Cassidy, R.A.; Elford, M.T.

1983-01-01

The analysis of mobility data is a valuable technique for deriving ion-atom interaction potentials or testing at initio potentials particularly at relatively large internuclear separations. In order to obtain the most complete information on the long range part of the potential it is necessary to have mobility data at sufficiently low gas temperatures and small values of E/N that the mobility is determined only by the dipole polarization force. Although this condition can be reasonably well met at room temperature for gases of high polarizability, this is not the case for ions in helium and in particular for the most well studied case, that of Li + in helium. The prime purpose of the present measurements was to obtain low temperature data for Li + in helium in order to determine more accurately the attractive long range tail of the potential. The measurements were also extended to argon to demonstrate the effect of the polarizability on the derivation of potentials. The mobility measurements were made using a drift tube-mass spectrometer system employing the Bradbury-Nielsen time of flight technique. Measurements were performed at 294 K and 80 K. The 'three temperature' theory of Lin, Viehland and Mason was used to fit interaction potentials to the present data. Detailed comparisons are made here only for the case of Li + ions in helium. The new data for 80 K provide additional information on the potential at internuclear separations which cover the range to 5 A. (Authors)

Preparation of Li4Ti5O12 by solution ion-exchange of sodium titanate nanotube and evaluation of electrochemical performance

International Nuclear Information System (INIS)

Zhang, Jingwei; Zhang, Fenli; Li, Jiuhe; Cai, Wei; Zhang, Jiwei; Yu, Laigui; Jin, Zhensheng; Zhang, Zhijun

2013-01-01

Nano-sized spinel lithium titanate (Li 4 Ti 5 O 12 ) was synthesized using sodium titanate nanotube as precursor via a facile solution ion-exchange method in association with subsequent calcination treatment at relatively low temperature. The influences of precursors, ion-exchange condition, and calcination temperature on the microstructure and electrochemical performance of the products were studied. Results indicate that pure-phase Li 4 Ti 5 O 12 can be harvested from sodium titanate nanotube precursor through an ion-exchanging at room temperature and calcination at 500 °C. The products exhibit a better performance as Li-ion battery anode material than the counterparts prepared from protonic titanate nanotube (H-titanate) precursor. The reason may lie in that sodium titanate nanotube is easier than protonic titanate nanotube to synthesize lithium titanate without TiO 2 impurity, resulting in reduced electron transfer ability and Li-ion transport ability. The capacity of Li 4 Ti 5 O 12 prepared from sodium titanate nanotube is 146 mAh/g at 10 C, and it has only 0.7 % decay after 200 charge/discharge cycles

Artificial Fish Swarm Algorithm-Based Particle Filter for Li-Ion Battery Life Prediction

Directory of Open Access Journals (Sweden)

Ye Tian

2014-01-01

Full Text Available An intelligent online prognostic approach is proposed for predicting the remaining useful life (RUL of lithium-ion (Li-ion batteries based on artificial fish swarm algorithm (AFSA and particle filter (PF, which is an integrated approach combining model-based method with data-driven method. The parameters, used in the empirical model which is based on the capacity fade trends of Li-ion batteries, are identified dependent on the tracking ability of PF. AFSA-PF aims to improve the performance of the basic PF. By driving the prior particles to the domain with high likelihood, AFSA-PF allows global optimization, prevents particle degeneracy, thereby improving particle distribution and increasing prediction accuracy and algorithm convergence. Data provided by NASA are used to verify this approach and compare it with basic PF and regularized PF. AFSA-PF is shown to be more accurate and precise.

Crystalline silicotitanates -- novel commercial cesium ion exchangers

International Nuclear Information System (INIS)

Braun, R.; Dangieri, T.J.; Fennelly, D.J.

1996-01-01

A new class of inorganic ion exchangers called crystalline silicotitanates (CST), invented by researchers at Sandia National Laboratories and Texas A ampersand M University, has been commercialized in a joint Sandia-UOP effort. The original developmental materials exhibited high selectivity for the ion exchange of cesium, strontium, and several other radionuclides from highly alkaline solutions containing molar concentrations of Na + . The materials also showed excellent chemical and radiation stability. These CST properties made them excellent candidates for treatment of solutions such as the Hanford tank supernates and other DOE radwastes. Sandia and UOP, under a Cooperative Research and Development Agreement (CRADA), developed CSTs in the powdered form and in an engineered form suitable for column ion exchange use. A continuous-flow, column ion exchange process is expected to be used to remove Cs and other radionuclides from the Hanford supernatant. The powder material invented by Sandia and Texas A ampersand M consists of submicron-size particles. It is not designed for column ion exchange but may be used in other applications such as batch waste processing. Data are also presented confirming the excellent stability of the commercial CSTs over a broad pH range and the high radiation stability of the exchangers. In addition, data are provided that demonstrate the high physical strength and attrition resistance of IONSIV reg-sign IE-911, critical properties for column ion exchange applications

The Second Life Ageing of the NMC/C Electric Vehicle Retired Li-Ion Batteries in the Stationary Applications

DEFF Research Database (Denmark)

Swierczynski, Maciej Jozef; Stroe, Daniel Loan; Martinez-Laserna, Egoitz

2016-01-01

Despite the cost of li-ion batteries is gradually falling, the price for li-ion batteries is still too high in order to significantly impact the mass market adoption of e-mobility and household battery applications. It is expected that it might take another several years before lithium-ion...... batteries obtain grid parity and Electric Vehicles (EVs) will become competitive in cost with conventional vehicles (Figure 1). In consequence, a different approach for battery cost reduction can be investigated....

OCV Hysteresis in Li-Ion Batteries including Two-Phase Transition Materials

Directory of Open Access Journals (Sweden)

Michael A. Roscher

2011-01-01

Full Text Available The relation between batteries' state of charge (SOC and open-circuit voltage (OCV is a specific feature of electrochemical energy storage devices. Especially NiMH batteries are well known to exhibit OCV hysteresis, and also several kinds of lithium-ion batteries show OCV hysteresis, which can be critical for reliable state estimation issues. Electrode potential hysteresis is known to result from thermodynamical entropic effects, mechanical stress, and microscopic distortions within the active electrode materials which perform a two-phase transition during lithium insertion/extraction. Hence, some Li-ion cells including two-phase transition active materials show pronounced hysteresis referring to their open-circuit voltage. This work points out how macroscopic effects, that is, diffusion limitations, superimpose the latte- mentioned microscopic mechanisms and lead to a shrinkage of OCV hysteresis, if cells are loaded with high current rates. To validate the mentioned interaction, Li-ion cells' state of charge is adjusted to 50% with various current rates, beginning from the fully charged and the discharged state, respectively. As a pronounced difference remains between the OCV after charge and discharge adjustment, obviously the hysteresis vanishes as the target SOC is adjusted with very high current rate.

Lifetime of the metastable 23S1 state in stored Li+ ions

International Nuclear Information System (INIS)

Knight, R.D.

1979-04-01

A laser-induced fluorescence technique combined with the observation of spontaneous magnetic dipole photons from the highly metastable 2 3 S 1 state of Li + was used to measure the radiative lifetime of this state. The ions are created by electron impact on a lithium atomic beam and are subsequently stored for periods of many seconds in an RF-quadrupole ion trap. A tunable dye laser excites the 2 3 S--2 3 P, transition at 5485A, and the intercombination electric dipole transition 2 3 P 1 --1 1 S 0 at 202A is observed. This process depletes the metastable population in a time tau/sub d/ 3 S 1 / and provides a measure of the total number of metastables. Comparison with the rate of 210A spontaneously emitted photons yields a measured value for the 2 3 S 1 radiative lifetime of tau/sub rad/ = 58.6 +- 12.9 sec, where the quoted error represents 95% confidence levels. The theoretical lifetime is tau/sub theory/ = 49.0 sec. The measured value includes data taken with both 6 Li + and 7 Li + isotopes and was corrected for the slightly different detector efficiencies at 202A and 210A. A careful study of nonradiative quenching of the metastable state was necessary to understand observed differences between tau/sub rad/ and tau/sub 3 S 1 /, the total metastable lifetime. Spatial density profiles of the ions within the trap, useful for determining the ion temperature, were obtained by scanning the laser beam horizontally across the ion trap while storing 2 3 P 1 -- 1 S 0 photon counts as a function of the laser beam's position. Agreement with a simple equilibrium model, including space charge effects, is satisfactory. A study of the optical pumping process is necessary to understand the laser-ion interaction, and observational and theoretical data are presented. 47 references

Effects of neutron and gamma radiation on lithium-ion batteries

Science.gov (United States)

Qiu, Jie; He, Dandan; Sun, Mingzhai; Li, Shimeng; Wen, Cun; Hattrick-Simpers, Jason; Zheng, Yuan F.; Cao, Lei

2015-02-01

Radiation induced deterioration in the performance of lithium-ion (Li-ion) batteries can result in functional failures of electronic devices in modern electronic systems. The stability of the Li-ion battery under a radiation environment is of crucial importance. In this work, the surface morphology of the cathode material of a commercial Li-ion battery before and after neutron and gamma ray irradiation was characterized by atomic force microscopy (AFM). We found growth in the particle size of the cathode material in the range of 36-45% as a result of the irradiation. In addition, X-ray diffraction (XRD) patterns revealed a disordering of the crystal structure occurring in the post-irradiation sample. All of these led to a 8.4% capacity loss of the battery for the maximum received irradiation dose (2.744 Mrad) at post-irradiation. The effects of the radiation on the Li-ion battery are discussed in this paper.

Effects of neutron and gamma radiation on lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Qiu, Jie; He, Dandan [Nuclear Engineering Program, Department of Mechanical and Aerospace, The Ohio State University, Columbus, OH 43210 (United States); Sun, Mingzhai [Davis Heart and Lung Research Institute, The Ohio State University, Columbus, OH 43210 (United States); Li, Shimeng [Department of Electrical and Computer Engineering, The Ohio State University, Columbus, OH 43210 (United States); Wen, Cun; Hattrick-Simpers, Jason [Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208 (United States); Zheng, Yuan F. [Department of Electrical and Computer Engineering, The Ohio State University, Columbus, OH 43210 (United States); Cao, Lei, E-mail: cao.152@osu.edu [Nuclear Engineering Program, Department of Mechanical and Aerospace, The Ohio State University, Columbus, OH 43210 (United States)

2015-02-15

Radiation induced deterioration in the performance of lithium-ion (Li-ion) batteries can result in functional failures of electronic devices in modern electronic systems. The stability of the Li-ion battery under a radiation environment is of crucial importance. In this work, the surface morphology of the cathode material of a commercial Li-ion battery before and after neutron and gamma ray irradiation was characterized by atomic force microscopy (AFM). We found growth in the particle size of the cathode material in the range of 36–45% as a result of the irradiation. In addition, X-ray diffraction (XRD) patterns revealed a disordering of the crystal structure occurring in the post-irradiation sample. All of these led to a 8.4% capacity loss of the battery for the maximum received irradiation dose (2.744 Mrad) at post-irradiation. The effects of the radiation on the Li-ion battery are discussed in this paper.

Effects of neutron and gamma radiation on lithium-ion batteries

International Nuclear Information System (INIS)

Qiu, Jie; He, Dandan; Sun, Mingzhai; Li, Shimeng; Wen, Cun; Hattrick-Simpers, Jason; Zheng, Yuan F.; Cao, Lei

2015-01-01

Radiation induced deterioration in the performance of lithium-ion (Li-ion) batteries can result in functional failures of electronic devices in modern electronic systems. The stability of the Li-ion battery under a radiation environment is of crucial importance. In this work, the surface morphology of the cathode material of a commercial Li-ion battery before and after neutron and gamma ray irradiation was characterized by atomic force microscopy (AFM). We found growth in the particle size of the cathode material in the range of 36–45% as a result of the irradiation. In addition, X-ray diffraction (XRD) patterns revealed a disordering of the crystal structure occurring in the post-irradiation sample. All of these led to a 8.4% capacity loss of the battery for the maximum received irradiation dose (2.744 Mrad) at post-irradiation. The effects of the radiation on the Li-ion battery are discussed in this paper

Charge Localization in the Lithium Iron Phosphate Li3Fe2(PO4)3at High Voltages in Lithium-Ion Batteries

DEFF Research Database (Denmark)

Younesi, Reza; Christiansen, Ane Sælland; Loftager, Simon

2015-01-01

Possible changes in the oxidation state of the oxygen ion in the lithium iron phosphate Li3Fe2(PO4)3 at high voltages in lithium-ion (Li-ion) batteries are studied using experimental and computational analysis. Results obtained from synchrotron-based hard X-ray photoelectron spectroscopy...

Patterning of lithium lanthanum titanium oxide films by soft lithography as electrolyte for all-solid-state Li-ion batteries

NARCIS (Netherlands)

Kokal, I.; Göbel, Ole; van den Ham, E.J.; ten Elshof, Johan E.; Notten, P.H.L.; Hintzen, H.T.

2015-01-01

The combination of sol–gel processing and soft-lithographic patterning presents a promising route towards three-dimensional (3D) micro Li-ion electrodes, and may offer a viable approach for the fabrication of all-solid-state 3D Li-ion batteries. The methods are relatively simple and therefore cheap

Patterning of lithium lanthanum titanium oxide films by soft lithography as electrolyte for all-solid-state Li-ion batteries

NARCIS (Netherlands)

Kokal, I.; Göbel, O.F.; van den Ham, E.J.; ten Elshof, J.E.; Notten, P.H.L.; Hintzen, H.T.

2015-01-01

The combination of sol-gel processing and soft-lithographic patterning presents a promising route towards three-dimensional (3D) micro Li-ion electrodes, and may offer a viable approach for the fabrication of all-solid-state 3D Li-ion batteries. The methods are relatively simple and therefore cheap

Nickel-Tin Electrode Materials for Nonaqueous Li-Ion Cells

Science.gov (United States)

Ehrlich, Grant M.; Durand, Christopher

2005-01-01

Experimental materials made from mixtures of nickel and tin powders have shown promise for use as the negative electrodes of rechargeable lithium-ion electrochemical power cells. During charging (or discharging) of a lithium-ion cell, lithium ions are absorbed into (or desorbed from, respectively) the negative electrode, typically through an intercalation or alloying process. The negative electrodes (for this purpose, designated as anodes) in state-of-the-art Li-ion cells are made of graphite, in which intercalation occurs. Alternatively, the anodes can be made from metals, in which alloying can occur. For reasons having to do with the electrochemical potential of intercalated lithium, metallic anode materials (especially materials containing tin) are regarded as safer than graphite ones; in addition, such metallic anode materials have been investigated in the hope of obtaining reversible charge/discharge capacities greater than those of graphite anodes. However, until now, each of the tin-containing metallic anode formulations tested has been found to be inadequate in some respect.

Investigation of pUC19 DNA damage induced by direct and indirect effect of 7Li ions radiation

International Nuclear Information System (INIS)

Sui Li; Zhao Kui; Guo Jiyu; Ni Meinan; Kong Fuquan; Cai Minghui; Yang Mingjian

2006-01-01

The effect of direct and indirect action on DNA damage in 7 Li ions radiation is investigated. Using 7 Li ions generated by HI-13 tandem accelerator, three conditions of pUC19 plasmid DNA samples including dry, with or without mannitol are irradiated at different doses in air. These irradiated DNA samples are analyzed with atomic force microscopy (AFM) in nanometer-scale. The changes of DNA forms as the dose increases are observed. The results show that free radical is the main factor in DNA strand breaks induced by 7 Li ions radiation under condition of aqueous solution. The mannitol can effectively scavenge free radical and reduce the yields of DNA strand breaks. The experimental results of this report can offered valuable basal data for cancer therapy by boron neutron capture therapy (BNCT) or heavy ion radiation method, etc. (author)

Li ⁺ -Desolvation Dictating Lithium-Ion Battery’s Low-Temperature Performances

Energy Technology Data Exchange (ETDEWEB)

Li, Qiuyan [Energy and Environmental; Lu, Dongping [Energy and Environmental; Zheng, Jianming [Energy and Environmental; Jiao, Shuhong [Energy and Environmental; Luo, Langli [Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 3335 Innovation Boulevard, Richland, Washington 99354, United States; Wang, Chong-Min [Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 3335 Innovation Boulevard, Richland, Washington 99354, United States; Xu, Kang [Electrochemistry Branch, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi, Maryland 20783, United States; Zhang, Ji-Guang [Energy and Environmental; Xu, Wu [Energy and Environmental

2017-11-28

Lithium (Li) ion battery (LIB) has penetrated almost every aspects of human life, from portable electronics, vehicles to grids, and its operation stability in extreme environments becomes increasingly important. Among these, sub-zero temperature presents a kinetic challenge to the electrochemical reactions required to deliver the stored energy. In this work, we attempted to identify the rate-determining process for Li+ migration under such low temperatures, so that an optimum electrolyte formulation could be designed to maximize the energy output. Substantial increase in available capacities from graphite||LiNi0.80Co0.15Al0.05O2 chemistry down to -40°C is achieved by reducing the solvent molecule that more tightly binds to Li+ and thus constitutes high desolvation energy barrier. The fundamental understanding is applicable universally to all electrochemical devices that have to operate in similar environments.

Determination of B and Li in nuclear materials by secondary-ion mass spectrometry

International Nuclear Information System (INIS)

Eby, R.E.; Christie, W.H.

1981-01-01

Secondary ion mass spectrometry (SIMS) was used to perform mass and isotopic analysis for B and Li in samples that are not readily amenable to more conventional mass spectrometric techniques (e.g., surface ionization, electron impact, etc.). In this paper three specific applications of SIMS analysis to nuclear materials are discussed: first, the quantitative determination of B and its isotopic composition in borosilicate glasses; second, the determination of the isotopic composition of B and Li in irradiated nuclear-grade aluminum oxide/boron carbide composite pellets, and, lastly, the quantitative and isotopic determination of B and Li in highly radioactive solutions of unknown composition

Intermittent microwave heating synthesized high performance spherical LiFePO4/C for Li-ion batteries

International Nuclear Information System (INIS)

Zou, Hongli; Zhang, Guanghui; Shen, Pei Kang

2010-01-01

An intermittent microwave heating method was used to synthesize spherical LiFePO 4 /C in the presence of glucose as reductive agent and carbon source without the use of the inert gas in the oven processes. The FePO 4 was used as iron precursor to reduce the cost and three lithium salts of Li 2 CO 3 , LiOH and CH 3 COOLi were chosen for comparison of the resulting materials. The materials can be alternatively heated by this method at a temperature controllable mode for crystallization and phase transformation and to provide relaxation time for protecting particles growth. The X-ray diffraction and scanning electron microscope measurements confirmed that the LiFePO 4 /C is olivine structured with the average particle size of 50-100 nm. The spherical LiFePO 4 /C as cathode material showed better electrochemical performance in terms of the specific capacity and the cycling stability, which might be attributed to the highly crystallized phase, small particle distribution and improved conductivity by carbon connection.

A novel BEV concept based on fixed and swappable li-ion battery packs

DEFF Research Database (Denmark)

Barreras, Jorge Varela; Pinto, C.; de Castro, R.

2015-01-01

-based ownership models to distribute the cost of the large battery pack over the vehicle lifetime. A methodology is proposed for the analysis and evaluation of the proposed concept in comparison with a direct owned non swappable single pack BEV, proving that significant improvements on city fuel economy (up to 20......In this paper a novel battery electric vehicle (BEV) concept based on a small fixed and a big swappable li-ion battery pack is proposed in order to achieve: longer range, lower initial purchase price and lower energy consumption at short ranges. For short ranges the BEV is only powered...... by the relatively small fixed battery pack, without the large swappable battery pack. In this way the mass of the vehicle is reduced and therefore the energy consumed per unit distance is improved. For higher ranges the BEV is powered by both battery packs. This concept allows the introduction of subscription...

The ion exchange properties and equilibrium constants of Li+, Na+ and K+ on zirconium phosphate highly dispersed on a cellulose acetate fibers surface

Directory of Open Access Journals (Sweden)

Borgo Claudemir Adriano

2004-01-01

Full Text Available Highly dispersed zirconium phosphate was prepared by reacting celullose acetate/ZrO2 (ZrO2 = 11 wt%, 1.0 mmol g-1 of zirconium atom per gram of the material with phosphoric acid. High power decoupling magic angle spinning (HPDEC-MAS 31P NMR and X-ray photoelectron spectroscopy data indicated that HPO4(2- is the species present on the membrane surface. The specific concentration of acidic centers, determined by ammonia gas adsorption, is 0.60 mmol g-1. The ion exchange capacities for Li+, Na+ and K+ ions were determined from ion exchange isotherms at 298 K and showed the following values (in mmol g-1: Li+= 0.05, Na+= 0.38 and K+= 0.57. Due to the strong cooperative effect, the H+/Na+ and H+/K+ ion exchange is of non ideal nature. These ion exchange equilibria were treated with the use of models of fixed tridentate centers, which consider the surface of the sorbent as polyfunctional sorption centers. Both the observed ion exchange capacities with respect to the alkaline metal ions and the equilibrium constants are discussed by taking into consideration the sequence of the ionic hydration radii for Li+, Na+ and K+. The matrix affinity for the ions decreases with increasing the cations hydration radii from K+ to Li+. The high values of the separation factors S Na+/Li+ and S K+/Li+ (up to several hundreds support the application of this material for the quantitative separation of Na+ and K+ from Li+ from a mixture containing these three ions.

Nanomaterials Enabled High Energy and Power Density Li-ion Batteries, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — There is a need for high energy (~ 200 Wh/kg) and high power (> 500 W/kg) density rechargeable Li-ion batteries that are safe and reliable for several space and...

Facile design and synthesis of Li-rich nanoplates cathodes with habit-tuned crystal for lithium ion batteries

Science.gov (United States)

Li, Jili; Jia, Tiekun; Liu, Kai; Zhao, Junwei; Chen, Jian; Cao, Chuanbao

2016-11-01

Li-ion batteries with high-energy and high-power density are pursued to apply in the electronic vehicles and renewable energy storage systems. In this work, layered Li-rich transition-metal oxide cathode Li1.2Ni0.2Mn0.6O2 nanoplates with enhanced growth of {010} planes (LNMO-NP) is successfully synthesized through a facile and versatile strategy. Ethylene glycol plays an important role in the formation of LNMO-NP nanoplates with {010} electrochemically active surface planes exposure. As cathode for Li-ion batteries, LNMO-NP demonstrates a high specific discharge capacity of 270.2 mAh g-1 at 0.1 C (1 C = 300 mA g-1) and an excellent rate capability. The good electrochemical performance can be attributed to the nanoplates with the growth of {010} electrochemically active planes which is in favor of Li+ intercalation/deintercalation.

Environmental impact assessment and end-of-life treatment policy analysis for Li-ion batteries and Ni-MH batteries.

Science.gov (United States)

Yu, Yajuan; Chen, Bo; Huang, Kai; Wang, Xiang; Wang, Dong

2014-03-18

Based on Life Cycle Assessment (LCA) and Eco-indicator 99 method, a LCA model was applied to conduct environmental impact and end-of-life treatment policy analysis for secondary batteries. This model evaluated the cycle, recycle and waste treatment stages of secondary batteries. Nickel-Metal Hydride (Ni-MH) batteries and Lithium ion (Li-ion) batteries were chosen as the typical secondary batteries in this study. Through this research, the following results were found: (1) A basic number of cycles should be defined. A minimum cycle number of 200 would result in an obvious decline of environmental loads for both battery types. Batteries with high energy density and long life expectancy have small environmental loads. Products and technology that help increase energy density and life expectancy should be encouraged. (2) Secondary batteries should be sorted out from municipal garbage. Meanwhile, different types of discarded batteries should be treated separately under policies and regulations. (3) The incineration rate has obvious impact on the Eco-indicator points of Nickel-Metal Hydride (Ni-MH) batteries. The influence of recycle rate on Lithium ion (Li-ion) batteries is more obvious. These findings indicate that recycling is the most promising direction for reducing secondary batteries' environmental loads. The model proposed here can be used to evaluate environmental loads of other secondary batteries and it can be useful for proposing policies and countermeasures to reduce the environmental impact of secondary batteries.

Environmental Impact Assessment and End-of-Life Treatment Policy Analysis for Li-Ion Batteries and Ni-MH Batteries

Directory of Open Access Journals (Sweden)

Yajuan Yu

2014-03-01

Full Text Available Based on Life Cycle Assessment (LCA and Eco-indicator 99 method, a LCA model was applied to conduct environmental impact and end-of-life treatment policy analysis for secondary batteries. This model evaluated the cycle, recycle and waste treatment stages of secondary batteries. Nickel-Metal Hydride (Ni-MH batteries and Lithium ion (Li-ion batteries were chosen as the typical secondary batteries in this study. Through this research, the following results were found: (1 A basic number of cycles should be defined. A minimum cycle number of 200 would result in an obvious decline of environmental loads for both battery types. Batteries with high energy density and long life expectancy have small environmental loads. Products and technology that help increase energy density and life expectancy should be encouraged. (2 Secondary batteries should be sorted out from municipal garbage. Meanwhile, different types of discarded batteries should be treated separately under policies and regulations. (3 The incineration rate has obvious impact on the Eco-indicator points of Nickel-Metal Hydride (Ni-MH batteries. The influence of recycle rate on Lithium ion (Li-ion batteries is more obvious. These findings indicate that recycling is the most promising direction for reducing secondary batteries’ environmental loads. The model proposed here can be used to evaluate environmental loads of other secondary batteries and it can be useful for proposing policies and countermeasures to reduce the environmental impact of secondary batteries.

Environmental Impact Assessment and End-of-Life Treatment Policy Analysis for Li-Ion Batteries and Ni-MH Batteries

Science.gov (United States)

Yu, Yajuan; Chen, Bo; Huang, Kai; Wang, Xiang; Wang, Dong

2014-01-01

Based on Life Cycle Assessment (LCA) and Eco-indicator 99 method, a LCA model was applied to conduct environmental impact and end-of-life treatment policy analysis for secondary batteries. This model evaluated the cycle, recycle and waste treatment stages of secondary batteries. Nickel-Metal Hydride (Ni-MH) batteries and Lithium ion (Li-ion) batteries were chosen as the typical secondary batteries in this study. Through this research, the following results were found: (1) A basic number of cycles should be defined. A minimum cycle number of 200 would result in an obvious decline of environmental loads for both battery types. Batteries with high energy density and long life expectancy have small environmental loads. Products and technology that help increase energy density and life expectancy should be encouraged. (2) Secondary batteries should be sorted out from municipal garbage. Meanwhile, different types of discarded batteries should be treated separately under policies and regulations. (3) The incineration rate has obvious impact on the Eco-indicator points of Nickel-Metal Hydride (Ni-MH) batteries. The influence of recycle rate on Lithium ion (Li-ion) batteries is more obvious. These findings indicate that recycling is the most promising direction for reducing secondary batteries’ environmental loads. The model proposed here can be used to evaluate environmental loads of other secondary batteries and it can be useful for proposing policies and countermeasures to reduce the environmental impact of secondary batteries. PMID:24646862

Evaluation of commercial lithium-ion cells based on composite positive electrode for plug-in hybrid electric vehicle applications. Part I: Initial characterizations

International Nuclear Information System (INIS)

Dubarry, Matthieu; Truchot, Cyril; Cugnet, Mikael; Liaw, Bor Yann; Gering, Kevin; Sazhin, Sergiy; Jamison, David; Michelbacher, Christopher

2011-01-01

Evaluating commercial Li-ion batteries presents some unique benefits. One of them is to use cells made from established fabrication process and form factor, such as those offered by the 18650 cylindrical configuration, to provide a common platform to investigate and understand performance deficiency and aging mechanism of target chemistry. Such an approach shall afford us to derive relevant information without influence from processing or form factor variability that may skew our understanding on cell-level issues. A series of 1.9 Ah 18650 lithium ion cells developed by a commercial source using a composite positive electrode comprising (LiMn1/3Ni1/3Co1/3O2 + LiMn2O4) is being used as a platform for the investigation of certain key issues, particularly path-dependent aging and degradation in future plug-in hybrid electric vehicle (PHEV) applications, under the US Department of Energy's Applied Battery Research (ABR) program. Here we report in Part I the initial characterizations of the cell performance and Part II some aspects of cell degradation in 2C cycle aging. The initial characterizations, including cell-to-cell variability, are essential for life cycle performance characterization in the second part of the report when cell-aging phenomena are discussed. Due to the composite nature of the positive electrode, the features (or signature) derived from the incremental capacity (IC) of the cell appear rather complex. In this work, the method to index the observed IC peaks is discussed. Being able to index the IC signature in details is critical for analyzing and identifying degradation mechanism later in the cycle aging study.

Tri-(4-methoxythphenyl) phosphate: A new electrolyte additive with both fire-retardancy and overcharge protection for Li-ion batteries

International Nuclear Information System (INIS)

Feng, J.K.; Cao, Y.L.; Ai, X.P.; Yang, H.X.

2008-01-01

A novel compound, tri-(4-methoxythphenyl) phosphate, was synthesized and investigated as a safety electrolyte additive for lithium-ion batteries. It was found that this additive could lower the flammability of the electrolyte, and thereby enhance the thermal stability of the Li-ion battery. Moreover, this molecule can also be polymerized at 4.35 V (vs. Li/Li + ) to form a conducting polymer, which can protect the batteries from voltage runaway at overcharge by internal bypassing the overcharging current in the batteries. Thus, it is possible to use this electrolyte additive to provide both overcharge protection and flame retardancy for lithium-ion batteries without much influence on the battery performance

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)

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.

Acid leaching of mixed spent Li-ion batteries

Directory of Open Access Journals (Sweden)

A.A. Nayl

2017-05-01

Full Text Available Acid leaching for different types of mixed spent Li-ion mobile batteries is carried out after alkali decomposition using NH4OH followed by H2SO4 + H2O2 leaching. In the alkali decomposition step, the effects of reaction time, NH4OH concentration, liquid/solid mass ratio and reaction temperature on the decomposition process are investigated to remove Al, Cu, Mn, Ni, Co, and Li. After alkaline treatment, the alkali paste is treated to leach the remaining metals using H2SO4 + H2O2. The significant effects of reaction time, acid concentration, H2O2 concentration, liquid/solid mass ratios and reaction temperature on the leaching rate are studied. More than 97% of Al, Mn, Ni, Co, and Li and about 65% Cu are leached in two stages. Kinetic analysis shows that, the data fit with chemical reaction control mechanism and the activation energies for the investigated metals using the Arrhenius equation ranged from 30.1 to 41.4 kJ/mol. Recovered metals are precipitated from the leaching liquor at varying pH values using NaOH solution and Na2CO3. Firstly, Mn is precipitated as MnCO3 at pH = 7.5. Secondly, at pH = 9.0, nickel is precipitated as NiCO3. Thirdly, as the pH of the leaching liquor reaches 11–12, Co(OH2 is precipitated and the remaining Li is readily precipitated as Li2CO3 using a saturated Na2CO3 solution. Based on the experimental data, a flow sheet is developed and tested for the recovery process.

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.

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

Atomic Layer Deposition of Stable LiAlF4 Lithium Ion Conductive Interfacial Layer for Stable Cathode Cycling.

Science.gov (United States)

Xie, Jin; Sendek, Austin D; Cubuk, Ekin D; Zhang, Xiaokun; Lu, Zhiyi; Gong, Yongji; Wu, Tong; Shi, Feifei; Liu, Wei; Reed, Evan J; Cui, Yi

2017-07-25

Modern lithium ion batteries are often desired to operate at a wide electrochemical window to maximize energy densities. While pushing the limit of cutoff potentials allows batteries to provide greater energy densities with enhanced specific capacities and higher voltage outputs, it raises key challenges with thermodynamic and kinetic stability in the battery. This is especially true for layered lithium transition-metal oxides, where capacities can improve but stabilities are compromised as wider electrochemical windows are applied. To overcome the above-mentioned challenges, we used atomic layer deposition to develop a LiAlF 4 solid thin film with robust stability and satisfactory ion conductivity, which is superior to commonly used LiF and AlF 3 . With a predicted stable electrochemical window of approximately 2.0 ± 0.9 to 5.7 ± 0.7 V vs Li + /Li for LiAlF 4 , excellent stability was achieved for high Ni content LiNi 0.8 Mn 0.1 Co 0.1 O 2 electrodes with LiAlF 4 interfacial layer at a wide electrochemical window of 2.75-4.50 V vs Li + /Li.

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.

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.

Porous-Nickel-Scaffolded Tin-Antimony Anodes with Enhanced Electrochemical Properties for Li/Na-Ion Batteries.

Science.gov (United States)

Li, Jiachen; Pu, Jun; Liu, Ziqiang; Wang, Jian; Wu, Wenlu; Zhang, Huigang; Ma, Haixia

2017-08-02

The energy and power densities of rechargeable batteries urgently need to be increased to meet the ever-increasing demands of consumer electronics and electric vehicles. Alloy anodes are among the most promising candidates for next-generation high-capacity battery materials. However, the high capacities of alloy anodes usually suffer from some serious difficulties related to the volume changes of active materials. Porous supports and nanostructured alloy materials have been explored to address these issues. However, these approaches seemingly increase the active material-based properties and actually decrease the electrode-based capacity because of the oversized pores and heavy mass of mechanical supports. In this study, we developed an ultralight porous nickel to scaffold with high-capacity SnSb alloy anodes. The porous-nickel-supported SnSb alloy demonstrates a high specific capacity and good cyclability for both Li-ion and Na-ion batteries. Its capacity retains 580 mA h g -1 at 2 A g -1 after 100 cycles in Li-ion batteries. For a Na-ion battery, the composite electrode can even deliver a capacity of 275 mA h g -1 at 1 A g -1 after 1000 cycles. This study demonstrates that combining the scaffolding function of ultralight porous nickel and the high capacity of the SnSb alloy can significantly enhance the electrochemical performances of Li/Na-ion batteries.

Raman and NMR studies of aged LiFePO4 cathode

International Nuclear Information System (INIS)

Nagpure, Shrikant C.; Bhushan, Bharat; Babu, S.S.

2012-01-01

Highlights: ► Raman spectroscopy used to characterize the quality of carbon coating in LiFePO 4 commercial cells aged with C-rate. ► Structural change in the carbon coating leading to low electrical conductivity is observed for the cells aged at higher C-rate. ► Nuclear magnetic spectroscopy used to characterize LiFePO 4 nanoparticles for the presence of Li. ► 7 Li peak is observed in an unaged cell, while the similar peak is absent in the aged cells. - Abstract: The carbon coated LiFePO 4 nanoparticles are used in advanced lithium-ion batteries due to low cost, high energy and power density. In this paper Raman spectroscopy is used to analyze the degradation of carbon coating around these nanoparticles in several commercial cells aged with different C-rate. Magic angle spinning 7 Li Nuclear magnetic resonance (NMR) spectroscopy is used to characterize these nanoparticles for the presence of Li. In Raman spectroscopy data, structural change in the carbon leading to low electrical conductivity is observed for the cells aged at higher C-rate. In NMR spectroscopy data, isotropic 7 Li peak is observed in an unaged cell, while the similar peak is absent in the aged cells.

Cradle-to-Gate Emissions from a Commercial Electric Vehicle Li-Ion Battery: A Comparative Analysis.

Science.gov (United States)

Kim, Hyung Chul; Wallington, Timothy J; Arsenault, Renata; Bae, Chulheung; Ahn, Suckwon; Lee, Jaeran

2016-07-19

We report the first cradle-to-gate emissions assessment for a mass-produced battery in a commercial battery electric vehicle (BEV); the lithium-ion battery pack used in the Ford Focus BEV. The assessment was based on the bill of materials and primary data from the battery industry, that is, energy and materials input data from the battery cell and pack supplier. Cradle-to-gate greenhouse gas (GHG) emissions for the 24 kWh Ford Focus lithium-ion battery are 3.4 metric tonnes of CO2-eq (140 kg CO2-eq per kWh or 11 kg CO2-eq per kg of battery). Cell manufacturing is the key contributor accounting for 45% of the GHG emissions. We review published studies of GHG emissions associated with battery production to compare and contrast with our results. Extending the system boundary to include the entire vehicle we estimate a 39% increase in the cradle-to-gate GHG emissions of the Focus BEV compared to the Focus internal combustion engine vehicle (ICEV), which falls within the range of literature estimates of 27-63% increases for hypothetical nonproduction BEVs. Our results reduce the uncertainties associated with assessment of BEV battery production, serve to identify opportunities to reduce emissions, and confirm previous assessments that BEVs have great potential to reduce GHG emissions over the full life cycle and provide local emission free mobility.

Selective sodium intercalation into sodium nickel-manganese sulfate for dual Na-Li-ion batteries.

Science.gov (United States)

Marinova, Delyana M; Kukeva, Rosica R; Zhecheva, Ekaterina N; Stoyanova, Radostina K

2018-04-26

Double sodium transition metal sulfates combine in themselves unique intercalation properties with eco-compatible compositions - a specific feature that makes them attractive electrode materials for lithium and sodium ion batteries. Herein, we examine the intercalation properties of novel double sodium nickel-manganese sulfate, Na2Ni1/2Mn1/2(SO4)2, having a large monoclinic unit cell, through electrochemical and ex situ diffraction and spectroscopic methods. The sulfate salt Na2Ni1/2Mn1/2(SO4)2 is prepared by thermal dehydration of the corresponding hydrate salt Na2Ni1/2Mn1/2(SO4)2·4H2O having a blödite structure. The intercalation reactions on Na2Ni1-xMnx(SO4)2 are studied in two model cells: half-ion cell versus Li metal anode and full-ion cell versus Li4Ti5O12 anode by using lithium (LiPF6 dissolved in EC/DMC) and sodium electrolytes (NaPF6 dissolved in EC:DEC). Based on ex situ XRD and TEM analysis, it is found that sodium intercalation into Na2Ni1/2Mn1/2(SO4)2 takes place via phase separation into the Ni-rich monoclinic phase and Mn-rich alluaudite phase. The redox reactions involving participation of manganese and titanium ions are monitored by ex situ EPR spectroscopy. It has been demonstrated that manganese ions from the sulfate salt are participating in the electrochemical reaction, while the nickel ions remain intact. As a result, a reversible capacity of about 65 mA h g-1 is reached. The selective intercalation properties determine sodium nickel-manganese sulfate as a new electrode material for hybrid lithium-sodium ion batteries that is thought to combine the advantages of individual lithium and sodium batteries.

Influence of memory effect on the state-of-charge estimation of large-format Li-ion batteries based on LiFePO4 cathode

Science.gov (United States)

Shi, Wei; Wang, Jiulin; Zheng, Jianming; Jiang, Jiuchun; Viswanathan, Vilayanur; Zhang, Ji-Guang

2016-04-01

In this work, we systematically investigated the influence of the memory effect of LiFePO4 cathodes in large-format full batteries. The electrochemical performance of the electrodes used in these batteries was also investigated separately in half-cells to reveal their intrinsic properties. We noticed that the memory effect of LiFePO4/graphite cells depends not only on the maximum state of charge reached during the memory writing process, but is also affected by the depth of discharge reached during the memory writing process. In addition, the voltage deviation in a LiFePO4/graphite full battery is more complex than in a LiFePO4/Li half-cell, especially for a large-format battery, which exhibits a significant current variation in the region near its terminals. Therefore, the memory effect should be taken into account in advanced battery management systems to further extend the long-term cycling stabilities of Li-ion batteries using LiFePO4 cathodes.

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.

Enhanced thermal safety and high power performance of carbon-coated LiFePO4 olivine cathode for Li-ion batteries

Science.gov (United States)

Zaghib, K.; Dubé, J.; Dallaire, A.; Galoustov, K.; Guerfi, A.; Ramanathan, M.; Benmayza, A.; Prakash, J.; Mauger, A.; Julien, C. M.

2012-12-01

The carbon-coated LiFePO4 Li-ion oxide cathode was studied for its electrochemical, thermal, and safety performance. This electrode exhibited a reversible capacity corresponding to more than 89% of the theoretical capacity when cycled between 2.5 and 4.0 V. Cylindrical 18,650 cells with carbon-coated LiFePO4 also showed good capacity retention at higher discharge rates up to 5C rate with 99.3% coulombic efficiency, implying that the carbon coating improves the electronic conductivity. Hybrid Pulse Power Characterization (HPPC) test performed on LiFePO4 18,650 cell indicated the suitability of this carbon-coated LiFePO4 for high power HEV applications. The heat generation during charge and discharge at 0.5C rate, studied using an Isothermal Microcalorimeter (IMC), indicated cell temperature is maintained in near ambient conditions in the absence of external cooling. Thermal studies were also investigated by Differential Scanning Calorimeter (DSC) and Accelerating Rate Calorimeter (ARC), which showed that LiFePO4 is safer, upon thermal and electrochemical abuse, than the commonly used lithium metal oxide cathodes with layered and spinel structures. Safety tests, such as nail penetration and crush test, were performed on LiFePO4 and LiCoO2 cathode based cells, to investigate on the safety hazards of the cells upon severe physical abuse and damage.

Countering the Segregation of Transition-Metal Ions in LiMn1/3 Co1/3 Ni1/3 O2 Cathode for Ultralong Life and High-Energy Li-Ion Batteries.

Science.gov (United States)

Luo, Dong; Fang, Shaohua; Tamiya, Yu; Yang, Li; Hirano, Shin-Ichi

2016-08-01

High-voltage layered lithium transition-metal oxides are very promising cathodes for high-energy Li-ion batteries. However, these materials often suffer from a fast degradation of cycling stability due to structural evolutions. It seriously impedes the large-scale application of layered lithium transition-metal oxides. In this work, an ultralong life LiMn1/3 Co1/3 Ni1/3 O2 microspherical cathode is prepared by constructing an Mn-rich surface. Its capacity retention ratio at 700 mA g(-1) is as large as 92.9% after 600 cycles. The energy dispersive X-ray maps of electrodes after numerous cycles demonstrate that the ultralong life of the as-prepared cathode is attributed to the mitigation of TM-ions segregation. Additionally, it is discovered that layered lithium transition-metal oxide cathodes with an Mn-rich surface can mitigate the segregation of TM ions and the corrosion of active materials. This study provides a new strategy to counter the segregation of TM ions in layered lithium transition-metal oxides and will help to the design and development of high-energy cathodes with ultralong life. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relevance of LiPF6 as Etching Agent of LiMnPO4 Colloidal Nanocrystals for High Rate Performing Li-ion Battery Cathodes.

Science.gov (United States)

Chen, Lin; Dilena, Enrico; Paolella, Andrea; Bertoni, Giovanni; Ansaldo, Alberto; Colombo, Massimo; Marras, Sergio; Scrosati, Bruno; Manna, Liberato; Monaco, Simone

2016-02-17

LiMnPO4 is an attractive cathode material for the next-generation high power Li-ion batteries, due to its high theoretical specific capacity (170 mA h g(-1)) and working voltage (4.1 V vs Li(+)/Li). However, two main drawbacks prevent the practical use of LiMnPO4: its low electronic conductivity and the limited lithium diffusion rate, which are responsible for the poor rate capability of the cathode. The electronic resistance is usually lowered by coating the particles with carbon, while the use of nanosize particles can alleviate the issues associated with poor ionic conductivity. It is therefore of primary importance to develop a synthetic route to LiMnPO4 nanocrystals (NCs) with controlled size and coated with a highly conductive carbon layer. We report here an effective surface etching process (using LiPF6) on colloidally synthesized LiMnPO4 NCs that makes the NCs dispersible in the aqueous glucose solution used as carbon source for the carbon coating step. Also, it is likely that the improved exposure of the NC surface to glucose facilitates the formation of a conductive carbon layer that is in intimate contact with the inorganic core, resulting in a high electronic conductivity of the electrode, as observed by us. The carbon coated etched LiMnPO4-based electrode exhibited a specific capacity of 118 mA h g(-1) at 1C, with a stable cycling performance and a capacity retention of 92% after 120 cycles at different C-rates. The delivered capacities were higher than those of electrodes based on not etched carbon coated NCs, which never exceeded 30 mA h g(-1). The rate capability here reported for the carbon coated etched LiMnPO4 nanocrystals represents an important result, taking into account that in the electrode formulation 80% wt is made of the active material and the adopted charge protocol is based on reasonable fast charge times.

Flexible Nb2O5 nanowires/graphene film electrode for high-performance hybrid Li-ion supercapacitors

Science.gov (United States)

Song, Hao; Fu, Jijiang; Ding, Kang; Huang, Chao; Wu, Kai; Zhang, Xuming; Gao, Biao; Huo, Kaifu; Peng, Xiang; Chu, Paul K.

2016-10-01

The hybrid Li-ion electrochemical supercapacitor (Li-HSC) combining the battery-like anode with capacitive cathode is a promising energy storage device boasting large energy and power densities. Orthorhombic Nb2O5 is a good anode material in Li-HSCs because of its large pseudocapacitive Li-ion intercalation capacity. Herein, we report a high-performance, binder-free and flexible anode consisting of long Nb2O5 nanowires and graphene (L-Nb2O5 NWs/rGO). The paper-like L-Nb2O5 NWs/rGO film electrode has a large mass loading of Nb2O5 of 93.5 wt% as well as short solid-state ion diffusion length, and enhanced conductivity (5.1 S cm-1). The hybrid L-Nb2O5 NWs/rGO paper electrode shows a high reversible specific capacity of 160 mA h g-1 at a current density of 0.2 A g-1, superior rate capability with capacitance retention of 60% when the current density increases from 0.2 to 5 A g-1, as well as excellent cycle stability. The Li-HSC device based on the L-Nb2O5/rGO anode and the cathode of biomass-derived carbon nanosheets delivers an energy density of 106 Wh kg-1 at 580 W kg-1 and 32 Wh kg-1 at a large power density of 14 kW kg-1. Moreover, the Li-HSC device exhibits excellent cycling performance without obvious capacitance decay after 1000 cycles.

Ab initio identification of the Li-rich phase in LiFePO4.

Science.gov (United States)

Zeng, Hua; Gu, Yue; Teng, Gaofeng; Liu, Yimeng; Zheng, Jiaxin; Pan, Feng

2018-06-27

A recent discovery of anionic redox activity in Li-rich layered compounds opens a new direction for the design of high-capacity cathode materials for lithium-ion batteries. Here using extensive ab initio calculations, the thermodynamic existence of the Li-rich phase in LiFePO4 to form Li1+xFe1-xPO4 with x not exceeding 12.5% has been proved. Anionic redox activity and structural stability during delithiation are further investigated. Interestingly, it is found that Li1+xFe1-xPO4 cannot be delithiated completely and thus cannot achieve extra capacity by anionic redox activity, because the local oxygen-ion redox will cause the fracture of the rigid framework formed by phosphate tetrahedral polyanions. Although an extra capacity cannot be realized, the excess Li-ions at Fe sites can enhance the Li-ion diffusivity along the adjacent [010] channel and contribute to the shift from 1D to 2D/3D diffusion. This study provides a fresh perspective on olivine-type LiFePO4 and offers some important clues on designing Li-rich cathode materials with high energy density.

Atomic-Scale Observations of (010) LiFePO4 Surfaces Before and After Chemical Delithiation.

Science.gov (United States)

Kobayashi, Shunsuke; Fisher, Craig A J; Kato, Takeharu; Ukyo, Yoshio; Hirayama, Tsukasa; Ikuhara, Yuichi

2016-09-14

The ability to view directly the surface structures of battery materials with atomic resolution promises to dramatically improve our understanding of lithium (de)intercalation and related processes. Here we report the use of state-of-the-art scanning transmission electron microscopy techniques to probe the (010) surface of commercially important material LiFePO4 and compare the results with theoretical models. The surface structure is noticeably different depending on whether Li ions are present in the topmost surface layer or not. Li ions are also found to migrate back to surface regions from within the crystal relatively quickly after partial delithiation, demonstrating the facile nature of Li transport in the [010] direction. The results are consistent with phase transformation models involving metastable phase formation and relaxation, providing atomic-level insights into these fundamental processes.

Hyperenhanced Li - Li Chemonuclear Fusion

International Nuclear Information System (INIS)

Ikegami, Hidetsugu

2006-01-01

A new fusion scheme, the Li - Li chemonuclear fusion is presented, where nuclear fusion reactions are linked to atomic fusion reactions. Lithium ions are implanted on a surface of metallic Li liquid at an energy of nuclear stopping (several keV/amu). The ions collide slowly with liquid Li atoms without electronic excitation and lead to the Li - Li chemonuclear fusion through the formation of united atoms or quasi-C atoms at their turning points. Inside the quasi-atoms twin nuclei are confined within respective sub-pm scale spheres of zero-point oscillation and form themselves into ultradense intermediate nuclear complexes. Their density is million times as large as the solar interior density and close to densities of white dwarfs or white-dwarf progenitors of supernovae. This confinement of nuclear complexes is enormously prolonged towards the pycno-nuclear reactions induced by the zero-point oscillation under the presence of thermodynamic force specified by the Gibbs energy change in the quasi-atom formation in the liquid. Resulted rate enhancement of nuclear fusion by a factor of 10 48 has been anticipated. The enhancement is also argued in connection with the Bose-Einstein condensation

Conductivity and applications of Li-biphenyl-1,2-dimethoxyethane solution for lithium ion batteries

Institute of Scientific and Technical Information of China (English)

Geng Chu; Bo-Nan Liu; Fei Luo; Wen-Jun Li; Hao Lu; Li-Quan Chen; Hong Li

2017-01-01

The total conductivity of Li-biphenyl-l,2-dimethoxyethane solution (LixBp(DME)9.65,Bp =biphenyl,DME =1,2-dimethoxyethane,x =0.25,0.50,1.00,1.50,2.00) is measured by impedance spectroscopy at a temperature range from 0 ℃C to 40 ℃C.The Li1.50Bp(DME)9.65 has the highest total conductivity 10.7 mS/cm.The conductivity obeys Arrhenius law with the activation energy (Ea(x=0.50) =0.014 eV,Ea(x=1.00) =0.046 eV).The ionic conductivity and electronic conductivity of LixBp(DME)9.65 solutions are investigated at 20 ℃C using the isothermal transient ionic current (ITIC) technique with an ion-blocking stainless steal electrode.The ionic conductivity and electronic conductivity of Li1.00Bp(DME)9.65 are measured as 4.5 mS/cm and 6.6 mS/cm,respectively.The Li1.00Bp(DME)9.65 solution is tested as an anode material of half liquid lithium ion battery due to the coexistence of electronic conductivity and ionic conductivity.The lithium iron phosphate (LFP) and Li1.5Al0.5Ti1.5(PO4)3 (LATP) are chosen to be the counter electrode and electrolyte,respectively.The assembled cell is cycled in the voltage range of 2.2 V-3.75 V at a current density of 50 mA/g.The potential of Lit.00Bp(DME)9.65 solution is about 0.3 V vs.Li+/Li,which indicates the solution has a strong reducibility.The Li1.00Bp(DME)9.65 solution is also used to prelithiate the anode material with low first efficiency,such as hard carbon,soft carbon and silicon.

Supervalent doping of LiFePO4 for enhanced electrochemical performance

Directory of Open Access Journals (Sweden)

N. V. Kosova

2015-12-01

Full Text Available The orthophosphates LiFe0.9M0.1PO4 with the structure of olivine doped with vanadium and titanium were obtained by mechanochemically stimulated solidphase synthesis using high-energy planetary mill AGO-2 and subsequent annealing at 750 °C. It is shown that V- and Ti- ions do not completely substitute for Fe2+ ions in the LiFePO4 structure. The remaining part of these ions involve in the formation of second phase with nashiko-like structure: monoclinic Li3V2(PO43 (space group P21/n and rhombohedral LiTi2(PO43 (space group R-3c. According to TEM, the average size of the particle of nanocomposites is about 100-300 nm. EMF of microanalysis showed that the small particles of secondary phases are segregated at the surface of larger particles of LiFePO4. On the charge-discharge curves of LiFe0.9M0.1PO4 there are plateau corresponding to LiFePO4 and the second phase. The doping with vanadium increases the resistance of the cycling of LiFePO4 and improves its cyclability at high speeds to a greater extent than in the case of doping with titanium.

Upcycling of Packing-Peanuts into Carbon Microsheet Anodes for Lithium-Ion Batteries.

Science.gov (United States)

Etacheri, Vinodkumar; Hong, Chulgi Nathan; Pol, Vilas G

2015-09-15

Porous carbon microsheet anodes with Li-ion storage capacity exceeding the theoretical limit are for the first time derived from waste packing-peanuts. Crystallinity, surface area, and porosity of these 1 μm thick carbon sheets were tuned by varying the processing temperature. Anodes composed of the carbon sheets outperformed the electrochemical properties of commercial graphitic anode in Li-ion batteries. At a current density of 0.1 C, carbon microsheet anodes exhibited a specific capacity of 420 mAh/g, which is slightly higher than the theoretical capacity of graphite (372 mAh/g) in Li-ion half-cell configurations. At a higher rate of 1 C, carbon sheets retained 4-fold higher specific capacity (220 mAh/g) compared to those of commercial graphitic anode. After 100 charge-discharge cycles at current densities of 0.1 and 0.2 C, optimized carbon sheet anodes retained stable specific capacities of 460 and 370 mAh/g, respectively. Spectroscopic and microscopic investigations proved the structural integrity of these high-performance carbon anodes during numerous charge-discharge cycles. Considerably higher electrochemical performance of the porous carbon microsheets are endorsed to their disorderness that facilitate to store more Li-ions than the theoretical limit, and porous 2-D microstructure enabling fast solid-state Li-ion diffusion and superior interfacial kinetics. The work demonstrated here illustrates an inexpensive and environmentally benign method for the upcycling of packaging materials into functional carbon materials for electrochemical energy storage.

Advanced Space Power Systems (ASPS): High Specific Energy Li-ion Battery Cells

Data.gov (United States)

National Aeronautics and Space Administration — The goal of this project element is to increase the specific energy of Li-ion battery cells to 265 Wh/kg and the energy density to 500 Wh/L at 10oC while maintaining...

Evidence for nano-Si clusters in amorphous SiO anode materials for rechargeable Li-ion batteries

International Nuclear Information System (INIS)

Sepehri-Amin, H.; Ohkubo, T.; Kodzuka, M.; Yamamura, H.; Saito, T.; Iba, H.; Hono, K.

2013-01-01

Atom probe tomography and high resolution transmission electron microscopy have shown the presence of nano-sized amorphous Si clusters in non-disproportionated amorphous SiO powders are under consideration for anode materials in Li-ion batteries. After Li insertion/extraction, no change was found in the chemistry and structure of the Si clusters. However, Li atoms were found to be trapped at the amorphous SiO phase after Li insertion/extraction, which may be attributed to the large capacity fade after the first charge/discharge cycle

Borophene as an anode material for Ca, Mg, Na or Li ion storage: A first-principle study

Science.gov (United States)

Mortazavi, Bohayra; Dianat, Arezoo; Rahaman, Obaidur; Cuniberti, Gianaurelio; Rabczuk, Timon

2016-10-01

Borophene, the boron atom analogue to graphene, being atomic thick have been just recently experimentally fabricated. In this work, we employ first-principles density functional theory calculations to investigate the interaction of Ca, Mg, Na or Li atoms with single-layer and free-standing borophene. We first identified the most stable binding sites and their corresponding binding energies as well and then we gradually increased the ions concentration. Our calculations predict strong binding energies of around 4.03 eV, 2.09 eV, 2.92 eV and 3.28 eV between the borophene substrate and Ca, Mg, Na or Li ions, respectively. We found that the binding energy generally decreases by increasing the ions content. Using the Bader charge analysis, we evaluate the charge transfer between the adatoms and the borophene sheet. Our investigation proposes the borophene as a 2D material with a remarkably high capacity of around 800 mA h/g, 1960 mA h/g, 1380 mA h/g and 1720 mA h/g for Ca, Mg, Na or Li ions storage, respectively. This study can be useful for the possible application of borophene for the rechargeable ion batteries.

Fabrication and demonstration of high energy density lithium ion microbatteries

Science.gov (United States)

Sun, Ke

Since their commercialization by Sony two decades ago, Li-ion batteries have only experienced mild improvement in energy and power performance, which remains one of the main hurdles for their widespread implementation in applications outside of powering compact portable devices, such as in electric vehicles. Li-ion batteries must be advanced through a disruptive technological development or a series of incremental improvements in chemistry and design in order to be competitive enough for advanced applications. As it will be introduced in this work, achieving this goal by new chemistries and chemical modifications does not seem to be promising in the short term, so efforts to fully optimize existing systems must be pursued at in parallel. This optimization must be mainly relying on the modification and optimizations of micro and macro structures of current battery systems. This kind of battery architecture study will be even more important when small energy storage devices are desired to power miniaturized and autonomous gadgets, such as MEMs, micro-robots, biomedical sensors, etc. In this regime, the limited space available makes requirements on electrode architecture more stringent and the assembly process more challenging. Therefore, the study of battery assembly strategies for Li-ion microbatteries will benefit not only micro-devices but also the development of more powerful and energetic large scale battery systems based on available chemistries. In chapter 2, preliminary research related to the mechanism for the improved rate capability of cathodes by amorphous lithium phosphate surficial films will be used to motivate the potential for structural optimization of existing commercial lithium ion battery electrode. In the following chapters, novel battery assembly techniques will be explored to achieve new battery architectures. In chapter 3, direct ink writing will be used to fabricate 3D interdigitated microbattery structures that have superior areal energy

An area and power-efficient analog li-ion battery charger circuit.

Science.gov (United States)

Do Valle, Bruno; Wentz, Christian T; Sarpeshkar, Rahul

2011-04-01

The demand for greater battery life in low-power consumer electronics and implantable medical devices presents a need for improved energy efficiency in the management of small rechargeable cells. This paper describes an ultra-compact analog lithium-ion (Li-ion) battery charger with high energy efficiency. The charger presented here utilizes the tanh basis function of a subthreshold operational transconductance amplifier to smoothly transition between constant-current and constant-voltage charging regimes without the need for additional area- and power-consuming control circuitry. Current-domain circuitry for end-of-charge detection negates the need for precision-sense resistors in either the charging path or control loop. We show theoretically and experimentally that the low-frequency pole-zero nature of most battery impedances leads to inherent stability of the analog control loop. The circuit was fabricated in an AMI 0.5-μm complementary metal-oxide semiconductor process, and achieves 89.7% average power efficiency and an end voltage accuracy of 99.9% relative to the desired target 4.2 V, while consuming 0.16 mm(2) of chip area. To date and to the best of our knowledge, this design represents the most area-efficient and most energy-efficient battery charger circuit reported in the literature.

Silicon clathrates for lithium ion batteries: A perspective

International Nuclear Information System (INIS)

Warrier, Pramod; Koh, Carolyn A.

2016-01-01

Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15–20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

Silicon clathrates for lithium ion batteries: A perspective

Science.gov (United States)

Warrier, Pramod; Koh, Carolyn A.

2016-12-01

Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15-20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

Silicon clathrates for lithium ion batteries: A perspective

Energy Technology Data Exchange (ETDEWEB)

Warrier, Pramod, E-mail: pramod.warrier@gmail.com; Koh, Carolyn A. [Center for Hydrate Research, Chemical & Biological Engineering Department, Colorado School of Mines, Golden, Colorado 80401 (United States)

2016-12-15

Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15–20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

Lignin as a Binder Material for Eco-Friendly Li-Ion Batteries

Science.gov (United States)

Lu, Huiran; Cornell, Ann; Alvarado, Fernando; Behm, Mårten; Leijonmarck, Simon; Li, Jiebing; Tomani, Per; Lindbergh, Göran

2016-01-01

The industrial lignin used here is a byproduct from Kraft pulp mills, extracted from black liquor. Since lignin is inexpensive, abundant and renewable, its utilization has attracted more and more attention. In this work, lignin was used for the first time as binder material for LiFePO4 positive and graphite negative electrodes in Li-ion batteries. A procedure for pretreatment of lignin, where low-molecular fractions were removed by leaching, was necessary to obtain good battery performance. The lignin was analyzed for molecular mass distribution and thermal behavior prior to and after the pretreatment. Electrodes containing active material, conductive particles and lignin were cast on metal foils, acting as current collectors and characterized using scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge cycles. Good reversible capacities were obtained, 148 mAh·g−1 for the positive electrode and 305 mAh·g−1 for the negative electrode. Fairly good rate capabilities were found for both the positive electrode with 117 mAh·g−1 and the negative electrode with 160 mAh·g−1 at 1C. Low ohmic resistance also indicated good binder functionality. The results show that lignin is a promising candidate as binder material for electrodes in eco-friendly Li-ion batteries. PMID:28773252

High Energy Density Li-Ion Batteries Designed for Low Temperature Applications, Phase II

Data.gov (United States)

National Aeronautics and Space Administration — The state-of-the-art Li-ion batteries do not fully meet the energy density, power density and safety requirements specified by NASA for future exploration missions....

High Energy Density Solid State Li-ion Battery with Enhanced Safety, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — We propose to develop an all solid state Li-ion battery which is capable of delivering high energy density, combined with high safety over a wide operating...

Heavy ion beam micromachining on LiNbO3

International Nuclear Information System (INIS)

Nesprias, F.; Venturino, M.; Debray, M.E.; Davidson, J.; Davidson, M.; Kreiner, A.J.; Minsky, D.; Fischer, M.; Lamagna, A.

2009-01-01

In this work 3D micromachining of x-cut lithium niobate crystals was performed using the high energy heavy ion microbeam (HIM) at the Tandar Laboratory, Buenos Aires. The samples were machined using 35 Cl beams at 70 MeV bombarding energy combined with wet etching with hydrofluoric acid solutions at room temperature. As the ion beam penetrates the sample, it induces lattice damage increasing dramatically the local etching rate of the material. This technique was applied to the fabrication of 3D waveguides with long control electrodes. The resulting structures indicate that well defined contours with nearly vertical sidewalls can be made. The results also show that with fluences of only 5 x 10 12 ions/cm 2 , this technique is suitable for the fabrication of different shapes of LiNbO 3 control-waveguides that can be used in different optical devices and matched with the existing optical fibers.

Low Li+ Insertion Barrier Carbon for High Energy Efficient Lithium-Ion Capacitor.

Science.gov (United States)

Lee, Wee Siang Vincent; Huang, Xiaolei; Tan, Teck Leong; Xue, Jun Min

2018-01-17

Lithium-ion capacitor (LIC) is an attractive energy-storage device (ESD) that promises high energy density at moderate power density. However, the key challenge in its design is the low energy efficient negative electrode, which barred the realization of such research system in fulfilling the current ESD technological inadequacy due to its poor overall energy efficiency. Large voltage hysteresis is the main issue behind high energy density alloying/conversion-type materials, which reduces the electrode energy efficiency. Insertion-type material though averted in most research due to the low capacity remains to be highly favorable in commercial application due to its lower voltage hysteresis. To further reduce voltage hysteresis and increase capacity, amorphous carbon with wider interlayer spacing has been demonstrated in the simulation result to significantly reduce Li + insertion barrier. Hence, by employing such amorphous carbon, together with disordered carbon positive electrode, a high energy efficient LIC with round-trip energy efficiency of 84.3% with a maximum energy density of 133 Wh kg -1 at low power density of 210 W kg -1 can be achieved.

A mesoporous WO{sub 3−X}/graphene composite as a high-performance Li-ion battery anode

Energy Technology Data Exchange (ETDEWEB)

Liu, Fei [C-Industry Incubation Center, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600 (Korea, Republic of); Kim, Jong Gu [C-Industry Incubation Center, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600 (Korea, Republic of); Department of Fine Chemical Engineering and Applied Chemistry, Chungnam National University, Daejeon 305-764 (Korea, Republic of); Lee, Chul Wee [C-Industry Incubation Center, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600 (Korea, Republic of); University of Science and Technology (UST), Gajeong-ro, Yuseong-gu, Daejeon 305-333 (Korea, Republic of); Im, Ji Sun, E-mail: jsim@krict.re.kr [C-Industry Incubation Center, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600 (Korea, Republic of); University of Science and Technology (UST), Gajeong-ro, Yuseong-gu, Daejeon 305-333 (Korea, Republic of)

2014-10-15

Graphical abstract: The highly flexible and conductive graphene layer can enhance electron transfer, protect metal oxides against disintegration and aggregation and buffer the strain induced by volume expansion during cycles. The mesoporous surface layer provides an open network for Li+ diffusion. - Highlights: • Novel cocktail effects of 2D mesoporous WO{sub 3−X}/graphene for lithium ion battery. • New approach for lithium ion battery by easy and unique synthesis method. • Mechanism study with proper data for understanding a reaction on anode surface. - Abstract: A novel mesoporous WO{sub 3−X}/graphene composite was developed. This material allowed rapid electron and Li{sup +} ion diffusion when used as a Li-ion battery (LIB) anode material. Remarkably, the graphene support protected WO{sub 3−X} from changing volume during the electrochemical cycling process; this process generally induces capacity loss. The current work describes a high-performance anode material for LIB that has highly dense WO{sub 3−X}, as well as high capacity, rate capability and stability.

Biological effects induced by the inner-target reaction of accelerated 7Li+3 ions with wheat embryo

International Nuclear Information System (INIS)

Yang Juncheng; Pan Wei; Zheng Qicheng; Liu Luxiang; Wang Jing; Zhao Linshu; Yu Weixiang; Zhao Wenrong; Bai Xixiang

2004-01-01

Using the mechanism of the nuclear reaction of accelerated 7 Li +3 ions with the inner target in mutant material i.e 1 H( 7 Li, 7 Be)n, the biological effects were studied. The wheat seeds were irradiated with the doses ranged from 1.416 x 10 10 ions/cm 2 to 1.416 x 10 12 ions/cm 2 . It was found that the cell membrane ruptured, the plasmolysis occurred, the nucleus shape changed. The serious changes of the chloroplast were as follows: the membrane protuberance, the grand disorder, the membrane disappearance, crista of mitochondrion rupture etc. by checking of the sub-microstructure of leaf cell. The single micronucleus and multi-micronucleus were observed at the interphase. The chromosome aberrational cells including chromosome fragment, lagging chromosome, chromosome bridge and circular chromosome were found during the mitosis. RAPD analysis of seedling genomic DNA variation in M 2 generation of three mutants showed their DNA sequences had changed. The result confirmed that the implantation of 7 Li +3 ions could induce genetic mutation in wheat

Configuring PSx tetrahedral clusters in Li-excess Li7P3S11 solid electrolyte

Directory of Open Access Journals (Sweden)

Wo Dum Jung

2018-04-01

Full Text Available We demonstrate that the Li-ion conductivity can be improved by adding a certain amount of Li (x = 0.25–0.5 as a charge carrier to the composition of glass-ceramic Li7+xP3S11. Structural analysis clarified that the structural changes caused by the ratio of ortho-thiophosphate tetrahedra PS43− and pyro-thiophosphate ditetrahedra P2S74− affect the Li-ion conductivity. The ratio of PS43− and P2S74− varies depending on x and the highest Li-ion conductivity (2.5 × 10−3 S cm−1 at x = 0.25. All-solid-state LiNi0.8Co0.15Al0.05O2/Li7.25P3S11/In-metal cell exhibits the discharge capacity of 106.2 mAh g−1. This ion conduction enhancement from excess Li is expected to contribute to the future design of sulfide-type electrolytes.

Lithium-ion battery dynamic model for wide range of operating conditions

DEFF Research Database (Denmark)

Stroe, Ana-Irina; Stroe, Daniel-Ioan; Swierczynski, Maciej Jozef

2017-01-01

In order to analyze the dynamic behavior of a Lithium-ion (Li-ion) battery and to determine their suitability for various applications, battery models are needed. An equivalent electrical circuit model is the most common way of representing the behavior of a Li-ion battery. There are different...... characterization tests performed for a wide range of operating conditions (temperature, load current and state-of-charge) on a commercial available 13Ah high-power lithium titanate oxide battery cell. The obtained results were used to parametrize the proposed dynamic model of the battery cell. To assess...

Real-time mass spectroscopy analysis of Li-ion battery electrolyte degradation under abusive thermal conditions

Science.gov (United States)

Gaulupeau, B.; Delobel, B.; Cahen, S.; Fontana, S.; Hérold, C.

2017-02-01

The lithium-ion batteries are widely used in rechargeable electronic devices. The current challenges are to improve the capacity and safety of these systems in view of their development to a larger scale, such as for their application in electric and hybrid vehicles. Lithium-ion batteries use organic solvents because of the wide operating voltage. The corresponding electrolytes are usually based on combinations of linear, cyclic alkyl carbonates and a lithium salt such as LiPF6. It has been reported that in abusive thermal conditions, a catalytic effect of the cathode materials lead to the formation fluoro-organics compounds. In order to understand the degradation phenomenon, the study at 240 °C of the interaction between positive electrode materials (LiCoO2, LiNi1/3Mn1/3Co1/3O2, LiMn2O4 and LiFePO4) and electrolyte in dry and wet conditions has been realized by an original method which consists in analyzing by mass spectrometry in real time the volatile molecules produced. The evolution of specific gases channels coupled to the NMR reveal the formation of rarely discussed species such as 2-fluoroethanol and 1,4-dioxane. Furthermore, it appears that the presence of water or other protic impurities greatly influence their formation.

Contribution to the study of Li{sub x}(Co,M)O{sub 2} phases used as cathodes in Li-ion batteries. Combined effects of the lithium sur-stoichiometry and of the substitution (M = Ni, Mg); Contribution a l'etude des phases Li{sub x}(Co,M)O{sub 2} en tant que materiaux d'electrode positive des batteries Li-ion. Effets combines de la surstoechiometrie en lithium et de la substitution (M = Ni, Mg)

Energy Technology Data Exchange (ETDEWEB)

Levasseur, St.

2001-12-01

Li{sub x0}(Co,M)O{sub 2} (M = Ni, Mg; x0 {<=} 1.0) materials used as positive electrode for Li-ion batteries have been prepared at high temperature (900 degrees C) and characterized by X-ray diffraction, galvano-static measurements, {sup 7}Li MAS NMR spectroscopy and electrical properties measurements. If the results on the LiCoO{sub 2} phase agree with the literature, the adding of an excess of lithium during synthesis leads to the presence in the actual materials to the presence of oxygen vacancies and intermediate spin Co{sup 3+} ions (Co{sup 3+(IS)}) in a square-based environment. This defect suppresses all the phase transitions usually observed upon lithium de-intercalation in Li{sub x}CoO{sub 2}. The partial substitution by Ni ions allows us to separate the relative contribution of Ni(III) and Co{sup 3+(IS)} ions in the suppression of the various phase transitions upon cycling. Mg doping, even without any lithium excess, systematically induces some oxygen vacancies and Co{sup 3+(IS)} ions in the material. This observation had been correlated to the behaviour of the Li{sub x}(Co,Mg)O{sub 2} system upon cycling. (author)

Spectroscopic and quantum-chemical investigation of association of ions in acetonitrile - LiX (X=I, ClO4, NCS) systems

International Nuclear Information System (INIS)

Semenov, S.G.; Solov'eva, L.A.; Akopyan, S.Kh.

1995-01-01

Data on association constants of ions in acetonitrile-salt binary systems, obtained from the data on intensity of IR absorption bands of acetonitrile (Acn) molecules contained in solvate shells of Li + cations, have been analyzed. Using the CCP MO LCAO semiempirical method in the PPDP approximation, electronic structure of acetonitrile molecule and Acn k Li + and Acn m Li + X - complexes has been studied. It is ascertained that relative stability of ionic pairs Acn 3 Li + X - , estimated by the squares of their dipole momenta (characterizing solvation energy) increases in the series X=I, ClO 4 , NCS in agreement with data of spectroscopic experiment, according to which the constant of ion association for LiNCS solution in acetonitrile is much higher than for the systems CH 3 CN-LiI and CH 3 CN-LiClO 4 . 13 refs.,2 figs., 2 tabs.64

Synthesis and characterization of Li2FeP2O7/C nanocomposites as cathode materials for Li-ion batteries

International Nuclear Information System (INIS)

Du, Juan; Jiao, Lifang; Wu, Qiong; Liu, Yongchang; Zhao, Yanping; Guo, Lijing; Wang, Yijing; Yuan, Huatang

2013-01-01

Highlights: • Li 2 FeP 2 O 7 /C were prepared by a simple solid-state reaction. • Carbon coating and reducing particle size are adopted to improve the discharge capacity. • The detailed study about the electrochemical properties of Li 2 FeP 2 O 7 is scarce. • Li 2 FeP 2 O 7 /C show superior electrochemical properties. -- Abstract: The pristine Li 2 FeP 2 O 7 and Li 2 FeP 2 O 7 /C nanocomposites with different content of carbon have been successfully synthesized via a simple solid-state reaction, using cheap glucose as carbon source. XRD and EDS patterns demonstrate the high purity of the products. SEM images exhibit that the size of the particles is about 50–500 nm. Electrochemical measurements reveal that carbon coating and reducing particle size significantly enhance the electrochemical performances of Li 2 FeP 2 O 7 . Particularly, the Li 2 FeP 2 O 7 /C sample with a carbon content of 4.88 wt.% displays the best performance with a specific discharge capacity of 103.1 mAh g −1 at 0.1 C, which is 93.7% of its one-electron theoretical capacity, meaning 110 mAh g −1 . Meanwhile, it shows favorable cycling stability and excellent rate performance, indicating its potential applicability in Li-ion batteries in the long term

Structural and Electrochemical Characterization of Pure LiFePO4 and Nanocomposite C-LiFePO4 Cathodes for Lithium Ion Rechargeable Batteries