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Sample records for advanced li-ion batteries

  1. Novel materials for advanced supercapacitors and Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Yushin, Gleb

    2009-11-01

    High power energy storage devices, such as supercapacitors and Li-ion batteries, are critical for the development of zero-emission electrical vehicles, large scale smart grid, and energy efficient cargo ships and locomotives. The energy storage characteristics of supercapacitors and Li-ion batteries are mostly determined by the specific capacities of their electrodes, while their power characteristics are influenced by the maximum rate of the ion transport. The talk will focus on the development of nanocomposite electrodes capable to improve both the energy and power storage characteristics of the state of the art devices. Advanced ultra-high surface area carbons, carbon-polymer, and carbon-metal oxide nanocomposites have been demonstrated to greatly exceed the specific capacitance of traditional electrodes for supercapacitors. In addition, selected materials showed the unprecedented ultra-fast charging and discharging characteristics. Intelligently designed Si-C composites showed up to 5 times higher specific capacity than graphite, the conventional anode material in Li-ion batteries. Achieving stable performance of Si anodes is commonly a challenge. Recent experiments suggest that individual Si nanoparticles and thin films below a critical size do not fracture and exhibit high reversible capacity for Li. The often observed rapid degradation of Si-based anodes is related not to the intrinsic property of Si but to the loss of electrical contact within the anodes caused by the large volume changes that takes place during Li insertion and extraction. Successful synthesis of high capacity nanocomposite Si-C particles that do not exhibit volume changes during Li insertion and extraction allowed us to achieve stable performance. In order to overcome the limitations of traditional composites precise control over the materials' structure and porosity at the nanoscale was required.

  2. Developing New Electrolytes for Advanced Li-ion Batteries

    NASA Astrophysics Data System (ADS)

    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

  3. Direct synthesis and coating of advanced nanocomposite negative electrodes for Li-ion batteries via electrospraying

    NASA Astrophysics Data System (ADS)

    Valvo, M.; García-Tamayo, E.; Lafont, U.; Kelder, E. M.

    A direct approach for the synthesis and coating of advanced nanocomposite negative electrodes via a single-step process at low temperature is presented. Metal-oxide/PVdF nanocomposites are obtained in one step by electrospray pyrolysis of precursor solutions containing dissolved metal salts together with polyvinylidene fluoride (PVdF) as binder. In this way, small oxide nanoparticles are generated and dispersed in situ in the binder creating nanocomposite structures, while being coated at once as thin electrode layers on stainless steel coin cell cans. The intimate contact between the nanoparticles and the binder favours enhanced adhesion of the materials in the overall electrode structure and adequate electrochemical performances are obtained without any conductive additive. Three nanocomposite oxide/PVdF materials (i.e. SnO 2, CoO and Fe 2O 3) are reported here as preliminary examples of negative electrodes. The results show that this approach is suitable, not only for the fabrication of nanocomposite electrodes for Li-ion batteries, but also for other novel applications.

  4. Ultrathin spinel membrane-encapsulated layered lithium-rich cathode material for advanced Li-ion batteries.

    PubMed

    Wu, Feng; Li, Ning; Su, Yuefeng; Zhang, Linjing; Bao, Liying; Wang, Jing; Chen, Lai; Zheng, Yu; Dai, Liqin; Peng, Jingyuan; Chen, Shi

    2014-06-11

    Lack of high-performance cathode materials has become a technological bottleneck for the commercial development of advanced Li-ion batteries. We have proposed a biomimetic design and versatile synthesis of ultrathin spinel membrane-encapsulated layered lithium-rich cathode, a modification by nanocoating. The ultrathin spinel membrane is attributed to the superior high reversible capacity (over 290 mAh g(-1)), outstanding rate capability, and excellent cycling ability of this cathode, and even the stubborn illnesses of the layered lithium-rich cathode, such as voltage decay and thermal instability, are found to be relieved as well. This cathode is feasible to construct high-energy and high-power Li-ion batteries. PMID:24844948

  5. Highly Flexible Graphene/Mn3O4 Nanocomposite Membrane as Advanced Anodes for Li-Ion Batteries.

    PubMed

    Wang, Jian-Gan; Jin, Dandan; Zhou, Rui; Li, Xu; Liu, Xing-Rui; Shen, Chao; Xie, Keyu; Li, Baohua; Kang, Feiyu; Wei, Bingqing

    2016-06-28

    Advanced electrode design is crucial in the rapid development of flexible energy storage devices for emerging flexible electronics. Herein, we report a rational synthesis of graphene/Mn3O4 nanocomposite membranes with excellent mechanical flexibility and Li-ion storage properties. The strong interaction between the large-area graphene nanosheets and long Mn3O4 nanowires not only enables the membrane to endure various mechanical deformations but also produces a strong synergistic effect of enhanced reaction kinetics by providing enlarged electrode/electrolyte contact area and reduced electron/ion transport resistance. The mechanically robust membrane is explored as a freestanding anode for Li-ion batteries, which delivers a high specific capacity of ∼800 mAh g(-1) based on the total electrode mass, along with superior high-rate capability and excellent cycling stability. A flexible full Li-ion battery is fabricated with excellent electrochemical properties and high flexibility, demonstrating its great potential for high-performance flexible energy storage devices. PMID:27172485

  6. Specification For ST-5 Li Ion Battery

    NASA Technical Reports Server (NTRS)

    Castell, Karen D.; Day, John H. (Technical Monitor)

    2000-01-01

    This Specification defines the general requirements for rechargeable Space Flight batteries intended for use in the ST-5 program. The battery chemistry chosen for this mission is lithium ion (Li-Ion).

  7. Nanotechnology in Li-ion Batteries

    SciTech Connect

    Mukaibo, Hitomi

    2010-06-04

    This is the second of three talks on nanostructures for li-ion batteries. The talks provide an up-to-date review of the issues and challenges facing Li-ion battery research with special focus on how nanostructures/ nanotechnology are being applied to this field. Novel materials reported as prospective candidates for anode, cathode and electrolyte will be summarized. The expected role of nanostructures in improving the performance of Li-ion batteries and the actual pros and cons of using such structures in this device will be addressed. Electrochemical experiments used to study Li-ion batteries will also be discussed. This includes the introduction to the standard experimental set-up and how experimental data (from charge-discharge experiments, cyclic voltammetry, impedance spectroscopy, etc) are interpreted.

  8. Negative Electrodes for Li-Ion Batteries

    SciTech Connect

    Kinoshita, Kim; Zaghib, Karim

    2001-10-01

    Graphitized carbons have played a key role in the successful commercialization of Li-ion batteries. The physicochemical properties of carbon cover a wide range; therefore identifying the optimum active electrode material can be time consuming. The significant physical properties of negative electrodes for Li-ion batteries are summarized, and the relationship of these properties to their electrochemical performance in nonaqueous electrolytes, are discussed in this paper.

  9. Material review of Li ion battery separators

    SciTech Connect

    Weber, Christoph J. Geiger, Sigrid; Falusi, Sandra; Roth, Michael

    2014-06-16

    Separators for Li Ion batteries have a strong impact on cell production, cell performance, life, as well as reliability and safety. The separator market volume is about 500 million m{sup 2} mainly based on consumer applications. It is expected to grow strongly over the next decade for mobile and stationary applications using large cells. At present, the market is essentially served by polyolefine membranes. Such membranes have some technological limitations, such as wettability, porosity, penetration resistance, shrinkage and meltdown. The development of a cell failure due to internal short circuit is potentially closely related to separator material properties. Consequently, advanced separators became an intense area of worldwide research and development activity in academia and industry. New separator technologies are being developed especially to address safety and reliability related property improvements.

  10. Material review of Li ion battery separators

    NASA Astrophysics Data System (ADS)

    Weber, Christoph J.; Geiger, Sigrid; Falusi, Sandra; Roth, Michael

    2014-06-01

    Separators for Li Ion batteries have a strong impact on cell production, cell performance, life, as well as reliability and safety. The separator market volume is about 500 million m2 mainly based on consumer applications. It is expected to grow strongly over the next decade for mobile and stationary applications using large cells. At present, the market is essentially served by polyolefine membranes. Such membranes have some technological limitations, such as wettability, porosity, penetration resistance, shrinkage and meltdown. The development of a cell failure due to internal short circuit is potentially closely related to separator material properties. Consequently, advanced separators became an intense area of worldwide research and development activity in academia and industry. New separator technologies are being developed especially to address safety and reliability related property improvements.

  11. Recent progress in theoretical and computational investigations of Li-ion battery materials and electrolytes.

    PubMed

    Bhatt, Mahesh Datt; O'Dwyer, Colm

    2015-02-21

    There is an increasing worldwide demand for high energy density batteries. In recent years, rechargeable Li-ion batteries have become important power sources, and their performance gains are driving the adoption of electrical vehicles (EV) as viable alternatives to combustion engines. The exploration of new Li-ion battery materials is an important focus of materials scientists and computational physicists and chemists throughout the world. The practical applications of Li-ion batteries and emerging alternatives may not be limited to portable electronic devices and circumventing hurdles that include range anxiety and safety among others, to their widespread adoption in EV applications in the future requires new electrode materials and a fuller understanding of how the materials and the electrolyte chemistries behave. Since this field is advancing rapidly and attracting an increasing number of researchers, it is crucial to summarise the current progress and the key scientific challenges related to Li-ion batteries from theoretical point of view. Computational prediction of ideal compounds is the focus of several large consortia, and a leading methodology in designing materials and electrolytes optimized for function, including those for Li-ion batteries. In this Perspective, we review the key aspects of Li-ion batteries from theoretical perspectives: the working principles of Li-ion batteries, the cathodes, anodes, and electrolyte solutions that are the current state of the art, and future research directions for advanced Li-ion batteries based on computational materials and electrolyte design. PMID:25613366

  12. Recent advances on the understanding of structural and composition evolution of LMR cathodes for Li-ion batteries

    SciTech Connect

    Yan, Pengfei; Zheng, Jianming; Xiao, Jie; Wang, Chong-Min; Zhang, Jiguang

    2015-06-08

    Lithium-rich, magnesium-rich (LMR) cathode materials have been regarded as one of the very promising cathodes for Li-ion battery applications. However, their practical application is still limited by several challenges, especially by their limited electrochemical stability rate capability. In this work, we present recent progresses on the understanding of the structural and composition evolution of LMR cathode materials with emphasis being placed on the correlation between structural/chemical evolution and electrochemical properties. In particular, using Li [Li0.2Ni0.2Mn0.6O2 as a typical example, we clearly illustrate the structural characteristics of the pristine materials and their dependence on the materials processing history, cycling induced structural degradation/chemical partition and their correlation with degradation of electrochemical performance. The fundamental understanding obtained in this work may also guide the design and preparation of new cathode materials based on ternary system of transitional metal oxide.

  13. Advanced technology development program for lithium-ion batteries : thermal abuse performance of 18650 Li-ion cells.

    SciTech Connect

    Crafts, Chris C.; Doughty, Daniel Harvey; McBreen, James.; Roth, Emanuel Peter

    2004-03-01

    Li-ion cells are being developed for high-power applications in hybrid electric vehicles currently being designed for the FreedomCAR (Freedom Cooperative Automotive Research) program. These cells offer superior performance in terms of power and energy density over current cell chemistries. Cells using this chemistry are the basis of battery systems for both gasoline and fuel cell based hybrids. However, the safety of these cells needs to be understood and improved for eventual widespread commercial application in hybrid electric vehicles. The thermal behavior of commercial and prototype cells has been measured under varying conditions of cell composition, age and state-of-charge (SOC). The thermal runaway behavior of full cells has been measured along with the thermal properties of the cell components. We have also measured gas generation and gas composition over the temperature range corresponding to the thermal runaway regime. These studies have allowed characterization of cell thermal abuse tolerance and an understanding of the mechanisms that result in cell thermal runaway.

  14. Recent advances on the understanding of structural and composition evolution of LMR cathodes for Li-ion batteries

    DOE PAGESBeta

    Yan, Pengfei; Zheng, Jianming; Xiao, Jie; Wang, Chong-Min; Zhang, Jiguang

    2015-06-08

    Lithium-rich, magnesium-rich (LMR) cathode materials have been regarded as one of the very promising cathodes for Li-ion battery applications. However, their practical application is still limited by several challenges, especially by their limited electrochemical stability rate capability. In this work, we present recent progresses on the understanding of the structural and composition evolution of LMR cathode materials with emphasis being placed on the correlation between structural/chemical evolution and electrochemical properties. In particular, using Li [Li0.2Ni0.2Mn0.6O2 as a typical example, we clearly illustrate the structural characteristics of the pristine materials and their dependence on the materials processing history, cycling induced structuralmore » degradation/chemical partition and their correlation with degradation of electrochemical performance. The fundamental understanding obtained in this work may also guide the design and preparation of new cathode materials based on ternary system of transitional metal oxide.« less

  15. Screening Li-Ion Batteries for Internal Shorts

    NASA Technical Reports Server (NTRS)

    Darcy, Eric

    2006-01-01

    The extremely high cost of aerospace battery failures due to internal shorts makes it essential that their occurrence be very rare, if not eliminated altogether. With Li-ion cells/batteries, the potentially catastrophic safety hazard that some internal shorts present adds additional incentive for prevention. Prevention can be achieved by design, manufacturing measures, and testing. Specifically for NASA s spacesuit application, a Li-ion polymer pouch cell battery design is in its final stages of production. One of the 20 flight batteries fabricated and tested developed a cell internal short, which did not present a safety hazard, but has required revisiting the entire manufacturing and testing process. Herein are the details of the failure investigation that followed to get to root cause of the internal short and the corrective actions that will be taken. The resulting lessons learned are applicable to most Li-ion battery applications.

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Review on Current State of Li-ion Batteries

    SciTech Connect

    Mukaibo, Hitomi

    2010-06-04

    This is an up-to-date review of the issues and challenges facing Li-ion battery research with special focus on how nanostructures/ nanotechnology are being applied to this field. Novel materials reported as prospective candidates for anode, cathode and electrolyte will be summarized. The expected role of nanostructures in improving the performance of Li-ion batteries and the actual pros and cons of using such structures in this device will be addressed. Electrochemical experiments used to study Li-ion batteries will also be discussed. This includes the introduction to the standard experimental set-up and how experimental data (from charge-discharge experiments, cyclic voltammetry, impedance spectroscopy, etc) are interpreted.

  18. Enhancing Interfacial Bonding between Anisotropically Oriented Grains Using a Glue-Nanofiller for Advanced Li-Ion Battery Cathode.

    PubMed

    Kim, Hyejung; Lee, Sanghan; Cho, Hyeon; Kim, Junhyeok; Lee, Jieun; Park, Suhyeon; Joo, Se Hun; Kim, Su Hwan; Cho, Yoon-Gyo; Song, Hyun-Kon; Kwak, Sang Kyu; Cho, Jaephil

    2016-06-01

    Formation of a glue-nanofiller layer between grains, consisting of a middle-temperature spinel-like Lix CoO2 phase, reinforces the strength of the incoherent interfacial binding between anisotropically oriented grains by enhancing the face-to-face adhesion strength. The cathode treated with the glue-layer exhibits steady cycling performance at both room-temperature and 60 °C. These results represent a step forward in advanced lithium-ion batteries via simple cathode coating. PMID:27074141

  19. COTS Li-Ion Cells in High Voltage Batteries

    NASA Technical Reports Server (NTRS)

    Davies, Francis; Darcy, Eric; Jeevarajan, Judy; Cowles, Phil

    2003-01-01

    Testing at NASA JSC and COMDEV shows that Commercial Off the Shelf (COTS) Li Ion cells can not be used in high voltage batteries safely without considering the voltage stresses that may be put on the protective devices in them during failure modes.

  20. Potential Alternatives for Advanced Energy Material Processing in High Performance Li-ion Batteries (LIBs) via Atmospheric Pressure Plasma Treatment

    NASA Astrophysics Data System (ADS)

    Duh, Jenq-Gong; Chuang, Shang-I.; Lan, Chun-Kai; Yang, Hao; Chen, Hsien-Wei

    2015-09-01

    A new processing technique by atmospheric pressure plasma (APP) jet treatment of LIBs was introduced. Ar/N2 plasma enhanced the high-rate anode performance of Li4Ti5O12. Oxygen vacancies were discovered and nitrogen doping were achieved by the surface reaction between pristine Li4Ti5O12 and plasma reactive species (N* and N2+). Electrochemical impedance spectra confirm that plasma modification increases Li ions diffusivity and reduces internal charge-transfer resistance, leading to a superior capacity (132 mAh/g) and excellent stability with negligible capacity decay over 100 cycles under 10C rate. Besides 2D material surface treatment, a specially designed APP generator that are feasible to modify 3D TiO2 powders is proposed. The rate capacity of 20 min plasma treated TiO2 exhibited 20% increment. Plasma diagnosis revealed that excited Ar and N2 was contributed to TiO2 surface reduction as companied by formation of oxygen vacancy. A higher amount of oxygen vacancy increased the chance for excited nitrogen doped onto surface of TiO2 particle. These findings promote the understanding of APP on processing anode materials in high performance LIBs.

  1. Core-shell nano-FeS2@N-doped graphene as an advanced cathode material for rechargeable Li-ion batteries.

    PubMed

    Tan, Rui; Yang, Jinlong; Hu, Jiangtao; Wang, Kai; Zhao, Yan; Pan, Feng

    2016-01-18

    We report the formation of core-shell nano-FeS2@N-doped graphene as a novel cathode material and its mechanism for use in rechargeable Li-ion batteries. A benefit of the amount of FeS2 nano-crystals as the core for Li-ion storage with high capacity and using coated N-doped graphene as the shell is that FeS2@N-graphene exhibits a remarkable specific energy (950 W h kg(-1) at 0.15 kW g(-1)) and higher specific power (543 W h kg(-1) at 2.79 kW g(-1)) than commercial rechargeable LIB cathodes, as well as stable cycling performance (∼600 W h kg(-1) at 0.75 kW g(-1) after 400 cycles). PMID:26592428

  2. Predictive Models of Li-ion Battery Lifetime

    SciTech Connect

    Smith, Kandler; Wood, Eric; Santhanagopalan, Shriram; Kim, Gi-heon; Shi, Ying; Pesaran, Ahmad

    2015-06-15

    It remains an open question how best to predict real-world battery lifetime based on accelerated calendar and cycle aging data from the laboratory. Multiple degradation mechanisms due to (electro)chemical, thermal, and mechanical coupled phenomena influence Li-ion battery lifetime, each with different dependence on time, cycling and thermal environment. The standardization of life predictive models would benefit the industry by reducing test time and streamlining development of system controls.

  3. Predictive Models of Li-ion Battery Lifetime (Presentation)

    SciTech Connect

    Smith, K.; Wood, E.; Santhanagopalan, S.; Kim, G.; Shi, Y.; Pesaran, A.

    2014-09-01

    Predictive models of Li-ion battery reliability must consider a multiplicity of electrochemical, thermal and mechanical degradation modes experienced by batteries in application environments. Complicating matters, Li-ion batteries can experience several path dependent degradation trajectories dependent on storage and cycling history of the application environment. Rates of degradation are controlled by factors such as temperature history, electrochemical operating window, and charge/discharge rate. Lacking accurate models and tests, lifetime uncertainty must be absorbed by overdesign and warranty costs. Degradation models are needed that predict lifetime more accurately and with less test data. Models should also provide engineering feedback for next generation battery designs. This presentation reviews both multi-dimensional physical models and simpler, lumped surrogate models of battery electrochemical and mechanical degradation. Models are compared with cell- and pack-level aging data from commercial Li-ion chemistries. The analysis elucidates the relative importance of electrochemical and mechanical stress-induced degradation mechanisms in real-world operating environments. Opportunities for extending the lifetime of commercial battery systems are explored.

  4. Hierarchical self-assembled structures based on nitrogen-doped carbon nanotubes as advanced negative electrodes for Li-ion batteries and 3D microbatteries

    NASA Astrophysics Data System (ADS)

    Sharifi, Tiva; Valvo, Mario; Gracia-Espino, Eduardo; Sandström, Robin; Edström, Kristina; Wågberg, Thomas

    2015-04-01

    Hierarchical structures based on carbon paper and multi-walled nitrogen-doped carbon nanotubes were fabricated and subsequently decorated with hematite nanorods to obtain advanced 3D architectures for Li-ion battery negative electrodes. The carbon paper provides a versatile metal-free 3D current collector ensuring a good electrical contact of the active materials to its carbon fiber network. Firstly, the nitrogen-doped carbon nanotubes onto the carbon paper were studied and a high footprint area capacity of 2.1 mAh cm-2 at 0.1 mA cm-2 was obtained. The Li can be stored in the inter-wall regions of the nanotubes, mediated by the defects formed on their walls by the nitrogen atoms. Secondly, the incorporation of hematite nanorods raised the footprint area capacity to 2.25 mAh cm-2 at 0.1 mA cm-2. However, the repeated conversion/de-conversion of Fe2O3 limited both coulombic and energy efficiencies for these electrodes, which did not perform as well as those including only the N-doped carbon nanotubes at higher current densities. Thirdly, long-cycling tests showed the robust Li insertion mechanism in these N-doped carbonaceous structures, which yielded an unmatched footprint area capacity enhancement up to 1.95 mAh cm-2 after 60 cycles at 0.3 mA cm-2 and an overall capacity of 204 mAh g-1 referred to the mass of the entire electrode.

  5. Green Template-Free Synthesis of Hierarchical Shuttle-Shaped Mesoporous ZnFe2 O4 Microrods with Enhanced Lithium Storage for Advanced Li-Ion Batteries.

    PubMed

    Hou, Linrui; Hua, Hui; Lian, Lin; Cao, Hui; Zhu, Siqi; Yuan, Changzhou

    2015-09-01

    In the work, a facile and green two-step synthetic strategy was purposefully developed to efficiently fabricate hierarchical shuttle-shaped mesoporous ZnFe2 O4 microrods (MRs) with a high tap density of ∼0.85 g cm(3) , which were assembled by 1D nanofiber (NF) subunits, and further utilized as a long-life anode for advanced Li-ion batteries. The significant role of the mixed solvent of glycerin and water in the formation of such hierarchical mesoporous MRs was systematically investigated. After 488 cycles at a large current rate of 1000 mA g(-1) , the resulting ZnFe2 O4 MRs with high loading of ∼1.4 mg per electrode still preserved a reversible capacity as large as ∼542 mAh g(-1) . Furthermore, an initial charge capacity of ∼1150 mAh g(-1) is delivered by the ZnFe2 O4 anode at 100 mA g(-1) , resulting in a high Coulombic efficiency of ∼76 % for the first cycle. The superior Li-storage properties of the as-obtained ZnFe2 O4 were rationally associated with its mesoprous micro-/nanostructures and 1D nanoscaled building blocks, which accelerated the electron transportation, facilitated Li(+) transfer rate, buffered the large volume variations during repeated discharge/charge processes, and provided rich electrode-electrolyte sur-/interfaces for efficient lithium storage, particularly at high rates. PMID:26220562

  6. Li-ion rechargeable batteries on Mars Exploration Rovers

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar; Smart, M.; Whitacanack, L.; Ewell, R.; Surampudi, S.

    2006-01-01

    Lithium-ion batteries have contributed significantly to the success of NASA's Mars Rovers, Spirit and Opportunity that have been exploring the surface of Mars for the last two years and performing astounding geological studies to answer the ever-puzzling questions of life beyond Earth and the origin of our planets. Combined with the triple-junction solar cells, the lithium-ion batteries have been powering the robotic rovers, and assist in keeping the rover electronics warm, and in supporting nighttime experimentation and communications. The use of Li-ion batteries has resulted in significant benefits in several categories, such as mass, volume, energy efficiency, self discharge, and above all low temperature performance. Designed initially for the primary mission needs of 300 cycles over 90 days of surface operation, the batteries have been performing admirably, over the last two years. After about 670 days of exploration and at least as many cycles, there is little change in the end-of discharge (EOD) voltages or capacities of these batteries, as estimated from the in-flight data and corroborated by ground testing. Aided by such impressive durability from the Li-ion batteries, both from cycling and calendar life stand point, these rovers are poised to extend their exploration well beyond two years. In this paper, we will describe the performance characteristics of these batteries during launch, cruise phase and on the surface of Mars thus far.

  7. Li-Ion Battery Cathodes: Enhancing Interfacial Bonding between Anisotropically Oriented Grains Using a Glue-Nanofiller for Advanced Li-Ion Battery Cathode (Adv. Mater. 23/2016).

    PubMed

    Kim, Hyejung; Lee, Sanghan; Cho, Hyeon; Kim, Junhyeok; Lee, Jieun; Park, Suhyeon; Joo, Se Hun; Kim, Su Hwan; Cho, Yoon-Gyo; Song, Hyun-Kon; Kwak, Sang Kyu; Cho, Jaephil

    2016-06-01

    The formation of a spinel Lix CoO2 layer in a Ni-rich secondary particle for lithium-ion batteries is reported by S. K. Kwak, J. Cho, and co-workers on page 4705, who find that the spinel-like Lix CoO2 layer, between layered primary particles, can enhance the mechanical strength of secondary particles by enhancing the interfacial binding energy among the grains. Moreover, the layer can effectively protect the unstable surface of the primary particles and offers a fast electron-ion pathway, resulting in overall enhancements of stability and kinetics in battery performance. PMID:27281047

  8. Probing anode degradation in automotive Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Kwon, Ou Jung

    The lithium-ion battery is drawing attention as a power source for future clean and fuel-efficient vehicles. Although the Li-ion battery presently shows best performance for energy density and power density compared to other rechargeable batteries, some degradation problems still remain as key challenges for long-term durability in automotive applications. Among those problems, Li deposition is well known for causing permanent capacity loss. Fundamental mechanisms of Li deposition in the carbon anode are, however, not fully understood, especially at subzero temperature and/or under high rate charge. This dissertation introduces comprehensive study of Li deposition using automotive 18650 Li-ion cells. The mechanism and relevant diagnostic methods as well as preventive charging protocol are discussed. In part one, a new diagnostic tool is introduced utilizing 3-electrode cell system, which measures thermodynamic and kinetic parameters of cathode and anode, respectively, as a function of temperature and SOC (state of charge): open circuit potential (OCP); Li diffusion coefficient in active particles; and internal resistance. These data are employed to understand electrochemical reaction and its thermal interaction under charging conditions that result in Li deposition. Part two provides a threshold parameter for the onset of Li deposition, which is not commonly used anode potential but charge capacity, or more specifically the amount of Li+ ions participating in intercalation reaction without Li deposition at given charging circumstances. This is called the critical charge capacity in this thesis, beyond which capacity loss at normal operating condition is observed, which becomes more serious as temperature is lowered and/or charge C-rate increases. Based on these experimental results, the mechanism of Li deposition is proposed as the concept of anode particle surface saturation, meaning that once the anode particle surface is saturated with Li in any charging

  9. Novel Energy Sources -Material Architecture and Charge Transport in Solid State Ionic Materials for Rechargeable Li ion Batteries

    SciTech Connect

    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.

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

    NASA Technical Reports Server (NTRS)

    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.

  11. Polymer electrolyte-based Li ion batteries for space power

    NASA Astrophysics Data System (ADS)

    Abraham, K. M.; Choe, H. S.; Pasquariello, D. M.

    1997-01-01

    Polyacrylonitrile-based electrolytes have been identified to be appropriate for the fabrication of solid-state Li ion batteries. Prototype battery cells have been fabricated with spinel LiMn2O4 cathode and either a graphite or a petroleum coke anode. Lower capacity fade and longer cycle life were observed in the petroleum coke-based cells. A specific energy of >120 Wh/kg and a cycle life of >500 cycles at the C/3 rate have been demonstrated in these cells. The capacity fade rate in coke/LiMn2O4 cells has been found to be between 0.04 and 0.05% per cycle, about half of that in cells with the graphite anode.

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

    SciTech Connect

    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.

  13. Conjugated dicarboxylate anodes for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Armand, M.; Grugeon, S.; Vezin, H.; Laruelle, S.; Ribière, P.; Poizot, P.; Tarascon, J.-M.

    2009-02-01

    Present Li-ion batteries for portable electronics are based on inorganic electrodes. For upcoming large-scale applications the notion of materials sustainability produced by materials made through eco-efficient processes, such as renewable organic electrodes, is crucial. We here report on two organic salts, Li2C8H4O4 (Li terephthalate) and Li2C6H4O4(Li trans-trans-muconate), with carboxylate groups conjugated within the molecular core, which are respectively capable of reacting with two and one extra Li per formula unit at potentials of 0.8 and 1.4V, giving reversible capacities of 300 and 150mAhg-1. The activity is maintained at 80∘C with polyethyleneoxide-based electrolytes. A noteworthy advantage of the Li2C8H4O4 and Li2C6H4O4 negative electrodes is their enhanced thermal stability over carbon electrodes in 1M LiPF6 ethylene carbonate-dimethyl carbonate electrolytes, which should result in safer Li-ion cells. Moreover, as bio-inspired materials, both compounds are the metabolites of aromatic hydrocarbon oxidation, and terephthalic acid is available in abundance from the recycling of polyethylene terephthalate.

  14. Scanning electrochemical microscopy of Li-ion batteries.

    PubMed

    Ventosa, E; Schuhmann, W

    2015-11-21

    Li-ion batteries (LIBs) are receiving increasing attention over the past decade due to their high energy density. This energy storage technology is expected to continue improving the performance, especially for its large-scale deployment in plug-in hybrid electric vehicles (PHEVs) and full electric vehicles (EVs). Such improvement requires having a large variety of analytical techniques at scientists' disposal in order to understand and address the multiple mechanisms and processes occurring simultaneously in this complex system. This perspective article aims to highlight the strength and potential of scanning electrochemical microscopy (SECM) in this field. After a brief description of a LIB system and the most commonly used techniques in this field, the unique information provided by SECM is illustrated by discussing several recent examples from the literature. PMID:26076998

  15. Nanostructured electrode materials for Li-ion battery

    NASA Astrophysics Data System (ADS)

    Balaya, Palani; Saravanan, Kuppan; Hariharan, Srirama

    2010-04-01

    Nanostructured materials have triggered a great excitement in recent times due to both fundamental interest as well as technological impact relevant for lithium ion batteries (LIBs). Size reduction in nanocrystals leads to a variety of unexpected exciting phenomena due to enhanced surface-to-volume ratio and reduced transport length. We will consider a few examples of nanostructured electrode materials in the context of lithium batteries for achieving high storage and high rate performances: 1) LiFePO4 nanoplates synthesized using solvothermal method could store Li-ions comparable to its theoretical capacity at C/10, while at 30C, they exhibit storage capacity up to 45 mAh/g. Size reduction (~30 nm) at the b-axis favors the fast Li-ion diffusion. In addition to this, uniform ~5 nm carbon coating throughout the plates provides excellent electronically conducting path for electrons. This nano architecture enables fast insertion/extraction of both Li-ions as well as electrons; 2) Mesporous-TiO2 with high surface area (135m2/g) synthesized using soft-template method exhibits high volumetric density compared to commercial nanopowder (P25), with excellent Li-storage behavior. C16 meso-TiO2 synthesized from CTAB exhibits reversible storage capacity of 288mAh/g at 0.2C and 109 mAh/g at 30C; 3) Zero strain Li4Ti5O12 anode material has been synthesized using several wet chemical routes. The best condition has been optimized to achieve storage capability close to theoretical limit of 175mAh/g at C/10. At 10C, we could retain lithium storage up to 88 mAh/g; 4) We report our recent results on α-Fe2O3 and γ-Fe2O3 using conversion reaction, providing insight for a better storage capability in γ-phase than the α-phase at 2C resulting solely from the nanocrystallinity.

  16. Current and Prospective Li-Ion Battery Recycling and Recovery Processes

    NASA Astrophysics Data System (ADS)

    Heelan, Joseph; Gratz, Eric; Zheng, Zhangfeng; Wang, Qiang; Chen, Mengyuan; Apelian, Diran; Wang, Yan

    2016-06-01

    The lithium ion (Li-ion) battery industry has been growing exponentially since its initial inception in the late 20th century. As battery materials evolve, the applications for Li-ion batteries have become even more diverse. To date, the main source of Li-ion battery use varies from consumer portable electronics to electric/hybrid electric vehicles. However, even with the continued rise of Li-ion battery development and commercialization, the recycling industry is lagging; approximately 95% of Li-ion batteries are landfilled instead of recycled upon reaching end of life. Industrialized recycling processes are limited and only capable of recovering secondary raw materials, not suitable for direct reuse in new batteries. Most technologies are also reliant on high concentrations of cobalt to be profitable, and intense battery sortation is necessary prior to processing. For this reason, it is critical that a new recycling process be commercialized that is capable of recovering more valuable materials at a higher efficiency. A new technology has been developed by the researchers at Worcester Polytechnic Institute which is capable of recovering LiNi x Mn y Co z O2 cathode material from a hydrometallurgical process, making the recycling system as a whole more economically viable. By implementing a flexible recycling system that is closed-loop, recycling of Li-ion batteries will become more prevalent saving millions of pounds of batteries from entering the waste stream each year.

  17. NREL's PHEV/EV Li-Ion Battery Secondary-Use Project

    SciTech Connect

    Newbauer, J.; Pesaran, A.

    2010-06-01

    Accelerated development and market penetration of plug-in hybrid electric vehicles (PHEVs) and electric vehicles (EVs) is 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 Li-ion battery's cost via reuse in other applications after it is retired from service in the vehicle, when the battery may still have sufficient performance to meet the requirements of other energy storage applications.

  18. High energy xLi2MnO3-(1-x)LiNi2/3Co1/6Mn1/6O2 composite cathode for advanced Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Shojan, Jifi; Chitturi, Venkateswara Rao; Soler, Jess; Resto, Oscar; West, William C.; Katiyar, Ram S.

    2015-01-01

    Novel composite cathode materials, xLi2MnO3-(1-x)LiNi2/3Co1/6Mn1/6O2 (where x = 0.3, 0.5, and 0.7), were synthesized by sol-gel route and characterized by advanced techniques for rechargeable Li-ion battery applications. Phase purity of the composites was examined by XRD as well as Raman spectroscopy and the studies revealed good crystallinity and the formation of pure composite phases with monoclinic (C2/m) and hexagonal (R3m) crystal structures for Li2MnO3 and LiNi2/3Co1/6Mn1/6O2, respectively. Polyhedral agglomerates seen in the scanning and transmission electron microscopic images elucidated the better electrochemical properties of the composites. Valence states of transition metals in the composites were examined by X-ray photoelectron spectroscopy and the analysis suggested predominant oxidation states of Ni, Co, and Mn as 2+, 3+, and 4+, respectively. Galvanostatic charge-discharge tests, performed at different C-rates between 2.0 and 4.8 V, indicated high discharge capacity (∼250 mAh g-1), good rate capability, and excellent cycleability of the composite with x = 0.5 compared to the composites with x = 0.3 and 0.7. In-situ Raman spectroscopic studies revealed the activation of Li2MnO3 component in all composite cathode materials during the first cycle charging process with structural stability thereby enhancing performance of the composite with x = 0.5. These results demonstrated the feasibility of using 0.5Li2MnO3-0.5LiNi2/3Co1/6Mn1/6O2 composite as advanced cathode for high power Li-ion batteries.

  19. The Li-ion rechargeable battery: a perspective.

    PubMed

    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

  20. Perspectives on Li and transition metal fluoride phosphates as cathode materials for a new generation of Li-ion batteries.

    PubMed

    Antipov, Evgeny V; Khasanova, Nellie R; Fedotov, Stanislav S

    2015-01-01

    To satisfy the needs of rapidly growing applications, Li-ion batteries require further significant improvements of their key properties: specific energy and power, cyclability, safety and costs. The first generation of cathode materials for Li-ion batteries based on mixed oxides with either spinel or rock-salt derivatives has already been widely commercialized, but the potential to improve the performance of these materials further is almost exhausted. Li and transition metal inorganic compounds containing different polyanions are now considered as the most promising cathode materials for the next generation of Li-ion batteries. Further advances in cathode materials are considered to lie in combining different anions [such as (XO4) (n-) and F(-)] in the anion sublattice, which is expected to enhance the specific energy and power of these materials. This review focuses on recent advances related to the new class of cathode materials for Li-ion batteries containing phosphate and fluoride anions. Special attention is given to their crystal structures and the relationships between structure and properties, which are important for their possible practical applications. PMID:25610630

  1. Perspectives on Li and transition metal fluoride phosphates as cathode materials for a new generation of Li-ion batteries

    PubMed Central

    Antipov, Evgeny V.; Khasanova, Nellie R.; Fedotov, Stanislav S.

    2015-01-01

    To satisfy the needs of rapidly growing applications, Li-ion batteries require further significant improvements of their key properties: specific energy and power, cyclability, safety and costs. The first generation of cathode materials for Li-ion batteries based on mixed oxides with either spinel or rock-salt derivatives has already been widely commercialized, but the potential to improve the performance of these materials further is almost exhausted. Li and transition metal inorganic compounds containing different polyanions are now considered as the most promising cathode materials for the next generation of Li-ion batteries. Further advances in cathode materials are considered to lie in combining different anions [such as (XO4)n− and F−] in the anion sublattice, which is expected to enhance the specific energy and power of these materials. This review focuses on recent advances related to the new class of cathode materials for Li-ion batteries containing phosphate and fluoride anions. Special attention is given to their crystal structures and the relationships between structure and properties, which are important for their possible practical applications. PMID:25610630

  2. Red Mud and Li-Ion Batteries: A Magnetic Connection.

    PubMed

    Suryawanshi, Anil; Aravindan, Vanchiappan; Madhavi, Srinivasan; Ogale, Satishchandra

    2016-08-23

    Exceptional Li-ion battery performance is presented with the oxide component of the anode was extracted from red mud by simple magnetic separation and applied directly without any further processing. The extracted material has γ-Fe2 O3 as the major phase with inter-dispersed phases of Ti, Al, and Si oxides. In a half-cell assembly, the phase displayed a reversible capacity (∼697 mA h g(-1) ) with excellent stability upon cycling. Interestingly, the stability is rendered by the multiphase constitution of the material with the presence of other electrochemically inactive metal oxides, such as Al2 O3 , SiO2 , and Fe2 TiO4 , which could accommodate the strain and facilitate release during the charge-discharge processes in the electrochemically active maghemite component. We fabricated the full-cell assembly with eco-friendly cathode LiMn2 O4 by adjusting the mass loading. Prior to full-cell assembly, an electrochemical pre-lithiation was enforced to overcome the irreversible capacity loss obtained from the anode. The full-cell delivered a capacity of ∼100 mA h g(-1) (based on cathode loading) with capacity retention of ∼61 % after 2000 cycles under ambient conditions. PMID:27403736

  3. Battery-level material cost model facilitates high-power li-ion battery cost reductions.

    SciTech Connect

    Henriksen, G.; Chemical Engineering

    2003-01-01

    Under the FreedomCAR Partnership, Argonne National Laboratory (ANL) is working to identify and develop advanced anode, cathode, and electrolyte components that can significantly reduce the cost of the cell chemistry, while simultaneously enhancing the calendar life and inherent safety of high-power Li-Ion batteries. Material cost savings are quantified and tracked via the use of a cell and battery design model that establishes the quantity of each material needed in batteries designed to meet the requirements of hybrid electric vehicles (HEVs). In order to quantify the material costs, relative to the FreedomCAR battery cost goals, ANL uses (1) laboratory cell performance data, (2) its battery design model and (3) battery manufacturing process yields to create battery-level material cost models. Using these models and industry-supplied material cost information, ANL assigns battery-level material costs for different cell chemistries. These costs can then be compared to the battery cost goals to determine the probability of meeting the goals with these cell chemistries. The most recent freedomCAR cost goals for 25-kW and 40-kW power-assist HEV batteries are $500 and $800, respectively, which is $20/kW in both cases. In 2001, ANL developed a high-power cell chemistry that was incorporated into high-power 18650 cells for use in extensive accelerated aging and thermal abuse characterization studies. This cell chemistry serves as a baseline for this material cost study. It incorporates a LiNi0.8Co0.15Al0.05O2 cathode, a synthetic graphite anode, and a LiPF6 in EC:EMC electrolyte. Based on volume production cost estimates for these materials-as well as those for binders/solvents, cathode conductive additives, separator, and current collectors--the total cell winding material cost for a 25-kW power-assist HEV battery is estimated to be $399 (based on a 48- cell battery design, each cell having a capacity of 15.4 Ah). This corresponds to {approx}$16/kW. Our goal is to

  4. Silicon Based Anodes for Li-Ion Batteries

    SciTech Connect

    Zhang, Jiguang; Wang, Wei; Xiao, Jie; Xu, Wu; Graff, Gordon L.; Yang, Zhenguo; Choi, Daiwon; Li, Xiaolin; Wang, Deyu; Liu, Jun

    2012-06-15

    Silicon is environmentally benign and ubiquitous. Because of its high specific capacity, it is considered one of the most promising candidates to replace the conventional graphite negative electrode used in today's Li ion batteries. Silicon has a theoretical specific capacity of nearly 4200 mAh/g (Li21Si5), which is 10 times larger than the specific capacity of graphite (LiC6, 372 mAh/g). However, the high capacity of silicon is associated with huge volume changes (more than 300 percent) when alloyed with lithium, which can cause severe cracking and pulverization of the electrode and lead to significant capacity loss. Significant scientific research has been conducted to circumvent the deterioration of silicon based anode materials during cycling. Various strategies, such as reduction of particle size, generation of active/inactive composites, fabrication of silicon based thin films, use of alternative binders, and the synthesis of 1-D silicon nanostructures have been implemented by a number of research groups. Fundamental mechanistic research has also been performed to better understand the electrochemical lithiation and delithiation process during cycling in terms of crystal structure, phase transitions, morphological changes, and reaction kinetics. Although efforts to date have not attained a commercially viable Si anode, further development is expected to produce anodes with three to five times the capacity of graphite. In this chapter, an overview of research on silicon based anodes used for lithium-ion battery applications will be presented. The overview covers electrochemical alloying of the silicon with lithium, mechanisms responsible for capacity fade, and methodologies adapted to overcome capacity degradation observed during cycling. The recent development of silicon nanowires and nanoparticles with significantly improved electrochemical performance will also be discussed relative to the mechanistic understanding. Finally, future directions on the

  5. Synthesis and electrochemical properties of vanadium oxide materials and structures as Li-ion battery positive electrodes

    NASA Astrophysics Data System (ADS)

    McNulty, David; Buckley, D. Noel; O'Dwyer, Colm

    2014-12-01

    The electrochemical intercalation of lithium into vanadium pentoxide was first reported in the 1970's. Over the last 40 years vanadium oxides have continued to be the subject of much research due to their desirable physical properties. Initial results with bulk V2O5 and V2O5 gels demonstrated the potential for application as a cathode material for lithium batteries. Encouraging specific capacities exceeding 250 mAh g-1 were accompanied by severe capacity fading, which prevented widespread commercial application of V2O5-containing cathodes. Following the commercial release of the Li-ion battery, the development of layered materials that reversibly intercalated lithium, and the resurgence in nanoscale materials for Li-ion and alternative batteries, have opened new opportunities for the examination of the influence of material structure on cell performance. Recent decades have witnessed advances in the control of shape, structure and function of Li-ion battery materials. This review details the synthesis and structural properties of vanadium oxides, one of the model layered battery materials, and reviews the synthesis and structure of vanadium oxides and related polymorphs, bronzes and phases. Their electrochemical characteristics under a wide range of conditions are assessed and compared as positive electrode materials in lithium and lithium-ion batteries up to the present day.

  6. Li-Ion Battery and Supercapacitor Hybrid Design for Long Extravehicular Activities

    NASA Technical Reports Server (NTRS)

    Jeevarajan, Judith

    2013-01-01

    With the need for long periods of extravehicular activities (EVAs) on the Moon or Mars or a near-asteroid, the need for long-performance batteries has increased significantly. The energy requirements for the EVA suit, as well as surface systems such as rovers, have increased significantly due to the number of applications they need to power at the same time. However, even with the best state-of-the-art Li-ion batteries, it is not possible to power the suit or the rovers for the extended period of performance. Carrying a charging system along with the batteries makes it cumbersome and requires a self-contained power source for the charging system that is usually not possible. An innovative method to charge and use the Li-ion batteries for long periods seems to be necessary and hence, with the advent of the Li-ion supercapacitors, a method has been developed to extend the performance period of the Li-ion power system for future exploration applications. The Li-ion supercapacitors have a working voltage range of 3.8 to 2.5 V, and are different from a traditional supercapacitor that typically has a working voltage of 1 V. The innovation is to use this Li-ion supercapacitor to charge Liion battery systems on an as-needed basis. The supercapacitors are charged using solar arrays and have battery systems of low capacity in parallel to be able to charge any one battery system while they provide power to the application. Supercapacitors can safely take up fast charge since the electrochemical process involved is still based on charge separation rather than the intercalation process seen in Li-ion batteries, thus preventing lithium metal deposition on the anodes. The lack of intercalation and eliminating wear of the supercapacitors allows for them to be charged and discharged safely for a few tens of thousands of cycles. The Li-ion supercapacitors can be charged from the solar cells during the day during an extended EVA. The Liion battery used can be half the capacity

  7. Biomineralized multifunctional magnetite/carbon microspheres for applications in Li-ion batteries and water treatment.

    PubMed

    Shim, Hyun-Woo; Park, Sangbaek; Song, Hee Jo; Kim, Jae-Chan; Jang, Eunjin; Hong, Kug Sun; Kim, T Doohun; Kim, Dong-Wan

    2015-03-16

    Advanced functional materials incorporating well-defined multiscale architectures are a key focus for multiple nanotechnological applications. However, strategies for developing such materials, including nanostructuring, nano-/microcombination, hybridization, and so on, are still being developed. Here, we report a facile, scalable biomineralization process in which Micrococcus lylae bacteria are used as soft templates to synthesize 3D hierarchically structured magnetite (Fe3O4) microspheres for use as Li-ion battery anode materials and in water treatment applications. Self-assembled Fe3O4 microspheres with flower-like morphologies are systematically fabricated from biomineralized 2D FeO(OH) nanoflakes at room temperature and are subsequently subjected to post-annealing at 400 °C. In particular, because of their mesoporous properties with a hollow interior and the improved electrical conductivity resulting from the carbonized bacterial templates, the Fe3 O4 microspheres obtained by calcining the FeO(OH) in Ar exhibit enhanced cycle stability and rate capability as Li-ion battery anodes, as well as superior adsorption of organic pollutants and toxic heavy metals. PMID:25676609

  8. Mechanical-electrochemical modeling of Li-ion battery designed for an electric scooter

    NASA Astrophysics Data System (ADS)

    Khateeb, Siddique A.; Farid, Mohammed M.; Selman, J. Robert; Al-Hallaj, Said

    A macroscopic electrochemical-mechanical model was developed to predict the various power demands of an electric scooter and other outputs, such as the Li-ion battery pack current and voltage requirements for a randomly generated drive cycle using the Matlab-based Simulink software. The simulation results obtained were compared with the actual field test results of a commercial lead-acid battery pack used in a specific electric scooter. The simulation results appeared to give a realistic idea of the dynamic performance of a conceptual Li-ion battery pack in a typical drive pattern. These results, though, need to be validated in an actual field test.

  9. Mathematical Modeling of Ni/H2 and Li-Ion Batteries

    NASA Technical Reports Server (NTRS)

    Weidner, John W.; White, Ralph E.; Dougal, Roger A.

    2001-01-01

    The modelling effort outlined in this viewgraph presentation encompasses the following topics: 1) Electrochemical Deposition of Nickel Hydroxide; 2) Deposition rates of thin films; 3) Impregnation of porous electrodes; 4) Experimental Characterization of Nickel Hydroxide; 5) Diffusion coefficients of protons; 6) Self-discharge rates (i.e., oxygen-evolution kinetics); 7) Hysteresis between charge and discharge; 8) Capacity loss on cycling; 9) Experimental Verification of the Ni/H2 Battery Model; 10) Mathematical Modeling Li-Ion Batteries; 11) Experimental Verification of the Li-Ion Battery Model; 11) Integrated Power System Models for Satellites; and 12) Experimental Verification of Integrated-Systems Model.

  10. Composite Cathodes for Dual-Rate Li-Ion Batteries

    NASA Technical Reports Server (NTRS)

    Whitacre, Jay; West, William; Bugga, Ratnakumar

    2008-01-01

    Composite-material cathodes that enable Li-ion electrochemical cells and batteries to function at both high energy densities and high discharge rates are undergoing development. Until now, using commercially available cathode materials, it has been possible to construct cells that have either capability for high-rate discharge or capability to store energy at average or high density, but not both capabilities. However, both capabilities are needed in robotic, standby-power, and other applications that involve duty cycles that include long-duration, low-power portions and short-duration, high-power portions. The electrochemically active ingredients of the present developmental composite cathode materials are: carbon-coated LiFePO4, which has a specific charge capacity of about 160 mA h/g and has been used as a high-discharge-rate cathode material and Li[Li(0.17)Mn(0.58)Ni(0.25)]O2, which has a specific charge capacity of about 240 mA h/g and has been used as a high-energy-density cathode material. In preparation for fabricating the composite material cathode described, these electrochemically active ingredients are incorporated into two sub-composites: a mixture comprising 10 weight percent of poly(vinylidine fluoride); 10 weight percent of carbon and 80 weight percent of carbon coated LiFePO4; and, a mixture comprising 10 weight percent of PVDF, and 80 weight percent of Li[Li(0.17)Mn(0.58)Ni(0.25)]O2. In the fabrication process, these mixtures are spray-deposited onto an aluminum current collector. Electrochemical tests performed thus far have shown that better charge/discharge performance is obtained when either 1) each mixture is sprayed on a separate area of the current collector or (2) the mixtures are deposited sequentially (in contradistinction to simultaneously) on the same current-collector area so that the resulting composite cathode material consists of two different sub-composite layers.

  11. Effect of flame-retarding additives on surface chemistry in Li-ion batteries

    SciTech Connect

    Nam, N.D.; Park, I.J.; Kim, J.G.; Kim, H.S.

    2012-10-15

    This study examined the properties of 1 wt.% vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and diphenyl octyl phosphate (DPOF) additive electrolytes as a promising way of beneficially improving the surface and cell resistance of Li-ion batteries. Surface film formation on the negative and positive electrodes was analyzed by electrochemical impedance spectroscopy (EIS), Fourier transform infrared (FT-IR) spectroscopy, and scanning electron microscopy (SEM). In conclusion, EIS, FT-IR spectroscopy and SEM results confirmed that DPOF is an excellent additive to the electrolyte in the Li-ion batteries due to the improved co-intercalation of the solvent molecules.

  12. Performance Testing of Yardney Li-Ion Cells and Batteries in Support of Future NASA Missions

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Whitcanack, L. D.; Puglia, F. J.; Santee, S.; Gitzendanner, R.

    2009-01-01

    NASA requires lightweight rechargeable batteries for future missions to Mars and the outer planets that are capable of operating over a wide range of temperatures, with high specific energy and energy densities. Due to the attractive performance characteristics, Li-ion batteries have been identified as the battery chemistry of choice for a number of future applications. For example, JPL is planning to launch another unmanned rover mission to the planet Mars. This mission, referred to as the Mars Science Laboratory (MSL), will involve the use of a rover that is much larger than the previously developed Spirit and Opportunity Rovers for the 2003 Mars Exploration Rover (MER) mission, that are currently still in operation on the surface of the planet after more than five years. Part of the reason that the MER rovers have operated so successfully, far exceeding the required mission duration of 90 sols, is that they possess robust Li-ion batteries, manufactured by Yardney Technical Products, which have demonstrated excellent life characteristics. Given the excellent performance characteristics displayed, similar Li-ion batteries have been projected to successfully meet the mission requirements of the up-coming MSL mission. In addition to future missions to Mars, Li-ion technology is attractive for a number of other future NASA applications which require high specific energy, rechargeable batteries. To ascertain the viability of using Li-ion batteries for these applications, a number of performance validation tests have been performed on both Yardney cells and batteries of various sizes. These tests include mission simulation tests, charge and discharge rate characterization testing, cycle life testing under various conditions, and storage testing.

  13. Integrated li-ion ultracapacitor with lead acid battery for vehicular start-stop

    NASA Astrophysics Data System (ADS)

    Manla, Emad

    Advancements in automobile manufacturing aim at improving the driving experience at every level possible. One improvement aspect is increasing gas efficiency via hybridization, which can be achieved by introducing a feature called start-stop. This feature automatically switches the internal combustion engine off when it idles and switches it back on when it is time to resume driving. This application has been proven to reduce the amount of gas consumption and emission of greenhouse effect gases in the atmosphere. However, the repeated cranking of the engine puts a large amount of stress on the lead acid battery required to perform the cranking, which effectively reduces its life span. This dissertation presents a hybrid energy storage system assembled from a lead acid battery and an ultracapacitor module connected in parallel. The Li-ion ultracapacitor was tested and modeled to predict its behavior when connected in a system requiring pulsed power such as the one proposed. Both test and simulation results show that the proposed hybrid design significantly reduces the cranking loading and stress on the battery. The ultracapacitor module can take the majority of the cranking current, effectively reducing the stress on the battery. The amount of cranking current provided by the ultracapacitor can be easily controlled via controlling the resistance of the cable connected directly between the ultracapacitor module and the car circuitry.

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

    PubMed

    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. PMID:25728092

  15. Low Defect FeFe(CN)6 Framework as Stable Host Material for High Performance Li-Ion Batteries.

    PubMed

    Wu, Xianyong; Shao, Miaomiao; Wu, Chenghao; Qian, Jiangfeng; Cao, Yuliang; Ai, Xinping; Yang, Hanxi

    2016-09-14

    Low cost and high performance Li-ion batteries have been extensively pursued for grid-scale energy storage applications; however, their development has been impeded for a long time due to the lack of qualified cathode materials with not only decent electrochemical performance but also resource abundance and low price. In this paper, we report Prussian-blue type FeFe(CN)6 nanocrystals with well-controlled lattice defects and perfect nanocubic morphology, which can exhibit a high Li-storage capacity of 160 mAh g(-1), a strong rate performance at 24 C, and a superior cycle stability with 90% capacity retention over 300 cycles. This low defect lattice and its excellent Li-insertion performance might provide a new insight into the design of advanced Li-ion battery materials and also a competitive alternative to the presently developed Li(+) insertion cathodes to develop low cost and high performance Li-ion batteries for grid-scale energy storage applications. PMID:27556906

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

    PubMed

    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. PMID:20695466

  17. Reaction temperature sensing (RTS)-based control for Li-ion battery safety.

    PubMed

    Zhang, Guangsheng; Cao, Lei; Ge, Shanhai; Wang, Chao-Yang; Shaffer, Christian E; Rahn, Christopher D

    2015-01-01

    We report reaction temperature sensing (RTS)-based control to fundamentally enhance Li-ion battery safety. RTS placed at the electrochemical interface inside a Li-ion cell is shown to detect temperature rise much faster and more accurately than external measurement of cell surface temperature. We demonstrate, for the first time, that RTS-based control shuts down a dangerous short-circuit event 3 times earlier than surface temperature- based control and prevents cell overheating by 50 °C and the resultant cell damage. PMID:26658957

  18. Reaction temperature sensing (RTS)-based control for Li-ion battery safety

    PubMed Central

    Zhang, Guangsheng; Cao, Lei; Ge, Shanhai; Wang, Chao-Yang; Shaffer, Christian E.; Rahn, Christopher D.

    2015-01-01

    We report reaction temperature sensing (RTS)-based control to fundamentally enhance Li-ion battery safety. RTS placed at the electrochemical interface inside a Li-ion cell is shown to detect temperature rise much faster and more accurately than external measurement of cell surface temperature. We demonstrate, for the first time, that RTS-based control shuts down a dangerous short-circuit event 3 times earlier than surface temperature- based control and prevents cell overheating by 50 °C and the resultant cell damage. PMID:26658957

  19. A novel preparation of core-shell electrode materials via evaporation-induced self-assembly of nanoparticles for advanced Li-ion batteries.

    PubMed

    Xie, Zhiqiang; Ellis, Sarah; Xu, Wangwang; Dye, Dara; Zhao, Jianqing; Wang, Ying

    2015-10-18

    We report, for the first time, a simple and novel synthesis of a Li-rich layered-spinel core-shell heterostructure (L@S core-shell) via evaporation-induced self-assembly (EISA) of Ni-doped Li4Mn5O12 nanoparticles (Li4Mn4.5Ni0.5O12) onto the surface of layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 (LMNCO) without using any surfactant during the coating process. The resultant L@S core-shell as a cathode in lithium ion batteries demonstrates significantly improved specific capacity, cycling performance and rate capability compared to pristine LMNCO. PMID:26313024

  20. High performance Li-ion sulfur batteries enabled by intercalation chemistry.

    PubMed

    Lv, Dongping; Yan, Pengfei; Shao, Yuyan; Li, Qiuyan; Ferrara, Seth; Pan, Huilin; Graff, Gordon L; Polzin, Bryant; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

    2015-09-11

    The unstable interface of lithium metal in high energy density Li sulfur (Li-S) batteries raises concerns of poor cycling, low efficiency and safety issues, which may be addressed by using intercalation types of anode. Herein, a new prototype of Li-ion sulfur battery with high performance has been demonstrated by coupling a graphite anode with a sulfur cathode (2 mA h cm(-2)) after successfully addressing the interface issue of graphite in an ether based electrolyte. PMID:26214797

  1. Low-temperature performance of Li-ion batteries: The behavior of lithiated graphite

    NASA Astrophysics Data System (ADS)

    Senyshyn, A.; Mühlbauer, M. J.; Dolotko, O.; Ehrenberg, H.

    2015-05-01

    Safety issues along with the substantially reduced energy and power capabilities of Li-ion cells, operated at low temperatures, pose a technical barrier limiting their use in electric vehicles and aerospace applications. A combined in situ high-resolution neutron powder diffraction and electrochemical study on Li-ion cells of the 18650-type over a temperature range from 230 K to 320 K is reported with a focus on the graphite anode and the low temperature performance of the cell. Instead of a quasi-continuous behavior as observed at ambient temperatures, an anomalous behavior occurs upon discharge at low temperature, primarily reflected in the abrupt character of the LiC12 - to - graphite phase transformation and the unusual temperature dependence of the amount of LiC6. An instability of lithiated graphite phases at temperatures below 250 K is observed, which affects the performance of Li-ion batteries at low temperatures.

  2. Pyro-synthesis of a high rate nano-Li3V2(PO4)3/C cathode with mixed morphology for advanced Li-ion batteries

    PubMed Central

    Kang, Jungwon; Mathew, Vinod; Gim, Jihyeon; Kim, Sungjin; Song, Jinju; Im, Won Bin; Han, Junhee; Lee, Jeong Yong; Kim, Jaekook

    2014-01-01

    A monoclinic Li3V2(PO4)3/C (LVP/C) cathode for lithium battery applications was synthesized by a polyol-assisted pyro-synthesis. The polyol in the present synthesis acts not only as a solvent, reducing agent and a carbon source but also as a low-cost fuel that facilitates a combustion process combined with the release of ultrahigh exothermic energy useful for nucleation process. Subsequent annealing of the amorphous particles at 800°C for 5 h is sufficient to produce highly crystalline LVP/C nanoparticles. A combined analysis of X-ray diffraction (XRD) and neutron powder diffraction (NPD) patterns was used to determine the unit cell parameters of the prepared LVP/C. Electron microscopic studies revealed rod-type particles of length ranging from nanometer to micrometers dispersed among spherical particles with average particle-sizes in the range of 20–30 nm. When tested for Li-insertion properties in the potential windows of 3–4.3 and 3–4.8 V, the LVP/C cathode demonstrated initial discharge capacities of 131 and 196 mAh/g (~100% theoretical capacities) at 0.15 and 0.1 C current densities respectively with impressive capacity retentions for 50 cycles. Interestingly, the LVP/C cathode delivered average specific capacities of 125 and 90 mAh/g at current densities of 9.6 C and 15 C respectively within the lower potential window. PMID:24509825

  3. European Non-Dissipative Bypass Switch For Li-Ion Batteries And Prospective

    NASA Astrophysics Data System (ADS)

    Pasquier, E.; Castric, AF.; Mosset, E.; Chandeneau, A.

    2011-10-01

    Li-ion batteries are made of cells or modules connected in series. In case one may be too weak or failed, it becomes necessary to remove it from the serial circuit. This is the by-pass operation which provides overcharge/open-circuitprotection,limitation of possible constraints linked to over- discharge/reversal/"self-short" and avoid to jeopardize rest of battery. One system is particularly adapted to Space Li-ion batteries: the "make before break" Single Pole Double Throw (SPDT) switch which avoids open- circuit on power circuit when correctly activated. This paper presents the component constraints, the development in the frame of ESA Artès 3 program up to its qualification, as well as the motorization approach linked to ECSS-E-30 (mechanical - Part 3: Mechanisms) and future opportunities of such system.

  4. Sampling based State of Health estimation methodology for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Camci, Fatih; Ozkurt, Celil; Toker, Onur; Atamuradov, Vepa

    2015-03-01

    Storage and management of energy is becoming a more and more important problem every day, especially for electric and hybrid vehicle applications. Li-ion battery is one of the most important technological alternatives for high capacity energy storage and related industrial applications. State of Health (SoH) of Li-ion batteries plays a critical role in their deployment from economic, safety, and availability aspects. Most, if not all, of the studies related to SoH estimation focus on the measurement of a new parameter/physical phenomena related to SoH, or development of new statistical/computational methods using several parameters. This paper presents a new approach for SoH estimation for Li-ion battery systems with multiple battery cells: The main idea is a new circuit topology which enables separation of battery cells into two groups, main and test batteries, whenever a SoH related measurement is to be conducted. All battery cells will be connected to the main battery during the normal mode of operation. When a measurement is needed for SoH estimation, some of the cells will be separated from the main battery, and SoH estimation related measurements will be performed on these units. Compared to classical SoH measurement methods which deal with whole battery system, the proposed method estimates the SoH of the system by separating a small but representative set of cells. While SoH measurements are conducted on these isolated cells, remaining cells in the main battery continue to function in normal mode, albeit in slightly reduced performance levels. Preliminary experimental results are quite promising, and validate the feasibility of the proposed approach. Technical details of the proposed circuit architecture are also summarized in the paper.

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

    PubMed

    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. PMID:27253620

  6. Review on recent progress of nanostructured anode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Goriparti, Subrahmanyam; Miele, Ermanno; De Angelis, Francesco; Di Fabrizio, Enzo; Proietti Zaccaria, Remo; Capiglia, Claudio

    2014-07-01

    This review highlights the recent research advances in active nanostructured anode materials for the next generation of Li-ion batteries (LIBs). In fact, in order to address both energy and power demands of secondary LIBs for future energy storage applications, it is required the development of innovative kinds of electrodes. Nanostructured materials based on carbon, metal/semiconductor, metal oxides and metal phosphides/nitrides/sulfides show a variety of admirable properties for LIBs applications such as high surface area, low diffusion distance, high electrical and ionic conductivity. Therefore, nanosized active materials are extremely promising for bridging the gap towards the realization of the next generation of LIBs with high reversible capacities, increased power capability, long cycling stability and free from safety concerns. In this review, anode materials are classified, depending on their electrochemical reaction with lithium, into three groups: intercalation/de-intercalation, alloy/de-alloy and conversion materials. Furthermore, the effect of nanoscale size and morphology on the electrochemical performance is presented. Synthesis of the nanostructures, lithium battery performance and electrode reaction mechanisms are also discussed. To conclude, the main aim of this review is to provide an organic outline of the wide range of recent research progresses and perspectives on nanosized active anode materials for future LIBs.

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Superhalogens: A Bridge between Complex Metal Hydrides and Li Ion Batteries.

    PubMed

    Jena, Puru

    2015-04-01

    Complex metal hydrides and Li ion batteries play an integral role in the pursuit of clean and sustainable energy. The former stores hydrogen and can provide a clean energy solution for the transportation industry, while the latter can store energy harnessed from the sun and the wind. However, considerable materials challenges remain in both cases, and research for finding solutions has traditionally followed parallel paths. In this Perspective, I show that there is a common link between these two seemingly disparate fields that can be unveiled by studying the electronic structure of the anions in complex metal hydrides and in electrolytes of Li ion batteries; they are both superhalogens. I demonstrate that considerable progress made in our understanding of superhalogens in the past decade can provide solutions to some of the materials challenges in both of these areas. PMID:26262959

  9. NANOSTRUCTURED METAL OXIDES FOR ANODES OF LI-ION RECHARGEABLE BATTERIES

    SciTech Connect

    Au, M.

    2009-12-04

    The aligned nanorods of Co{sub 3}O{sub 4} and nanoporous hollow spheres (NHS) of SnO{sub 2} and Mn{sub 2}O{sub 3} were investigated as the anodes for Li-ion rechargeable batteries. The Co{sub 3}O{sub 4} nanorods demonstrated 1433 mAh/g reversible capacity. The NHS of SnO{sub 2} and Mn{sub 2}O{sub 3} delivered 400 mAh/g and 250 mAh/g capacities respectively in multiple galvonastatic discharge-charge cycles. It was found that high capacity of NHS of metal oxides is sustainable attributed to their unique structure that maintains material integrity during cycling. The nanostructured metal oxides exhibit great potential as the new anode materials for Li-ion rechargeable batteries with high energy density, low cost and inherent safety.

  10. Garnet-type solid-state fast Li ion conductors for Li batteries: critical review.

    PubMed

    Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana

    2014-07-01

    Batteries are electrochemical devices that store electrical energy in the form of chemical energy. Among known batteries, Li ion batteries (LiBs) provide the highest gravimetric and volumetric energy densities, making them ideal candidates for use in portable electronics and plug-in hybrid and electric vehicles. Conventional LiBs use an organic polymer electrolyte, which exhibits several safety issues including leakage, poor chemical stability and flammability. The use of a solid-state (ceramic) electrolyte to produce all-solid-state LiBs can overcome all of the above issues. Also, solid-state Li batteries can operate at high voltage, thus, producing high power density. Various types of solid Li-ion electrolytes have been reported; this review is focused on the most promising solid Li-ion electrolytes based on garnet-type metal oxides. The first studied Li-stuffed garnet-type compounds are Li5La3M2O12 (M = Nb, Ta), which show a Li-ion conductivity of ∼10(-6) at 25 °C. La and M sites can be substituted by various metal ions leading to Li-rich garnet-type electrolytes, such as Li6ALa2M2O12, (A = Mg, Ca, Sr, Ba, Sr0.5Ba0.5) and Li7La3C2O12 (C = Zr, Sn). Among the known Li-stuffed garnets, Li6.4La3Zr1.4Ta0.6O12 exhibits the highest bulk Li-ion conductivity of 10(-3) S cm(-1) at 25 °C with an activation energy of 0.35 eV, which is an order of magnitude lower than that of the currently used polymer, but is chemically stable at higher temperatures and voltages compared to polymer electrolytes. Here, we discuss the chemical composition-structure-ionic conductivity relationship of the Li-stuffed garnet-type oxides, as well as the Li ion conduction mechanism. PMID:24681593

  11. Nanostructured ion beam-modified Ge films for high capacity Li ion battery anodes

    SciTech Connect

    Rudawski, N. G.; Darby, B. L.; Yates, B. R.; Jones, K. S.; Elliman, R. G.; Volinsky, A. A.

    2012-02-20

    Nanostructured ion beam-modified Ge electrodes fabricated directly on Ni current collector substrates were found to exhibit excellent specific capacities during electrochemical cycling in half-cell configuration with Li metal for a wide range of cycling rates. Structural characterization revealed that the nanostructured electrodes lose porosity during cycling but maintain excellent electrical contact with the metallic current collector substrate. These results suggest that nanostructured Ge electrodes have great promise for use as high performance Li ion battery anodes.

  12. Antiperovskite Li 3 OCl superionic conductor films for solid-state Li-ion batteries

    DOE PAGESBeta

    Lü, Xujie; Howard, John W.; Chen, Aiping; Zhu, Jinlong; Li, Shuai; Wu, Gang; Dowden, Paul; Xu, Hongwu; Zhao, Yusheng; Jia, Quanxi

    2016-02-02

    We prepared antiperovskite Li3OCl superionic conductor films via pulsed laser deposition using a composite target. A significantly enhanced ionic conductivity of 2.0 × 10-4 S cm-1 at room temperature is achieved, and this value is more than two orders of magnitude higher than that of its bulk counterpart. Moreover, the applicability of Li3OCl as a solid electrolyte for Li-ion batteries is demonstrated.

  13. Synthesis, Characterization and Testing of Novel Anode and Cathode Materials for Li-Ion Batteries

    SciTech Connect

    White, Ralph E.; Popov, Branko N.

    2002-10-31

    During this program we have synthesized and characterized several novel cathode and anode materials for application in Li-ion batteries. Novel synthesis routes like chemical doping, electroless deposition and sol-gel method have been used and techniques like impedance, cyclic voltammetry and charge-discharge cycling have been used to characterize these materials. Mathematical models have also been developed to fit the experimental result, thus helping in understanding the mechanisms of these materials.

  14. Enhanced autonomic shutdown of Li-ion batteries by polydopamine coated polyethylene microspheres

    SciTech Connect

    Baginska, Marta; Blaiszik, Benjamin J.; Rajh, Tijana; Sottos, Nancy R.; White, Scott R.

    2014-07-17

    Thermally triggered autonomic shutdown of a Lithium-ion (Li-ion) battery is demonstrated using polydopamine (PDA)-coated polyethylene microspheres applied onto a battery anode. The microspheres are dispersed in a buffered 10 mM dopamine salt solution and the pH is raised to initiate the polymerization and coat the microspheres. Coated microspheres are then mixed with an aqueous binder, applied onto a battery anode surface, dried, and incorporated into Li-ion coin cells. FTIR and Raman spectroscopy are used to verify the presence of the polydopamine on the surface of the microspheres. Scanning electron microscopy is used to examine microsphere surface morphology and resulting anode coating quality. Charge and discharge capacity, as well as impedance, are measured for Li-ion coin cells as a function of microsphere content. Autonomous shutdown is achieved by applying 1.7 mg cm–2 of PDA-coated microspheres to the electrode. Furthermore, the PDA coating significantly reduces the mass of microspheres for effective shutdown compared to our prior work with uncoated microspheres.

  15. Enhanced autonomic shutdown of Li-ion batteries by polydopamine coated polyethylene microspheres

    DOE PAGESBeta

    Baginska, Marta; Blaiszik, Benjamin J.; Rajh, Tijana; Sottos, Nancy R.; White, Scott R.

    2014-07-17

    Thermally triggered autonomic shutdown of a Lithium-ion (Li-ion) battery is demonstrated using polydopamine (PDA)-coated polyethylene microspheres applied onto a battery anode. The microspheres are dispersed in a buffered 10 mM dopamine salt solution and the pH is raised to initiate the polymerization and coat the microspheres. Coated microspheres are then mixed with an aqueous binder, applied onto a battery anode surface, dried, and incorporated into Li-ion coin cells. FTIR and Raman spectroscopy are used to verify the presence of the polydopamine on the surface of the microspheres. Scanning electron microscopy is used to examine microsphere surface morphology and resulting anodemore » coating quality. Charge and discharge capacity, as well as impedance, are measured for Li-ion coin cells as a function of microsphere content. Autonomous shutdown is achieved by applying 1.7 mg cm–2 of PDA-coated microspheres to the electrode. Furthermore, the PDA coating significantly reduces the mass of microspheres for effective shutdown compared to our prior work with uncoated microspheres.« less

  16. An Update on the Performance of Li-Ion Rechargeable Batteries on Mars Rovers

    NASA Technical Reports Server (NTRS)

    Ratnakumara, Bugga V.; Smart, M. C.; Whitcanack, L. D.; Chin, K. B.; Ewell, R. C.; Surampudi, S.; Puglia, F.; Gitzendanner, R.

    2006-01-01

    NASA's Mars Rovers, Spirit and Opportunity have been exploring the surface of Mars for the last thirty months, far exceeding the primary mission life of three months, performing astounding geological studies to examine the habitability of Mars. Such an extended mission life may be attributed to impressive performances of several subsystems, including power subsystem components, i.e., solar array and batteries. The novelty and challenge for this mission in terms of energy storage is the use of lithium-ion batteries, for the first time in a major NASA mission, for keeping the rover electronics warm, and supporting nighttime experimentation and communications. The use of Li-ion batteries has considerably enhanced or even enabled these rovers, by providing greater mass and volume allocations for the payload and wider range of operating temperatures for the power subsystem and thus reduced thermal management. After about 800 days of exploration, there is only marginal change in the end-of discharge (EOD) voltages of the batteries or in their capacities, as estimated from in-flight voltage data and corroborated by ground testing of prototype batteries. Enabled by such impressive durability from the Li-ion batteries, both from a cycling and calendar life stand point, these rovers are poised to extend their exploration well beyond 1000 sols, though other components have started showing signs of decay. In this paper, we will update the performance characteristics of these batteries on both Spirit and Opportunity.

  17. Improved Control of Charging Voltage for Li-Ion Battery

    NASA Technical Reports Server (NTRS)

    Timmerman, Paul; Bugga, Ratnakumar

    2006-01-01

    The protocol for charging a lithium-ion battery would be modified, according to a proposal, to compensate for the internal voltage drop (charging current internal resistance of the battery). The essence of the modification is to provide for measurement of the internal voltage drop and to increase the terminal-voltage setting by the amount of the internal voltage drop. Ordinarily, a lithium-ion battery is charged at constant current until its terminal voltage attains a set value equal to the nominal full-charge potential. The set value is chosen carefully so as not to exceed the lithium-plating potential, because plated lithium in metallic form constitutes a hazard. When the battery is charged at low temperature, the internal voltage drop is considerable because the electrical conductivity of the battery electrolyte is low at low temperature. Charging the battery at high current at any temperature also gives rise to a high internal voltage drop. In some cases, the internal voltage drop can be as high as 1 volt per cell. Because the voltage available for charging is less than the terminal voltage by the amount of the internal voltage drop, the battery is not fully charged (see figure), even when the terminal voltage reaches the set value. In the modified protocol, the charging current would be periodically interrupted so that the zero-current battery-terminal voltage indicative of the state of charge could be measured. The terminal voltage would also be measured at full charging current. The difference between the full-current and zero-current voltages would equal the internal voltage drop. The set value of terminal voltage would then be increased beyond the nominal full-charge potential by the amount of the internal voltage drop. This adjustment would be performed repeatedly, in real time, so that the voltage setting would track variations in the internal voltage drop to afford full charge without risk of lithium plating. If the charging current and voltage settings

  18. Bundled and densified carbon nanotubes (CNT) fabrics as flexible ultra-light weight Li-ion battery anode current collectors

    NASA Astrophysics Data System (ADS)

    Yehezkel, Shani; Auinat, Mahmud; Sezin, Nina; Starosvetsky, David; Ein-Eli, Yair

    2016-04-01

    Carbon nanotubes (CNT) fabrics were studied and evaluated as anode current collectors, replacing the traditional copper foil current collector in Li-ion batteries. Glavanostatic measurements reveal high values of irreversible capacities (as high as 28%), resulted mainly from the formation of the solid electrolyte interphase (SEI) layer at the CNT fabric surface. Various pre-treatments to the CNT fabric prior to active anode material loading have shown that the lowest irreversible capacity is achieved by immersing and washing the CNT fabric with iso-propanol (IPA), which dramatically modified the fabric surface. Additionally, the use of very thin CNT fabrics (5 μm) results in a substantial irreversible capacity minimization. A combination of IPA rinse action and utilization of the thinnest CNT fabric provides the lowest irreversible capacity of 13%. The paper describes innovative and rather simple techniques towards a complete implementation of CNT fabric as an anode current collector in Li-ion batteries, instead of the relatively heavy and expensive copper foil, enabling an improvement in the gravimetric and volumetric energy densities of such advanced batteries.

  19. Polymer electrolytes for a rechargeable li-Ion battery

    SciTech Connect

    Argade, S.D.; Saraswat, A.K.; Rao, B.M.L.; Lee, H.S.; Xiang, C.L.; McBreen, J.

    1996-10-01

    Lithium-ion polymer electrolyte battery technology is attractive for many consumer and military applications. A Li{sub x}C/Li{sub y}Mn{sub 2}O{sub 4} battery system incorporating a polymer electrolyte separator base on novel Li-imide salts is being developed under sponsorship of US Army Research Laboratory (Fort Monmouth NJ). This paper reports on work currently in progress on synthesis of Li-imide salts, polymer electrolyte films incorporating these salts, and development of electrodes and cells. A number of Li salts have been synthesized and characterized. These salts appear to have good voltaic stability. PVDF polymer gel electrolytes based on these salts have exhibited conductivities in the range 10{sup -4} to 10{sub -3} S/cm.

  20. Surface treated natural graphite as anode material for high-power Li-ion battery applications.

    SciTech Connect

    Liu, J.; Vissers, D. R.; Amine, K.; Barsukov, I. V.; Henry, F.; Doniger, J.; Chemical Engineering; Superior Graphite Co.

    2006-01-01

    High power application of Li-ion battery in hybrid electrical vehicles requires low cost and safe cell materials. Among the various carbon anode materials used in lithium ion batteries, natural graphite shows the most promise with advantages in performance and cost. However, natural graphite is not compatible with propylene carbonate (PC)-based electrolytes, which have a lower melting point and improved safety characteristics. The problem with it is that the molecules of propylene carbonate intercalate with Li+ into graphite, and that frequently leads to the exfoliation of the graphite matrix.

  1. An inorganic composite membrane as the separator of Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, S. S.; Xu, K.; Jow, T. R.

    We studied an inorganic composite membrane as the separator for Li-ion batteries. Being made of mainly CaCO 3 powder and a small amount of polymer binder, the composite membrane has excellent wettability with liquid electrolytes due to its high porosity and good capillarity. Ionic conductivity of the membrane can be easily achieved by absorbing a liquid electrolyte. Additional benefit of such a membrane is that the alkali CaCO 3 can scavenge acidic HF, which is inevitably present in the LiPF 6-based electrolytes used currently in the Li-ion batteries. In this work, we typically evaluated a membrane with the composition of 92:8 (wt.) CaCO 3/Telfon by using a 1.0 m LiPF 6 dissolved in a 3:7 (wt.) mixture of ethylene carbonate (EC) and ethylmethyl carbonate (EMC) as the liquid electrolyte. Ionic conductivity of the electrolyte-wetted membrane was measured to be 2.4 mS cm -1 at 20 °C versus 8.0 mS cm -1 of the liquid electrolyte. With the said membrane as a separator, both Li/graphite and Li/cathode half-cells exhibited good capacity retention. We also found that the Li-ion cell fabricated in this manner not only had stable capacity retention, but also showed good high-rate performance.

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

    PubMed

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

    2012-08-30

    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. PMID:22763226

  3. Polyacrylate bound TiSb2 electrodes for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Gómez-Cámer, Juan Luis; Novák, Petr

    2015-01-01

    Crystalline TiSb2 electrodes prepared using two different binders, PVDF and lithium polyacrylate (LiPAA), were examined as negative electrodes in Li-ion batteries. The cycle life of the electrodes is strongly influenced by the choice of the binder, reaching ca. 120 cycles with LiPAA vs. ca. 90 cycles achieved with the common binder PVDF. Moreover, rate capability is improved using LiPAA binder. The reduction in TiSb2 particle size is shown to influence the average practical specific charge at high charge/discharge rates. The reasons for this improvement are discussed and the optimized electrode was demonstrated in full Li-ion cells.

  4. Power-ion battery: bridging the gap between Li-ion and supercapacitor chemistries

    NASA Astrophysics Data System (ADS)

    Pasquier, A. Du; Plitz, I.; Gural, J.; Badway, F.; Amatucci, G. G.

    A 40 Wh/kg Li-ion battery using a Li 4Ti 5O 12 nanostructured anode and a composite activated carbon LiCoO 2 cathode was built using plastic Li-ion processing based on PVDF-HFP binder and soft laminate packaging. The specific power of the device is similar to that of an electrochemical double-layer supercapacitor (4000 W/kg). The high power is enabled by a combination of a nanostructured negative electrode, an acetonitrile based electrolyte and an activated carbon/LiCoO 2 composite positive electrode. This enables very fast charging (full recharge in 3 min). The effect of electrode formulation and matching ratio on energy, power and cycle-life are described. Optimization of these parameters led to a cycle-life of 20% capacity loss after 9000 cycles at full depth of discharge (DOD).

  5. Copper nanofiber-networked cobalt oxide composites for high performance Li-ion batteries

    PubMed Central

    2011-01-01

    We prepared a composite electrode structure consisting of copper nanofiber-networked cobalt oxide (CuNFs@CoOx). The copper nanofibers (CuNFs) were fabricated on a substrate with formation of a network structure, which may have potential for improving electron percolation and retarding film deformation during the discharging/charging process over the electroactive cobalt oxide. Compared to bare CoOxthin-film (CoOxTF) electrodes, the CuNFs@CoOxelectrodes exhibited a significant enhancement of rate performance by at least six-fold at an input current density of 3C-rate. Such enhanced Li-ion storage performance may be associated with modified electrode structure at the nanoscale, improved charge transfer, and facile stress relaxation from the embedded CuNF network. Consequently, the CuNFs@CoOxcomposite structure demonstrated here can be used as a promising high-performance electrode for Li-ion batteries. PMID:21711839

  6. Facile and Nonradiation Pretreated Membrane as a High Conductive Separator for Li-Ion Batteries.

    PubMed

    Li, Bao; Li, Yongjun; Dai, Dongmei; Chang, Kun; Tang, Hongwei; Chang, Zhaorong; Wang, Chunru; Yuan, Xiao-Zi; Wang, Haijiang

    2015-09-16

    Polyolefin membranes are widely used as separators in commercialized Li-ion batteries. They have less polarized surfaces compared with polarized molecules of electrolyte, leading to a poor wetting state for separators. Radiation pretreatments are often adopted to solve such a problem. Unfortunately, they can only activate several nanometers deep from the surface, which limits the performance improvement. Here we report a facile and scalable method to polarize polyolefin membranes via a chemical oxidation route. On the surfaces of pretreated membrane, layers of poly(ethylene oxide) and poly(acrylic acid) can easily be coated, thus resulting in a high Li-ion conductivity of the membrane. Assembled with this decorated separator in button cells, both high-voltage (Li1.2Mn0.54Co0.13Ni0.13O2) and moderate-voltage (LiFePO4) cathode materials show better electrochemical performances than those assembled with pristine polyolefin separators. PMID:26320596

  7. A β-VOPO4/ε-VOPO4 composite Li-ion battery cathode

    SciTech Connect

    Chen, Zehua; Chen, Qiyuan; Wang, Haiyan; Zhang, Ruibo; Zhou, Hui; Chen, Liquan; Whittingham, M. Stanley

    2014-09-01

    VOPO4 is an example of a Li-ion battery cathode that can achieve over 300 Ah/kg when two Li-ions are intercalated. A two phase β-VOPO4/ε-VOPO4 composite was found to improve the cycling capacity of ε-VOPO4 from tetragonal H2VOPO4, particularly as the rate is increased. In the potential range of 2.0–4.5 V, this composite showed an initial electrochemical capacity of 208 mAh/g at 0.08 mA/cm2, 190 mAh/g at 0.16 mA/cm2, and 160 mAh/g at 0.41 mA/cm2.

  8. Anion-redox nanolithia cathodes for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhu, Zhi; Kushima, Akihiro; Yin, Zongyou; Qi, Lu; Amine, Khalil; Lu, Jun; Li, Ju

    2016-08-01

    The development of lithium–air batteries is plagued by a high potential gap (>1.2 V) between charge and discharge, and poor cyclability due to the drastic phase change of O2 (gas) and Ox‑ (condensed phase) at the cathode during battery operations. Here we report a cathode consisting of nanoscale amorphous lithia (nanolithia) confined in a cobalt oxide, enabling charge/discharge between solid Li2O/Li2O2/LiO2 without any gas evolution. The cathode has a theoretical capacity of 1,341 Ah kg‑1, a mass density exceeding 2.2 g cm‑3, and a practical discharge capacity of 587 Ah kg‑1 at 2.55 V versus Li/Li+. It also displays stable cycling performance (only 1.8% loss after 130 cycles in lithium-matched full-cell tests against Li4Ti5O12 anode), as well as a round-trip overpotential of only 0.24 V. Interestingly, the cathode is automatically protected from O2 gas release and overcharging through the shuttling of self-generated radical species soluble in the carbonate electrolyte.

  9. Li-ion battery shut-off at high temperature caused by polymer phase separation in responsive electrolytes.

    PubMed

    Kelly, Jesse C; Degrood, Nicholas L; Roberts, Mark E

    2015-03-28

    For the purpose of realizing inherently safe high-power Li-ion batteries, a model Li4Ti5O12/LiFePO4 rechargeable battery is investigated using the thermally responsive polymer, poly(benzyl methacrylate), in an ionic liquid. At high temperature, battery operation is inhibited as a result of increased internal resistance caused by polymer and ionic liquid phase separation. Li-ion concentration is shown to affect the phase transition temperature and the extent to which batteries are deactivated. PMID:25731742

  10. Characterization of silicate based cathodes for Li Ion Batteries

    NASA Astrophysics Data System (ADS)

    Kumar, Ajay; Nazri, Gholam-Abbas; Nazri, Maryam; Nail, Vaman; Vaishnava, Prem; Naik, Ratna; Energy Group Collaboration; Energy Group Collaboration; Energy Group Collaboration

    2013-03-01

    The silicate compounds Li2MSiO4, where M = Mn, Fe, Co and Ni have gained interest as electrode materials for Lithium ion batteries due to their high theoretical capacity (>330mAh/g), high thermal stability due to strong Si-O covalent bonds, environmental friendliness, and low cost. However, these materials intrinsically have low electrical conductivity. To improve conductivity of these classes of electrode materials, we synthesized Li2MnSiO4 and Li2FeSiO4 by solid state reaction in an argon atmosphere. The lithium transition metal silicates were compounded with graphene nano-sheets and the composites were used as positive electrode in a coin cell configuration.. The materials structure-composition, morphology, conductivity and electrochemical performance were characterized by XRD, XPS, SEM, TEM and electrochemical techniques.The detail structure-composition analysis and electrochemical performance of the silicate electrodes will be reported.

  11. Searching for Sustainable and "Greener" Li-ion Batteries

    ScienceCinema

    Tarascon, Jean-Marie [University of Picardie at Aimens, France

    2010-01-08

    Lithium-ion batteries are strong candidates for powering upcoming generations of hybrid electric vehicles and plug-in hybrid electric vehicles. But improvements in safety must be achieved while keeping track of materials resources and abundances, as well as materials synthesis and recycling processes, all of which could inflict a heavy energy cost. Thus, electrode materials that have a minimum footprint in nature and are made via eco-efficient processes are sorely needed. The arrival of electrode materials based on minerals such as LiFePO4 (tryphilite) is a significant, but not sufficient, step toward the long-term demand for materials sustainability. The eco-efficient synthesis of LiFePO4 nanopowders via hydrothermal/ solvo-thermal processes using latent bases, structure directing templates, or other bio-related approaches will be presented in this talk. However, to secure sustainability and greeness, organic electrodes appear to be ideal candidates.... We took a fresh look at organic based electrodes; the results of this research into sequentially metal-organic-framework electrodes and Li-based organic electrodes (LixCyOz) will be reported and discussed.

  12. Time domain simulation of Li-ion batteries using non-integer order equivalent electrical circuit

    NASA Astrophysics Data System (ADS)

    Riu, D.; Montaru, M.; Bultel, Y.

    2013-06-01

    For electric vehicle (EV) or hybrid EV (HEV) development and integration of renewables in electrical networks, battery monitoring systems have to be more and more precise to take into account the state-of-charge and the dynamic behavior of the battery. Some non-integer order models of electrochemical batteries have been proposed in literacy with a good accuracy and a low number of parameters in the frequential domain. Nevertheless, time simulation of such models required to approximate this non-integer order system by an equivalent high integer order model. An adapted algorithm is then proposed in this article to simulate the non-integer order model without any approximation, thanks to the construction of a 3-order generalized state-space system. This algorithm is applied and validated on a 2.3 A.h Li-ion battery.

  13. Nanomechanical characterization and mechanical integrity of unaged and aged Li-ion battery cathodes

    NASA Astrophysics Data System (ADS)

    Ramdon, Sanjay; Bhushan, Bharat

    2014-01-01

    Lithium-ion (Li-ion) batteries have been implemented for numerous applications, one of which is in plug-in hybrid electric vehicles (PHEV) and pure electric vehicles (EV). In an effort to prolong battery life it is important to understand the mechanisms that cause reduced battery capacity with aging. In this work, nanomechanical characterization and mechanical integrity studies were carried out on unaged and aged LiFePO4 battery cathodes using atomic force microscopy (AFM) and nanoindentation. Changes in hardness, elastic modulus, creep, nanowear, nanoscratch and nanofriction properties were measured. Measured changes are believed to occur as a result of coarsening and agglomeration of LiFePO4 nanoparticles.

  14. Evaluation of Cycle Life and Characterization of YTP 45 Ah Li-Ion Battery for EMU

    NASA Technical Reports Server (NTRS)

    Deng, Yi; Jeevarajan, Judith; Rehm, Raymond; Bragg, Bobby; Strangways, Brad

    2002-01-01

    Li-ion batteries, with longer cycle life and higher energy density features, are now more and more attractive and applied in multiple fields. The YTP 45 Ah Li-ion battery has been evaluated here and may be employed in EMU in the future. Evaluations were on: (1) Cycle life tests - 500 cycles total (completed 40 cycles in simulated shuttle use mode and 460 cycles in an accelerated use mode, and recorded differential voltage of individual cell in battery); (2) Characterization test - discharge capacity measurement in environment temperature of -10, 25, 50 C before and after 500 cycles; and (3) Thermal testing - charge and discharge at 50 C and -10 C before and after 500 cycles. The battery showed less than a 9% drop of initial discharge capacity and energy within 500 cycles with 475 cycles 59% DOD plus 25 cycles 100% DOD. The EOD voltage ranged from 16.0 to 18.0 V, which fits the requirement for operating the EMU.

  15. High Voltage Li-Ion Battery Using Exfoliated Graphite/Graphene Nanosheets Anode.

    PubMed

    Agostini, Marco; Brutti, Sergio; Hassoun, Jusef

    2016-05-01

    The achievement of a new generation of lithium-ion battery, suitable for a continuously growing consumer electronic and sustainable electric vehicle markets, requires the development of new, low-cost, and highly performing materials. Herein, we propose a new and efficient lithium-ion battery obtained by coupling exfoliated graphite/graphene nanosheets (EGNs) anode and high-voltage, spinel-structure cathode. The anode shows a capacity exceeding by 40% that ascribed to commercial graphite in lithium half-cell, at very high C-rate, due to its particular structure and morphology as demonstrated by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The Li-ion battery reveals excellent efficiency and cycle life, extending up to 150 cycles, as well as an estimated practical energy density of about 260 Wh kg(-1), that is, a value well exceeding the one associated with the present-state Li-ion battery. PMID:27052542

  16. Selected test results from the neosonic polymer Li-ion battery.

    SciTech Connect

    Ingersoll, David T.; Hund, Thomas D.

    2010-07-01

    The performance of the Neosonic polymer Li-ion battery was measured using a number of tests including capacity, capacity as a function of temperature, ohmic resistance, spectral impedance, hybrid pulsed power test, utility partial state of charge (PSOC) pulsed cycle test, and an over-charge/voltage abuse test. The goal of this work was to evaluate the performance of the polymer Li-ion battery technology for utility applications requiring frequent charges and discharges, such as voltage support, frequency regulation, wind farm energy smoothing, and solar photovoltaic energy smoothing. Test results have indicated that the Neosonic polymer Li-ion battery technology can provide power levels up to the 10C{sub 1} discharge rate with minimal energy loss compared to the 1 h (1C) discharge rate. Two of the three cells used in the utility PSOC pulsed cycle test completed about 12,000 cycles with only a gradual loss in capacity of 10 and 13%. The third cell experienced a 40% loss in capacity at about 11,000 cycles. The DC ohmic resistance and AC spectral impedance measurements also indicate that there were increases in impedance after cycling, especially for the third cell. Cell No.3 impedance Rs increased significantly along with extensive ballooning of the foil pouch. Finally, at a 1C (10 A) charge rate, the over charge/voltage abuse test with cell confinement similar to a multi cell string resulted in the cell venting hot gases at about 45 C 45 minutes into the test. At 104 minutes into the test the cell voltage spiked to the 12 volt limit and continued out to the end of the test at 151 minutes. In summary, the Neosonic cells performed as expected with good cycle-life and safety.

  17. Fast microwave treatments of single source alkoxides for nanostructured Li-ion battery electrodes.

    PubMed

    Laveda, Josefa Vidal; Chandhok, Vibhuti; Murray, Claire A; Paterson, Gary W; Corr, Serena A

    2016-07-12

    Microwave or ultrasonic treatment of metal alkoxides presents a fast, low cost route to both anode and cathode nanomaterials for Li-ion battery applications. Here, we demonstrate the formation of LiMPO4 (M = Fe, Mn) and Mn3O4 nanostructures via this simple route which exhibit excellent electrochemical performances. This approach opens up a new avenue for the targeted design of nanostructured materials, where co-location of the desired metals in a single starting material shortens reaction times and temperatures since there is a decrease in diffusional energy requirements usually needed for these reactions to proceed. PMID:26486274

  18. Anodic polymerization of vinyl ethylene carbonate in Li-Ion battery electrolyte

    SciTech Connect

    Chen, Guoying; Zhuang, Guorong V.; Richardson, Thomas J.; Gao, Liu; Ross Jr., Philip N.

    2005-02-28

    A study of the anodic oxidation of vinyl ethylene carbonate (VEC) was conducted with post-mortem analysis of reaction products by ATR-FTIR and gel permeation chromatography (GPC). The half-wave potential (E1/2) for oxidation of VEC is ca. 3.6 V producing a resistive film on the electrode surface. GPC analysis of the film on a gold electrode produced by anodization of a commercial Li-ion battery electrolyte containing 2 percent VEC at 4.1 V showed the presence of a high molecular weight polymer. IR analysis indicated polycarbonate with alkyl carbonate rings linked by aliphatic methylene and methyl branches.

  19. New two-dimensional niobium and vanadium carbides as promising materials for Li-ion batteries.

    PubMed

    Naguib, Michael; Halim, Joseph; Lu, Jun; Cook, Kevin M; Hultman, Lars; Gogotsi, Yury; Barsoum, Michel W

    2013-10-30

    New two-dimensional niobium and vanadium carbides have been synthesized by selective etching, at room temperature, of Al from Nb2AlC and V2AlC, respectively. These new matrials are promising electrode materials for Li-ion batteries, demonstrating good capability to handle high charge-discharge rates. Reversible capacities of 170 and 260 mA·h·g(-1) at 1 C, and 110 and 125 mA·h·g(-1) at 10 C were obtained for Nb2C and V2C-based electrodes, respectively. PMID:24144164

  20. Scenario-based prediction of Li-ion batteries fire-induced toxicity

    NASA Astrophysics Data System (ADS)

    Lecocq, Amandine; Eshetu, Gebrekidan Gebresilassie; Grugeon, Sylvie; Martin, Nelly; Laruelle, Stephane; Marlair, Guy

    2016-06-01

    The development of high energy Li-ion batteries with improved durability and increased safety mostly relies on the use of newly developed electrolytes. A detailed appraisal of fire-induced thermal and chemical threats on LiPF6- and LiFSI-based electrolytes by means of the so-called "fire propagation apparatus" had highlighted that the salt anion was responsible for the emission of a non negligible content of irritant gas as HF (PF6-) or HF and SO2 (FSI-). A more thorough comparative investigation of the toxicity threat in the case of larger-size 0.4 kWh Li-ion modules was thus undertaken. A modeling approach that consists in extrapolating the experimental data obtained from 1.3Ah LiFePO4/graphite pouch cells under fire conditions and in using the state-of-the-art fire safety international standards for the evaluation of fire toxicity was applied under two different real-scale simulating scenarios. The obtained results reveal that critical thresholds are highly dependent on the nature of the salt, LiPF6 or LiFSI, and on the cells state of charge. Hence, this approach can help define appropriate fire safety engineering measures for a given technology (different chemistry) or application (fully charged backup batteries or batteries subjected to deep discharge).

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Scenario-based prediction of Li-ion batteries fire-induced toxicity

    NASA Astrophysics Data System (ADS)

    Lecocq, Amandine; Eshetu, Gebrekidan Gebresilassie; Grugeon, Sylvie; Martin, Nelly; Laruelle, Stephane; Marlair, Guy

    2016-06-01

    The development of high energy Li-ion batteries with improved durability and increased safety mostly relies on the use of newly developed electrolytes. A detailed appraisal of fire-induced thermal and chemical threats on LiPF6- and LiFSI-based electrolytes by means of the so-called "fire propagation apparatus" had highlighted that the salt anion was responsible for the emission of a non negligible content of irritant gas as HF (PF6-) or HF and SO2 (FSI-). A more thorough comparative investigation of the toxicity threat in the case of larger-size 0.4 kWh Li-ion modules was thus undertaken. A modeling approach that consists in extrapolating the experimental data obtained from 1.3Ah LiFePO4/graphite pouch cells under fire conditions and in using the state-of-the-art fire safety international standards for the evaluation of fire toxicity was applied under two different real-scale simulating scenarios. The obtained results reveal that critical thresholds are highly dependent on the nature of the salt, LiPF6 or LiFSI, and on the cells state of charge. Hence, this approach can help define appropriate fire safety engineering measures for a given technology (different chemistry) or application (fully charged backup batteries or batteries subjected to deep discharge).

  3. A three-dimensional meso-macroscopic model for Li-Ion intercalation batteries

    DOE PAGESBeta

    Allu, S.; Kalnaus, S.; Simunovic, S.; Nanda, J.; Turner, J. A.; Pannala, S.

    2016-06-09

    Through this study, we present a three-dimensional computational formulation for electrode-electrolyte-electrode system of Li-Ion batteries. The physical consistency between electrical, thermal and chemical equations is enforced at each time increment by driving the residual of the resulting coupled system of nonlinear equations to zero. The formulation utilizes a rigorous volume averaging approach typical of multiphase formulations used in other fields and recently extended to modeling of supercapacitors [1]. Unlike existing battery modeling methods which use segregated solution of conservation equations and idealized geometries, our unified approach can model arbitrary battery and electrode configurations. The consistency of multi-physics solution also allowsmore » for consideration of a wide array of initial conditions and load cases. The formulation accounts for spatio-temporal variations of material and state properties such as electrode/void volume fractions and anisotropic conductivities. The governing differential equations are discretized using the finite element method and solved using a nonlinearly consistent approach that provides robust stability and convergence. The new formulation was validated for standard Li-ion cells and compared against experiments. Finally, its scope and ability to capture spatio-temporal variations of potential and lithium distribution is demonstrated on a prototypical three-dimensional electrode problem.« less

  4. A three-dimensional meso-macroscopic model for Li-Ion intercalation batteries

    NASA Astrophysics Data System (ADS)

    Allu, S.; Kalnaus, S.; Simunovic, S.; Nanda, J.; Turner, J. A.; Pannala, S.

    2016-09-01

    In this paper we present a three-dimensional computational formulation for electrode-electrolyte-electrode system of Li-Ion batteries. The physical consistency between electrical, thermal and chemical equations is enforced at each time increment by driving the residual of the resulting coupled system of nonlinear equations to zero. The formulation utilizes a rigorous volume averaging approach typical of multiphase formulations used in other fields and recently extended to modeling of supercapacitors [1]. Unlike existing battery modeling methods which use segregated solution of conservation equations and idealized geometries, our unified approach can model arbitrary battery and electrode configurations. The consistency of multi-physics solution also allows for consideration of a wide array of initial conditions and load cases. The formulation accounts for spatio-temporal variations of material and state properties such as electrode/void volume fractions and anisotropic conductivities. The governing differential equations are discretized using the finite element method and solved using a nonlinearly consistent approach that provides robust stability and convergence. The new formulation was validated for standard Li-ion cells and compared against experiments. Its scope and ability to capture spatio-temporal variations of potential and lithium distribution is demonstrated on a prototypical three-dimensional electrode problem.

  5. Unravelling Li-Ion Transport from Picoseconds to Seconds: Bulk versus Interfaces in an Argyrodite Li6PS5Cl-Li2S All-Solid-State Li-Ion Battery.

    PubMed

    Yu, Chuang; Ganapathy, Swapna; de Klerk, Niek J J; Roslon, Irek; van Eck, Ernst R H; Kentgens, Arno P M; Wagemaker, Marnix

    2016-09-01

    One of the main challenges of all-solid-state Li-ion batteries is the restricted power density due to the poor Li-ion transport between the electrodes via the electrolyte. However, to establish what diffusional process is the bottleneck for Li-ion transport requires the ability to distinguish the various processes. The present work investigates the Li-ion diffusion in argyrodite Li6PS5Cl, a promising electrolyte based on its high Li-ion conductivity, using a combination of (7)Li NMR experiments and DFT based molecular dynamics simulations. This allows us to distinguish the local Li-ion mobility from the long-range Li-ion motional process, quantifying both and giving a coherent and consistent picture of the bulk diffusion in Li6PS5Cl. NMR exchange experiments are used to unambiguously characterize Li-ion transport over the solid electrolyte-electrode interface for the electrolyte-electrode combination Li6PS5Cl-Li2S, giving unprecedented and direct quantitative insight into the impact of the interface on Li-ion charge transport in all-solid-state batteries. The limited Li-ion transport over the Li6PS5Cl-Li2S interface, orders of magnitude smaller compared with that in the bulk Li6PS5Cl, appears to be the bottleneck for the performance of the Li6PS5Cl-Li2S battery, quantifying one of the major challenges toward improved performance of all-solid-state batteries. PMID:27511442

  6. Fuzzy-control-based five-step Li-ion battery charger by using AC impedance technique

    NASA Astrophysics Data System (ADS)

    Asadi, Houshyar; Aghay Kaboli, Seyed Hamidreza; Mohammadi, Arash; Oladazimi, Maysam

    2011-12-01

    In This paper the previous Li-Ion battery charger techniques are reviewed and compared and the new fuzzy logic battery charging method which is proposed to optimize and improve the battery charger efficiently. According to results of comparison, using the fuzzy control charging system can shorten the charging time with higher efficiency and lower temperature rise. Additionally, we have used optimal Li-ion battery charging frequency by using AC impedance technique which means if the battery is charged by the optimal charging frequency fZmin, that obtain from Bode Plot of the Li-ion battery, the charging time and charging efficiency will improve. Thus using the switching frequency (fZmin) of the battery charger and the fuzzy logic control on the same system can optimize the performance on the charging process. According to the experimental results, the proposed charger can charge the Li-ion batteries with higher efficiency 97.16%, lower temperature rise1.513degree celosias, fast charging period around 50.43 minute and long life cycle. The results in this paper are presented by using MATLAB and dsPIC30F2020 is used as controller applying designed fuzzy logic inside.

  7. Fuzzy-control-based five-step Li-ion battery charger by using AC impedance technique

    NASA Astrophysics Data System (ADS)

    Asadi, Houshyar; Aghay Kaboli, Seyed Hamidreza; Mohammadi, Arash; Oladazimi, Maysam

    2012-01-01

    In This paper the previous Li-Ion battery charger techniques are reviewed and compared and the new fuzzy logic battery charging method which is proposed to optimize and improve the battery charger efficiently. According to results of comparison, using the fuzzy control charging system can shorten the charging time with higher efficiency and lower temperature rise. Additionally, we have used optimal Li-ion battery charging frequency by using AC impedance technique which means if the battery is charged by the optimal charging frequency fZmin, that obtain from Bode Plot of the Li-ion battery, the charging time and charging efficiency will improve. Thus using the switching frequency (fZmin) of the battery charger and the fuzzy logic control on the same system can optimize the performance on the charging process. According to the experimental results, the proposed charger can charge the Li-ion batteries with higher efficiency 97.16%, lower temperature rise1.513degree celosias, fast charging period around 50.43 minute and long life cycle. The results in this paper are presented by using MATLAB and dsPIC30F2020 is used as controller applying designed fuzzy logic inside.

  8. ALD of Al2O3 for Highly Improved Performance in Li-Ion Batteries

    SciTech Connect

    Dillon, A.; Jung, Y. S.; Ban, C.; Riley, L.; Cavanagh, A.; Yan, Y.; George, S.; Lee, S. H.

    2012-01-01

    Significant advances in energy density, rate capability and safety will be required for the implementation of Li-ion batteries in next generation electric vehicles. We have demonstrated atomic layer deposition (ALD) as a promising method to enable superior cycling performance for a vast variety of battery electrodes. The electrodes range from already demonstrated commercial technologies (cycled under extreme conditions) to new materials that could eventually lead to batteries with higher energy densities. For example, an Al2O3 ALD coating with a thickness of ~ 8 A was able to stabilize the cycling of unexplored MoO3 nanoparticle anodes with a high volume expansion. The ALD coating enabled stable cycling at C/2 with a capacity of ~ 900 mAh/g. Furthermore, rate capability studies showed the ALD-coated electrode maintained a capacity of 600 mAh/g at 5C. For uncoated electrodes it was only possible to observe stable cycling at C/10. Also, we recently reported that a thin ALD Al2O3 coating with a thickness of ~5 A can enable natural graphite (NG) electrodes to exhibit remarkably durable cycling at 50 degrees C. The ALD-coated NG electrodes displayed a 98% capacity retention after 200 charge-discharge cycles. In contrast, bare NG showed a rapid decay. Additionally, Al2O3 ALD films with a thickness of 2 to 4 A have been shown to allow LiCoO2 to exhibit 89% capacity retention after 120 charge-discharge cycles performed up to 4.5 V vs Li/Li+. Bare LiCoO2 rapidly deteriorated in the first few cycles. The capacity fade is likely caused by oxidative decomposition of the electrolyte at higher potentials or perhaps cobalt dissolution. Interestingly, we have recently fabricated full cells of NG and LiCoO2 where we coated both electrodes, one or the other electrode as well as neither electrode. In creating these full cells, we observed some surprising results that lead us to obtain a greater understanding of the ALD coatings. We have also recently coated a binder free LiNi0.04Mn0

  9. High voltage spinel oxides for Li-ion batteries: From the material research to the application

    NASA Astrophysics Data System (ADS)

    Patoux, Sébastien; Daniel, Lise; Bourbon, Carole; Lignier, Hélène; Pagano, Carole; Le Cras, Frédéric; Jouanneau, Séverine; Martinet, Sébastien

    Li-ion batteries are already used in many nomad applications, but improvement of this technology is still necessary to be durably introduced on new markets such as electric vehicles (EVs), hybrid electric vehicles (HEVs) or eventually photovoltaic solar cells. Modification of the nature of the active materials of electrodes is the most challenging and innovative aspect. High voltage spinel oxides for Li-ion batteries, with general composition LiMn 2- xM xO 4 (M a transition metal element), may be used to face increasing power source demand. It should be possible to obtain up to 240 Wh kg -1 at cell level when combining a nickel manganese spinel oxide with graphite (even more with silicon/carbon nanocomposites at the anode). Specific composition and material processing have to be selected with care, as discussed in this paper. It is demonstrated that 'LiNi 0.5Mn 1.5O 4' and LiNi 0.4Mn 1.6O 4 have remarkable properties such as high potential, high energy density, good cycle life and high rate capability. Choice of the electrolyte is also of primary importance in order to prevent its degradation at high voltage in contact with active surfaces. We showed that a few percents of additive in the electrolyte were suitable for protecting the positive electrode/electrolyte interface, and reducing the self-discharge. High voltage materials are also possibly interesting to be used in safe and high power Li-ion cells. In this case, the negative electrode may be made of Li 4Ti 5O 12 or TiO 2 to give a '3 V' system.

  10. Solid-State Li-Ion Batteries Using Fast, Stable, Glassy Nanocomposite Electrolytes for Good Safety and Long Cycle-Life.

    PubMed

    Tan, Guoqiang; Wu, Feng; Zhan, Chun; Wang, Jing; Mu, Daobin; Lu, Jun; Amine, Khalil

    2016-03-01

    The development of safe, stable, and long-life Li-ion batteries is being intensively pursued to enable the electrification of transportation and intelligent grid applications. Here, we report a new solid-state Li-ion battery technology, using a solid nanocomposite electrolyte composed of porous silica matrices with in situ immobilizing Li(+)-conducting ionic liquid, anode material of MCMB, and cathode material of LiCoO2, LiNi1/3Co1/3Mn1/3O2, or LiFePO4. An injection printing method is used for the electrode/electrolyte preparation. Solid nanocomposite electrolytes exhibit superior performance to the conventional organic electrolytes with regard to safety and cycle-life. They also have a transparent glassy structure with high ionic conductivity and good mechanical strength. Solid-state full cells tested with the various cathodes exhibited high specific capacities, long cycling stability, and excellent high temperature performance. This solid-state battery technology will provide new avenues for the rational engineering of advanced Li-ion batteries and other electrochemical devices. PMID:26862941

  11. Li ion nanowire batteries and their in situ characterization in the TEM

    NASA Astrophysics Data System (ADS)

    Ruzmetov, Dmitry

    2012-02-01

    The ability to measure the morphological, chemical, and transport characteristics with nanoscale resolution in electrochemical energy storage devices is critical for understanding the complex interfacial reactions and phase transformation that accompany cycling of secondary batteries. In this talk I will describe the use of an all-nanowire Li ion battery for in situ characterization of charge and discharge reactions. The nanowire batteries (NWBs) consist of a metalized core, a LiCoO2 cathode, LiPON solid electrolyte, and a thin film Si anode. Measuring several micrometers in length and several hundred nanometers in diameter, the NWBs can be readily imaged and analyzed in transmission electron microscopes (TEM, STEM). We use focused ion beam milling and electron beam induced deposition to separate the cathode and anode and fabricate Pt contacts to a NWB. In situ electrical cycling of NWBs in TEM reveals that the most of the structural changes due to cycling happens in the electrolyte layer especially near the cathode/electrolyte interface. Electrical response from a single NWB was measured in the sub-pA range. For NWBs with the thinnest electrolyte, approximately 100 nm, we observe rapid self-discharge, along with void formation at the electrode/electrolyte interface, indicating electrical and chemical breakdown. The analysis of the NWB's electrical characteristics reveals space-charge limited electronic conduction, which effectively shorts the anode and cathode electrodes. When the electrolyte thickness is increased, the self-discharge rate is reduced substantially and the NWBs maintain a potential above 2 V. Our study illustrates that at reduced dimensions the increase in the electric field can lead to large electronic current in the electrolyte effectively shorting the battery even when the electrolyte layer is uniform and pinhole free. The scaling of this phenomenon provides useful guidelines for design of 3D Li ion batteries.

  12. Interaction of High Flash Point Electrolytes and PE-Based Separators for Li-Ion Batteries

    PubMed Central

    Hofmann, Andreas; Kaufmann, Christoph; Müller, Marcus; Hanemann, Thomas

    2015-01-01

    In this study, promising electrolytes for use in Li-ion batteries are studied in terms of interacting and wetting polyethylene (PE) and particle-coated PE separators. The electrolytes are characterized according to their physicochemical properties, where the flow characteristics and the surface tension are of particular interest for electrolyte–separator interactions. The viscosity of the electrolytes is determined to be in a range of η = 4–400 mPa∙s and surface tension is finely graduated in a range of γL = 23.3–38.1 mN∙m−1. It is verified that the technique of drop shape analysis can only be used in a limited matter to prove the interaction, uptake and penetration of electrolytes by separators. Cell testing of Li|NMC half cells reveals that those cell results cannot be inevitably deduced from physicochemical electrolyte properties as well as contact angle analysis. On the other hand, techniques are more suitable which detect liquid penetration into the interior of the separator. It is expected that the results can help fundamental researchers as well as users of novel electrolytes in current-day Li-ion battery technologies for developing and using novel material combinations. PMID:26343636

  13. Lithium salt of tetrahydroxybenzoquinone: toward the development of a sustainable Li-ion battery.

    PubMed

    Chen, Haiyan; Armand, Michel; Courty, Matthieu; Jiang, Meng; Grey, Clare P; Dolhem, Franck; Tarascon, Jean-Marie; Poizot, Philippe

    2009-07-01

    The use of lithiated redox organic molecules containing electrochemically active C=O functionalities, such as lithiated oxocarbon salts, is proposed. These represent alternative electrode materials to those used in current Li-ion battery technology that can be synthesized from renewable starting materials. The key material is the tetralithium salt of tetrahydroxybenzoquinone (Li(4)C(6)O(6)), which can be both reduced to Li(2)C(6)O(6) and oxidized to Li(6)C(6)O(6). In addition to being directly synthesized from tetrahydroxybenzoquinone by neutralization at room temperature, we demonstrate that this salt can readily be formed by the thermal disproportionation of Li(2)C(6)O(6) (dilithium rhodizonate phase) under an inert atmosphere. The Li(4)C(6)O(6) compound shows good electrochemical performance vs Li with a sustained reversibility of approximately 200 mAh g(-1) at an average potential of 1.8 V, allowing a Li-ion battery that cycles between Li(2)C(6)O(6) and Li(6)C(6)O(6) to be constructed. PMID:19476355

  14. Interaction of High Flash Point Electrolytes and PE-Based Separators for Li-Ion Batteries.

    PubMed

    Hofmann, Andreas; Kaufmann, Christoph; Müller, Marcus; Hanemann, Thomas

    2015-01-01

    In this study, promising electrolytes for use in Li-ion batteries are studied in terms of interacting and wetting polyethylene (PE) and particle-coated PE separators. The electrolytes are characterized according to their physicochemical properties, where the flow characteristics and the surface tension are of particular interest for electrolyte-separator interactions. The viscosity of the electrolytes is determined to be in a range of η = 4-400 mPa∙s and surface tension is finely graduated in a range of γL = 23.3-38.1 mN∙m(-1). It is verified that the technique of drop shape analysis can only be used in a limited matter to prove the interaction, uptake and penetration of electrolytes by separators. Cell testing of Li|NMC half cells reveals that those cell results cannot be inevitably deduced from physicochemical electrolyte properties as well as contact angle analysis. On the other hand, techniques are more suitable which detect liquid penetration into the interior of the separator. It is expected that the results can help fundamental researchers as well as users of novel electrolytes in current-day Li-ion battery technologies for developing and using novel material combinations. PMID:26343636

  15. New High Capacity Cathode Materials for Rechargeable Li-ion Batteries: Vanadate-Borate Glasses

    NASA Astrophysics Data System (ADS)

    Afyon, Semih; Krumeich, Frank; Mensing, Christian; Borgschulte, Andreas; Nesper, Reinhard

    2014-11-01

    V2O5 based materials are attractive cathode alternatives due to the many oxidation state switches of vanadium bringing about a high theoretical specific capacity. However, significant capacity losses are eminent for crystalline V2O5 phases related to the irreversible phase transformations and/or vanadium dissolution starting from the first discharge cycle. These problems can be circumvented if amorphous or glassy vanadium oxide phases are employed. Here, we demonstrate vanadate-borate glasses as high capacity cathode materials for rechargeable Li-ion batteries for the first time. The composite electrodes of V2O5 - LiBO2 glass with reduced graphite oxide (RGO) deliver specific energies around 1000 Wh/kg and retain high specific capacities in the range of ~ 300 mAh/g for the first 100 cycles. V2O5 - LiBO2 glasses are considered as promising cathode materials for rechargeable Li-ion batteries fabricated through rather simple and cost-efficient methods.

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Atomic-Scale Mechanisms for Electrolyte Decomposition in Li-ion Battery Cathodes

    NASA Astrophysics Data System (ADS)

    Fuhst, Mallory; Siegel, Donald

    Li-ion batteries using high energy density LiCoO2 (LCO) intercalation cathodes are known to generate gaseous species inside the cell, which can lead to venting flammable solvent vapor. It has been hypothesized that reactions at the cathode/electrolyte interface catalyze the production of these gaseous species. To elucidate the underlying reaction mechanism, first principles calculations were used to model interactions between LCO surfaces and Ethylene Carbonate (EC), a commonly used solvent in Li-ion batteries. A Metropolis Monte Carlo algorithm was used to identify likely low energy adsorption configurations for EC on the (10-14) surface of LCO. Several of these geometries were further analyzed with DFT. The thermodynamics and kinetics of EC decomposition were evaluated for plausible reaction pathways and associated various solvent decomposition mechanisms, such as hydrogen abstraction. Preliminary results indicate that hydrogen abstraction may lead to the spontaneous decomposition of EC into CO and other adsorbed species at the surface. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE 1256260.

  18. New high capacity cathode materials for rechargeable Li-ion batteries: vanadate-borate glasses.

    PubMed

    Afyon, Semih; Krumeich, Frank; Mensing, Christian; Borgschulte, Andreas; Nesper, Reinhard

    2014-01-01

    V2O5 based materials are attractive cathode alternatives due to the many oxidation state switches of vanadium bringing about a high theoretical specific capacity. However, significant capacity losses are eminent for crystalline V2O5 phases related to the irreversible phase transformations and/or vanadium dissolution starting from the first discharge cycle. These problems can be circumvented if amorphous or glassy vanadium oxide phases are employed. Here, we demonstrate vanadate-borate glasses as high capacity cathode materials for rechargeable Li-ion batteries for the first time. The composite electrodes of V2O5 - LiBO(2) glass with reduced graphite oxide (RGO) deliver specific energies around 1000 Wh/kg and retain high specific capacities in the range of ~ 300 mAh/g for the first 100 cycles. V2O5 - LiBO(2) glasses are considered as promising cathode materials for rechargeable Li-ion batteries fabricated through rather simple and cost-efficient methods. PMID:25408200

  19. Performance of Li-Ion Cells Under Battery Voltage Charge Control

    NASA Technical Reports Server (NTRS)

    Vaidyanathan, Hari; Rao, Gopalakrishna M.

    2002-01-01

    Li-ion cells manufactured by YTP, SAFT, and MSA have completed 6714, 6226, and 3441 cycles, respectively. An increase in the charge voltage limit was required in all cases to maintain the discharge voltage. SAFT and MSA cells were capable of cycling at -10 C and 0 C with an increase in the charge voltage limit, whereas Yardney cells could not be cycled. Reconditioning improved the discharge voltage of SAFT and MSA cells; it is important to note that the effect has been temporary as in Ni-H and Ni-Cd batteries. It was demonstrated that the charge operation with VT clamp at battery rather than at cell level is feasible. Continuation of testing depends on the health of the cells and on the funding situation.

  20. A Major Constituent of Brown Algae for Use in High-Capacity Li-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Kovalenko, Igor; Zdyrko, Bogdan; Magasinski, Alexandre; Hertzberg, Benjamin; Milicev, Zoran; Burtovyy, Ruslan; Luzinov, Igor; Yushin, Gleb

    2011-10-01

    The identification of similarities in the material requirements for applications of interest and those of living organisms provides opportunities to use renewable natural resources to develop better materials and design better devices. In our work, we harness this strategy to build high-capacity silicon (Si) nanopowder-based lithium (Li)-ion batteries with improved performance characteristics. Si offers more than one order of magnitude higher capacity than graphite, but it exhibits dramatic volume changes during electrochemical alloying and de-alloying with Li, which typically leads to rapid anode degradation. We show that mixing Si nanopowder with alginate, a natural polysaccharide extracted from brown algae, yields a stable battery anode possessing reversible capacity eight times higher than that of the state-of-the-art graphitic anodes.

  1. New Li-ion Battery Evaluation Research Based on Thermal Property and Heat Generation Behavior of Battery

    NASA Astrophysics Data System (ADS)

    Lv, Zhe; Guo, Xun; Qiu, Xin-ping

    2012-12-01

    We do a new Li-ion battery evaluation research on the effects of cell resistance and polarization on the energy loss in batteries based on thermal property and heat generation behavior of battery. Series of 18650 cells with different capacities and electrode materials are evaluated by measuring input and output energy which change with charge-discharge time and current. Based on the results of these tests, we build a model of energy loss in cells' charge-discharge process, which include Joule heat and polarization heat impact factors. It was reported that Joule heat was caused by cell resistance, which included DC-resistance and reaction resistance, and reaction resistance could not be easily obtained through routine test method. Using this new method, we can get the total resistance R and the polarization parameter η. The relationship between R, η, and temperature is also investigated in order to build a general model for series of different Li-ion batteries, and the research can be used in the performance evaluation, state of charge prediction and the measuring of consistency of the batteries.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Electron paramagnetic resonance imaging for real-time monitoring of Li-ion batteries

    PubMed Central

    Sathiya, M.; Leriche, J.-B.; Salager, E.; Gourier, D.; Tarascon, J.-M.; Vezin, H.

    2015-01-01

    Batteries for electrical storage are central to any future alternative energy paradigm. The ability to probe the redox mechanisms occurring at electrodes during their operation is essential to improve battery performances. Here we present the first report on Electron Paramagnetic Resonance operando spectroscopy and in situ imaging of a Li-ion battery using Li2Ru0.75Sn0.25O3, a high-capacity (>270 mAh g−1) Li-rich layered oxide, as positive electrode. By monitoring operando the electron paramagnetic resonance signals of Ru5+ and paramagnetic oxygen species, we unambiguously prove the formation of reversible (O2)n− species that contribute to their high capacity. In addition, we visualize by imaging with micrometric resolution the plating/stripping of Li at the negative electrode and highlight the zones of nucleation and growth of Ru5+/oxygen species at the positive electrode. This efficient way to locate ‘electron’-related phenomena opens a new area in the field of battery characterization that should enable future breakthroughs in battery research. PMID:25662295

  4. Evaluation on a water-based binder for the graphite anode of Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, S. S.; Xu, K.; Jow, T. R.

    We evaluate poly(acrylamide-co-diallyldimethylammonium chloride) (AMAC) as a water-based binder for the graphite anode of Li-ion batteries. It is shown that AMAC has a similar bonding ability as the conventional poly(vinylidene fluoride) (PVDF) binder, and that the graphite electrodes bonded by AMAC and PVDF have nearly the same cyclability. Advantages of AMAC binder include: (1) it assists in forming a more conductive solid electrolyte interface (SEI) on the surface of graphite and (2) organic liquid electrolyte exhibits better penetration on the AMAC-bonded electrode. Impedance analysis shows that formation of the SEI on the surface of graphite includes two stages. The first stage takes place above 0.15 V and the second stage between 0.15 and 0.04 V. The SEI formed in the first stage is relatively resistive, while that formed in the second stage is highly conductive. For the first stage, the presence of AMAC may enhance the conductivity of the SEI. We performed a storage test on the AMAC-bonded graphite by monitoring the change of open-circuit voltage (OCV) of fully lithiated Li/graphite cells and by comparing their capacity change before and after storage. We observed that OCV of the cell increased gradually, and that capacity loss during the storage recovered in the subsequent lithiation process. Therefore, the OCV increase could be considered a self-delithiation process, which does not consume permanently Li + ions.

  5. Hierarchically ordered mesoporous Co3O4 materials for high performance Li-ion batteries

    PubMed Central

    Sun, Shijiao; Zhao, Xiangyu; Yang, Meng; Wu, Linlin; Wen, Zhaoyin; Shen, Xiaodong

    2016-01-01

    Highly ordered mesoporous Co3O4 materials have been prepared via a nanocasting route with three-dimensional KIT-6 and two-dimensional SBA-15 ordered mesoporous silicas as templates and Co(NO3)2 · 6H2O as precursor. Through changing the hydrothermal treating temperature of the silica template, ordered mesoporous Co3O4 materials with hierarchical structures have been developed. The larger pores around 10 nm provide an efficient transport for Li ions, while the smaller pores between 3–5 nm offer large electrochemically active areas. Electrochemical impedance analysis proves that the hierarchical structure contributes to a lower charge transfer resistance in the mesoporous Co3O4 electrode than the mono-sized structure. High reversible capacities around 1141 mAh g−1 of the hierarchically mesoporous Co3O4 materials are obtained, implying their potential applications for high performance Li-ion batteries. PMID:26781265

  6. Flexible high-energy Li-ion batteries with fast-charging capability.

    PubMed

    Park, Mi-Hee; Noh, Mijung; Lee, Sanghan; Ko, Minseong; Chae, Sujong; Sim, Soojin; Choi, Sinho; Kim, Hyejung; Nam, Haisol; Park, Soojin; Cho, Jaephil

    2014-07-01

    With the development of flexible mobile devices, flexible Li-ion batteries have naturally received much attention. Previously, all reported flexible components have had shortcomings related to power and energy performance. In this research, in order to overcome these problems while maintaining the flexibility, honeycomb-patterned Cu and Al materials were used as current collectors to achieve maximum adhesion in the electrodes. In addition, to increase the energy and power multishelled LiNi0.75Co0.11Mn0.14O2 particles consisting of nanoscale V2O5 and LixV2O5 coating layers and a LiδNi0.75-zCo0.11Mn0.14VzO2 doping layer were used as the cathode-anode composite (denoted as PNG-AES) consisting of amorphous Si nanoparticles (<20 nm) loaded on expanded graphite (10 wt %) and natural graphite (85 wt %). Li-ion cells with these three elements (cathode, anode, and current collector) exhibited excellent power and energy performance along with stable cycling stability up to 200 cycles in an in situ bending test. PMID:24892499

  7. Do we need covalent bonding of Si nanoparticles on graphene oxide for Li-ion batteries?

    PubMed

    Miroshnikov, Yana; Grinbom, Gal; Gershinsky, Gregory; Nessim, Gilbert D; Zitoun, David

    2014-01-01

    In this manuscript, we report our investigation of anode materials for Li-ion batteries based on silicon-graphene oxide composites. Previous reports in the literature on silicon-graphene oxide (GO) composites as anodes have shown a large discrepancy between the electrochemical properties, mainly capacity and coulombic efficiency. In our research, the surface chemistry of Si nanoparticles has been functionalized to yield a chemical bond between the Si and GO, a further annealing step yields a Si-reduced GO (Si-rGO) composite while controlled experiments have been carried on mechanical mixing of GO and Si. For all samples, including a simple mixing of Si nanoparticles and GO, a high specific capacity of 2000 mA h g(Si)(-1) can be achieved for 50 cycles. The main difference between the samples can be observed in terms of coulombic efficiency, which will determine the future of these composites in full Li-ion cells. The Si-rGO composite shows a very low capacity fading and a coulombic efficiency above 99%. Furthermore, the Si-rGO composite can be cycled at very high rate to 20 C (charge in 3 minutes). PMID:25467631

  8. Use of phosphoranimines to reduce organic carbonate content in Li-ion battery electrolytes

    DOE PAGESBeta

    Dufek, Eric J.; Klaehn, John R.; McNally, Joshua S.; Rollins, Harry W.; Jamison, David K.

    2016-05-09

    In this study, the use of phosphoranimines (PAs), a class of linear, monomeric phosphazenes, as electrolytes for Li-ion battery applications has been investigated as a route to improve safety and stability for Li-ion batteries. Of the potential PAs for use in battery applications, this work focuses on the initial synthetic preparation and analysis of N-trimethylsilyl-P,P-bis((2-methoxyethoxy)ethoxy)-P-ethylphosphoranimine (PA-5). PA-5 has high LiPF6 solubility in excess of 2 M, high thermal stability with a melting point below -80°C and high thermal stability as a neat compound to at least 250°C. As part of electrolyte blends, the inclusion of PA-5 shifts the onset ofmore » thermal degradation by close to 40°C at 35% loading and by 20°C at a 10% loading, improves the low temperature performance of the electrolyte, and when used as a primary solvent leads to increases in the flash point (by 20°C) when compared to more traditional EC:EMC blends. Cycling capabilities of full-coin cells with graphite negative electrodes and Li1+w[Ni0.5Mn0.3Co0.2]1-wO2 positive electrodes using PA-5:EC:EMC electrolyte blends are comparable with the performance seen for traditional EC:EMC blends. Analysis of the impact of the use of additives such as vinylene carbonate in PA-5:EC:EMC blended electrolyte results in enhanced capacity retention and improved coulombic efficiency.« less

  9. Performance of Li-Ion Cells Under Battery Voltage Charge Control

    NASA Technical Reports Server (NTRS)

    Rao, Gopalakrishna M.; Vaidyanathan, Hari; Day, John H. (Technical Monitor)

    2001-01-01

    A study consisting of electrochemical characterization and Low-Earth-Orbit (LEO) cycling of Li-Ion cells from three vendors was initiated in 1999 to determine the cycling performance and to infuse the new technology in the future NASA missions. The 8-cell batteries included in this evaluation are prismatic cells manufactured by Mine Safety Appliances Company (MSA), cylindrical cells manufactured by SAFT and prismatic cells manufactured by Yardney Technical Products, Inc. (YTP). The three batteries were cycle tested in the LEO regime at 40% depth of discharge, and under a charge control technique that consists of battery voltage clamp with a current taper. The initial testing was conducted at 20 C; however, the batteries were cycled also intermittently at low temperatures. YTP 20 Ah cells consisted of mixed-oxide (Co and Ni) positive, graphitic carbon negative, LIPF6 salt mixed with organic carbonate solvents. The battery voltage clamp was 32 V. The low temperature cycling tests started after 4575 cycles at 20 C. The cells were not capable of cycling. at low temperature since the charge acceptance at battery level was poor. There was a cell in the battery that showed too high an end-of-charge (EOC) voltage thereby limiting the ability to charge the rest of the cells in the battery. The battery has completed 6714 cycles. SAFT 12 Ah cells consisted of mixed-oxide (Co and NO positive, graphitic carbon negative, LiPF6 salt mixed with organic carbonate solvents. The battery voltage clamp was for 30.8 V. The low temperature cycling tests started after 4594 cycles at 20 C. A cell that showed low end of discharge (EOD) and EOC voltages and three other cells that showed higher EOC voltages limited the charge acceptance at the selected voltage limit during charge. The cells were capable of cycling at 10 C and 0 C but the charge voltage limit had to be increased to 34.3 V (4.3 V per cell). The low temperature cycling may have induced poor chargeability since the voltage had to

  10. Quantitative Analysis of Three-dimensional Microstructure of Li-ion Battery Electrodes

    NASA Astrophysics Data System (ADS)

    Liu, Zhao

    Li-ion batteries (LIBs) have attracted considerable attention in the past two decades due to their widespread applications in portable electronics, and their growing use in electric vehicles and large-scale grid storage. Increasing battery energy density and powder density while maintaining long life, along with battery safety, are the biggest challenges that limit their further development. Various approaches with materials and chemistry have been employed to improve performance. However, one less-studied aspect that also impacts performance is the electrode microstructure. In particular, three-dimensional (3D) electrode microstructural data for LIB electrodes, which were not widely available prior to this thesis, can provide important input for understanding and improving LIB performance. The focus of this thesis is to apply 3D tomographic techniques, together with electrochemical performance data, to obtain LIB microstructure-performance correlations. Two advanced 3D structural analysis techniques, focused ion beam-scanning electron microscopy (FIB-SEM) and transmission X-ray microscopy (TXM) nanotomography, are used to quantify LIB electrode microstructure. 3D characterization of LIB electrode microstructure is used to obtain a deeper understanding of mechanisms that limit LIB performance. Microstructural characterization before and after cycling is used to explore capacity loss mechanisms. It is hoped that the results can guide electrode microstructures design to improve performance and stability. Two types of commercial electrodes, LiCoO2 and LiCoO 2/Li(Ni1/3Mn1/3Co1/3)O2, are studied using FIB-SEM and TXM. Both methods were found to be applicable to quantifying the oxide particle microstructure, including volume fraction, surface area, and particle size distribution, and results agreed well. However, structural inhomogeneity found in these commercial samples, limited the capability to resolve microstructural changes during cycling. In order to also quantify

  11. Flexible carbon nanotube--Cu2O hybrid electrodes for li-ion batteries.

    PubMed

    Goyal, Anubha; Reddy, Arava L M; Ajayan, Pulickel M

    2011-06-20

    This study demonstrates the formation of a flexible and free-standing carbon nanotube-copper oxide-poly(vinylidene fluoride) (CNT-Cu(2) O-PVDF) nanocomposite and its application as an electrode-separator material for Li-ion batteries. Binder-free hybrid electrodes are obtained by conformally coating CNTs with Cu(2) O via electrodeposition and then embedding the resulting architecture into a porous poly(vinylidene fluoride-hexafluoropropylene) PVDF-HFP-SiO(2) polymer electrolyte membrane. The synergistic presence of high-capacity transition metal oxides and conductive CNTs results in twice the reversible areal capacity of 2.3 mAh cm(-2) as compared to 1.2 mAh cm(-2) for pure CNTs. PMID:21574248

  12. Cross-Linked Chitosan as an Efficient Binder for Si Anode of Li-ion Batteries.

    PubMed

    Chen, Chao; Lee, Sang Ha; Cho, Misuk; Kim, Jaehoon; Lee, Youngkwan

    2016-02-01

    We investigate the use of chitosan (CS) as a new cross-linkable and water-soluble binder for the Si anode of Li-ion batteries. In contrast to the traditional binder utilizing a hydrogen bond and/or van der Waals force-linked anode electrodes, CS can easily form a 3D network to limit the movement of Si particles through the cross-linking between the amino groups of CS and the dialdehyde of glutaraldehyde (GA). Chemical, mechanical, and morphological analyses are conducted by Fourier transform infrared spectroscopy, tensile testing, and scanning electron microscopy. The cross-linked Si/CS-GA anode exhibits an initial discharge capacity of 2782 mAh g(-1) with a high initial Coulombic efficiency of 89% and maintained a capacity of 1969 mAh g(-1) at the current density of 500 mA g(-1) over 100 cycles. PMID:26745390

  13. Carbon supported tin-based nanocomposites as anodes for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhou, Xiangyang; Zou, Youlan; Yang, Juan

    2013-02-01

    SnO2 (Sn)/C composites as anodes for Li-ion batteries were fabricated by a simple chemical process of hydrothermal synthesis and subsequent heat treatment. The as-prepared materials were characterized by various analytic techniques. Results show that heat treatment temperature has a strong influence on physical and electrochemical performance of these composites. In these composites, irregular SnO2 lamellas arranged like chrysanthemum were dispersed among the elastic carbon matrix for rapid access of lithium ions to the material bulk. SnO2/C anode heat-treated at a temperature of 600 °C exhibits a reversible capacity of 533.4 mAh/g after 50 cycles at the current density of 100 mA/g.

  14. TUNING SILICON NANORODS FOR ANODES OF LI-ION RECHARGEABLE BATTERIES

    SciTech Connect

    Au, M.

    2010-11-23

    Silicon is a promising anode material for Li-ion batteries in regarding of high capacity, low cost and safety, but it suffers poor cycling stability due to the pulverization induced by severe volume expansion/shrinkage (297%) during lithium insertion/extraction. In our previous investigation on aluminum nanorods anodes, it is found the selection of substrates in which Al nanorods grown plays the role in prevention of pulverization resulting in the increase of cycling life. Adapting this knowledge, we investigated the Si based nanorods anodes by tuning its composition and element distribution. Our results show that although the Si nanorods demonstrated higher initial anodic capacity of 1500 mAh/g, it diminished after 50 cycles due to morphology change and pulverization. By codepositing Cu, the Si-Cu composite nanorods demonstrated sustainable capacity of 500 mAh/g in 100 cycles attributing to its flexible and less brittle nature.

  15. Experimental and theoretical investigations of functionalized boron nitride as electrode materials for Li-ion batteries

    SciTech Connect

    Zhang, Fan; Nemeth, Karoly; Bareño, Javier; Dogan, Fulya; Bloom, Ira D.; Shaw, Leon L.

    2016-01-01

    The feasibility of synthesizing functionalized h-BN (FBN) via the reaction between molten LiOH and solid h-BN is studied for the first time and its first ever application as an electrode material in Li-ion batteries is evaluated. Density functional theory (DFT) calculations are performed to provide mechanistic understanding of the possible electrochemical reactions derived from the FBN. Various materials characterizations reveal that the melt-solid reaction can lead to exfoliation and functionalization of h-BN simultaneously, while electrochemical analysis proves that the FBN can reversibly store charges through surface redox reactions with good cycle stability and coulombic efficiency. DFT calculations have provided physical insights into the observed electrochemical properties derived from the FBN.

  16. Combined operando studies of new electrode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Jumas, Jean-Claude; Sougrati, Moulay Tahar; Perea, Alexis; Aldon, Laurent; Olivier-Fourcade, Josette

    2013-04-01

    The performances of Li-ion batteries depend on many factors amongst which the important ones are the electrode materials and their structural and electronic evolution upon cycling. For a better understanding of lithium reactivity mechanism of many materials the combination of X-Ray Powder Diffraction (XRPD) and Transmission Mössbauer Spectroscopy (TMS) providing both structural and electronic information during the electrochemical cycling has been carried out. Thanks to the design of a specific electrochemical cell, derived from a conventional Swagelock cell, such measurements have been realised in operando mode. Two examples illustrate the greatness of combining XRPD and TMS for the study of LiFe0.75Mn0.25PO4 as positive electrode and TiSnSb as negative electrode. Different kinds of insertion or conversion reactions have been identified leading to a better optimization and design of performing electrodes.

  17. Nanostructured Si/Sn-Ni/C composite as negative electrode for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Edfouf, Z.; Cuevas, F.; Latroche, M.; Georges, C.; Jordy, C.; Hézèque, T.; Caillon, G.; Jumas, J. C.; Sougrati, M. T.

    2011-05-01

    A nanostructured composite with overall atomic composition Ni0.14Sn0.17Si0.32Al0.037C0.346 has been prepared combining powder metallurgy and mechanical milling techniques for being used as anode material in Li-ion battery. Chemical and structural properties of the nanocomposite have been determined by X-ray diffraction (XRD), 119Sn Transmission Mössbauer Spectroscopy (TMS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The composite consists of Si particles with typical size ∼150 nm embedded in a poorly crystallized and complex multielemental matrix. The matrix is composed mostly by Ni3.4Sn4, and disordered carbon. Electrochemical evaluation shows a high reversible capacity of 920 mAh g-1, with reasonable reversible capacity retention (∼0.1% loss/cycle) over 280 cycles.

  18. Parameter sensitivity analysis of a simplified electrochemical and thermal model for Li-ion batteries aging

    NASA Astrophysics Data System (ADS)

    Edouard, C.; Petit, M.; Forgez, C.; Bernard, J.; Revel, R.

    2016-09-01

    In this work, a simplified electrochemical and thermal model that can predict both physicochemical and aging behavior of Li-ion batteries is studied. A sensitivity analysis of all its physical parameters is performed in order to find out their influence on the model output based on simulations under various conditions. The results gave hints on whether a parameter needs particular attention when measured or identified and on the conditions (e.g. temperature, discharge rate) under which it is the most sensitive. A specific simulation profile is designed for parameters involved in aging equations in order to determine their sensitivity. Finally, a step-wise method is followed to limit the influence of parameter values when identifying some of them, according to their relative sensitivity from the study. This sensitivity analysis and the subsequent step-wise identification method show very good results, such as a better fitting of the simulated cell voltage with experimental data.

  19. A Combustion Chemistry Analysis of Carbonate Solvents in Li-Ion Batteries

    SciTech Connect

    Harris, S J; Timmons, A; Pitz, W J

    2008-11-13

    Under abusive conditions Li-ion batteries can rupture, ejecting electrolyte and other flammable gases. In this paper we consider some of the thermochemical properties of these gases that will determine whether they ignite and how energetically they burn. We show that flames of carbonate solvents are fundamentally less energetic than those of conventional hydrocarbons. An example of this difference is given using a recently developed mechanism for dimethyl carbonate (DMC) combustion, where we show that a diffusion flame burning DMC has only half the peak energy release rate of an analogous propane flame. We find a significant variation among the carbonate solvents in the factors that are important to determining flammability, such as combustion enthalpy and vaporization enthalpy. This result suggests that thermochemical and kinetic factors might well be considered when choosing solvent mixtures.

  20. Ultrafine LiCoO2 powders derived from electrospun nanofibers for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Ou, Yun; Wen, Jingjing; Xu, Haiping; Xie, Shuhong; Li, Jiangyu

    2013-02-01

    Sol-gel based electrospinning has been developed to synthesize phase pure LiCoO2 powders at relatively low temperature with excellent crystallinity and ultrafine particle size. Compared to LiCoO2 powders synthesized from regular sol-gel processes, the nanofiber derived powders possess high initial discharge capacity and good cyclic stability, and the retention of initial capacity is also much higher than bare LiCoO2 nanofibers reported in literature. With additional surface modification of La2O3 coating, the retention of initial capacity is increased to 91% at 30th cycle and 83% at 50th cycle without decreasing its initial capacity, making it attractive for Li-ion batteries.

  1. Polyethylene terephthalate/poly(vinylidene fluoride) composite separator for Li-ion battery

    NASA Astrophysics Data System (ADS)

    Wu, Dezhi; Huang, Shaohua; Xu, Zhiqin; Xiao, Zhiming; Shi, Chuan; Zhao, Jinbao; Zhu, Rui; Sun, Daoheng; Lin, Liwei

    2015-06-01

    Electrospun nanofiber membranes have been proved to enhance the performance of a Li-ion battery (LIB), but their poor mechanical strength hinders their industrial application. This paper combines a meltblown polyethylene terephthalate (PET) nonwoven and a electrospun poly(vinylidene fluoride) (PVDF) membrane together to improve the mechanical property via hot-pressing, wherein a dried 3 wt% PVDF solution coating on PET nonwoven is used as a binder. The experiment results indicate that the hot-pressing PET/PVDF separator exhibits an excellent mechanical property, whose transverse and longitudinal tensile strength could reach 13.70 MPa and 34.85 MPa respectively. Compared with a commercial PP separator, the hot-pressing PET/PVDF membrane separator shows better wettability, higher thermal shrinkage and excellent discharge capacity as well.

  2. Polyethylene terephthalate/poly (vinylidene fluoride) composite separator for Li-ion battery

    NASA Astrophysics Data System (ADS)

    Wu, Dezhi; Huang, Shaohua; Xu, Zhiqin; Xiao, Zhiming; Shi, Chuan; Zhao, Jinbao; Zhu, Rui; Sun, Daoheng; Lin, Liwei

    2015-07-01

    Electrospun nanofiber membranes have been proved to enhance performances of Li-ion batteries, but their poor mechanical strength hinders their industrial application. This paper combines meltblown polyethylene terephthalate (PET) nonwoven and electrospun poly (vinylidene fluoride) (PVDF) membrane together to improve the mechanical property via hot-pressing, wherein a dried 3 wt% PVDF solution coating on PET nonwoven is used as a binder. The hot-pressing temperature is optimized to be 145 °C and the composite PET/PVDF separator exhibits an excellent mechanical property, whose transverse and longitudinal tensile strength could reach 13.70 and 34.85 MPa respectively. Compared with a commercial PP separator, the hot-pressed PET/PVDF membrane separator shows better wettability, higher thermal shrinkage and improved electrochemical performance as well.

  3. Selected test results from the LiFeBatt iron phosphate Li-ion battery.

    SciTech Connect

    Ingersoll, David T.; Hund, Thomas D.

    2008-09-01

    In this paper the performance of the LiFeBatt Li-ion cell was measured using a number of tests including capacity measurements, capacity as a function of temperature, ohmic resistance, spectral impedance, high power partial state of charge (PSOC) pulsed cycling, pulse power measurements, and an over-charge/voltage abuse test. The goal of this work was to evaluate the performance of the iron phosphate Li-ion battery technology for utility applications requiring frequent charges and discharges, such as voltage support, frequency regulation, and wind farm energy smoothing. Test results have indicated that the LiFeBatt battery technology can function up to a 10C{sub 1} discharge rate with minimal energy loss compared to the 1 h discharge rate (1C). The utility PSOC cycle test at up to the 4C{sub 1} pulse rate completed 8,394 PSOC pulsed cycles with a gradual loss in capacity of 10 to 15% depending on how the capacity loss is calculated. The majority of the capacity loss occurred during the initial 2,000 cycles, so it is projected that the LiFeBatt should PSOC cycle well beyond 8,394 cycles with less than 20% capacity loss. The DC ohmic resistance and AC spectral impedance measurements also indicate that there were only very small changes after cycling. Finally, at a 1C charge rate, the over charge/voltage abuse test resulted in the cell venting electrolyte at 110 C after 30 minutes and then open-circuiting at 120 C with no sparks, fire, or voltage across the cell.

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

    PubMed

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

    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 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. PMID:26395323

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

    PubMed Central

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

    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 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. PMID:26395323

  6. Development and testing of 100 kW/1 min Li-ion battery systems for energy storage applications

    NASA Astrophysics Data System (ADS)

    Clark, N. H.; Doughty, D. H.

    Two 100 kW min -1 (1.67 kW h -1) Li-ion battery energy storage systems (BESS) are described. The systems include a high-power Li-ion battery and a 100 kW power conditioning system (PCS). The battery consists of 12 modules of 12 series-connected Saft Li-ion VL30P cells. The stored energy of the battery ranges from 1.67 to 14 kW h -1 and has an operating voltage window of 515-405 V (dc). Two complete systems were designed, built and successfully passed factory acceptance testing after which each was deployed in a field demonstration. The first demonstration used the system to supplement distributed microturbine generation and to provide load following capability. The system was run at its rated power level for 3 min, which exceeded the battery design goal by a factor of 3. The second demonstration used another system as a stand-alone uninterrupted power supply (UPS). The system was available (online) for 1146 h and ran for over 2 min.

  7. Development and testing of 100-kW/ 1-minute Li-ion battery systems for energy storage applications.

    SciTech Connect

    Doughty, Daniel Harvey; Clark, Nancy H.

    2004-07-01

    Two 100 kW min{sup -1} (1.67 kW h{sup -1}) Li-ion battery energy storage systems (BESS) are described. The systems include a high-power Li-ion battery and a 100 kW power conditioning system (PCS). The battery consists of 12 modules of 12 series-connected Saft Li-ion VL30P cells. The stored energy of the battery ranges from 1.67 to 14 kW h{sup -1} and has an operating voltage window of 515-405 V (dc). Two complete systems were designed, built and successfully passed factory acceptance testing after which each was deployed in a field demonstration. The first demonstration used the system to supplement distributed microturbine generation and to provide load following capability. The system was run at its rated power level for 3 min, which exceeded the battery design goal by a factor of 3. The second demonstration used another system as a stand-alone uninterrupted power supply (UPS). The system was available (online) for 1146 h and ran for over 2 min.

  8. Intelligent Li ion battery management based on a digital signal processor for a moving actuator total artificial heart.

    PubMed

    Kim, W E; Ahn, J M; Choi, S W; Min, B G

    1997-01-01

    An intelligent Li Ion battery management (ILBM) system was developed based on a digital signal processor (DSP). Instead of using relatively complicated hardware charging control, a DSP algorithm was used, and favorable characteristics in volume, mass, and temperature increase of the implantable battery were achieved. In vitro tests were performed to evaluate the DSP based algorithm for Li Ion charging control (24 V dc motor input power 16 W, 5 L/min, 100 mmHg afterload). In this article, the first improvement was volume reduction using a Li Ion battery (3.6 V/Cell, 900 mA, seven cells: 25.2 V, 22.7 W). Its volume and mass were decreased by 40% and 50% respectively (40*55*75 mm, 189 g), compared to previously reported results, with total energy capacity increased by 110% (more than 60 min vs 25 min run time in the other battery). The second improvement includes the ILBM, which can control the performance detection for each unit cell and has a low temperature rise. The ILBM's unit cell energy detection was important because the low performance of one cell dropped to 50% of the total performance along with a 20% increase in surface temperature. All electronics for a transcutaneous energy transmission (TET), battery, and telemetry were finalized for hybridization and used for total artificial heat (TAH) implantation. PMID:9360113

  9. Polytype and stacking faults in the Li2CoSiO4 Li-ion battery cathode.

    PubMed

    Truong, Quang Duc; Devaraju, Murukanahally Kempaiah; Sasaki, Yoshikazu; Hyodo, Hiroshi; Honma, Itaru

    2014-12-01

    Atomic-resolution imaging of the crystal defects of cathode materials is crucial to understand their formation and the correlation between the structure, electrical properties, and electrode performance in rechargeable batteries. The polytype, a stable form of varied crystal structure with uniform chemical composition, holds promise to engineer electronic band structure in nanoscale homojunctions.1-3 Analyzing the exact sites of atoms and the chemistry of the boundary in polytypes would advance our understanding of their formation and properties. Herein, the polytype and stacking faults in the lithium cobalt silicates are observed directly by aberration-corrected scanning transmission electron microscopy. The atomic-scale imaging allows clarification that the polytype is formed by stacking of two different close-packed crystal planes in three-dimensional space. The formation of the polytype was induced by Li-Co cation exchange, the transformation of one phase to the other, and their stacking. This finding provides insight into intrinsic structural defects in an important Li2 CoSiO4 Li-ion battery cathode. PMID:25298300

  10. 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

    NASA Technical Reports Server (NTRS)

    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).

  11. Fabrication of free-standing aligned multiwalled carbon nanotube array for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Bulusheva, L. G.; Arkhipov, V. E.; Fedorovskaya, E. O.; Zhang, Su; Kurenya, A. G.; Kanygin, M. A.; Asanov, I. P.; Tsygankova, A. R.; Chen, Xiaohong; Song, Huaihe; Okotrub, A. V.

    2016-04-01

    We show that a high-temperature CCl4 vapor treatment of vertically aligned multiwalled carbon nanotubes (VA-MWCNTs) grown on silicon substrate allows carefully detach the array from the substrate. Moreover, this procedure partially purifies the VA-MWCNTs from the residual iron catalyst. To improve electrical connectivity of free-standing VA-MWCNTs in an electrochemical cell, the array was placed between the layers of Ni foam. Such assembly demonstrated the better performance in Li-battery as compared to the disordered MWCNTs. After 50 cycles, the specific capacity of VA-MWCNT array synthesized from 0.5 wt% ferrocene solution in toluene was 350 mAh g-1 at a current density of 0.1 A g-1, while the battery with the disordered MWCNTs achieved 197 mAh g-1 only. By the results of electrochemical impedance spectroscopy, the higher capacity of VA-MWCNTs was attributed to larger surface area available for electrolyte and Li ions due to the absence of binder coating.

  12. A POM–organic framework anode for Li-ion battery

    SciTech Connect

    Yue, Yanfeng; Li, Yunchao; Bi, Zhonghe; Veith, Gabriel M.; Bridges, Craig A.; Guo, Bingkun; Chen, Jihua; Mullins, David R.; Surwade, Sumedh P.; Mahurin, Shannon M.; Liu, Hongjun; Paranthaman, M. Parans; Dai, Sheng

    2015-10-12

    Rechargeable Li-ion batteries (LIBs) are currently the dominant power source for portable electronic devices and electric vehicles, and for small-scale stationary energy storage. However, one bottleneck of the anode materials for LIBs is the poor cycling performance caused by the fact that the anodes cannot maintain their integrity over several charge–discharge cycles. In this work, we demonstrate an approach to improving the cycling performance of lithium-ion battery anodes by constructing an extended 3D network of flexible redox active polyoxometalate (POM) clusters with redox active organic linkers, herein described as POMOF. In addition, this architecture enables the accommodation of large volume changes during cycling at relatively high current rates. For example, the POMOF anode exhibits a high reversible capacity of 540 mA h g–1 after 360 cycles at a current rate of 0.25C and a long cycle life at a current rate of 1.25C (>500 cycles).

  13. Improved layered mixed transition metal oxides for Li-ion batteries

    SciTech Connect

    Doeff, Marca M.; Conry, Thomas; Wilcox, James

    2010-03-05

    Recent work in our laboratory has been directed towards development of mixed layered transition metal oxides with general composition Li[Ni, Co, M, Mn]O2 (M=Al, Ti) for Li ion battery cathodes. Compounds such as Li[Ni1/3Co1/3Mn1/3]O2 (often called NMCs) are currently being commercialized for use in consumer electronic batteries, but the high cobalt content makes them too expensive for vehicular applications such as electric vehicles (EV), plug-in hybrid electric vehicles (PHEVs), or hybrid electric vehicles (HEVs). To reduce materials costs, we have explored partial or full substitution of Co with Al, Ti, and Fe. Fe substitution generally decreases capacity and results in poorer rate and cycling behavior. Interestingly, low levels of substitution with Al or Ti improve aspects of performance with minimal impact on energy densities, for some formulations. High levels of Al substitution compromise specific capacity, however, so further improvements require that the Ni and Mn content be increased and Co correspondingly decreased. Low levels of Al or Ti substitution can then be used offset negative effects induced by the higher Ni content. The structural and electrochemical characterization of substituted NMCs is presented in this paper.

  14. Boron doped defective graphene as a potential anode material for Li-ion batteries.

    PubMed

    Hardikar, Rahul P; Das, Deya; Han, Sang Soo; Lee, Kwang-Ryeol; Singh, Abhishek K

    2014-08-21

    Graphene with large surface area and robust structure has been proposed as a high storage capacity anode material for Li ion batteries. While the inertness of pristine graphene leads to better Li kinetics, poor adsorption leads to Li clustering, significantly affecting the performance of the battery. Here, we show the role of defects and doping in achieving enhanced adsorption without compromising on the high diffusivity of Li. Using first principles density functional theory (DFT) calculations, we carry out a comprehensive study of diffusion kinetics of Li over the plane of the defective structures and calculate the change in the number of Li atoms in the vicinity of defects, with respect to pristine graphene. Our results show that the Li-C interaction, storage capacity and the energy barriers depend sensitively on the type of defects. The un-doped and boron doped mono-vacancy, doped di-vacancy up to two boron, one nitrogen doped di-vacancy, and Stone-Wales defects show low energy barriers that are comparable to pristine graphene. Furthermore, boron doping at mono-vacancy enhances the adsorption of Li. In particular, the two boron doped mono-vacancy graphene shows both a low energy barrier of 0.31 eV and better adsorption, and hence can be considered as a potential candidate for anode material. PMID:24986702

  15. Challenges in Accommodating Volume Change of Si Anodes for Li-Ion Batteries

    PubMed Central

    Ko, Minseong; Chae, Sujong; Cho, Jaephil

    2015-01-01

    Si has been considered as a promising alternative anode for next-generation Li-ion batteries (LIBs) because of its high theoretical energy density, relatively low working potential, and abundance in nature. However, Si anodes exhibit rapid capacity decay and an increase in the internal resistance, which are caused by the large volume changes upon Li insertion and extraction. This unfortunately limits their practical applications. Therefore, managing the total volume change remains a critical challenge for effectively alleviating the mechanical fractures and instability of solid-electrolyte-interphase products. In this regard, we review the recent progress in volume-change-accommodating Si electrodes and investigate their ingenious structures with significant improvements in the battery performance, including size-controlled materials, patterned thin films, porous structures, shape-preserving shell designs, and graphene composites. These representative approaches potentially overcome the large morphologic changes in the volume of Si anodes by securing the strain relaxation and structural integrity in the entire electrode. Finally, we propose perspectives and future challenges to realize the practical application of Si anodes in LIB systems. PMID:27525208

  16. A POM–organic framework anode for Li-ion battery

    DOE PAGESBeta

    Yue, Yanfeng; Li, Yunchao; Bi, Zhonghe; Veith, Gabriel M.; Bridges, Craig A.; Guo, Bingkun; Chen, Jihua; Mullins, David R.; Surwade, Sumedh P.; Mahurin, Shannon M.; et al

    2015-10-12

    Rechargeable Li-ion batteries (LIBs) are currently the dominant power source for portable electronic devices and electric vehicles, and for small-scale stationary energy storage. However, one bottleneck of the anode materials for LIBs is the poor cycling performance caused by the fact that the anodes cannot maintain their integrity over several charge–discharge cycles. In this work, we demonstrate an approach to improving the cycling performance of lithium-ion battery anodes by constructing an extended 3D network of flexible redox active polyoxometalate (POM) clusters with redox active organic linkers, herein described as POMOF. In addition, this architecture enables the accommodation of large volumemore » changes during cycling at relatively high current rates. For example, the POMOF anode exhibits a high reversible capacity of 540 mA h g–1 after 360 cycles at a current rate of 0.25C and a long cycle life at a current rate of 1.25C (>500 cycles).« less

  17. Development of in-situ full-field spectroscopic imaging analysis and application on Li-ion battery using transmission x-ray microscopy

    NASA Astrophysics Data System (ADS)

    Chen-Wiegart, Yu-chen K.; Wang, Jiajun; Wang, Jun

    2013-09-01

    This paper presents the advance in spectroscopic imaging technique and analysis method from the newly developed transmission x-ray microscopy (TXM) at the beamline X8C of National Synchrotron Light Source. Through leastsquares linear combination fitting we developed on the in situ spectroscopic images, a time-dependent and spatially resolved chemical composition mapping can be obtained and quantitatively analyzed undergone chemical/electrochemical reactions. A correlation of morphological evolution, chemical state distribution changes and reaction conditions can be revealed. We successfully applied this method to study the electrochemical evolution of CuO, an anode material of Li-ion battery, during the lithiation-delitiation cycling.

  18. Effects of Carbon Content on the Electrochemical Performances of MoS2-C Nanocomposites for Li-Ion Batteries.

    PubMed

    Sun, Weiyi; Hu, Zhe; Wang, Caiyun; Tao, Zhanliang; Chou, Shu-Lei; Kang, Yong-Mook; Liu, Hua-Kun

    2016-08-31

    Molybdenum disulfide is popular for rechargeable batteries, especially in Li-ion batteries, because of its layered structure and relatively high specific capacity. In this paper, we report MoS2-C nanocomposites that are synthesized by a hydrothermal process, and their use as anode material for Li-ion batteries. Ascorbic acid is used as the carbon source, and the carbon contents can be tuned from 2.5 wt % to 16.2 wt %. With increasing of carbon content, the morphology of MoS2-C nanocomposites changes from nanoflowers to nanospheres, and the particle size is decreased from 200 to 60 nm. This change is caused by the chemical complex interaction of ascorbic acid. The MoS2-C nanocomposite with 8.4 wt % C features a high capacity of 970 mAh g(-1) and sustains a capacity retention ratio of nearly 100% after 100 cycles. When the current increases to 1000 mA g(-1), the capacity still reaches 730 mAh g(-1). The above manifests that the carbon coating layer does not only accelerate the charge transfer kinetics to supply quick discharging and charging, but also hold the integrity of the electrode materials as evidenced by the long cycling stability. Therefore, MoS2-based nanocomposites could be used as commercial anode materials in Li-ion batteries. PMID:27502442

  19. Can the performance of graphene nanosheets for lithium storage in Li-ion batteries be predicted?

    NASA Astrophysics Data System (ADS)

    Vargas C., Oscar A.; Caballero, Álvaro; Morales, Julián

    2012-03-01

    Graphene nanosheets (GNS) were prepared from graphitic oxide (GO) in two different ways: (a) thermal exfoliation at different temperatures; and (b) wet chemistry, using aqueous N2H4 and KBH4 as reducing agents. Irrespective of the synthetic method used, the materials exhibited a high irreversible capacity and strong polarization in their charge curves, when used in a Li-ion battery. The GNS synthesized with N2H4 exhibited the best performance. Thus, at 149 mA g-1 the average specific capacity delivered was ca. 600 mA h g-1 after 100 cycles. On the other hand, the worst performance, irrespective of rate, was that of GNS synthesized with KBH4 and the thermal GNS obtained at 800 °C. The physical and chemical analyses allowed various parameters to be derived for correlation with the electrochemical properties. Unfortunately, no clear-cut correlation was apparent. A comparison with reported data revealed that no correlation appears to exist with physical and chemical properties that allows a simple strategy for tailoring an effective graphene anode to be designed.Graphene nanosheets (GNS) were prepared from graphitic oxide (GO) in two different ways: (a) thermal exfoliation at different temperatures; and (b) wet chemistry, using aqueous N2H4 and KBH4 as reducing agents. Irrespective of the synthetic method used, the materials exhibited a high irreversible capacity and strong polarization in their charge curves, when used in a Li-ion battery. The GNS synthesized with N2H4 exhibited the best performance. Thus, at 149 mA g-1 the average specific capacity delivered was ca. 600 mA h g-1 after 100 cycles. On the other hand, the worst performance, irrespective of rate, was that of GNS synthesized with KBH4 and the thermal GNS obtained at 800 °C. The physical and chemical analyses allowed various parameters to be derived for correlation with the electrochemical properties. Unfortunately, no clear-cut correlation was apparent. A comparison with reported data revealed that no

  20. Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries

    DOE PAGESBeta

    Byles, B. W.; West, P.; Cullen, D. A.; More, K. L.; Pomerantseva, E.

    2015-01-01

    Extended hydrothermal treatment at an elevated temperature of 220 °C allowed high yield synthesis of manganese oxide nanowires with a todorokite crystal structure suitable for ions intercalation. The flexible, high aspect ratio nanowires are 50–100 nm in diameter and up to several microns long, with 3 × 3 structural tunnels running parallel to the nanowire longitudinal axis. Moreover, the tunnels are occupied by magnesium ions and water molecules, with the chemical composition found to be Mg0.2MnO2·0.5H2O. The todorokite nanowires were, for the first time, electrochemically tested in both Li-ion and Na-ion cells. A first discharge capacity of 158 mA hmore » g-1 was achieved in a Na-ion system, which was found to be greater than the first discharge capacity in a Li-ion system (133 mA h g-1). In spite of the large structural tunnel dimensions, todorokite showed a significant first cycle capacity loss in a Na-ion battery. After 20 cycles, the capacity was found to stabilize around 50 mA h g-1 and remained at this level for 100 cycles. In a Li-ion system, todorokite nanowires showed significantly better capacity retention with 78% of its initial capacity remaining after 100 cycles. Rate capability tests also showed superior performance of todorokite nanowires in Li-ion cells compared to Na-ion cells at higher current rates. Finally, these results highlight the difference in electrochemical cycling behavior of Li-ion and Na-ion batteries for a host material with spacious 3 × 3 tunnels tailored for large Na+ ion intercalation.« less

  1. Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries

    SciTech Connect

    Byles, B. W.; West, P.; Cullen, D. A.; More, K. L.; Pomerantseva, E.

    2015-01-01

    Extended hydrothermal treatment at an elevated temperature of 220 °C allowed high yield synthesis of manganese oxide nanowires with a todorokite crystal structure suitable for ions intercalation. The flexible, high aspect ratio nanowires are 50–100 nm in diameter and up to several microns long, with 3 × 3 structural tunnels running parallel to the nanowire longitudinal axis. Moreover, the tunnels are occupied by magnesium ions and water molecules, with the chemical composition found to be Mg0.2MnO2·0.5H2O. The todorokite nanowires were, for the first time, electrochemically tested in both Li-ion and Na-ion cells. A first discharge capacity of 158 mA h g-1 was achieved in a Na-ion system, which was found to be greater than the first discharge capacity in a Li-ion system (133 mA h g-1). In spite of the large structural tunnel dimensions, todorokite showed a significant first cycle capacity loss in a Na-ion battery. After 20 cycles, the capacity was found to stabilize around 50 mA h g-1 and remained at this level for 100 cycles. In a Li-ion system, todorokite nanowires showed significantly better capacity retention with 78% of its initial capacity remaining after 100 cycles. Rate capability tests also showed superior performance of todorokite nanowires in Li-ion cells compared to Na-ion cells at higher current rates. Finally, these results highlight the difference in electrochemical cycling behavior of Li-ion and Na-ion batteries for a host material with spacious 3 × 3 tunnels tailored for large Na+ ion intercalation.

  2. Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries

    SciTech Connect

    Byles, B. W.; West, P.; Cullen, D. A.; More, K. L.; Pomerantseva, E.

    2015-12-03

    Extended hydrothermal treatment at an elevated temperature of 220 °C allowed high yield synthesis of manganese oxide nanowires with a todorokite crystal structure suitable for ions intercalation. The flexible, high aspect ratio nanowires are 50–100 nm in diameter and up to several microns long, with 3 × 3 structural tunnels running parallel to the nanowire longitudinal axis. Moreover, the tunnels are occupied by magnesium ions and water molecules, with the chemical composition found to be Mg0.2MnO2·0.5H2O. The todorokite nanowires were, for the first time, electrochemically tested in both Li-ion and Na-ion cells. A first discharge capacity of 158 mA h g-1 was achieved in a Na-ion system, which was found to be greater than the first discharge capacity in a Li-ion system (133 mA h g-1). In spite of the large structural tunnel dimensions, todorokite showed a significant first cycle capacity loss in a Na-ion battery. After 20 cycles, the capacity was found to stabilize around 50 mA h g-1 and remained at this level for 100 cycles. In a Li-ion system, todorokite nanowires showed significantly better capacity retention with 78% of its initial capacity remaining after 100 cycles. Rate capability tests also showed superior performance of todorokite nanowires in Li-ion cells compared to Na-ion cells at higher current rates. Finally, these results highlight the difference in electrochemical cycling behavior of Li-ion and Na-ion batteries for a host material with spacious 3 × 3 tunnels tailored for large Na+ ion intercalation.

  3. Development of non-enzymatic glucose sensor using recycled cobalt from cell phone Li-ion batteries.

    PubMed

    Gonçalves, Sicele A; Garcia, Eric M; Taroco, Hosane A; Teixeira, Rodrigo G; Guedes, Kassílio J; Gorgulho, Honória F; Martelli, Patrícia B; Fernandes, Antônio P L

    2015-12-01

    This article aims to present an alternative to recycling of spent Li-ion batteries applied to electrochemical sensor manufacturing. The cobalt, from cathode of Li-ion batteries, was recovered by electrodeposition onto AISI 430 stainless steel substrate and applied as glucose sensor. The composition of cathode utilized was obtained by AAS measures and corresponds to LiNi0,40Co0,60O2. Despite this composition, in the cobalt electrodeposition onto AISI 430 stainless steel the Ni is less of 1.7% (w/w) due the anomalous electrodeposition. The sensitivity of cobalt electrode for glucose detection is 70.2 μA/mmol cm(2) and the linear range is 1-10 mmol/L. This result shows that the Co electrodeposited onto AISI 430 stainless steel is a promissory and low-cost non-enzymatic glucose sensor. PMID:26321381

  4. Effect of polymer blending and drawing conditions on properties of polyethylene separator prepared for Li-ion secondary battery

    NASA Astrophysics Data System (ADS)

    Ihm, DaeWoo; Noh, JaeGeun; Kim, JinYeol

    A separator made of the polymer blends of high density polyethylene (HDPE) and ultra-high molecular weight polyethylene (UHMWPE) is prepared by a wet process for the Li-ion secondary battery. An investigation is made of the effect on the mechanical properties of the separator by the blending of the polymers and the drawing conditions. The mechanical strength is increased with increasing molecular weight and content of UHMWPE polymer. A film containing 6 wt.% UHMWPE has a tensile strength of about 1000 kg cm -2 at a draw ratio of 5. The pores of the separator are very uniform with a size of 0.1-0.12 μm. The shut-down (SD) characteristics increase rapidly in the vicinity of 130 °C and the fusion temperature is 160 °C. These features suggest that the separator is applicable to the Li-ion secondary battery.

  5. Structural and Electrochemical Impacts of Oxygen Doped and Surfactant Coated Activated Carbon Electrodes in Li-ion Batteries

    NASA Astrophysics Data System (ADS)

    Collins, John; Gourdin, Gerald; Qu, Deyang; Foster, Michelle

    2013-03-01

    Passive charge and discharge dynamics are necessary for advancing Li-ion batteries. Surfactant adsorption on activated carbon has been shown to promote advancements in the discharge capacity, time and cycle-ability of electrochemical systems--specifically by enhancing diffusion pathways for ion insertion/de-insertion and suppressing pore blockage from precipitates known to form during charge/discharge states. Enhancement of surfactant chemisorption on activated carbon is achieved through oxygen doping of the carbon surface. In addition, doping alters the degree of Faradaic processes occurring in solution, resulting in prolonged reduction at the carbon surface. The work presented describes how surface oxygen groups on a granulated activated carbon have been manipulated using nitric acid in a controlled, stepwise fashion. A nonionic surfactant was applied to oxidized and non-oxidized samples at various concentrations. The composition and structure of the activated carbon surface was characterized using DRIFTS, Raman Spectroscopy, SEM and Porosimetry. The charge/discharge Li insertion capacities along with correlating surface microstructure changes were analyzed for all treated electrodes at progressive oxidation stages.

  6. Novel polymer Li-ion binder carboxymethyl cellulose derivative enhanced electrochemical performance for Li-ion batteries.

    PubMed

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

    2014-11-01

    Novel water-based binder lithium carboxymethyl cellulose (CMC-Li) is synthesized by 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 water-soluble binder are investigated. Sodium carboxymethyl cellulose (CMC-Na, CMC) and CMC-Li are used as the binder. After 200 cycles, compared with conventional poly(vinylidene fluoride) (PVDF) binder, the CMC-Li binder significantly improves cycling performance of the LFP cathode 96.7% of initial reversible capacity achieved at 175 mA h g(-1). Constant current charge-discharge test results demonstrate that the LFP electrode using CMC-Li as the binder has the highest rate capability, followed closely by those using CMC and PVDF binders, respectively. Electrochemical impedance spectroscopy test results show that the electrode using CMC-Li as the binder has lower charge transfer resistance than the electrodes using CMC and PVDF as the binders. PMID:25129778

  7. CO₂ and O₂ evolution at high voltage cathode materials of Li-ion batteries: a differential electrochemical mass spectrometry study.

    PubMed

    Wang, Hongsen; Rus, Eric; Sakuraba, Takahito; Kikuchi, Jun; Kiya, Yasuyuki; Abruña, Héctor D

    2014-07-01

    A three-electrode differential electrochemical mass spectrometry (DEMS) cell has been developed to study the oxidative decomposition of electrolytes at high voltage cathode materials of Li-ion batteries. In this DEMS cell, the working electrode used was the same as the cathode electrode in real Li-ion batteries, i.e., a lithium metal oxide deposited on a porous aluminum foil current collector. A charged LiCoO2 or LiMn2O4 was used as the reference electrode, because of their insensitivity to air, when compared to lithium. A lithium sheet was used as the counter electrode. This DEMS cell closely approaches real Li-ion battery conditions, and thus the results obtained can be readily correlated with reactions occurring in real Li-ion batteries. Using DEMS, the oxidative stability of three electrolytes (1 M LiPF6 in EC/DEC, EC/DMC, and PC) at three cathode materials including LiCoO2, LiMn2O4, and LiNi(0.5)Mn(1.5)O4 were studied. We found that 1 M LiPF6 + EC/DMC electrolyte is quite stable up to 5.0 V, when LiNi(0.5)Mn(1.5)O4 is used as the cathode material. The EC/DMC solvent mixture was found to be the most stable for the three cathode materials, while EC/DEC was the least stable. The oxidative decomposition of the EC/DEC mixture solvent could be readily observed under operating conditions in our cell even at potentials as low as 4.4 V in 1 M LiPF6 + EC/DEC electrolyte on a LiCoO2 cathode, as indicated by CO2 and O2 evolution. The features of this DEMS cell to unveil solvent and electrolyte decomposition pathways are also described. PMID:24845246

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    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.

  9. Borophene as an extremely high capacity electrode material for Li-ion and Na-ion batteries.

    PubMed

    Zhang, Xiaoming; Hu, Junping; Cheng, Yingchun; Yang, Hui Ying; Yao, Yugui; Yang, Shengyuan A

    2016-08-18

    "Two-dimensional (2D) materials as electrodes" is believed to be the trend for future Li-ion and Na-ion battery technologies. Here, by using first-principles methods, we predict that the recently reported borophene (2D boron sheets) can serve as an ideal electrode material with high electrochemical performance for both Li-ion and Na-ion batteries. The calculations are performed on two experimentally stable borophene structures, namely β12 and χ3 structures. The optimized Li and Na adsorption sites are identified, and the host materials are found to maintain good electric conductivity before and after adsorption. Besides advantages including small diffusion barriers and low average open-circuit voltages, most remarkably, the storage capacity can be as high as 1984 mA h g(-1) in β12 borophene and 1240 mA h g(-1) in χ3 borophene for both Li and Na, which are several times higher than the commercial graphite electrode and are the highest among all the 2D materials discovered to date. Our results highly support that borophenes can be appealing anode materials for both Li-ion and Na-ion batteries with extremely high power density. PMID:27502997

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

    NASA Astrophysics Data System (ADS)

    Musheng, Wu; Bo, Xu; Chuying, Ouyang

    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. Project supported by the National High Technology Research and Development Program of China (Grant No. 2015AA034201), the National Natural Science Foundation of China (Grant Nos. 11234013 and 11264014), the Natural Science Foundation of Jiangxi Province, China (Grant Nos. 20133ACB21010 and 20142BAB212002), and the Foundation of Jiangxi Education Committee, China (Grant Nos. GJJ14254 and KJLD14024). C. Y. Ouyang is also supported by the “Gan-po talent 555” Project of Jiangxi Province, China.

  11. Bio-Derived, Binderless, Hierarchically Porous Carbon Anodes for Li-ion Batteries

    NASA Astrophysics Data System (ADS)

    Campbell, Brennan; Ionescu, Robert; Favors, Zachary; Ozkan, Cengiz S.; Ozkan, Mihrimah

    2015-09-01

    Here we explore the electrochemical performance of pyrolyzed skins from the species A. bisporus, also known as the Portobello mushroom, as free-standing, binder-free, and current collector-free Li-ion battery anodes. At temperatures above 900 °C, the biomass-derived carbon nanoribbon-like architectures undergo unique processes to become hierarchically porous. During heat-treatment, the oxygen and heteroatom-rich organics and potassium compounds naturally present in the mushroom skins play a mutual role in creating inner void spaces throughout the resulting carbon nanoribbons, which is a process analogous to KOH-activation of carbon materials seen in literature. The pores formed in the pyrolytic carbon nanoribbons range in size from sub-nanometer to tens of nanometers, making the nanoribbons micro, meso, and macroporous. Detailed studies were conducted on the carbon nanoribbons using SEM and TEM to study morphology, as well as XRD and EDS to study composition. The self-supporting nanoribbon anodes demonstrate significant capacity increase as they undergo additional charge/discharge cycles. After a pyrolysis temperature of 1100 °C, the pristine anodes achieve over 260 mAh/g after 700 cycles and a Coulombic efficiency of 101.1%, without the use of harmful solvents or chemical activation agents.

  12. Engineering study on TiSnSb-based composite negative electrode for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Wilhelm, H. A.; Marino, C.; Darwiche, A.; Soudan, P.; Morcrette, M.; Monconduit, L.; Lestriez, B.

    2015-01-01

    Micrometric TiSnSb is a promising negative electrode material for Li-ion batteries when formulated with carboxymethyl cellulose (CMC) binder and a mixture of carbon black and carbon nanofibers, and cycled in a fluoroethylene carbonate (FEC)-containing electrolyte. Here, other binder systems were evaluated, polyacrylic acid (PAAH) mixed with CMC, CMC in buffered solution at pH 3 and amylopectin. However CMC showed the better performance in terms of cycle life of the electrode. Whatever the binder, cycle life decreases with increasing the active mass loading, which is attributed to both the precipitation of liquid electrolyte degradation products and to the loss of electrical contacts within the composite electrode and with the current collector as a consequence of the active particles volume variations. Furthermore, calendaring the electrode unfortunately decreases the cycle life. The rate performance was studied as a function of the active mass loading and was shown to be determined by the electrode polarization resistance. Finally, full cells cycling tests with Li1Ni1/3Co1/3Mn1/3O2 at the positive electrode were done. 60% of the capacity is retained after 200 cycles at the surface capacity of 2.7 mAh cm-2.

  13. A new active Li-Mn-O compound for high energy density Li-ion batteries.

    PubMed

    Freire, M; Kosova, N V; Jordy, C; Chateigner, D; Lebedev, O I; Maignan, A; Pralong, V

    2016-02-01

    The search for new materials that could improve the energy density of Li-ion batteries is one of today's most challenging issues. Many families of transition metal oxides as well as transition metal polyanionic frameworks have been proposed during the past twenty years. Among them, manganese oxides, such as the LiMn2O4 spinel or the overlithiated oxide Li[Li1/3Mn2/3]O2, have been intensively studied owing to the low toxicity of manganese-based materials and the high redox potential of the Mn(3+)/Mn(4+) couple. In this work, we report on a new electrochemically active compound with the 'Li4Mn2O5' composition, prepared by direct mechanochemical synthesis at room temperature. This rock-salt-type nanostructured material shows a discharge capacity of 355 mAh g(-1), which is the highest yet reported among the known lithium manganese oxide electrode materials. According to the magnetic measurements, this exceptional capacity results from the electrochemical activity of the Mn(3+)/Mn(4+) and O(2-)/O(-) redox couples, and, importantly, of the Mn(4+)/Mn(5+) couple also. PMID:26595122

  14. Quinone-formaldehyde polymer as an active material in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Pirnat, Klemen; Mali, Gregor; Gaberscek, Miran; Dominko, Robert

    2016-05-01

    A benzoquinone polymer is synthesized by the polymerisation of hydrobenzoquinone and formaldehyde, followed by oxidation process using a hydrogen peroxide to convert hydroquinone to quinone. As prepared materials are characterized with FTIR, 1H-13C CPMAS NMR, pyrolysis coupled with gas chromatography (GC) and mass spectrometer (MS), TGA-MS analysis, EDX, elemental analysis, XRD, SEM and TEM microscopies and BET nitrogen adsorption. The benzoquinone polymer shows an excellent electrochemical performance when used as a positive electrode material in Li-ion secondary batteries. Using an electrolyte consisting 1 M bis(trifluoromethane)-sulfonimide lithium salt dissolved in 1,3-dioxolane and dimethoxyethane in a vol. ratio 1:1 (1 M LiTFSI/DOL + DME = 1:1) a stable capacity close to 150 mAh/g can be obtained. Compared to other electroactive materials based on benzoquinones it has a supreme capacity stability and is prepared by a simple synthesis using easily accessible starting materials. Further improvements in the capacity value (up to the theoretical value of 406 mAh/g) can be foreseen by achieving a higher degree of oxidation and by modification of polymerization process to enhance the electronic and ionic conductivity.

  15. A new active Li-Mn-O compound for high energy density Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Freire, M.; Kosova, N. V.; Jordy, C.; Chateigner, D.; Lebedev, O. I.; Maignan, A.; Pralong, V.

    2016-02-01

    The search for new materials that could improve the energy density of Li-ion batteries is one of today’s most challenging issues. Many families of transition metal oxides as well as transition metal polyanionic frameworks have been proposed during the past twenty years. Among them, manganese oxides, such as the LiMn2O4 spinel or the overlithiated oxide Li[Li1/3Mn2/3]O2, have been intensively studied owing to the low toxicity of manganese-based materials and the high redox potential of the Mn3+/Mn4+ couple. In this work, we report on a new electrochemically active compound with the `Li4Mn2O5’ composition, prepared by direct mechanochemical synthesis at room temperature. This rock-salt-type nanostructured material shows a discharge capacity of 355 mAh g-1, which is the highest yet reported among the known lithium manganese oxide electrode materials. According to the magnetic measurements, this exceptional capacity results from the electrochemical activity of the Mn3+/Mn4+ and O2-/O- redox couples, and, importantly, of the Mn4+/Mn5+ couple also.

  16. Bio-Derived, Binderless, Hierarchically Porous Carbon Anodes for Li-ion Batteries

    PubMed Central

    Campbell, Brennan; Ionescu, Robert; Favors, Zachary; Ozkan, Cengiz S.; Ozkan, Mihrimah

    2015-01-01

    Here we explore the electrochemical performance of pyrolyzed skins from the species A. bisporus, also known as the Portobello mushroom, as free-standing, binder-free, and current collector-free Li-ion battery anodes. At temperatures above 900 °C, the biomass-derived carbon nanoribbon-like architectures undergo unique processes to become hierarchically porous. During heat-treatment, the oxygen and heteroatom-rich organics and potassium compounds naturally present in the mushroom skins play a mutual role in creating inner void spaces throughout the resulting carbon nanoribbons, which is a process analogous to KOH-activation of carbon materials seen in literature. The pores formed in the pyrolytic carbon nanoribbons range in size from sub-nanometer to tens of nanometers, making the nanoribbons micro, meso, and macroporous. Detailed studies were conducted on the carbon nanoribbons using SEM and TEM to study morphology, as well as XRD and EDS to study composition. The self-supporting nanoribbon anodes demonstrate significant capacity increase as they undergo additional charge/discharge cycles. After a pyrolysis temperature of 1100 °C, the pristine anodes achieve over 260 mAh/g after 700 cycles and a Coulombic efficiency of 101.1%, without the use of harmful solvents or chemical activation agents. PMID:26415917

  17. Toward efficient binders for Li-ion battery Si-based anodes: polyacrylic acid.

    PubMed

    Magasinski, Alexandre; Zdyrko, Bogdan; Kovalenko, Igor; Hertzberg, Benjamin; Burtovyy, Ruslan; Huebner, Christopher F; Fuller, Thomas F; Luzinov, Igor; Yushin, Gleb

    2010-11-01

    Si-based Li-ion battery anodes offer specific capacity an order of magnitude beyond that of conventional graphite. However, the formation of stable Si anodes is a challenge because of significant volume changes occurring during their electrochemical alloying and dealloying with Li. Binder selection and optimization may allow significant improvements in the stability of Si-based anodes. Most studies of Si anodes have involved the use of carboxymethylcellulose (CMC) and poly(vinylidene fluoride) (PVDF) binders. Herein, we show for the first time that pure poly(acrylic acid) (PAA), possessing certain mechanical properties comparable to those of CMC but containing a higher concentration of carboxylic functional groups, may offer superior performance as a binder for Si anodes. We further show the positive impact of carbon coating on the stability of the anode. The carbon-coated Si nanopowder anodes, tested between 0.01 and 1 V vs Li/Li+ and containing as little as 15 wt % of PAA, showed excellent stability during the first hundred cycles. The results obtained open new avenues to explore a novel series of binders from the polyvinyl acids (PVA) family. PMID:21053920

  18. Extraction of Li and Co from Li-ion Batteries by Chemical Methods

    NASA Astrophysics Data System (ADS)

    Guzolu, Jafar Sharrivar; Gharabaghi, Mahdi; Mobin, Mohammad; Alilo, Hojat

    2016-05-01

    In this work a process involving ultrasonic washing and leaching and precipitation was used to recover Li and Co from spent Li-ion batteries. Ultrasonic washing was used to reduce energy consumption and pollution whereas hydrochloric acid was used as leaching reagent. 98 % of Li and nearly 99 % of Co were obtained under optimum condition of 5 M hydrochloric acid solution, temperature of 95 °C, reaction time of 70 min, and solid-liquid ratio of 10 g/L. In this process at first nickel, copper, iron, aluminum, cobalt, and manganese were precipitated from leaching solution using sodium hydroxide at pH f 12.5 and reaction time of 1 h and temperature was 55 °C and all metal recoveries were more than 99 %. In the precipitation experiments, lithium loss was only 18.34 %. In the next stage, white lithium carbonate was precipitated by addition of saturated sodium carbonate solution to the left filtrate from first precipitation step. The purity of the recovered powder of lithium was 95 %.

  19. Reduced Graphene Oxide Films with Ultrahigh Conductivity as Li-Ion Battery Current Collectors.

    PubMed

    Chen, Yanan; Fu, Kun; Zhu, Shuze; Luo, Wei; Wang, Yanbin; Li, Yiju; Hitz, Emily; Yao, Yonggang; Dai, Jiaqi; Wan, Jiayu; Danner, Valencia A; Li, Teng; Hu, Liangbing

    2016-06-01

    Solution processed, highly conductive films are extremely attractive for a range of electronic devices, especially for printed macroelectronics. For example, replacing heavy, metal-based current collectors with thin, light, flexible, and highly conductive films will further improve the energy density of such devices. Films with two-dimensional building blocks, such as graphene or reduced graphene oxide (RGO) nanosheets, are particularly promising due to their low percolation threshold with a high aspect ratio, excellent flexibility, and low cost. However, the electrical conductivity of these films is low, typically less than 1000 S/cm. In this work, we for the first time report a RGO film with an electrical conductivity of up to 3112 S/cm. We achieve high conductivity in RGO films through an electrical current-induced annealing process at high temperature of up to 2750 K in less than 1 min of anneal time. We studied in detail the unique Joule heating process at ultrahigh temperature. Through a combination of experimental and computational studies, we investigated the fundamental mechanism behind the formation of a highly conductive three-dimensional structure composed of well-connected RGO layers. The highly conductive RGO film with high direct current conductivity, low thickness (∼4 μm) and low sheet resistance (0.8 Ω/sq.) was used as a lightweight current collector in Li-ion batteries. PMID:27148884

  20. Phosphorene ribbons as anode materials with superhigh rate and large capacity for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Da; Guo, Gen-Cai; Wei, Xiao-Lin; Liu, Li-Min; Zhao, Shi-Jin

    2016-01-01

    By means of density functional theory calculations, we systematically investigated the adsorption and diffusion properties of lithium ions on the armchair and zigzag phosphorene nanoribbons (AC-PNR and ZZ-PNR), in comparison with the pristine phosphorene. It is shown that both AC- and ZZ-PNR have a significantly enhanced Li binding strength but without sacrificing the Li mobility due to the presence of unique edge states. Besides, the ZZ-PNR with the width of 21.5 Å has a moderate working voltage (0.504-0.021 V), high capacity (541 mA h/g) and fast charge/discharge rate, which is more promising to be used as an anode material for LIBs. By contrast, the obvious depravation of the voltage is found in AC-PNR, which is mainly due to its weak stiffness that cannot afford the observed structural deformation during the lithiated process. Thus, it is highly expected to avoid the undesirable structural expansion in AC-PNR. The results presented here provide valuable insights into exploring high performance armchair/zigzag phosphorene nanoribbons for potential Li-ion battery applications.

  1. Quinone-formaldehyde polymer as an active material in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Pirnat, Klemen; Mali, Gregor; Gaberscek, Miran; Dominko, Robert

    2016-05-01

    A benzoquinone polymer is synthesized by the polymerisation of hydrobenzoquinone and formaldehyde, followed by oxidation process using a hydrogen peroxide to convert hydroquinone to quinone. As prepared materials are characterized with FTIR, 1H-13C CPMAS NMR, pyrolysis coupled with gas chromatography (GC) and mass spectrometer (MS), TGA-MS analysis, EDX, elemental analysis, XRD, SEM and TEM microscopies and BET nitrogen adsorption. The benzoquinone polymer shows an excellent electrochemical performance when used as a positive electrode material in Li-ion secondary batteries. Using an electrolyte consisting 1 M bis(trifluoromethane)-sulfonimide lithium salt dissolved in 1,3-dioxolane and dimethoxyethane in a vol. ratio 1:1 (1 M LiTFSI/DOL + DME = 1:1) a stable capacity close to 150 mAh/g can be obtained. Compared to other electroactive materials based on benzoquinones it has a supreme capacity stability and is prepared by a simple synthesis using easily accessible starting materials. Further improvements in the capacity value (up to the theoretical value of 406 mAh/g) can be foreseen by achieving a higher degree of oxidation and by modification of polymerization process to enhance the electronic and ionic conductivity.

  2. Electrochemical characteristics of plasma-etched black silicon as anodes for Li-ion batteries

    SciTech Connect

    Lee, Gibaek; Wehrspohn, Ralf B.; Schweizer, Stefan L.

    2014-11-01

    Nanostructured silicon as an anode material for Li-ion batteries is produced for the first time by inductively coupled plasma–plasma etching of Si wafers in the black silicon regime. The microscopic structure strongly resembles other types of nanostructured silicon, with a well-arranged nanostructure possessing a sufficient porosity for accommodating large volume expansion. Despite these features, however, a high first-cycle irreversible capacity loss and a poor cycle life are observed. The main reason for these poor features is the formation of a thick solid-electrolyte interphase (SEI) layer related to the surface condition of the pristine nanostructured black silicon (b-Si) electrode. Therefore, the cycle life of the b-Si electrode is heavily influenced by the constant reformation of the SEI layer depending upon the surface composition in spite of the presence of nanostructured Si. In the fast lithiation experiments, the nanostructure region of the b-Si electrode is detached from the Si substrate owing to the kinetics difference between the lithium ion diffusion and the electron injection and phase transformation in the nanostructured Si region. This means that more Si substrate is involved in lithiation at high current rates. It is therefore important to maintain balance in the chemical kinetics during the lithiation of nanostructured Si electrodes with a Si substrate.

  3. Application of physical electric circuit modeling to characterize Li-ion battery electrochemical processes

    NASA Astrophysics Data System (ADS)

    Greenleaf, M.; Li, H.; Zheng, J. P.

    2014-12-01

    A physical electric circuit model (PECM) was used to identify several electrochemical processes occurring in two commercial Li-ion batteries of different cathode materials (LixFePO4 and LixCoO2) via electrochemical impedance spectroscopy (EIS). Through defining these electrochemical processes in these two cells, it was determined that the charge transfer resistance (or exchange current density) observed via EIS was due to the cathodic exchange current densities in both the LixFePO4 and LixCoO2 full cells. In discussing the ionic diffusion of the examined cells, the anode of one cell and the cathode of the other were primarily responsible for the observed diffusion of the full cells. Lastly, the measured double layer capacitance was determined to be represented in EIS scans by the anodes of both full cells. The diffusion coefficient was calculated using Fick's1st Law estimation, and from this coefficient, the particle size was calculated and evaluated against scanning electron microscopy (SEM).

  4. Polyvinylidene fluoride membrane by novel electrospinning system for separator of Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Yang, Cuiru; Jia, Zhidong; Guan, Zhicheng; Wang, Liming

    The remarkable characteristics of nanofibers mats electrospun are large surface area to volume ratio and high porosity, which are crucial to increase the ionic conductivity of membrane full of liquid electrolyte, in this aspect, electrospinning is prior to the other methods, such as dry method, wet method, etc. Therefore, fabricating the separator of Li-ion batteries by electrospinning is potential and promising. The PVDF membranes were fabricated by electrospinning. The experiment demonstrated that the main deficiency in the fabricating separators process by electrospinning was low mechanical property, which induced partial short circuits inside the cells. Several methods were presented to enhance the mechanical strength. The experiments demonstrated that the higher the solution concentration was, the stronger the mechanical strength was, and the higher the voltage was, the stronger the mechanical strength was. Additionally, the spherical hat collection target instead of conditional plane target was applied in the electrospinning system, as a result, the thickness of the membrane was more uniform and the fiber diameter was also more uniform. Therefore, the charge and discharge capacity of the coin type cell composed of the separator collected by spherical hat target exceeded the plane target, and the electrospinning separators exceeded the commercial polypropylene separator.

  5. Bio-Derived, Binderless, Hierarchically Porous Carbon Anodes for Li-ion Batteries.

    PubMed

    Campbell, Brennan; Ionescu, Robert; Favors, Zachary; Ozkan, Cengiz S; Ozkan, Mihrimah

    2015-01-01

    Here we explore the electrochemical performance of pyrolyzed skins from the species A. bisporus, also known as the Portobello mushroom, as free-standing, binder-free, and current collector-free Li-ion battery anodes. At temperatures above 900 °C, the biomass-derived carbon nanoribbon-like architectures undergo unique processes to become hierarchically porous. During heat-treatment, the oxygen and heteroatom-rich organics and potassium compounds naturally present in the mushroom skins play a mutual role in creating inner void spaces throughout the resulting carbon nanoribbons, which is a process analogous to KOH-activation of carbon materials seen in literature. The pores formed in the pyrolytic carbon nanoribbons range in size from sub-nanometer to tens of nanometers, making the nanoribbons micro, meso, and macroporous. Detailed studies were conducted on the carbon nanoribbons using SEM and TEM to study morphology, as well as XRD and EDS to study composition. The self-supporting nanoribbon anodes demonstrate significant capacity increase as they undergo additional charge/discharge cycles. After a pyrolysis temperature of 1100 °C, the pristine anodes achieve over 260 mAh/g after 700 cycles and a Coulombic efficiency of 101.1%, without the use of harmful solvents or chemical activation agents. PMID:26415917

  6. Post oxygen treatment characteristics of coke as an anode material for Li-ion batteries.

    PubMed

    Kim, Jae-Hun; Park, Min-Sik; Jo, Yong Nam; Yu, Ji-Sang; Jeong, Goojin; Kim, Young-Jun

    2013-05-01

    The effect of a oxygen treatment on the electrochemical characteristics of a soft carbon anode material for Li-ion batteries was investigated. After a coke carbonization process at 1000 degrees C in an argon atmosphere, the samples were treated under a flow of oxygen gas to obtain a mild oxidation effect. After this oxygen treatment, the coke samples exhibited an improved initial coulombic efficiency and cycle performance as compared to the carbonized sample. High-resolution transmission electron microscopy revealed that the carbonized cokes consisted of disordered and nanosized graphene layers and the surface of the modified carbon was significantly changed after the treatment. The chemical state of the cokes was analyzed using X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The enhanced electrochemical properties of the surface modified cokes could be attributed to the mild oxidation effect induced by the oxygen treatment. The mild oxidation process could have led to the elimination of surface imperfections and the reinforcement of a solid electrolyte interphase film, which resulted in the improved electrochemical characteristics. PMID:23858847

  7. Internal and External Temperature Monitoring of a Li-Ion Battery with Fiber Bragg Grating Sensors.

    PubMed

    Novais, Susana; Nascimento, Micael; Grande, Lorenzo; Domingues, Maria Fátima; Antunes, Paulo; Alberto, Nélia; Leitão, Cátia; Oliveira, Ricardo; Koch, Stephan; Kim, Guk Tae; Passerini, Stefano; Pinto, João

    2016-01-01

    The integration of fiber Bragg grating (FBG) sensors in lithium-ion cells for in-situ and in-operando temperature monitoring is presented herein. The measuring of internal and external temperature variations was performed through four FBG sensors during galvanostatic cycling at C-rates ranging from 1C to 8C. The FBG sensors were placed both outside and inside the cell, located in the center of the electrochemically active area and at the tab-electrode connection. The internal sensors recorded temperature variations of 4.0 ± 0.1 °C at 5C and 4.7 ± 0.1 °C at 8C at the center of the active area, and 3.9 ± 0.1 °C at 5C and 4.0 ± 0.1 °C at 8C at the tab-electrode connection, respectively. This study is intended to contribute to detection of a temperature gradient in real time inside a cell, which can determine possible damage in the battery performance when it operates under normal and abnormal operating conditions, as well as to demonstrate the technical feasibility of the integration of in-operando microsensors inside Li-ion cells. PMID:27589749

  8. Composit, Nanoparticle-Based Anode material for Li-ion Batteries Applied in Hybrid Electric (HEV's)

    SciTech Connect

    Dr. Malgorzata Gulbinska

    2009-08-24

    Lithium-ion batteries are promising energy storage devices in hybrid and electric vehicles with high specific energy values ({approx}150 Wh/kg), energy density ({approx}400 Wh/L), and long cycle life (>15 years). However, applications in hybrid and electric vehicles require increased energy density and improved low-temperature (<-10 C) performance. Silicon-based anodes are inexpensive, environmentally benign, and offer excellent theoretical capacity values ({approx}4000 mAh/g), leading to significantly less anode material and thus increasing the overall energy density value for the complete battery (>500 Wh/L). However, tremendous volume changes occur during cycling of pure silicon-based anodes. The expansion and contraction of these silicon particles causes them to fracture and lose electrical contact to the current collector ultimately severely limiting their cycle life. In Phase I of this project Yardney Technical Products, Inc. proposed development of a carbon/nano-silicon composite anode material with improved energy density and silicon's cycleability. In the carbon/nano-Si composite, silicon nanoparticles were embedded in a partially-graphitized carbonaceous matrix. The cycle life of anode material would be extended by decreasing the average particle size of active material (silicon) and by encapsulation of silicon nanoparticles in a ductile carbonaceous matrix. Decreasing the average particle size to a nano-region would also shorten Li-ion diffusion path and thus improve rate capability of the silicon-based anodes. Improved chemical inertness towards PC-based, low-temperature electrolytes was expected as an additional benefit of a thin, partially graphitized coating around the active electrode material.

  9. General approach for high-power li-ion batteries: multiscale lithographic patterning of electrodes.

    PubMed

    Choi, Sinho; Kim, Tae-Hee; Lee, Jung-In; Kim, Jieun; Song, Hyun-Kon; Park, Soojin

    2014-12-01

    We demonstrate multiscale patterned electrodes that provide surface-area enhancement and strong adhesion between electrode materials and current collector. The combination of multiscale structured current collector and active materials (anodes and cathodes) enables us to make high-performance Li-ion batteries (LIBs). When LiFePO4 (LFP) cathode and Li4 Ti5 O12 (LTO) anode materials are combined with patterned current collectors, their electrochemical performances are significantly improved, including a high rate capability (LiFePO4 : 100 mAh g(-1) , Li4 Ti5 O12 : 60 mAh g(-1) at 100C rate) and highly stable cycling (LiFePO4 : capacity retention of 99.8% after 50 cycles at 10C rate). Moreover, we successfully fabricate full cell system consisting of patterned LFP cathode and patterned LTO anode, exhibiting high-power battery performances [capacity of approximately 70 mAh g(-1) during 1000 cycles at 10C rate (corresponding to charging/discharging time of 6 min)]. We extend this idea to Si anode that exhibits a large volume change during lithiation/delithiation process. The patterned Si electrodes show significantly enhanced electrochemical performances, including a high specific capacity (825 mAh g(-1) ) at high rate of 5C and a stable cycling retention (88% after 100 cycle at a 0.1C rate). This simple strategy can be extended to other cathode and anode materials for practical LIB applications. PMID:25333718

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

    PubMed

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

    2014-03-01

    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

  11. Probing the pseudo-1-D ion diffusion in lithium titanium niobate anode for Li-ion battery.

    PubMed

    Das, Suman; Dutta, Dipak; Araujo, Rafael B; Chakraborty, Sudip; Ahuja, Rajeev; Bhattacharyya, Aninda J

    2016-08-10

    Comprehensive understanding of the charge transport mechanism in the intrinsic structure of an electrode material is essential in accounting for its electrochemical performance. We present here systematic experimental and theoretical investigations of Li(+)-ion diffusion in a novel layered material, viz. lithium titanium niobate. Lithium titanium niobate (exact composition Li0.55K0.45TiNbO5·1.06H2O) is obtained from sol-gel synthesized potassium titanium niobate (KTiNbO5) by an ion-exchange method. The Li(+)-ions are inserted and de-inserted preferentially into the galleries between the octahedral layers formed by edge and corner sharing TiO6 and NbO6 octahedral units and the effective chemical diffusion coefficient, is estimated to be 3.8 × 10(-11) cm(2) s(-1) using the galvanostatic intermittent titration technique (GITT). Calculations based on density functional theory (DFT) strongly confirm the anisotropic Li(+)-ion diffusion in the interlayer galleries and that Li(+)-ions predominantly diffuse along the crystallographic b-direction. The preferential Li(+)-ion diffusion along the b-direction is assisted by line-defects, which are observed to be higher in concentration along the b-direction compared to the a- and c-directions, as revealed by high resolution electron microscopy. The Li-Ti niobate can be cycled to low voltages (≈0.2 V) and show stable and satisfactory battery performance over 100 cycles. Due to the possibility of cycling to low voltages, cyclic voltammetry and X-ray photoelectron spectroscopy convincingly reveal the reversibility of Ti(3+) ↔ Ti(2+) along with Ti(4+) ↔ Ti(3+) and Nb(5+) ↔ Nb(4+). PMID:27459636

  12. Battery Control Boards for Li-Ion Batteries on Mars Exploration Rovers

    NASA Technical Reports Server (NTRS)

    Ewell, R.; Ratnakumar, B. V.; Smart, M.; Chin, K. B.; Whitcanack, L.; Narayanan, S. R.; Surampudi, S.

    2006-01-01

    Rechargeable Lithium-ion batteries have been operating successfully on both Spirit and Opportunity rovers for the last two years, which includes six months of Assembly Launch and Test Operations (ATLO), seven months of cruise and about eleven months of surface operations. The Battery Control Boards designed and fabricated in-house would protect cells against overcharge and over-discharge and provide cell balance. Their performance has thus far been quite satisfactory. The ground data o the mission simulation battery project little capacity loss of less than 3% during cruise and 180 sols. Batteries are poised to extend the mission beyond six months, if not a couple of years.

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

    PubMed Central

    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

  14. Green synthesis of boron doped graphene and its application as high performance anode material in Li ion battery

    SciTech Connect

    Sahoo, Madhumita; Sreena, K.P.; Vinayan, B.P.; Ramaprabhu, S.

    2015-01-15

    Graphical abstract: Boron doped graphene (B-G), synthesized by simple hydrogen induced reduction technique using boric acid as boron precursor, have more uneven surface as a result of smaller bonding distance of boron compared to carbon, showed high capacity and high rate capability compared to pristine graphene as an anode material for Li ion battery application. - Abstract: The present work demonstrates a facile route for the large-scale, catalyst free, and green synthesis approach of boron doped graphene (B-G) and its use as high performance anode material for Li ion battery (LIB) application. Boron atoms were doped into graphene framework with an atomic percentage of 5.93% via hydrogen induced thermal reduction technique using graphite oxide and boric acid as precursors. Various characterization techniques were used to confirm the boron doping in graphene sheets. B-G as anode material shows a discharge capacity of 548 mAh g{sup −1} at 100 mA g{sup −1} after 30th cycles. At high current density value of 1 A g{sup −1}, B-G as anode material enhances the specific capacity by about 1.7 times compared to pristine graphene. The present study shows a simplistic way of boron doping in graphene leading to an enhanced Li ion adsorption due to the change in electronic states.

  15. The study of capacity fading processes of Li-ion batteries: major factors that play a role

    NASA Astrophysics Data System (ADS)

    Markovsky, B.; Rodkin, A.; Cohen, Y. S.; Palchik, O.; Levi, E.; Aurbach, D.; Kim, H.-J.; Schmidt, M.

    In this work, we studied the impact of some factors on the behavior of practical electrodes of Li-ion batteries. These included elevated temperatures (45-80 °C), prolonged storage of Li-ion cells, and additives in the electrolyte solution. The Li-ion battery systems studied included negative electrodes (anodes) comprising of mesocarbon microbeads (MCMB) and mesocarbon fibers (MCF), and Li xCoO 2 positive electrodes (cathodes) in an ethylene carbonate (EC)/ethyl-methyl carbonate (EMC) (1:2)/LiPF 6 1 M solution. Vinylene carbonate (VC) and a Li-organo-borate complex (Li-OBC) were tested as additives. It is shown that the electrochemical response of Li-C negative electrodes depends on the structure of the surface films controlling their behavior, which change upon storage, temperature, and cycling. We established that impedance of these electrodes increased with storage time due to the enrichment of the surface films by LiF and other fluorine-containing species. The capacity fading of the Li xCoO 2 electrodes in cycling/storage processes at elevated temperatures relates mostly to surface phenomena, whereas the bulk structural characteristics of the electrodes do not change.

  16. Mussel-Inspired Polydopamine Coating for Enhanced Thermal Stability and Rate Performance of Graphite Anodes in Li-Ion Batteries.

    PubMed

    Park, Seong-Hyo; Kim, Hyeon Jin; Lee, Junmin; Jeong, You Kyeong; Choi, Jang Wook; Lee, Hochun

    2016-06-01

    Despite two decades of commercial history, it remains very difficult to simultaneously achieve both high rate capability and thermal stability in the graphite anodes of Li-ion batteries because the stable solid electrolyte interphase (SEI) layer, which is essential for thermal stability, impedes facile Li(+) ion transport at the interface. Here, we resolve this longstanding challenge using a mussel-inspired polydopamine (PD) coating via a simple immersion process. The nanometer-thick PD coating layer allows the formation of an SEI layer on the coating surface without perturbing the intrinsic properties of the SEI layer of the graphite anodes. PD-coated graphite exhibits far better performances in cycling test at 60 °C and storage test at 90 °C than bare graphite. The PD-coated graphite also displays superior rate capability during both lithiation and delithiation. As evidenced by surface free energy analysis, the enhanced performance of the PD-coated graphite can be ascribed to the Lewis basicity of the PD, which scavenges harmful hydrofluoric acid and forms an intermediate triple-body complex among a Li(+) ion, solvent molecules, and the PD's basic site. The usefulness of the proposed PD coating can be expanded to various electrodes in rechargeable batteries that suffer from poor thermal stability and interfacial kinetics. PMID:27183170

  17. Li-Metal-Free Prelithiation of Si-Based Negative Electrodes for Full Li-Ion Batteries.

    PubMed

    Zhou, Haitao; Wang, Xuehang; Chen, De

    2015-08-24

    Most of the high-capacity positive-electrode materials [for example, S, O2 (air), and MOx (M: V, Mn, Fe, etc.)] are Li-deficient and require the use of a Li-metal electrode or prelithiation. Herein, we report a novel electrolytic cell in which the Si electrode can be prelithiated in a well-controlled manner from Li-containing aqueous solution in a Li-metal-free way. MnOx/Si and S/Si Li-ion full cells were assembled by using the prelithiated Si negative electrodes, which resulted in high specific energies of 349 and 732 Wh kg(-1), respectively. The MnOx/Si full cell still retains 138 Wh kg(-1) even at a high specific power of 1710 W kg(-1). This is the first report of a whole process of making a full Li-ion battery with both Li-deficient electrodes without the use of Li metal as the Li source. This novel prelithiation process, with high controllability, no short circuiting, and an abundant Li source, is expected to contribute significantly to the development of safe, green, and powerful Li-ion batteries. PMID:26216592

  18. The testing of batteries linked to supercapacitors with electrochemical impedance spectroscopy: A comparison between Li-ion and valve regulated lead acid batteries

    NASA Astrophysics Data System (ADS)

    Ferg, Ernst; Rossouw, Claire; Loyson, Peter

    2013-03-01

    For electric vehicles, a supercapacitor can be coupled to the electrical system in order to increase and optimize the energy and power densities of the drive system during acceleration and regenerative breaking. This study looked at the charge acceptance and maximum discharge ability of a valve regulated lead acid (VRLA) and a Li-ion battery connected in parallel to supercapacitors. The test procedure evaluated the advantage of using a supercapacitor at a 2 F:1 Ah ratio with the battery types at various states of charge (SoC). The results showed that about 7% of extra charge was achieved over a 5-s test time for a Li-ion hybrid system at 20% SoC, whereas at the 80% SoC the additional capacity was approximately 16%. While for the VRLA battery hybrid system, an additional charge of up to 20% was achieved when the battery was at 80% SoC, with little or no benefit at the 20% SoC. The advantage of the supercapacitor in parallel with a VRLA battery was noticeable on its discharge ability, where significant extra capacity was achieved for short periods of time for a battery at the 60% and 40% SoC when compared to the Li-ion hybrid system. The study also made use of Electrochemical Impedance Spectroscopy (EIS) with a suitable equivalent circuit model to explain, in particular, the internal resistance and capacitance differences observed between the different battery chemistries with and without a supercapacitor.

  19. Application of electrolyte using novel ionic liquid to Si thick film anode of Li-ion battery

    NASA Astrophysics Data System (ADS)

    Usui, Hiroyuki; Yamamoto, Yoshihisa; Yoshiyama, Kazuhide; Itoh, Toshiyuki; Sakaguchi, Hiroki

    An applicability of a novel ionic liquid, consisting of 1-methoxyethoxymethyl(tri- n-butyl)phosphonium cation and bis(trifluoromethanesulfonyl)amide anion, was investigated as an electrolyte of Li-ion battery using a thick film electrode of Si prepared by a gas-deposition method. The electrochemical properties in the novel ionic liquid were compared to those in a commercial ionic liquid and a typical organic solvent of propylene carbonate. The initial discharge capacity of 3450 mAh g -1 and excellent cycling performance were achieved in the novel ionic liquid. The novel ionic liquid was confirmed to effectively suppress a collapse and an electrical isolation of the Si thick film induced by pulverization during charge-discharge cycling. The excellent performance is possibly attributed to more effective desolvation of Li ions from the anions due to its lower dielectric constant compared with the propylene carbonate solvent.

  20. Flexible Paper Electrodes for Li-Ion Batteries Using Low Amount of TEMPO-Oxidized Cellulose Nanofibrils as Binder.

    PubMed

    Lu, Huiran; Behm, Mårten; Leijonmarck, Simon; Lindbergh, Göran; Cornell, Ann

    2016-07-20

    Flexible Li-ion batteries attract increasing interest for applications in bendable and wearable electronic devices. TEMPO-oxidized cellulose nanofibrils (TOCNF), a renewable material, is a promising candidate as binder for flexible Li-ion batteries with good mechanical properties. Paper batteries can be produced using a water-based paper making process, avoiding the use of toxic solvents. In this work, finely dispersed TOCNF was used and showed good binding properties at concentrations as low as 4 wt %. The TOCNF was characterized using atomic force microscopy and found to be well dispersed with fibrils of average widths of about 2.7 nm and lengths of approximately 0.1-1 μm. Traces of moisture, trapped in the hygroscopic cellulose, is a concern when the material is used in Li-ion batteries. The low amount of binder reduces possible moisture and also increases the capacity of the electrodes, based on total weight. Effects of moisture on electrochemical battery performance were studied on electrodes dried at 110 °C in a vacuum for varying periods. It was found that increased drying time slightly increased the specific capacities of the LiFePO4 electrodes, whereas the capacities of the graphite electrodes decreased. The Coulombic efficiencies of the electrodes were not much affected by the varying drying times. Drying the electrodes for 1 h was enough to achieve good electrochemical performance. Addition of vinylene carbonate to the electrolyte had a positive effect on cycling for both graphite and LiFePO4. A failure mechanism observed at high TOCNF concentrations is the formation of compact films in the electrodes. PMID:27362635

  1. Carbon supported tin-based nanocomposites as anodes for Li-ion batteries

    SciTech Connect

    Zhou, Xiangyang; Zou, Youlan; Yang, Juan

    2013-02-15

    SnO{sub 2} (Sn)/C composites as anodes for Li-ion batteries were fabricated by a simple chemical process of hydrothermal synthesis and subsequent heat treatment. The as-prepared materials were characterized by various analytic techniques. Results show that heat treatment temperature has a strong influence on physical and electrochemical performance of these composites. In these composites, irregular SnO{sub 2} lamellas arranged like chrysanthemum were dispersed among the elastic carbon matrix for rapid access of lithium ions to the material bulk. SnO{sub 2}/C anode heat-treated at a temperature of 600 Degree-Sign C exhibits a reversible capacity of 533.4 mAh/g after 50 cycles at the current density of 100 mA/g. - Graphical abstract: Chrysanthemum-like microstructures SnO{sub 2} grains expand along two-dimensional direction during cycling. The intervals among adjacent SnO{sub 2} lamellas provide the sites for lithium insertion and the space for volume expansion. After long cycling, SnO{sub 2} lamellas adhere together to form compact layers, which preserved the integrity of the structure. Highlights: Black-Right-Pointing-Pointer Carbon supported SnO{sub 2} (Sn)/C composites have been synthesized. Black-Right-Pointing-Pointer Temperature control affects the physical and electrochemical performance. Black-Right-Pointing-Pointer Clusters of chrysanthemum-like microstructures were observed. Black-Right-Pointing-Pointer Intervals exist between SnO{sub 2} layers. Black-Right-Pointing-Pointer Integrity structure of SnO{sub 2}/C composites was preserved.

  2. Layered Li-Mn-M-oxides as cathodes for Li-ion batteries:. Recent trends

    NASA Astrophysics Data System (ADS)

    Shaju, K. M.; Subba Rao, G. V.; Chowdari, B. V. R.

    2002-12-01

    There is an increasing demand for manganese (Mn) based mixed oxides which can effectively replace the presently used LiCoO2 as cathode in Li-ion batteries (LIB). The well-studied spinel, LiMn2O4 and its doped derivatives give a capacity of 100-120 mAh/g, but show capacity-fading on cycling especially above 55°C. The layered LiMnO2, isostructural to LiCoO2 (so called O3-structure) can be a viable cathode. However, studies have shown that it undergoes conversion to spinel structure on cycling and thus gives capacity-fading. Other alternative systems recently studied are: O2-structured layered Li-M-Mn-oxides with the general formula Li(2/3)+x(MyMn1-y)O2, M = Li, Ni, Co; x ≤ 0.33 and y = 0.1-0.67, O3-Li(Ni1/2Mn1/2)O2, Li(NixCo1-2xMnx)O2, and M'-substituted Li2MnO3 (M' = Ni, Co, Cr). Some of them are shown to have stable cycling performance, good rate-capability and structural stability over charge-discharge cycling in the 2.5-4.6 V region. Further, the electrochemical processes in the above mixed oxides have been shown to involve Ni2+/4+ or Cr3+/6+ redox couple, thus invoking novel ideas to develop new cathode materials. A brief review of the work done on the above O2- and O3-layered Li-Mn-M-oxides (M = metal) as cathodes for LIB is presented.

  3. High-Capacity Layered-Spinel Cathodes for Li-Ion Batteries.

    PubMed

    Nayak, Prasant Kumar; Levi, Elena; Grinblat, Judith; Levi, Mikhael; Markovsky, Boris; Munichandraiah, N; Sun, Yang Kook; Aurbach, Doron

    2016-09-01

    Li and Mn-rich layered oxides with the general structure x Li2 MnO3 ⋅(1-x) LiMO2 (M=Ni, Mn, Co) are promising cathode materials for Li-ion batteries because of their high specific capacity, which may be greater than 250 mA h g(-1) . However, these materials suffer from high first-cycle irreversible capacity, gradual capacity fading, limited rate capability and discharge voltage decay upon cycling, which prevent their commercialization. The decrease in average discharge voltage is a major issue, which is ascribed to a structural layered-to-spinel transformation upon cycling of these oxide cathodes in wide potential ranges with an upper limit higher than 4.5 V and a lower limit below 3 V versus Li. By using four elements systems (Li, Mn, Ni, O) with appropriate stoichiometry, it is possible to prepare high capacity composite cathode materials that contain LiMn1.5 Ni0.5 O4 and Lix Mny Niz O2 components. The Li and Mn-rich layered-spinel cathode materials studied herein exhibit a high specific capacity (≥200 mA h g(-1) ) with good capacity retention upon cycling in a wide potential domain (2.4-4.9 V). The effect of constituent phases on their electrochemical performance, such as specific capacity, cycling stability, average discharge voltage, and rate capability, are explored here. This family of materials can provide high specific capacity, high rate capability, and promising cycle life. Using Co-free cathode materials is also an obvious advantage of these systems. PMID:27530465

  4. Computer-Aided Engineering of Batteries for Designing Better Li-Ion Batteries (Presentation)

    SciTech Connect

    Pesaran, A.; Kim, G. H.; Smith, K.; Lee, K. J.; Santhanagopalan, S.

    2012-02-01

    This presentation describes the current status of the DOE's Energy Storage R and D program, including modeling and design tools and the Computer-Aided Engineering for Automotive Batteries (CAEBAT) program.

  5. Designing and Diagnosing Novel Electrode Materials for Na-ion Batteries: Potential Alternatives to Current Li-ion Batteries

    NASA Astrophysics Data System (ADS)

    Xu, Jing

    Owing to outstanding energy density, Li-ion batteries have dominated the portable electronic industry for the past 20 years and they are now moving forward powering electric vehicles. In light of concerns over limited lithium reserve and rising lithium costs in the future, Na-ion batteries have re-emerged as potential alternatives for large scale energy storage. On the other hand, though both sodium and lithium are alkali metals sharing many chemical similarities, research on Na-ion batteries is still facing many challenges due to the larger size and unique bonding characteristics of Na ions. In this thesis, a series of sodium transition metal oxides are investigated as cathode materials for Na-ion batteries. P2 - Na2/3[Ni1/3 Mn2/3]O2 is firstly studied with a combination of first principles calculation and experiment, and battery performance is improved by excluding the phase transformation region. Li substituted compound, P2-Na0.8[Li0.12Ni0.22Mn0.66]O 2, is then explored. Its crystal / electronic structure evolution upon cycling is tracked by combing in situ synchrotron X-ray diffraction, ex situ X-ray absorption spectroscopy and solid state NMR. It is revealed that the presence of Li-ions in the transition metal layer allows increased amount of Na-ions to maintain the P2 structure during cycling. The design principles for the P2 type Na cathodes are devised based on this in-depth understanding and an optimized composition is proposed. The idea of Li substitution is then transferred to O3 type cathode. The new material, O3 - Na0.78 Li0.18Ni0.25Mn0.583O2, shows discharge capacity of 240 mAh/g, which is the highest capacity and highest energy density so far among cathode materials in Na-ion batteries. With significant progress on cathode materials, a comprehensive understanding of Na2Ti3O7 as anode for Na-ion batteries is discussed. The electrochemical performance is enhanced, due to increased electronic conductivity and reduced SEI formation with carbon coating

  6. Flexible Batteries: Hierarchical Assemblies of Carbon Nanotubes for Ultraflexible Li-Ion Batteries (Adv. Mater. 31/2016).

    PubMed

    Ahmad, Shahab; Copic, Davor; George, Chandramohan; De Volder, Michael

    2016-08-01

    An advanced battery architecture composed of 3D carbon nanotube (CNT) current collectors is used to mitigate stresses in flexible batteries. On Page 6705, C. George, M. De Volder, and co-workers describe the fabrication process and characteristics of this new generation of ultraflexible batteries, which show high rate and cyclablility. These batteries may find applications in the powering of flexible displays and logics. PMID:27511532

  7. Preparation and characterization of core–shell battery materials for Li-ion batteries manufactured by substrate induced coagulation

    PubMed Central

    Basch, Angelika; Albering, Jörg H.

    2011-01-01

    In this work Substrate Induced Coagulation (SIC) was used to coat the cathode material LiCoO2, commonly used in Li-ion batteries, with fine nano-sized particulate titania. Substrate Induced Coagulation is a self-assembled dip-coating process capable of coating different surfaces with fine particulate materials from liquid media. A SIC coating consists of thin and rinse-prove layers of solid particles. An advantage of this dip-coating method is that the method is easy and cheap and that the materials can be handled by standard lab equipment. Here, the SIC coating of titania on LiCoO2 is followed by a solid-state reaction forming new inorganic layers and a core–shell material, while keeping the content of active battery material high. This titania based coating was designed to confine the reaction of extensively delithiated (charged) LiCoO2 and the electrolyte. The core–shell materials were characterized by SEM, XPS, XRD and Rietveld analysis. PMID:21415909

  8. Preparation and characterization of core-shell battery materials for Li-ion batteries manufactured by substrate induced coagulation

    NASA Astrophysics Data System (ADS)

    Basch, Angelika; Albering, Jörg H.

    2011-03-01

    In this work Substrate Induced Coagulation (SIC) was used to coat the cathode material LiCoO2, commonly used in Li-ion batteries, with fine nano-sized particulate titania. Substrate Induced Coagulation is a self-assembled dip-coating process capable of coating different surfaces with fine particulate materials from liquid media. A SIC coating consists of thin and rinse-prove layers of solid particles. An advantage of this dip-coating method is that the method is easy and cheap and that the materials can be handled by standard lab equipment. Here, the SIC coating of titania on LiCoO2 is followed by a solid-state reaction forming new inorganic layers and a core-shell material, while keeping the content of active battery material high. This titania based coating was designed to confine the reaction of extensively delithiated (charged) LiCoO2 and the electrolyte. The core-shell materials were characterized by SEM, XPS, XRD and Rietveld analysis.

  9. Flexible and Conducting Metal-Fabric Composites Using the Flame Spray Process for the Production of Li-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Voyer, Joel

    2013-06-01

    The wire flame spray process was used to produce electrically conductive and flexible Al coatings onto diverse textile fabrics. The investigation studied the influence of the spraying parameters and fabric materials on the electrical conductivity of the metal-fabric composites. Furthermore, this study showed that the production of flexible Li-ion batteries having good electrical properties based on the use of such flame-sprayed aluminium cathode current collectors is viable. Results show that a coating quantity threshold of about 20 mg/cm2 exists to obtain a sufficient electrical surface conductivity for a commercial use of the produced metal-fabric composites. An excellent electrical surface conductivity of the composites (about 500 SA) could be achieved through an adequate optimization of the spraying parameters. This conductivity increase enabled a reduction of the coating quantity and thus the flexibility of the fabric materials is better conserved, rendering the use of such composites for flexible batteries even more interesting. This study showed that the production of electrically conductive and flexible metal-fabric composites having sufficient electrical conductivity for the manufacture of flexible Li ions batteries is possible. This new method of producing such batteries represents an alternative to other chemically based processes which are hazardous to the environment because of their chemical nature.

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

    NASA Astrophysics Data System (ADS)

    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.

  11. Spatially resolved in operando neutron scattering studies on Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Senyshyn, A.; Mühlbauer, M. J.; Dolotko, O.; Hofmann, M.; Pirling, T.; Ehrenberg, H.

    2014-01-01

    Spatially-resolved neutron diffraction has been applied to probe the lithium distribution in radial direction of a commercial Li-ion cell of 18650-type. The spatial evolution of selected Bragg reflections for LiCoO2 (positive electrode, "cathode") and graphite and lithium intercalated graphite (negative electrode, "anode") was observed and evaluated by taking beam attenuation and cell geometry effects into account. No evidences for lithium inhomogeneities have been found for the investigated set of cells. Computed neutron tomography using a monochromatic neutron beam confirmed the homogeneous lithium distribution. The relevance of the monochromatic beam to neutron imaging studies of Li-ion cells is discussed.

  12. Influence of memory effect on the state-of-charge estimation of large-format Li-ion batteries based on LiFePO4 cathode

    NASA Astrophysics Data System (ADS)

    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.

  13. CoSn5 Phase: Crystal Structure Resolving and Stable High Capacity as Anodes for Li Ion Batteries.

    PubMed

    Wang, Xiao-Liang; Chen, Haiyan; Bai, Jianming; Han, Wei-Qiang

    2012-06-01

    Tin alloys form a class of interesting high-energy-density anode materials for Li ion batteries, but the improvement of their cycling stability is elusive. Here, we provide new insight on this fatal issue by synthesizing novel CoSn5-phase nanospheres via a conversion chemistry route and directly comparing their cell behavior with that of recently found FeSn5-phase nanospheres. The CoSn5 phase is absent in previous Co-Sn phase diagrams. Co0.83Sn5 nanospheres show a much longer cycle life, which partially is related to milder evolution of their cycling profiles over time. PMID:26285626

  14. Facile synthetic route towards nanostructured Fe-TiO2(B), used as negative electrode for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Grosjean, Remi; Fehse, Marcus; Pigeot-Remy, Stéphanie; Stievano, Lorenzo; Monconduit, Laure; Cassaignon, Sophie

    2015-03-01

    We present here a novel simple method for the synthesis of highly pure TiO2(B). The fast microwave-assisted synthetic route allows facile scale-up of the process. Aiming at an application of the titania polymorph as negative electrode for Li-ion batteries, we have prepared a Fe-containing TiO2(B) and tested the electrochemical performances of both pure and Fe-containing materials. Fe insertion in TiO2(B) allows enhancing capacity and rate capability.

  15. Heterostructure composites of rGO/GeO2/PANI with enhanced performance for Li ion battery anode material

    NASA Astrophysics Data System (ADS)

    Sarkar, Sumanta; Borah, Rohan; Santhosha, A. L.; Dhanya, R.; Narayana, Chandrabhas; Bhattacharyya, Aninda J.; Peter, Sebastian C.

    2016-02-01

    A novel solvothermal method has been used for the synthesis of porous ellipsoidal GeO2 particles with oleic acid and oleylamine as solvent and co-surfactant, respectively and its performance has been studied as an anode material for Li ion battery applications. The presence of highly hydrophobic oleic acid and oleylamine on the surface of the as synthesized sample imparts a detrimental effect on its performance. Although removal of the capping agents with glacial acetic acid improves the performance to some extent, a drastic enhancement in both the specific capacity and cycling stability is observed when the nanoparticles are wrapped with rGO/PANI composites at low temperature.

  16. Power capability improvement of LiBOB/PC electrolyte for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Kaneko, Hiroaki; Sekine, Kyoichi; Takamura, Tsutomu

    Lithium bis(oxalto)borate (LiBOB) is quite effective to prevent vigorous decomposition of propylene carbonate (PC) at the graphite anode of a Li-ion battery during Li insertion. PC is a very good solvent that is inexpensive, has high conductivity and a low melting point; however, the power capability of PC electrolyte containing LiBOB is unsatisfactory. In an attempt to improve the power capability of the LiBOB/PC electrolyte, mixed electrolytes containing both LiBOB and LiClO 4 were examined. An integrated fiber felt of highly graphitized carbon was used as the working electrode and the performance was evaluated by cyclic voltammetry (CV), constant current followed by constant voltage charge (CCCV) and constant current discharge. The CV produced a stable peak for Li extraction, but the peak height was as low as half that obtained in a conventional electrolyte such as a 1:1 mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) containing 1 M LiClO 4. However, the peak height in PC, containing 1/49 M LiBOB and 1 M LiClO 4, became 1.5 times higher than that in PC containing 1 M LiBOB. The peak height was increased further using a 1:1 mixture of PC and acetonitrile (AN) containing 1/49 M LiBOB and 1 M LiClO 4, although the cycleability was poor. A similar tendency was observed with the CCCV test. The CV peak height was plotted against the ionic conductivity of several solvents and showed no linear relationship, implying that the reaction activity was influenced by the solid electrolyte interphase (SEI) formed. The charge transfer resistance was evaluated by impedance spectroscopy. The results revealed that not only the surface film resistance but also the charge transfer resistance was markedly increased in the electrolyte containing LiBOB; however, they were reduced by the addition of LiClO 4.

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

    SciTech Connect

    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.

  18. Ab initio molecular dynamics simulations of organic electrolytes, electrodes, and lithium ion transport for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Kent, P. R. C.; Ganesh, P.; Jiang, De-En; Borodin, O.

    2012-02-01

    Optimizing the choice of electrolyte in lithium ion batteries and an understanding of the solid-electrolyte interphase (SEI) is required to optimize the balance between high-energy storage, high rate capability, and lifetime. We perform accurate ab initio molecular-dynamics simulations of common cyclic carbonates and LiPF6 to build solvation models which explain available Neutron and NMR spectroscopies. Our results corroborate why ethylene carbonate is a preferred choice for battery applications over propylene carbonate and how mixtures with dimethyl carbonate improve Li-ion diffusion. We study the role of functionalization of graphite-anode edges on the reducibility of the electrolyte and the ease of Li-ion intercalation at the initial stages of SEI formation. We find that oxygen terminated edges readily act as strong reductive sites, while hydrogen terminated edges are less reactive and allow faster Li diffusion. Orientational ordering of the solvent molecules precedes reduction at the interphase. Inorganic reductive components are seen to readily migrate to the anode edges, leading to increased surface passivation of the anode. We are currently quantifying Li-intercalation barriers across realistic SEI models, and progress along these lines will be presented.

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

    NASA Astrophysics Data System (ADS)

    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.

  20. Component-/structure-dependent elasticity of solid electrolyte interphase layer in Li-ion batteries: Experimental and computational studies

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    The mechanical instability of the Solid Electrolyte Interphase (SEI) layer in lithium ion (Li-ion) batteries causes significant side reactions resulting in Li-ion consumption and cell impedance rise by forming further SEI layers, which eventually leads to battery capacity fade and power fade. In this paper, the composition-/structure-dependent elasticity of the SEI layer is investigated via Atomic Force Microscopy (AFM) measurements coupled with X-ray Photoelectron Spectroscopy (XPS) analysis, and atomistic calculations. It is observed that the inner layer is stiffer than the outer layer. The measured Young's moduli are mostly in the range of 0.2-4.5 GPa, while some values above 80 GPa are also observed. This wide variation of the observed elastic modulus is elucidated by atomistic calculations with a focus on chemical and structural analysis. The numerical analysis shows the Young's moduli range from 2.4 GPa to 58.1 GPa in the order of the polymeric, organic, and amorphous inorganic components. The crystalline inorganic component (LiF) shows the highest value (135.3 GPa) among the SEI species. This quantitative observation on the elasticity of individual components of the SEI layer must be essential to analyzing the mechanical behavior of the SEI layer and to optimizing and controlling it.

  1. Microscale failure mechanisms leading to internal short circuit in Li-ion batteries under complex loading scenarios

    NASA Astrophysics Data System (ADS)

    Sahraei, Elham; Bosco, Emanuela; Dixon, Brandy; Lai, Benjamin

    2016-07-01

    One of the least understood mechanisms of Li-ion batteries is the development of internal short circuits under mechanical loads. In this study, a micro mechanical model is developed and subjected to various loading scenarios to understand the sequence of failure in the multi-layer, multi-material structure of a Li-ion battery jellyroll. The constitutive response of each component of the electrode stack is obtained by comprehensive experimental tests using uniaxial and biaxial tensile and compressive loads. The homogenized response of the model is recovered through the computational homogenization theory. The model is validated by comparing the results of a macroscale simulation against experimental data. The study focuses next on the development of a failure criterion for the electrode stack based on the microstructural observations. Results show distinct failure mechanisms when the loading is predominantly tensile versus when it is compressive or combined tensile/compressive. A failure locus is plotted from the results of the simulations as a criterion to detect the onset of short circuit under complex multi-axial loading scenarios.

  2. Facile synthesis of nano-Li4 Ti5O12 for high-rate Li-ion battery anodes

    NASA Astrophysics Data System (ADS)

    Jin, Yun-Ho; Min, Kyung-Mi; Shim, Hyun-Woo; Seo, Seung-Deok; Hwang, In-Sung; Park, Kyung-Soo; Kim, Dong-Wan

    2012-01-01

    One of the most promising anode materials for Li-ion batteries, Li4Ti5O12, has attracted attention because it is a zero-strain Li insertion host having a stable insertion potential. In this study, we suggest two different synthetic processes to prepare Li4Ti5O12 using anatase TiO2 nanoprecursors. TiO2 powders, which have extraordinarily large surface areas of more than 250 m2 g-1, were initially prepared through the urea-forced hydrolysis/precipitation route below 100°C. For the synthesis of Li4Ti5O12, LiOH and Li2CO3 were added to TiO2 solutions prepared in water and ethanol media, respectively. The powders were subsequently dried and calcined at various temperatures. The phase and morphological transitions from TiO2 to Li4Ti5O12 were characterized using X-ray powder diffraction and transmission electron microscopy. The electrochemical performance of nanosized Li4Ti5O12 was evaluated in detail by cyclic voltammetry and galvanostatic cycling. Furthermore, the high-rate performance and long-term cycle stability of Li4Ti5O12 anodes for use in Li-ion batteries were discussed.

  3. Manganese sequestration and improved high-temperature cycling of Li-ion batteries by polymeric aza-15-crown-5

    NASA Astrophysics Data System (ADS)

    Li, Zicheng; Pauric, Allen D.; Goward, Gillian R.; Fuller, Timothy J.; Ziegelbauer, Joseph M.; Balogh, Michael P.; Halalay, Ion C.

    2014-12-01

    Mn cation trapping by polymeric aza-15-crown-5 ethers is an effective means for mitigating the consequences of Mn dissolution in Li-ion batteries. Mn cations trapping was investigated in lithium manganese oxide (LMO) spinel-graphite (GR) cells containing 1 M LiPF6 in ethylene carbonate (EC):diethyl carbonate (DEC) 1:2 v/v. A commercial polyolefin separator membrane coated with poly[divinylbenzene-(vinylbenzyl-aza-15-crown-5)-vinylbenzylchloride)] effected a 39% reduction in capacity loss rate during cycling at 50 °C with 100% depth of discharge (DOD) at C/5 rate. Simultaneously, a 50-60% reduction in the Mn deposited at the negative electrode, and a 6× to 10× increase in the Mn on the coated separator were observed for cells with coated separators, over baseline cells with plain separators. X-ray absorption near-edge spectroscopy (XANES) yielded average oxidation states near +3 for Mn cations in graphite electrodes and separators from cycled cells, suggesting that Mn metal or in oxidation state +2 can only be minor fractions of the Mn existing outside the positive electrode. We discuss the implications of these results for choosing an optimal chelating agent. We also show that the cation chelating polymer reported here is compatible with existing manufacturing processes for Li-ion battery separators.

  4. Use of mild organic acid reagents to recover the Co and Li from spent Li-ion batteries.

    PubMed

    Nayaka, Girish Praveen; Pai, Karkala Vasantakumar; Manjanna, Jayappa; Keny, Sangita J

    2016-05-01

    New organic acid mixtures have been investigated to recover the valuable metal ions from the cathode material of spent Li-ion batteries. The cathodic active material (LiCoO2) collected from spent Li-ion batteries (LIBs) is dissolved in mild organic acids, iminodiacetic acid (IDA) and maleic acid (MA), to recover the metals. Almost complete dissolution occurred in slightly excess (than the stoichiometric requirement) of IDA or MA at 80°C for 6h, based on the Co and Li released. The reducing agent, ascorbic acid (AA), converts the dissolved Co(III)- to Co(II)-L (L=IDA or MA) thereby selective recovery of Co as Co(II)-oxalate is possible. The formation of Co(III)- and Co(II)-L is evident from the UV-Vis spectra of the dissolved solution as a function of dissolution time. Thus, the reductive-complexing dissolution mechanism is proposed here. These mild organic acids are environmentally benign unlike the mineral acids. PMID:26709049

  5. Finding out the optimal boron concentration in BCx sheets for high capacity anode material in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Das, Deya; Hardikar, Rahul; Han, Sang Soo; Lee, Kwang Ryeol; Singh, Abhishek Kumar

    Boron doped graphene shows better adsorption of Li compared to pristine graphene and has been investigated as a potential anode material for Li-ion batteries. Using first principles density functional theory calculations, we investigate the effect of increasing boron concentration on the gravimetric capacity of mono-layered boron doped graphene sheets, BCx (x = 7, 5, 3, 2 and 1). Li storage capacity increases with the increase in boron concentration giving highest capacity for monolayer BC2 (~ 1400 mAh/g), and is about 1.6 times higher than previously reported capacity of BC3. This is due to the more number of available empty states above the Fermi level in BC2 compared to other sheets. Moreover, owing to a very low Li diffusion barrier, the Li kinetics in BC2 is also found to be better among all the layered boron doped carbon sheets. Further enhancement of B concentration, as in BC, leads to strong binding of Li, thereby hindering the delithiation processes. Hence, BC2 with optimal concentration of B among the BCx phases, emerges as a promising choice for anode material in rechargeable Li ion battery.

  6. From single cell model to battery pack simulation for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Dubarry, Matthieu; Vuillaume, Nicolas; Liaw, Bor Yann

    A practical universal modeling and simulation approach is presented in this paper to show that accurate battery pack simulation can be achieved if cell-to-cell variations were taken into account. A generic equivalent circuit model was used in the approach with parameters deduced from cell testing with proper protocols, which could come from live cell monitoring in a control circuitry. Using a single cell model, which was validated against experimental data and demonstrated with validity of high accuracy in predicting cell performance, we showed that such a high accuracy in single cell model is essential for a high fidelity pack simulation. It is also important to derive statistical confidence intervals accurately from experiments to characterize intrinsic cell-to-cell variations in capacity and internal resistance, which need to be considered in the pack model. If parameters for each individual cell were correctly approximated and used in the pack model, the accuracy in the prediction of pack performance could be significantly improved.

  7. Li-Ion Batteries from LiFePO4 Cathode and Anatase/Graphene Composite Anode for Stationary Energy Storage

    SciTech Connect

    Choi, Daiwon; Wang, Donghai; Viswanathan, Vilayanur V.; Bae, In-Tae; Wang, Wei; Nie, Zimin; Zhang, Jiguang; Graff, Gordon L.; Liu, Jun; Yang, Zhenguo; Duong, Tien Q.

    2009-11-06

    Li-ion batteries based on LiFePO4 cathode and anatase TiO2/graphene anode were investigated for possible stationary energy storage application. Fine-structured LiFePO4 was synthesized by novel molten surfactant approach. Anatase TiO2/graphene nanocomposite was prepared via self assembly method. The full cell that operated at flat 1.6V demonstrated negligible fade after more than 700 cycles. The LiFePO4/TiO2 combination Li-ion battery is inexpensive, environmentally benign, safe and stable. Therefore, it can be practically applied as stationary energy storage for renewable power sources.

  8. Miniature all-solid-state heterostructure nanowire Li-ion batteries as a tool for engineering and structural diagnostics of nanoscale electrochemical processes

    NASA Astrophysics Data System (ADS)

    Oleshko, Vladimir P.; Lam, Thomas; Ruzmetov, Dmitry; Haney, Paul; Lezec, Henri J.; Davydov, Albert V.; Krylyuk, Sergiy; Cumings, John; Talin, A. Alec

    2014-09-01

    Complex interfacial phenomena and phase transformations that govern the operation of Li-ion batteries require detailed nanoscale 3D structural and compositional characterization that can be directly related to their capacity and electrical transport properties. For this purpose, we have designed model miniature all solid-state radial heterostructure Li-ion batteries composed of LiCoO2 cathode, LiPON electrolyte and amorphous Si anode shells, which were deposited around metallized high-aspect-ratio Si nanowires as a scaffolding core. Such diagnostic batteries, the smallest, complete secondary Li-ion batteries realized to date, were specifically designed for in situ electrical testing in a field-emission scanning electron microscope and/or transmission electron microscope. The results of electrochemical testing were described in detail in a previous publication (Nano Lett., 2012, 12, 505-511). The model Li-ion batteries allow analysis of the correlations between electrochemical properties and their structural evolution during cycling in various imaging, diffraction and spectroscopic modes down to the atomic level. Employing multimode analytical scanning/transmission electron microscopy imaging coupled with correlative multivariate statistical analysis and tomography, we have analyzed and quantified the 3D morphological and structural arrangement of the batteries, including textured platelet-like LiCoO2 nanocrystallites, buried electrode-electrolyte interfaces and hidden internal defects to clarify effects of scaling on a battery's electrochemical performance. Characterization of the nanoscale interfacial processes using model heterostructure nanowire-based Li-ion batteries provides useful guidelines for engineering of prospective nano-sized building blocks in future electrochemical energy storage systems.Complex interfacial phenomena and phase transformations that govern the operation of Li-ion batteries require detailed nanoscale 3D structural and compositional

  9. Vacancy-induced manganese vanadates and their potential application to Li-ion batteries.

    PubMed

    Dufficy, Martin K; Luo, Lan; Fedkiw, Peter S; Maggard, Paul A

    2016-06-14

    We report on the synthesis and characterization of a novel manganese vanadate, Mn1.5(H2O)(NH4)V4O12, with rare in situ disorder of Mn(H2O)2(2+)/2NH4(+). We show that vacancies created by ammonium ions and coordinating water molecules within the manganese vanadate crystal structure yield high-charge capacity, favorable rate capability, and long cycle life in Li-ion half-cells. PMID:27210595

  10. Silicon Nanoparticles-Graphene Paper Composites for Li Ion Battery Anodes

    SciTech Connect

    Lee, Jeong K.; Smith, Kurt B.; Hayner, Cary M.; Kung, Harold H.

    2010-02-10

    Composites of Si nanoparticles highly dispersed between graphene sheets, and supported by a 3-D network of graphite formed by reconstituting regions of graphene stacks exhibit high Li ion storage capacities and cycling stability. An electrode was prepared with a storage capacity >2200 mA h g-1 after 50 cycles and >1500 mA hg-1 after 200 cycles that decreased by <0.5% per cycle.

  11. High-performance graphene/sulphur electrodes for flexible Li-ion batteries using the low-temperature spraying method

    NASA Astrophysics Data System (ADS)

    Kumar, Pushpendra; Wu, Feng-Yu; Hu, Lung-Hao; Ali Abbas, Syed; Ming, Jun; Lin, Chia-Nan; Fang, Jason; Chu, Chih-Wei; Li, Lain-Jong

    2015-04-01

    Elementary sulphur (S) has been shown to be an excellent cathode material in energy storage devices such as Li-S batteries owing to its very high capacity. The major challenges associated with the sulphur cathodes are structural degradation, poor cycling performance and instability of the solid-electrolyte interphase caused by the dissolution of polysulfides during cycling. Tremendous efforts made by others have demonstrated that encapsulation of S materials improves their cycling performance. To make this approach practical for large scale applications, the use of low-cost technology and materials has become a crucial and new focus of S-based Li-ion batteries. Herein, we propose to use a low temperature spraying process to fabricate graphene/S electrode material, where the ink is composed of graphene flakes and the micron-sized S particles prepared by grinding of low-cost S powders. The S particles are found to be well hosted by highly conductive graphene flakes and consequently superior cyclability (~70% capacity retention after 250 cycles), good coulombic efficiency (~98%) and high capacity (~1500 mA h g-1) are obtained. The proposed approach does not require high temperature annealing or baking; hence, another great advantage is to make flexible Li-ion batteries. We have also demonstrated two types of flexible batteries using sprayed graphene/S electrodes.Elementary sulphur (S) has been shown to be an excellent cathode material in energy storage devices such as Li-S batteries owing to its very high capacity. The major challenges associated with the sulphur cathodes are structural degradation, poor cycling performance and instability of the solid-electrolyte interphase caused by the dissolution of polysulfides during cycling. Tremendous efforts made by others have demonstrated that encapsulation of S materials improves their cycling performance. To make this approach practical for large scale applications, the use of low-cost technology and materials has become

  12. Miniature all-solid-state heterostructure nanowire Li-ion batteries as a tool for engineering and structural diagnostics of nanoscale electrochemical processes.

    PubMed

    Oleshko, Vladimir P; Lam, Thomas; Ruzmetov, Dmitry; Haney, Paul; Lezec, Henri J; Davydov, Albert V; Krylyuk, Sergiy; Cumings, John; Talin, A Alec

    2014-10-21

    Complex interfacial phenomena and phase transformations that govern the operation of Li-ion batteries require detailed nanoscale 3D structural and compositional characterization that can be directly related to their capacity and electrical transport properties. For this purpose, we have designed model miniature all solid-state radial heterostructure Li-ion batteries composed of LiCoO2 cathode, LiPON electrolyte and amorphous Si anode shells, which were deposited around metallized high-aspect-ratio Si nanowires as a scaffolding core. Such diagnostic batteries, the smallest, complete secondary Li-ion batteries realized to date, were specifically designed for in situ electrical testing in a field-emission scanning electron microscope and/or transmission electron microscope. The results of electrochemical testing were described in detail in a previous publication (Nano Lett., 2012, 12, 505-511). The model Li-ion batteries allow analysis of the correlations between electrochemical properties and their structural evolution during cycling in various imaging, diffraction and spectroscopic modes down to the atomic level. Employing multimode analytical scanning/transmission electron microscopy imaging coupled with correlative multivariate statistical analysis and tomography, we have analyzed and quantified the 3D morphological and structural arrangement of the batteries, including textured platelet-like LiCoO2 nanocrystallites, buried electrode-electrolyte interfaces and hidden internal defects to clarify effects of scaling on a battery's electrochemical performance. Characterization of the nanoscale interfacial processes using model heterostructure nanowire-based Li-ion batteries provides useful guidelines for engineering of prospective nano-sized building blocks in future electrochemical energy storage systems. PMID:25157420

  13. First principle study of LiXS2 (X = Ga, In) as cathode materials for Li ion batteries

    NASA Astrophysics Data System (ADS)

    Feng-Ya, Rao; Fang-Hua, Ning; Li-Wei, Jiang; Xiang-Ming, Zeng; Mu-Sheng, Wu; Bo, Xu; Chu-Ying, Ouyang

    2016-02-01

    From first principle calculations, we demonstrate that LiXS2 (X = Ga, In) compounds have potential applications as cathode materials for Li ion batteries. It is shown that Li can be extracted from the LiXS2 lattice with relatively small volume change and the XS4 tetrahedron structure framework remains stable upon delithiation. The theoretical capacity and average intercalation potential of the LiGaS2 (LiInS2) cathode are 190.4 (144.2) mAh/g and 3.50 V (3.53 V). The electronic structures of the LiXS2 are insulating with band gaps of 2.88 eV and 1.99 eV for X = Ga and In, respectively. However, Li vacancies, which are formed through delithiation, change the electronic structure substantially from insulating to metallic structure, indicating that the electrical conductivities of the LiXS2 compounds should be good during cycling. Li ion migration energy barriers are also calculated, and the results show that Li ion diffusions in the LiXS2 compounds can be as good as those in the currently widely used electrode materials. Project supported by the National High Technology and Development Key Program, China (Grant No. 2015AA034201), the National Natural Science Foundation of China (Grant Nos. 11234013 and 11264014), the Natural Science Foundation of Jiangxi Province, China (Grant Nos. 20133ACB21010, 20142BAB212002, and 20132BAB212005), and the Foundation of Jiangxi Provincial Education Committee, China (Grant Nos. GJJ14254 and KJLD14024).

  14. Probing the Degradation Mechanisms in Electrolyte Solutions for Li-ion Batteries by In-Situ Transmission Electron Microscopy

    SciTech Connect

    Abellan Baeza, Patricia; Mehdi, Beata L.; Parent, Lucas R.; Gu, Meng; Park, Chiwoo; Xu, Wu; Zhang, Yaohui; Arslan, Ilke; Zhang, Jiguang; Wang, Chong M.; Evans, James E.; Browning, Nigel D.

    2014-02-21

    One of the goals in the development of new battery technologies is to find new electrolytes with increased electrochemical stability. In-situ (scanning) transmission electron microscopy ((S)TEM) using an electrochemical fluid cell provides the ability to rapidly and directly characterize electrode/electrolyte interfacial reactions under battery relevant electrochemical conditions. Furthermore, as the electron beam itself causes a localized electrochemical reaction when it interacts with the electrolyte, the breakdown products that occur during the first stages of battery operation can potentially be simulated and characterized using a straightforward in-situ liquid stage (without electrochemical biasing capabilities). In this paper, we have studied the breakdown of a range of inorganic/salt complexes that are used in state-of-the-art Li-ion battery systems. The results of the in-situ (S)TEM experiments matches with previous stability tests performed during battery operation and the breakdown products and mechanisms are also consistent with known mechanisms. This analysis indicates that in-situ liquid stage (S)TEM observations can be used to directly test new electrolyte designs and provide structural insights into the origin of the solid electrolyte interphase (SEI) formation mechanism.

  15. High Anodic Performance of Co 1,3,5-Benzenetricarboxylate Coordination Polymers for Li-Ion Battery.

    PubMed

    Li, Chao; Lou, Xiaobing; Shen, Ming; Hu, Xiaoshi; Guo, Zhi; Wang, Yong; Hu, Bingwen; Chen, Qun

    2016-06-22

    We report the designed synthesis of Co 1,3,5-benzenetricarboxylate coordination polymers (CPs) via a straightforward hydrothermal method, in which three kinds of reaction solvents are selected to form CPs with various morphologies and dimensions. When tested as anode materials in Li-ion battery, the cycling stabilities of the three CoBTC CPs at a current density of 100 mA g(-1) have not evident difference; however, the reversible capacities are widely divergent when the current density is increased to 2 A g(-1). The optimized product CoBTC-EtOH maintains a reversible capacity of 473 mAh g(-1) at a rate of 2 A g(-1) after 500 galvanostatic charging/discharging cycles while retaining a nearly 100% Coulombic efficiency. The hollow microspherical morphology, accessible specific area, and the absence of coordination solvent of CoBTC-EtOH might be responsible for such difference. Furthermore, the ex situ soft X-ray absorption spectroscopy studies of CoBTC-EtOH under different states-of-charge suggest that the Co ions remain in the Co(2+) state during the charging/discharging process. Therefore, Li ions are inserted to the organic moiety (including the carboxylate groups and the benzene ring) of CoBTC without the direct engagement of Co ions during electrochemical cycling. PMID:27142789

  16. Electrolytes with Improved Safety Characteristics for High Voltage, High Specific Energy Li-ion Cells

    NASA Technical Reports Server (NTRS)

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

    2012-01-01

    (1) NASA is actively pursuing the development of advanced electrochemical energy storage and conversion devices for future lunar and Mars missions; (2) The Exploration Technology Development Program, Energy Storage Project is sponsoring the development of advanced Li-ion batteries and PEM fuel cell and regenerative fuel cell systems for the Altair Lunar Lander, Extravehicular Activities (EVA), and rovers and as the primary energy storage system for Lunar Surface Systems; (3) At JPL, in collaboration with NASA-GRC, NASA-JSC and industry, we are actively developing advanced Li-ion batteries with improved specific energy, energy density and safety. One effort is focused upon developing Li-ion battery electrolyte with enhanced safety characteristics (i.e., low flammability); and (4) A number of commercial applications also require Li-ion batteries with enhanced safety, especially for automotive applications.

  17. Attainable gravimetric and volumetric energy density of Li-S and li ion battery cells with solid separator-protected Li metal anodes.

    PubMed

    McCloskey, Bryan D

    2015-11-19

    As a result of sulfur's high electrochemical capacity (1675 mA h/gs), lithium-sulfur batteries have received significant attention as a potential high-specific-energy alternative to current state-of-the-art rechargeable Li ion batteries. For Li-S batteries to compete with commercially available Li ion batteries, high-capacity anodes, such as those that use Li metal, will need to be enabled to fully exploit sulfur's high capacity. The development of Li metal anodes has focused on eliminating Coulombically inefficient and dendritic Li cycling, and to this end, an interesting direction of research is to protect Li metal by employing mechanically stiff solid-state Li(+) conductors, such as garnet phase Li7La3Zr2O12 (LLZO), NASICON-type Li1+xAlxTi2-x(PO4)3 (LATP), and Li2S-P2S5 glasses (LPS), as electrode separators. Basic calculations are used to quantify useful targets for solid Li metal protective separator thickness and cost to enable Li metal batteries in general and Li-S batteries specifically. Furthermore, maximum electrolyte-to-sulfur ratios that allow Li-S batteries to compete with Li ion batteries are calculated. The results presented here suggest that controlling the complex polysulfide speciation chemistry in Li-S cells with realistic, minimal electrolyte loading presents a meaningful opportunity to develop Li-S batteries that are competitive on a specific energy basis with current state-of-the-art Li ion batteries. PMID:26722800

  18. Suppressing the voltage-fading of layered lithium-rich cathode materials via an aqueous binder for Li-ion batteries.

    PubMed

    Zhang, Tao; Li, Jun-tao; Liu, Jie; Deng, Ya-ping; Wu, Zhen-guo; Yin, Zu-wei; Guo, Dong; Huang, Ling; Sun, Shi-gang

    2016-03-28

    Guar gum (GG) has been applied as a binder for layered lithium-rich cathode materials of Li-ion batteries for the first time. Compared with the conventional PVDF binder, electrodes with GG as the binder exhibit significantly suppressed voltage and capacity fading. This study has introduced a multi-functional binder for layered lithium-rich cathode materials. PMID:26954264

  19. Recycling of Advanced Batteries for Electric Vehicles

    SciTech Connect

    JUNGST,RUDOLPH G.

    1999-10-06

    The pace of development and fielding of electric vehicles is briefly described and the principal advanced battery chemistries expected to be used in the EV application are identified as Ni/MH in the near term and Li-ion/Li-polymer in the intermediate to long term. The status of recycling process development is reviewed for each of the two chemistries and future research needs are discussed.

  20. Scalable Synthesis of Nano-Silicon from Beach Sand for Long Cycle Life Li-ion Batteries

    PubMed Central

    Favors, Zachary; Wang, Wei; Bay, Hamed Hosseini; Mutlu, Zafer; Ahmed, Kazi; Liu, Chueh; Ozkan, Mihrimah; Ozkan, Cengiz S.

    2014-01-01

    Herein, porous nano-silicon has been synthesized via a highly scalable heat scavenger-assisted magnesiothermic reduction of beach sand. This environmentally benign, highly abundant, and low cost SiO2 source allows for production of nano-silicon at the industry level with excellent electrochemical performance as an anode material for Li-ion batteries. The addition of NaCl, as an effective heat scavenger for the highly exothermic magnesium reduction process, promotes the formation of an interconnected 3D network of nano-silicon with a thickness of 8-10 nm. Carbon coated nano-silicon electrodes achieve remarkable electrochemical performance with a capacity of 1024 mAhg−1 at 2 Ag−1 after 1000 cycles. PMID:25001507

  1. Facile molten salt synthesis of Li2NiTiO4 cathode material for Li-ion batteries.

    PubMed

    Wang, Yanming; Wang, Yajing; Wang, Fei

    2014-01-01

    Well-crystallized Li2NiTiO4 nanoparticles are rapidly synthesized by a molten salt method using a mixture of NaCl and KCl salts. X-ray diffraction pattern and scanning electron microscopic image show that Li2NiTiO4 has a cubic rock salt structure with an average particle size of ca. 50 nm. Conductive carbon-coated Li2NiTiO4 is obtained by a facile ball milling method. As a novel 4 V positive cathode material for Li-ion batteries, the Li2NiTiO4/C delivers high discharge capacities of 115 mAh g(-1) at room temperature and 138 mAh g(-1) and 50°C, along with a superior cyclability. PMID:24855459

  2. Silicene/germanene on MgX2 (X = Cl, Br, and I) for Li-ion battery applications

    NASA Astrophysics Data System (ADS)

    Zhu, Jiajie; Chroneos, Alexander; Schwingenschlögl, Udo

    2016-03-01

    Silicene is a promising electrode material for Li-ion batteries due to its high Li capacity and low Li diffusion barrier. Germanene is expected to show a similar performance due to its analogous structural and electronic properties. However, the performance of both the materials will be determined by the substrate, since freestanding configurations are unstable. We propose Si/MgX2 and Ge/MgX2 (X = Cl, Br, and I) as suitable hybrid structures, based on first-principles calculations. We find that Li will not cluster and that the Li capacity is very high (443 and 279 mA h g-1 for silicene and germanene on MgCl2, respectively). Sandwich structures can be used to further enhance the performance. Low diffusion barriers of less than 0.3 eV are predicted for all the hybrid structures.

  3. Silicene/germanene on MgX2 (X = Cl, Br, and I) for Li-ion battery applications.

    PubMed

    Zhu, Jiajie; Chroneos, Alexander; Schwingenschlögl, Udo

    2016-03-24

    Silicene is a promising electrode material for Li-ion batteries due to its high Li capacity and low Li diffusion barrier. Germanene is expected to show a similar performance due to its analogous structural and electronic properties. However, the performance of both the materials will be determined by the substrate, since freestanding configurations are unstable. We propose Si/MgX2 and Ge/MgX2 (X = Cl, Br, and I) as suitable hybrid structures, based on first-principles calculations. We find that Li will not cluster and that the Li capacity is very high (443 and 279 mA h g(-1) for silicene and germanene on MgCl2, respectively). Sandwich structures can be used to further enhance the performance. Low diffusion barriers of less than 0.3 eV are predicted for all the hybrid structures. PMID:26976115

  4. Synthesis, characterization and electrochemical properties of α-MoO3 nanobelts for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Yayapao, Oranuch; Phuruangrat, Anukorn; Thongtem, Titipun; Thongtem, Somchai

    2016-06-01

    Orthorhombic molybdenum trioxide (α-MoO3) nanobelts have been successfully synthesized by hydrothermal method at 180°C for 20 h. The prepared α-MoO3 samples were investigated by X-ray diffraction, Fourier transform IR spectroscopy, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy methods. It was found that α-MoO3 nanobelts grow along the c-axis, with ±(100) top or bottom surfaces and ±(010) side surfaces. The prepared α-MoO3 nanobelts were used as cathode materials for Li-ion batteries. They exhibit specific capacity of 1340 and 1250 mA h g-1 at a current density of 100 and 400 mA/g, respectively.

  5. Are ionic liquids based on pyrrolidinium imide able to wet separators and electrodes used for Li-ion batteries?

    NASA Astrophysics Data System (ADS)

    Stefan, Claudia Simona; Lemordant, Daniel; Claude-Montigny, Bénédicte; Violleau, David

    Surface free energy and contact angle measurements were conducted with a series of room temperature ionic liquids (RTILs) based on N,N‧-alkyl-pyrrolidinium imide. Wetting characteristics of various separators (Celgard ® and Separion ®) and electrodes (LiCoO 2, Li 4Ti 5O 12 and graphite), commonly used in Li-ion batteries, were performed. Initially, the free surface energies were determined for both smooth polymeric materials, constituent of the separators, and pyrrolidinium RTILs. Experimental results and calculations show that (i) N-methyl-N-pentyl pyrrolidinium imide is the most wetting RTIL whatever the separator used, and that (ii) the separator wettability is one of the most important factor to take into account in electrochemical devices.

  6. Sandwich-like SnS/Polypyrrole Ultrathin Nanosheets as High-Performance Anode Materials for Li-Ion Batteries.

    PubMed

    Liu, Jun; Gu, Mingzhe; Ouyang, Liuzhang; Wang, Hui; Yang, Lichun; Zhu, Min

    2016-04-01

    Sandwich-like SnS/polypyrrole ultrathin nanosheets were synthesized via a pyrrole reduction and in situ polymerization route, in which room-temperature synthesized ZnSn(OH)6 microcubes were used as the tin source. As anode materials for Li-ion batteries, they exhibit an extremely high reversible capacity (about 1000 mA h g(-1) at 0.1C), outstanding rate capability (with reversible capabilities of 878, 805, 747, 652, and 576 mA h g(-1) at 0.2C, 0.5C, 1C, 2C, and 5C, respectively), stable cycling performance, and high capacity retention (a high capacity of 703 mA h g(-1) at 1C after long 500 cycles). PMID:26984512

  7. H2O2 assisted room temperature oxidation of Ti2C MXene for Li-ion battery anodes

    NASA Astrophysics Data System (ADS)

    Ahmed, Bilal; Anjum, Dalaver H.; Hedhili, Mohamed N.; Gogotsi, Yury; Alshareef, Husam N.

    2016-03-01

    Herein we demonstrate that a prominent member of the MXene family, Ti2C, undergoes surface oxidation at room temperature when treated with hydrogen peroxide (H2O2). The H2O2 treatment results in opening up of MXene sheets and formation of TiO2 nanocrystals on their surface, which is evidenced by the high surface area of H2O2 treated MXene and X-ray diffraction (XRD) analysis. We show that the reaction time and the amount of hydrogen peroxide used are the limiting factors, which determine the morphology and composition of the final product. Furthermore, it is shown that the performance of H2O2 treated MXene as an anode material in Li ion batteries (LIBs) was significantly improved as compared to as-prepared MXenes. For instance, after 50 charge/discharge cycles, specific discharge capacities of 389 mA h g-1, 337 mA h g-1 and 297 mA h g-1 were obtained for H2O2 treated MXene at current densities of 100 mA g-1, 500 mA g-1 and 1000 mA g-1, respectively. In addition, when tested at a very high current density, such as 5000 mA g-1, the H2O2 treated MXene showed a specific capacity of 150 mA h g-1 and excellent rate capability. These results clearly demonstrate that H2O2 treatment of Ti2C MXene improves MXene properties in energy storage applications, such as Li ion batteries or capacitors.Herein we demonstrate that a prominent member of the MXene family, Ti2C, undergoes surface oxidation at room temperature when treated with hydrogen peroxide (H2O2). The H2O2 treatment results in opening up of MXene sheets and formation of TiO2 nanocrystals on their surface, which is evidenced by the high surface area of H2O2 treated MXene and X-ray diffraction (XRD) analysis. We show that the reaction time and the amount of hydrogen peroxide used are the limiting factors, which determine the morphology and composition of the final product. Furthermore, it is shown that the performance of H2O2 treated MXene as an anode material in Li ion batteries (LIBs) was significantly improved as

  8. Formation of Nanocrystalline Surface of Cu-Sn Alloy Foam Electrochemically Produced for Li-Ion Battery Electrode.

    PubMed

    Ye, Bora; Kim, Sunjung

    2015-10-01

    Cu-Sn alloy foam is a promising electrode material for Li-ion batteries. In this study, Cu-Sn alloy foam was produced by diffusion-limited electrodeposition in alkaline electrolyte using polyurethane (PU) foam template. Our major concern is to form Cu-Sn alloy foam with nanocrystalline surface morphology by adjusting electrodeposition conditions such as deposition potential and metal ion concentration. Cu-Sn alloy layers comprising of nanoclusters such as nanospheres, nanoellipsoids, and nanoflakes were created depending on electrodeposition conditions. Larger surface area of nanocluster-interconnected Cu-Sn alloy layer was created when both Sn concentration and negative deposition potential were higher. After decomposing PU template thermally, Cu-Sn alloy foam of Cu, Cu6Sn5, and Cu3Sn phases was finally produced. PMID:26726491

  9. Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries.

    PubMed

    McCalla, Eric; Abakumov, Artem M; Saubanère, Matthieu; Foix, Dominique; Berg, Erik J; Rousse, Gwenaelle; Doublet, Marie-Liesse; Gonbeau, Danielle; Novák, Petr; Van Tendeloo, Gustaaf; Dominko, Robert; Tarascon, Jean-Marie

    2015-12-18

    Lithium-ion (Li-ion) batteries that rely on cationic redox reactions are the primary energy source for portable electronics. One pathway toward greater energy density is through the use of Li-rich layered oxides. The capacity of this class of materials (>270 milliampere hours per gram) has been shown to be nested in anionic redox reactions, which are thought to form peroxo-like species. However, the oxygen-oxygen (O-O) bonding pattern has not been observed in previous studies, nor has there been a satisfactory explanation for the irreversible changes that occur during first delithiation. By using Li2IrO3 as a model compound, we visualize the O-O dimers via transmission electron microscopy and neutron diffraction. Our findings establish the fundamental relation between the anionic redox process and the evolution of the O-O bonding in layered oxides. PMID:26680196

  10. A stepwise recovery of metals from hybrid cathodes of spent Li-ion batteries with leaching-flotation-precipitation process

    NASA Astrophysics Data System (ADS)

    Huang, Yanfang; Han, Guihong; Liu, Jiongtian; Chai, Wencui; Wang, Wenjuan; Yang, Shuzhen; Su, Shengpeng

    2016-09-01

    The recovering of valuable metals in spent lithium-ion battery cathodes brings about economic and environmental benefits. A stepwise leaching-flotation-precipitation process is adopted to separate and recover Li/Fe/Mn from the mixed types of cathode materials (hybrid wastes of LiFePO4 and LiMn2O4). The optimal operating conditions for the stepwise recovery process are determined and analyzed by factorial design, thermodynamics calculation, XRD and SEM characterization in this study. First, Li/Fe/Mn ions are released from the cathode using HCl assisted with H2O2 in the acid leaching step. The leachability of metals follows the series Li > Fe > Mn in the acidic environment. Then Fe3+ ions are selectively floated and recovered as FeCl3 from the leachate in the flotation step. Finally, Mn2+/Mn3+ and Li+ ions are sequentially precipitated and separated as MnO2/Mn2O3 and Li3PO4 using saturated KMnO4 solution and hot saturated Na3PO4 solution, respectively. Under the optimized and advisable conditions, the total recovery of Li, Fe and Mn is respectively 80.93 ± 0.16%, 85.40 ± 0.12% and 81.02 ± 0.08%. The purity for lithium, ferrum and manganese compounds is respectively 99.32 ± 0.07%, 97.91 ± 0.05% and 98.73 ± 0.05%. This stepwise process could provide an alternative way for the effective separation and recovery of metal values from spent Li-ion battery cathodes in industry.

  11. Growth of linked silicon/carbon nanospheres on copper substrate as integrated electrodes for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Zailei; Wang, Yanhong; Tan, Qiangqiang; Li, Dan; Chen, Yunfa; Zhong, Ziyi; Su, Fabing

    2013-12-01

    We report the growth of linked silicon/carbon (Si/C) nanospheres on Cu substrate as an integrated anode for Li-ion batteries. The Si/C nanospheres were synthesized by a catalytic chemical vapor deposition (CCVD) on Cu substrate as current collector using methyltrichlorosilane as precursor, a cheap by-product of the organosilane industry. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermal gravimetry, Raman spectroscopy, nitrogen adsorption, inductively coupled plasma optical emission spectrometry, and X-ray photoelectron spectroscopy. It was found that the linked Si/C nanospheres with a diameter of 400-500 nm contain Si, CuxSi, and Cu nanocrystals, which are highly dispersed in the amorphous carbon nanospheres. A CCVD mechanism was tentatively proposed, in which the evaporated Cu atoms play a critical role to catalytically grown Si nanocrystals embedded within linked Si/C nanospheres. The electrochemical measurement shows that these Si/C nanospheres delivered a capacity of 998.9, 713.1, 320.6, and 817.8 mA h g-1 at 50, 200, 800, and 50 mA g-1 respectively after 50 cycles, much higher than that of commercial graphite anode. This is because the amorphous carbon, CuxSi, and Cu in the Si/C nanospheres could buffer the volume change of Si nanocrystals during the Li insertion and extraction reactions, thus hindering the cracking or crumbling of the electrode. Furthermore, the incorporation of conductive CuxSi and Cu nanocrystals and the integration of active electrode materials with Cu substrate may improve the electrical conductivity from the current collector to individual Si active particles, resulting in a remarkably enhanced reversible capacity and cycling stability. The work will be helpful in the fabrication of low cost binder-free Si/C anode materials for Li-ion batteries.

  12. Surface Passivation of MoO₃ Nanorods by Atomic Layer Deposition toward High Rate Durable Li Ion Battery Anodes.

    PubMed

    Ahmed, B; Shahid, Muhammad; Nagaraju, D H; Anjum, D H; Hedhili, Mohamed N; Alshareef, H N

    2015-06-24

    We demonstrate an effective strategy to overcome the degradation of MoO3 nanorod anodes in lithium (Li) ion batteries at high-rate cycling. This is achieved by conformal nanoscale surface passivation of the MoO3 nanorods by HfO2 using atomic layer deposition (ALD). At high current density such as 1500 mA/g, the specific capacity of HfO2-coated MoO3 electrodes is 68% higher than that of bare MoO3 electrodes after 50 charge/discharge cycles. After 50 charge/discharge cycles, HfO2-coated MoO3 electrodes exhibited specific capacity of 657 mAh/g; on the other hand, bare MoO3 showed only 460 mAh/g. Furthermore, we observed that HfO2-coated MoO3 electrodes tend to stabilize faster than bare MoO3 electrodes because nanoscale HfO2 layer prevents structural degradation of MoO3 nanorods. Additionally, the growth temperature of MoO3 nanorods and the effect of HfO2 layer thickness was studied and found to be important parameters for optimum battery performance. The growth temperature defines the microstructural features and HfO2 layer thickness defines the diffusion coefficient of Li-ions through the passivation layer to the active material. Furthermore, ex situ high resolution transmission electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray diffraction were carried out to explain the capacity retention mechanism after HfO2 coating. PMID:26039512

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

    PubMed

    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. PMID:25372361

  14. H2O2 assisted room temperature oxidation of Ti2C MXene for Li-ion battery anodes.

    PubMed

    Ahmed, Bilal; Anjum, Dalaver H; Hedhili, Mohamed N; Gogotsi, Yury; Alshareef, Husam N

    2016-04-14

    Herein we demonstrate that a prominent member of the MXene family, Ti2C, undergoes surface oxidation at room temperature when treated with hydrogen peroxide (H2O2). The H2O2 treatment results in opening up of MXene sheets and formation of TiO2 nanocrystals on their surface, which is evidenced by the high surface area of H2O2 treated MXene and X-ray diffraction (XRD) analysis. We show that the reaction time and the amount of hydrogen peroxide used are the limiting factors, which determine the morphology and composition of the final product. Furthermore, it is shown that the performance of H2O2 treated MXene as an anode material in Li ion batteries (LIBs) was significantly improved as compared to as-prepared MXenes. For instance, after 50 charge/discharge cycles, specific discharge capacities of 389 mA h g(-1), 337 mA h g(-1) and 297 mA h g(-1) were obtained for H2O2 treated MXene at current densities of 100 mA g(-1), 500 mA g(-1) and 1000 mA g(-1), respectively. In addition, when tested at a very high current density, such as 5000 mA g(-1), the H2O2 treated MXene showed a specific capacity of 150 mA h g(-1) and excellent rate capability. These results clearly demonstrate that H2O2 treatment of Ti2C MXene improves MXene properties in energy storage applications, such as Li ion batteries or capacitors. PMID:26984324

  15. Growth of linked silicon/carbon nanospheres on copper substrate as integrated electrodes for Li-ion batteries.

    PubMed

    Zhang, Zailei; Wang, Yanhong; Tan, Qiangqiang; Li, Dan; Chen, Yunfa; Zhong, Ziyi; Su, Fabing

    2014-01-01

    We report the growth of linked silicon/carbon (Si/C) nanospheres on Cu substrate as an integrated anode for Li-ion batteries. The Si/C nanospheres were synthesized by a catalytic chemical vapor deposition (CCVD) on Cu substrate as current collector using methyltrichlorosilane as precursor, a cheap by-product of the organosilane industry. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermal gravimetry, Raman spectroscopy, nitrogen adsorption, inductively coupled plasma optical emission spectrometry, and X-ray photoelectron spectroscopy. It was found that the linked Si/C nanospheres with a diameter of 400-500 nm contain Si, Cu(x)Si, and Cu nanocrystals, which are highly dispersed in the amorphous carbon nanospheres. A CCVD mechanism was tentatively proposed, in which the evaporated Cu atoms play a critical role to catalytically grown Si nanocrystals embedded within linked Si/C nanospheres. The electrochemical measurement shows that these Si/C nanospheres delivered a capacity of 998.9, 713.1, 320.6, and 817.8 mA h g(-1) at 50, 200, 800, and 50 mA g(-1) respectively after 50 cycles, much higher than that of commercial graphite anode. This is because the amorphous carbon, Cu(x)Si, and Cu in the Si/C nanospheres could buffer the volume change of Si nanocrystals during the Li insertion and extraction reactions, thus hindering the cracking or crumbling of the electrode. Furthermore, the incorporation of conductive Cu(x)Si and Cu nanocrystals and the integration of active electrode materials with Cu substrate may improve the electrical conductivity from the current collector to individual Si active particles, resulting in a remarkably enhanced reversible capacity and cycling stability. The work will be helpful in the fabrication of low cost binder-free Si/C anode materials for Li-ion batteries. PMID:24201898

  16. A review of blended cathode materials for use in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Chikkannanavar, Satishkumar B.; Bernardi, Dawn M.; Liu, Lingyun

    2014-02-01

    Several commercial automotive battery suppliers have developed lithium ion cells which use cathodes that consist of a mixture of two different active materials. This approach is intended to take advantage of the unique properties of each material and optimize the performance of the battery with respect to the automotive operating requirements. Certain cathode materials have high coulombic capacity and good cycling characteristics, but are costly and exhibit poor thermal stability (e.g., LiNixCo1-x-yAlyO2). Alternately, other cathode materials exhibit good thermal stability, high voltage and high rate capability, but have low capacity (e.g., LiMn2O4). By blending two cathode materials the shortcomings of the parent materials could be minimized and the resultant blend can be tailored to have a higher energy or power density coupled with enhanced stability and lower cost. In this review, we survey the developing field of blended cathode materials from a new perspective. Targeting a range of cathode materials, we survey the advances in the field in the current review. Limitations, such as capacity decay due to metal dissolution are also discussed, as well as how the appropriate balance of characteristics of the blended materials can be optimized for hybrid- and electric-vehicle applications.

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

    PubMed

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

    2015-02-01

    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. PMID:25584530

  18. Metal hydrides used as negative electrode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Sartori, Sabrina; Cuevas, Fermin; Latroche, Michel

    2016-02-01

    Energy is a key issue for future generation. Researches are conducted worldwide to develop new efficient means for energy conversion and storage. Electrochemical storage is foreseen as an efficient way to handle intermittent renewable energy production. The most advanced batteries are nowadays based on lithium-ion technology though their specific capacities should be significantly increased to bring solution to mass storage. Conversion reactions are one way to step forward larger capacities at the anode. We here review the possibility to use metallic or complex hydrides as negative electrode using conversion reaction of hydride with lithium. Moreover, promising alloying of lithium with the metallic species might provide additional reversible capacities. Both binary and ternary systems are reviewed and results are compared in the frame of the electrochemical application.

  19. Electrospun nanofibers: a prospective electro-active material for constructing high performance Li-ion batteries.

    PubMed

    Aravindan, Vanchiappan; Sundaramurthy, Jayaraman; Suresh Kumar, Palaniswamy; Lee, Yun-Sung; Ramakrishna, Seeram; Madhavi, Srinivasan

    2015-02-11

    In the present review, we describe the development of a high energy density LIB fabricated with all 1D nanofibers as the anode and cathode, as well as a separator-cum-electrolyte prepared by an electrospinning technique without compromising the power capability and cycle life. Such a unique assembly certainly enables realizing the advantages of using 1D nanostructures in practical LIBs, irrespective of the anode or cathode in the presence of gelled polyvinylidene fluoride-co-hexafluoropropylene as the separator-cum-electrolyte. Outstanding cycling profiles with high power densities were noted for all the configurations evaluated. This excellent performance opens up new avenues for the development of high performance Li-ion power packs with a long cycle life and high energy and power densities to drive zero emission transportation applications in the near future, and opens up new research activities in this field as well. PMID:25493289

  20. Scalable process for application of stabilized lithium metal powder in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Ai, Guo; Wang, Zhihui; Zhao, Hui; Mao, Wenfeng; Fu, Yanbao; Yi, Ran; Gao, Yue; Battaglia, Vincent; Wang, Donghai; Lopatin, Sergey; Liu, Gao

    2016-03-01

    A simple solution processing method is developed to achieve a uniform and scalable stabilized lithium metal powder (SLMP) coating on a Li-ion negative electrode. A solvent and binder system for the SLMP coating is developed, including the selection of solvent, polymer binder, and optimization of polymer concentration. The optimized binder solution is a 1% concentration of polymer binder in xylene; a mixture of poly(styrene-co-butadiene) rubber (SBR) and polystyrene (PS) is chosen as the polymer binder. Results show that long-sustained, uniformly dispersed SLMP suspension can be achieved with the optimized binder solution. The uniform SLMP coating can be achieved using a simple "doctor blade" coating method, and the resulting SLMP coating can be firmly glued on the anode surface. By using SLMP to prelithiate the negative electrode, improvements in electrochemical performances are demonstrated in both graphite/NMC and SiO/NMC full cells.

  1. Homogeneity of lithium distribution in cylinder-type Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Senyshyn, A.; Mühlbauer, M. J.; Dolotko, O.; Hofmann, M.; Ehrenberg, H.

    2015-12-01

    Spatially-resolved neutron powder diffraction with a gauge volume of 2 × 2 × 20 mm3 has been applied as an in situ method to probe the lithium concentration in the graphite anode of different Li-ion cells of 18650-type in charged state. Structural studies performed in combination with electrochemical measurements and X-ray computed tomography under real cell operating conditions unambiguously revealed non-homogeneity of the lithium distribution in the graphite anode. Deviations from a homogeneous behaviour have been found in both radial and axial directions of 18650-type cells and were discussed in the frame of cell geometry and electrical connection of electrodes, which might play a crucial role in the homogeneity of the lithium distribution in the active materials within each electrode.

  2. Homogeneity of lithium distribution in cylinder-type Li-ion batteries.

    PubMed

    Senyshyn, A; Mühlbauer, M J; Dolotko, O; Hofmann, M; Ehrenberg, H

    2015-01-01

    Spatially-resolved neutron powder diffraction with a gauge volume of 2 × 2 × 20 mm(3) has been applied as an in situ method to probe the lithium concentration in the graphite anode of different Li-ion cells of 18650-type in charged state. Structural studies performed in combination with electrochemical measurements and X-ray computed tomography under real cell operating conditions unambiguously revealed non-homogeneity of the lithium distribution in the graphite anode. Deviations from a homogeneous behaviour have been found in both radial and axial directions of 18650-type cells and were discussed in the frame of cell geometry and electrical connection of electrodes, which might play a crucial role in the homogeneity of the lithium distribution in the active materials within each electrode. PMID:26681110

  3. An alternative cooling system to enhance the safety of Li-ion battery packs

    NASA Astrophysics Data System (ADS)

    Kizilel, Riza; Sabbah, Rami; Selman, J. Robert; Al-Hallaj, Said

    A passive thermal management system is evaluated for high-power Li-ion packs under stressful or abusive conditions, and compared with a purely air-cooling mode under normal and abuse conditions. A compact and properly designed passive thermal management system utilizing phase change material (PCM) provides faster heat dissipation than active cooling during high pulse power discharges while preserving sufficiently uniform cell temperature to ensure the desirable cycle life for the pack. This study investigates how passive cooling with PCM contributes to preventing the propagation of thermal runaway in a single cell or adjacent cells due to a cell catastrophic failure. Its effectiveness is compared with that of active cooling by forced air flow or natural convection using the same compact module and pack configuration corresponding to the PCM matrix technology. The effects of nickel tabs and spacing between the cells were also studied.

  4. Homogeneity of lithium distribution in cylinder-type Li-ion batteries

    PubMed Central

    Senyshyn, A.; Mühlbauer, M. J.; Dolotko, O.; Hofmann, M.; Ehrenberg, H.

    2015-01-01

    Spatially-resolved neutron powder diffraction with a gauge volume of 2 × 2 × 20 mm3 has been applied as an in situ method to probe the lithium concentration in the graphite anode of different Li-ion cells of 18650-type in charged state. Structural studies performed in combination with electrochemical measurements and X-ray computed tomography under real cell operating conditions unambiguously revealed non-homogeneity of the lithium distribution in the graphite anode. Deviations from a homogeneous behaviour have been found in both radial and axial directions of 18650-type cells and were discussed in the frame of cell geometry and electrical connection of electrodes, which might play a crucial role in the homogeneity of the lithium distribution in the active materials within each electrode. PMID:26681110

  5. Design and use of multisine signals for Li-ion battery equivalent circuit modelling. Part 2: Model estimation

    NASA Astrophysics Data System (ADS)

    Widanage, W. D.; Barai, A.; Chouchelamane, G. H.; Uddin, K.; McGordon, A.; Marco, J.; Jennings, P.

    2016-08-01

    An Equivalent Circuit Model (ECM) of a lithium ion (Li-ion) battery is an empirical, linear dynamic model and the bandwidth of the input current signal and level of non-linearity in the voltage response are important for the model's validity. An ECM is, however, generally parametrised with a pulse current signal, which is low in signal bandwidth (Part 1) and any non-linear dependence of the voltage on the current due to transport limitations is ignored. This paper presents a general modelling methodology which utilises the higher bandwidth and number of signal levels of a pulse-multisine signal to estimate the battery dynamics and non-linear characteristics without the need of a 3D look-up table for the model parameters. In the proposed methodology a non-parametric estimate of the battery dynamics and non-linear characteristics are first obtained which assists in the model order selection, and to assess the level of non-linearity. The new model structure, termed as the Non-linear ECM (NL-ECM), gives a lower Root Mean Square (RMS) and peak error when compared to an ECM estimated using a pulse data set.

  6. Li-Ion Battery Studies at NASA/Goddard Space Flight Center

    NASA Technical Reports Server (NTRS)

    Lee, Leonine; Rao, Gopalakrishna M.

    2006-01-01

    This viewgraph presentation reviews NASA and GSFC's interest in Lithium Ion Batteries as power suupplies for space usage, the tests, and results on several commercially available batteries. Severl batteries were tested for Geosynchronous orbit, Low Earth Orbit, and Low Lunar Orbit conditions.

  7. Electrode-electrolyte interface in Li-ion batteries: current understanding and new insights.

    PubMed

    Gauthier, Magali; Carney, Thomas J; Grimaud, Alexis; Giordano, Livia; Pour, Nir; Chang, Hao-Hsun; Fenning, David P; Lux, Simon F; Paschos, Odysseas; Bauer, Christoph; Maglia, Filippo; Lupart, Saskia; Lamp, Peter; Shao-Horn, Yang

    2015-11-19

    Understanding reactions at the electrode/electrolyte interface (EEI) is essential to developing strategies to enhance cycle life and safety of lithium batteries. Despite research in the past four decades, there is still limited understanding by what means different components are formed at the EEI and how they influence EEI layer properties. We review findings used to establish the well-known mosaic structure model for the EEI (often referred to as solid electrolyte interphase or SEI) on negative electrodes including lithium, graphite, tin, and silicon. Much less understanding exists for EEI layers for positive electrodes. High-capacity Li-rich layered oxides yLi2-xMnO3·(1-y)Li1-xMO2, which can generate highly reactive species toward the electrolyte via oxygen anion redox, highlight the critical need to understand reactions with the electrolyte and EEI layers for advanced positive electrodes. Recent advances in in situ characterization of well-defined electrode surfaces can provide mechanistic insights and strategies to tailor EEI layer composition and properties. PMID:26510477

  8. First Principles Study of Electrochemical and Chemical Stability of the Solid Electrolyte-Electrode Interfaces in All-Solid-State Li-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Zhu, Yizhou; He, Xingfeng; Mo, Yifei

    All-solid-state Li-ion battery is a promising next-generation energy-storage technology. Using novel ceramic solid electrolyte materials, all-solid-state battery has advantages of intrinsic safety and high energy density compared to current Li-ion batteries based on organic liquid electrolyte. However, the power density achieved in all-solid-state battery is still unsatisfactory. The high interfacial resistance at electrode-electrolyte interface is one of the major limiting factors. Here we demonstrated a computational approach based on first principles calculation to systematically investigate the chemical and electrochemical stability of solid electrolyte materials, and provide insightful understanding of the degradation and passivation mechanisms at the interface. Our calculation revealed that the intrinsic stability of solid electrolyte materials and solid electrolyte-electrode interfaces is limited and the formation of interphase layers are thermodynamically favorable. Our study demonstrated a computational scheme to evaluate the electrochemical and chemical stability of the solid interfaces. Our newly gained understanding provided principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries. This work was supported by Office of Energy Efficiency and Renewable Energy (DE-EE0006860).

  9. New materials for Li-ion batteries: synthesis and spectroscopic characterization of Li2(FeMnCo)SiO4 cathode materials.

    PubMed

    Ferrari, Stefania; Mozzati, Maria Cristina; Lantieri, Marco; Spina, Gabriele; Capsoni, Doretta; Bini, Marcella

    2016-01-01

    Improving cathode materials is mandatory for next-generation Li-ion batteries. Exploring polyanion compounds with high theoretical capacity such as the lithium metal orthosilicates, Li2MSiO4 is of great importance. In particular, mixed silicates represent an advancement with practical applications. Here we present results on a rapid solid state synthesis of mixed Li2(FeMnCo)SiO4 samples in a wide compositional range. The solid solution in the P21/n space group was found to be stable for high iron concentration or for a cobalt content up to about 0.3 atom per formula unit. Other compositions led to a mixture of polymorphs, namely Pmn21 and Pbn21. All the samples contained a variable amount of Fe(3+) ions that was quantified by Mössbauer spectroscopy and confirmed by the TN values of the paramagnetic to antiferromagnetic transition. Preliminary characterization by cyclic voltammetry revealed the effect of Fe(3+) on the electrochemical response. Further work is required to determine the impact of these electrode materials on lithium batteries. PMID:27293181

  10. New materials for Li-ion batteries: synthesis and spectroscopic characterization of Li2(FeMnCo)SiO4 cathode materials

    NASA Astrophysics Data System (ADS)

    Ferrari, Stefania; Mozzati, Maria Cristina; Lantieri, Marco; Spina, Gabriele; Capsoni, Doretta; Bini, Marcella

    2016-06-01

    Improving cathode materials is mandatory for next-generation Li-ion batteries. Exploring polyanion compounds with high theoretical capacity such as the lithium metal orthosilicates, Li2MSiO4 is of great importance. In particular, mixed silicates represent an advancement with practical applications. Here we present results on a rapid solid state synthesis of mixed Li2(FeMnCo)SiO4 samples in a wide compositional range. The solid solution in the P21/n space group was found to be stable for high iron concentration or for a cobalt content up to about 0.3 atom per formula unit. Other compositions led to a mixture of polymorphs, namely Pmn21 and Pbn21. All the samples contained a variable amount of Fe3+ ions that was quantified by Mössbauer spectroscopy and confirmed by the TN values of the paramagnetic to antiferromagnetic transition. Preliminary characterization by cyclic voltammetry revealed the effect of Fe3+ on the electrochemical response. Further work is required to determine the impact of these electrode materials on lithium batteries.

  11. New materials for Li-ion batteries: synthesis and spectroscopic characterization of Li2(FeMnCo)SiO4 cathode materials

    PubMed Central

    Ferrari, Stefania; Mozzati, Maria Cristina; Lantieri, Marco; Spina, Gabriele; Capsoni, Doretta; Bini, Marcella

    2016-01-01

    Improving cathode materials is mandatory for next-generation Li-ion batteries. Exploring polyanion compounds with high theoretical capacity such as the lithium metal orthosilicates, Li2MSiO4 is of great importance. In particular, mixed silicates represent an advancement with practical applications. Here we present results on a rapid solid state synthesis of mixed Li2(FeMnCo)SiO4 samples in a wide compositional range. The solid solution in the P21/n space group was found to be stable for high iron concentration or for a cobalt content up to about 0.3 atom per formula unit. Other compositions led to a mixture of polymorphs, namely Pmn21 and Pbn21. All the samples contained a variable amount of Fe3+ ions that was quantified by Mössbauer spectroscopy and confirmed by the TN values of the paramagnetic to antiferromagnetic transition. Preliminary characterization by cyclic voltammetry revealed the effect of Fe3+ on the electrochemical response. Further work is required to determine the impact of these electrode materials on lithium batteries. PMID:27293181

  12. Hierarchical Assemblies of Carbon Nanotubes for Ultraflexible Li-Ion Batteries.

    PubMed

    Ahmad, Shahab; Copic, Davor; George, Chandramohan; De Volder, Michael

    2016-08-01

    The flexible batteries that are needed to power flexible circuits and displays remain challenging, despite considerable progress in the fabrication of such devices. Here, it is shown that flexible batteries can be fabricated using arrays of carbon nanotube microstructures, which decouple stress from the energy-storage material. It is found that this battery architecture imparts exceptional flexibility (radius ≈ 300 μm), high rate (20 A g(-1) ), and excellent cycling stability. PMID:27184630

  13. A flexible freestanding Si/rGO hybrid film anode for stable Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Haoxuan; Jing, Shilong; Hu, Yanjie; Jiang, Hao; Li, Chunzhong

    2016-03-01

    The fabrication of flexible freestanding electrodes with superior electrochemical performance is challenging now in consumer electronics miniaturization. Herein, we demonstrate a simple and scalable synthesis of hollow silicon nanosheets, which then hybridizes with rGO into flexible films by layer-by-layer assembly process. The resulting Si/rGO films, when applied as a free-standing LIBs anode, exhibit a high reversible specific capacity of 904 mAh g-1 at 200 mA g-1 (about 2 times higher than theoretical value of graphite anode), and meanwhile maintain a long cycle life (650 mAh g-1 after 150 cycles). In addition, a flexible full battery has also been assembled based on the flexible film as an anode and the commercial LiCoO2 as a cathode, which impressively delivers a high specific capacity of 700 and 613 mAh g-1 at 50 mA g-1 after 15 cycles in flat and bent state, respectively. Such intriguing electrochemical performances can be mainly attributed to the two-dimensional hollow nanostructure of silicon and their strong synergistic effect with rGO. It is reckoned that our Si/rGO films are a promising anode for advanced flexible LIBs.

  14. Metal-induced crystallization of highly corrugated silicon thick films as potential anodes for Li-ion batteries.

    PubMed

    Qu, Fei; Li, Chilin; Wang, Zumin; Strunk, Horst P; Maier, Joachim

    2014-06-11

    Silicon has turned into one of the most promising anodes for high energy rechargeable Li-ion batteries. However, a huge volume expansion during alloying with Li always induces serious pulverization/delamination for microsized electrodes as well as undesired accumulation of solid electrolyte interphase (SEI). Many efforts have focused on various nanoengineering and binding strategies to construct integrated, robust ionic/electronic wiring networks but with a trade-off between active/inactive material ratio and performance retention. Here, we first apply a metal-induced crystallization (AIC) principle for immiscible metal/semiconductor systems (Si/Al bilayers in this work) to prepare microthick Si films consisting of a high density of isolated nanocolumns. This method furthermore brings about low temperature crystallization of initial amorphous Si and conformal coating of ion-conductive oxide to enhance the Li transport kinetics of bulk and interface. Both highly satisfactory capacity retention (1650 mAh/g after 500 cycles) and rate performance (∼1000 mAh/g at 8C) are achieved for such thick Si film anodes. This methodology can be used to prepare thick film samples with well-defined nanostructures but free of extra binder and conductive additives. It enables much higher area specific capacity than for inactive-component contained slurry samples and thin film samples. This postdeposition pore-creating can be extended to more alloying or conversion electrodes of thick films for high capacity Li/Na ion batteries. PMID:24797020

  15. Influence of Binder Adhesion Ability on the Performance of Silicon/Carbon Composite as Li-Ion Battery Anode

    NASA Astrophysics Data System (ADS)

    Kierzek, Krzysztof

    2016-04-01

    A series of anodes for Li-ion battery was prepared by conventional homogenization of active material, percolator, and Na-CMC or several kinds of PVDF as a binder. Si/C composite was synthesized by embedding micro-sized silicon and synthetic battery-grade graphite in a pitch-derived carbon matrix and taken as active material. Adhesion strength of anodic film to a current collector was determined by peeling test. Thermal relaxation (120-180 °C) after calendering of PVDF-based anode slightly increases the adhesion of the film to the collector. The highest peeling strength was recorded for ultrahigh molecular weight PVDF (~0.05 N cm-1) but without advantage for cycling stability of the cell. An initial reversible capacity of 512 mAh g-1, with average capacity decay only of 0.5% per cycle, was achieved for CMC-based anode of moderate peeling strength (~0.035 N cm-1). Such good performance was attributed to a specific Si/C composite structure as well as profitable physicochemical properties of the binder.

  16. Influence of Binder Adhesion Ability on the Performance of Silicon/Carbon Composite as Li-Ion Battery Anode

    NASA Astrophysics Data System (ADS)

    Kierzek, Krzysztof

    2016-06-01

    A series of anodes for Li-ion battery was prepared by conventional homogenization of active material, percolator, and Na-CMC or several kinds of PVDF as a binder. Si/C composite was synthesized by embedding micro-sized silicon and synthetic battery-grade graphite in a pitch-derived carbon matrix and taken as active material. Adhesion strength of anodic film to a current collector was determined by peeling test. Thermal relaxation (120-180 °C) after calendering of PVDF-based anode slightly increases the adhesion of the film to the collector. The highest peeling strength was recorded for ultrahigh molecular weight PVDF (~0.05 N cm-1) but without advantage for cycling stability of the cell. An initial reversible capacity of 512 mAh g-1, with average capacity decay only of 0.5% per cycle, was achieved for CMC-based anode of moderate peeling strength (~0.035 N cm-1). Such good performance was attributed to a specific Si/C composite structure as well as profitable physicochemical properties of the binder.

  17. Highly monodispersed tin oxide/mesoporous starbust carbon composite as high-performance Li-ion battery anode.

    PubMed

    Chen, Jiajun; Yano, Kazuhisa

    2013-08-28

    The widespread commercialization of today's plug-in hybrid and all electric vehicles will rely on improved lithium batteries with higher energy density, greater power, and durability.To take advantage of the high density of SnO2 anodes for Li ion batteries, we achieved a smart design of monodispersed SnO2/MSCS composite with very high content of SnO2 by a simple infiltration procedure. The synergistic effects of the unique nanoarchitecture of MSCS and the ultrafine size of SnO2 nanoparticle endowed the composite with superior electrochemical performance. Because of the high density of the composite resulting from its monodispersed submicrometer spherical morphology, an exceptionally high reversible lithium storage capacity (both gravimetric and volumetric), very close to the theoretical capacity (1491 mA h/g), can be achieved with good cyclability (capacity retention of 92.5% after 15 cycles). The SnO2/MSCS composite anode exhibited a high reversible average capacity of about 1200 mAh/g over 30 cycles at a current of 80 mAh/g, which corresponds to about 1440 mAh/cm(3) (practical volumetric capacity). In addition, a Coulombic efficiency close to 100% was achieved, and less than 25% first irreversible capacity loss was observed. PMID:23947639

  18. A combustion chemistry analysis of carbonate solvents used in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Harris, Stephen J.; Timmons, Adam; Pitz, William J.

    Under abusive conditions Li-ion cells can rupture, ejecting electrolyte and other flammable gases. In this paper we consider some of the thermochemical and combustion properties of these gases that determine whether they ignite and how energetically they burn. We find a significant variation among the carbonate solvents in the factors that are important to determining flammability, such as combustion enthalpy and vaporization enthalpy. We also show that flames of carbonate solvents are fundamentally less energetic than those of conventional hydrocarbons. An example of this contrast is given using a recently developed mechanism for dimethyl carbonate (DMC) combustion, where we show that a diffusion flame burning DMC has only half the peak heat release rate of an analogous propane flame. Interestingly, peak temperatures differ by only 25%. We argue that heat release rate is a more useful parameter than temperature when evaluating the likelihood that a flame in one cell will ignite a neighboring cell. Our results suggest that thermochemical and combustion property factors might well be considered when choosing solvent mixtures when flammability is a concern.

  19. Characterization of commercial Li-ion batteries using electrochemical-calorimetric measurements

    NASA Astrophysics Data System (ADS)

    Al Hallaj, S.; Prakash, J.; Selman, J. R.

    Commercial Li-ion cells of Type 18650 dimensions and prismatic designs from different manufacturers have been tested to evaluate their performance and to study their thermal behavior using electrochemical-calorimetric methods. All cells tested in this work showed good performance and cyclability under normal operating conditions. The measured heat effect for the cells were exothermic during discharge and partially endothermic during charge. Cell impedance was measured for selected cells and showed some dependence on the state of charge or depth of discharge, with significant increase at the end of discharge due to concentration polarization. The entropy coefficient (d Eeq/d T) for the A&T (18650) and Panasonic (CGR 18650) cells were measured using potentiometric methods at different depths of discharge (DOD). The measured values for both cells showed some dependence on the DOD with some perturbation near 4.0 V, where the measured d Eeq/d T for Panasonic cell had an unexpected positive value. This was found to be consistent with the measured endothermic heat effect during discharge for the Panasonic cell near Eeq=4.0 V. This may be related to a phase change in the LiCoO 2 cathode material, as reported in the literature, and to structural transformation in the graphite used as anode material, in the Panasonic cell.

  20. Performance Testing of Yardney Li-Ion Cells and Batteries in Support of JPL's 2009 Mars Science Laboratory Mission

    NASA Technical Reports Server (NTRS)

    Smart, M.C.; Ratnakumar, B.V.; Whitcanack, L. D.; Dewell, E. A.; Jones, L. E.; Salvo, C. G.; Puglia, F. J.; Cohen, S.; Gitzendanner, R.

    2008-01-01

    In 2009, JPL is planning to launch an unmanned rover mission to the planet Mars. This mission, referred to as the Mars Science Laboratory (MSL), will involve the use of a rover that is much larger than the previously developed Spirit and Opportunity Rovers for the 2003 Mars Exploration Rover (MER) mission, that are currently still in operation on the surface of the planet after more than three years. Part of the reason that the MER rovers have operated so successfully, far exceeding the required mission duration of 90 sols, is that they possess robust Li-ion batteries, manufactured by Yardney Technical Products, which have demonstrated excellent life characteristics. Given the excellent performance characteristics displayed, similar lithium-ion batteries have been projected to successfully meet the mission requirements of the up-coming MSL mission. Although comparable in many facets, such as being required to operate over a wide temperature range (-20 to 40 C), the MSL mission has more demanding performance requirements compared to the MER mission, including much longer mission duration (approx. 687 sols vs. 90 sols), higher power capability, and the need to withstand higher temperature excursions. In addition, due to the larger rover size, the MSL mission necessitates the use of a much larger battery to meet the energy, life, and power requirements. In order to determine the viability of meeting these requirements, a number of performance verification tests were performed on 10 Ah Yardney lithium-ion cells (MER design) under MSL-relevant conditions, including mission surface operation simulation testing. In addition, the performance of on-going ground life testing of 10 Ah MER cells and 8-cell batteries will be discussed in the context of capacity loss and impedance growth predictions.

  1. A techno-economic analysis and optimization of Li-ion batteries for light-duty passenger vehicle electrification

    NASA Astrophysics Data System (ADS)

    Sakti, Apurba; Michalek, Jeremy J.; Fuchs, Erica R. H.; Whitacre, Jay F.

    2015-01-01

    We conduct a techno-economic analysis of Li-ion NMC-G prismatic pouch battery and pack designs for electric vehicle applications. We develop models of power capability and manufacturing operations to identify the minimum cost cell and pack designs for a variety of plug-in hybrid electric vehicle (PHEV) and battery electric vehicle (BEV) requirements. We find that economies of scale in battery manufacturing are reached quickly at a production volume of ∼200-300 MWh annually. Increased volume does little to reduce unit costs, except potentially indirectly through factors such as experience, learning, and innovation. We also find that vehicle applications with larger energy requirements are able to utilize cheaper cells due in part to the use of thicker electrodes. The effect on cost can be substantial. In our base case, we estimate pack-level battery production costs of ∼545 kWh-1 for a PHEV with a 10 mile (16 km) all-electric range (PHEV10) and ∼230 kWh-1 for a BEV with a 200 mile (320 km) all-electric range (BEV200). This 58% reduction, from 545 kWh-1 to 230 kWh-1, is a larger effect than the uncertainty represented by our optimistic and pessimistic scenarios. Electrodes thicker than about 100 or 125 microns are not currently used in practice due to manufacturing and durability concerns, but relaxing this constraint could further lower the cost of larger capacity BEV200 packs by up to an additional 8%.

  2. Model-Based Design and Integration of Large Li-ion Battery Systems

    SciTech Connect

    Smith, Kandler; Kim, Gi-Heon; Santhanagopalan, Shriram; Shi, Ying; Pesaran, Ahmad; Mukherjee, Partha; Barai, Pallab; Maute, Kurt; Behrou, Reza; Patil, Chinmaya

    2015-11-17

    This presentation introduces physics-based models of batteries and software toolsets, including those developed by the U.S. Department of Energy's (DOE) Computer-Aided Engineering for Electric-Drive Vehicle Batteries Program (CAEBAT). The presentation highlights achievements and gaps in model-based tools for materials-to-systems design, lifetime prediction and control.

  3. Classification of discarded NiMH and Li-Ion batteries and reuse of the cells still in operational conditions in prototypes

    NASA Astrophysics Data System (ADS)

    Schneider, E. L.; Oliveira, C. T.; Brito, R. M.; Malfatti, C. F.

    2014-09-01

    The growing production of high-tech devices is strongly associated to a great waste of natural resources and to environmental contamination caused either by the production process of such devices as the quick disposal of them. Cell phones have stood out from the most commercialized electronic devices, which have increased the demand for rechargeable batteries which are afterward discarded before the end of its useful life. The main objective of this paper is to improve a methodology for classify the amount of NiMH and Li-Ion batteries discarded still in operating condition through concepts given to the cells. Tests with 3 NiMH and 3 Li-Ion different battery models were done. This paper also aimed to promote the efficient use of batteries cells through their reuse in academic activities related to the manufacturing of prototypes. It presents the construction of an illuminator and of a portable power supply. The results obtained showed that approximately 40% of NiMH cells and 45% of Li-Ion cells assessed were in operational condition, with charge capacity between 62% and 90%, when compared to a new cell. Such results warn about the waste of natural resources and the proposal to test the same before the final disposal.

  4. Efficient exfoliation N-doped graphene from N-containing bamboo-like carbon nanotubes for anode materials of Li-ion battery and Na-ion battery

    NASA Astrophysics Data System (ADS)

    Feng, Jian-Min; Dong, Lei; Han, Yan; Li, Xi-Fei; Li, De-Jun

    2015-08-01

    Nanosize N-doped graphene is prepared from N-containing carbon nanotubes (CNTs) by chemical exfoliation. The CNTs adopted for graphene are characterized by a discontinuous wall that consists of nanosize graphite layers, exhibiting a bamboo-like appearance. Take advantage of this characterization, the most time-consuming process of chemical oxidation that involves intercalation in graphene from CNT has been markedly reduced. The reduction in processing time is attributed to the diffusion distance of chemical oxidation intercalation into nanosize graphite composed of a bamboo-like carbon nanotube (BCNT) wall being far less than that of conventional chemical exfoliation into microsize graphite. The as-prepared nanosize N-doped graphene from BCNTs has shown an excellent electrochemical performance for Li-ion battery and Na-ion battery anode materials.

  5. Etched Colloidal LiFePO4 Nanoplatelets toward High-Rate Capable Li-Ion Battery Electrodes

    PubMed Central

    2014-01-01

    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. PMID:25372361

  6. Dynamical observation of lithium insertion/extraction reaction during charge-discharge processes in Li-ion batteries by in situ spatially resolved electron energy-loss spectroscopy.

    PubMed

    Shimoyamada, Atsushi; Yamamoto, Kazuo; Yoshida, Ryuji; Kato, Takehisa; Iriyama, Yasutoshi; Hirayama, Tsukasa

    2015-12-01

    All-solid-state Li-ion batteries (LIBs) with solid electrolytes are expected to be the next generation devices to overcome serious issues facing conventional LIBs with liquid electrolytes. However, the large Li-ion transfer resistance at the electrode/solid-electrolyte interfaces causes low power density and prevents practical use. In-situ-formed negative electrodes prepared by decomposing the solid electrolyte Li(1+x+3z)Alx(Ti,Ge)(2-x)Si(3z)P(3-z)O12 (LASGTP) with an excess Li-ion insertion reaction are effective electrodes providing low Li-ion transfer resistance at the interfaces. Prior to our work, however, it had still been unclear how the negative electrodes were formed in the parent solid electrolytes. Here, we succeeded in dynamically visualizing the formation by in situ spatially resolved electron energy-loss spectroscopy in a transmission electron microscope mode (SR-TEM-EELS). The Li-ions were gradually inserted into the solid electrolyte region around 400 nm from the negative current-collector/solid-electrolyte interface in the charge process. Some of the ions were then extracted in the discharge process, and the rest were diffused such that the distribution was almost flat, resulting in the negative electrodes. The redox reaction of Ti(4+)/Ti(3+) in the solid electrolyte was also observed in situ during the Li insertion/extraction processes. The in situ SR-TEM-EELS revealed the mechanism of the electrochemical reaction in solid-state batteries. PMID:26337787

  7. Thermal Runaway Severity Reduction Assessment and Implementation: On Li-Ion Batteries

    NASA Technical Reports Server (NTRS)

    Darcy, Eric

    2015-01-01

    Preventing cell-cell thermal runaway propagation and flames/sparks from exiting battery enclosure is possible with proper thermal & electrical design and cell thermal runaway ejecta/effluent management and can be had with minimal mass/volume penalty.

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

    NASA Astrophysics Data System (ADS)

    Gu, Meng; Shi, Wei; Zheng, Jianming; Yan, Pengfei; Zhang, Ji-guang; Wang, Chongmin

    2015-05-01

    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 and electron energy loss spectroscopy 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 can guide the design and improvement of LiFePO4 cathode for high-energy and high-power rechargeable battery for electric transportation.

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

    SciTech Connect

    Gu, Meng; Shi, Wei; Zheng, Jianming; Yan, Pengfei; Zhang, Ji-guang; Wang, Chongmin

    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.

  10. Li-Ion Battery with LiFePO4 Cathode and Li4Ti5O12 Anode for Stationary Energy Storage

    SciTech Connect

    Wang, Wei; Choi, Daiwon; Yang, Zhenguo

    2013-01-01

    i-ion batteries based on commercially available LiFePO4 cathode and Li4Ti5O12 anode were investigated for potential stationary energy storage applications. The full cell that operated at flat 1.85V demonstrated stable cycling for 200 cycles followed by a rapid fade. A significant improvement in cycling stability was achieved via Ketjen black coating of the cathode. A Li-ion full cell with Ketjen black modified LiFePO4 cathode and an unmodified Li4Ti5O12 anode exhibited negligible fade after more than 1200 cycles with a capacity of ~130mAh/g. The improved stability, along with its cost-effectiveness, environmentally benignity and safety, make the LiFePO4/ Li4Ti5O12 Li-ion battery a promising option of storing renewable energy.

  11. A novel phenomenological multi-physics model of Li-ion battery cells

    NASA Astrophysics Data System (ADS)

    Oh, Ki-Yong; Samad, Nassim A.; Kim, Youngki; Siegel, Jason B.; Stefanopoulou, Anna G.; Epureanu, Bogdan I.

    2016-09-01

    A novel phenomenological multi-physics model of Lithium-ion battery cells is developed for control and state estimation purposes. The model can capture electrical, thermal, and mechanical behaviors of battery cells under constrained conditions, e.g., battery pack conditions. Specifically, the proposed model predicts the core and surface temperatures and reaction force induced from the volume change of battery cells because of electrochemically- and thermally-induced swelling. Moreover, the model incorporates the influences of changes in preload and ambient temperature on the force considering severe environmental conditions electrified vehicles face. Intensive experimental validation demonstrates that the proposed multi-physics model accurately predicts the surface temperature and reaction force for a wide operational range of preload and ambient temperature. This high fidelity model can be useful for more accurate and robust state of charge estimation considering the complex dynamic behaviors of the battery cell. Furthermore, the inherent simplicity of the mechanical measurements offers distinct advantages to improve the existing power and thermal management strategies for battery management.

  12. Demonstrating the steady performance of iron oxide composites over 2000 cycles at fast charge-rates for Li-ion batteries.

    PubMed

    Sun, Z; Madej, E; Genç, A; Muhler, M; Arbiol, J; Schuhmann, W; Ventosa, E

    2016-05-31

    The feasibility of using iron oxides as negative electrode materials for safe high-power Li-ion batteries is demonstrated by the carbon-coated FeOx/CNT composite synthesized by controlled pyrolysis of ferrocene, which delivered a specific capacity retention of 84% (445 mA h g(-1)) after 2000 cycles at 2000 mA g(-1) (4C). PMID:27097794

  13. Activation analysis study on Li-ion batteries for nuclear forensic applications

    NASA Astrophysics Data System (ADS)

    Johnson, Erik B.; Whitney, Chad; Holbert, Keith E.; Zhang, Taipeng; Stannard, Tyler; Christie, Anthony; Harper, Peter; Anderson, Blake; Christian, James F.

    2015-06-01

    The nuclear materials environment has been increasing significantly in complexity over the past couple of decades. The prevention of attacks from nuclear weapons is becoming more difficult, and nuclear forensics is a deterrent by providing detailed information on any type of nuclear event for proper attribution. One component of the nuclear forensic analysis is a measurement of the neutron spectrum. As an example, the neutron component provides information on the composition of the weapons, whether boosting is involved or the mechanisms used in creating a supercritical state. As 6Li has a large cross-section for thermal neutrons, the lithium battery is a primary candidate for assessing the neutron spectrum after detonation. The absorption process for 6Li yields tritium, which can be measured at a later point after the nuclear event, as long as the battery can be processed in a manner to successfully extract the tritium content. In addition, measuring the activated constituents after exposure provides a means to reconstruct the incident neutron spectrum. The battery consists of a spiral or folded layers of material that have unique, energy dependent interactions associated with the incident neutron flux. A detailed analysis on the batteries included a pre-irradiated mass spectrometry analysis to be used as input for neutron spectrum reconstruction. A set of batteries were exposed to a hard neutron spectrum delivered by the University of Massachusetts, Lowell research reactor Fast Neutron Irradiator (FNI). The gamma spectra were measured from the batteries within a few days and within a week after the exposure to obtain sufficient data on the activated materials in the batteries. The activity was calculated for a number of select isotopes, indicating the number of associated neutron interactions. The results from tritium extraction are marginal. A measurable increase in detected particles (gammas and betas) below 50 keV not self-attenuated by the battery was observed

  14. Nanoscale Silicon as Anode for Li-ion Batteries: The Fundamentals, Promise, and Challenges

    SciTech Connect

    Gu, Meng; He, Yang; Zheng, Jianming; Wang, Chong M.

    2015-09-24

    Silicon (Si), associated with its natural abundance, low discharge voltage vs. Li/Li+, and extremely high theoretical discharge capacity (~ 4200 mAh g-1,), has been extensively explored as anode for lithium ion battery. One of the key challenges for using Si as anode is the large volume change upon lithiation and delithiation, which causes a fast capacity fading. Over the last few years, dramatic progress has been made for addressing this issue. In this paper, we summarize the progress towards tailoring of Si as anode for lithium ion battery. The paper is organized such that it covers the fundamentals, the promise offered based on nanoscale designing, and the remaining challenges that need to be attacked to allow using of Si based materials as anode for battery.

  15. Silicon as a potential anode material for Li-ion batteries: where size, geometry and structure matter

    NASA Astrophysics Data System (ADS)

    Ashuri, Maziar; He, Qianran; Shaw, Leon L.

    2015-12-01

    Silicon has attracted huge attention in the last decade because it has a theoretical capacity ~10 times that of graphite. However, the practical application of Si is hindered by three major challenges: large volume expansion during cycling (~300%), low electrical conductivity, and instability of the SEI layer caused by repeated volume changes of the Si material. Significant research efforts have been devoted to addressing these challenges, and significant breakthroughs have been made particularly in the last two years (2014 and 2015). In this review, we have focused on the principles of Si material design, novel synthesis methods to achieve such structural designs, and the synthesis-structure-performance relationships to enhance the properties of Si anodes. To provide a systematic overview of the Si material design strategies, we have grouped the design strategies into several categories: (i) particle-based structures (containing nanoparticles, solid core-shell structures, hollow core-shell structures, and yolk-shell structures), (ii) porous Si designs, (iii) nanowires, nanotubes and nanofibers, (iv) Si-based composites, and (v) unusual designs. Finally, our personal perspectives on outlook are offered with an aim to stimulate further discussion and ideas on the rational design of durable and high performance Si anodes for the next generation Li-ion batteries in the near future.

  16. Poly L-lysine (PLL)-mediated porous hematite clusters as anode materials for improved Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Kim, Kun-Woo; Lee, Sang-Wha

    2015-09-01

    Porous hematite clusters were prepared as anode materials for improved Li-ion batteries. First, poly-L-lysine (PLL)-linked Fe3O4 was facilely prepared via cross-linking between the positive amine groups of PLL and carboxylate-bound Fe3O4. The subsequent calcination transformed the PLL-linked Fe3O4 into porous hematite clusters (Fe2O3@PLL) consisting of spherical α-Fe2O3 particles. Compared with standard Fe2O3, Fe3O4@PLL exhibited improved electrochemical performance as anode materials. The discharge capacity of Fe2O3@PLL was retained at 814.7 mAh g-1 after 30 cycles, which is equivalent to 80.4% of the second discharge capacity, whereas standard Fe2O3 exhibited a retention capacity of 352.3 mAh g-1. The improved electrochemical performance of Fe2O3@PLL was mainly attributed to the porous hematite clusters with mesoporosity (20-40 nm), which was beneficial for facilitating ion transport, suggesting a useful guideline for the design of porous architectures with higher retention capacity. [Figure not available: see fulltext.

  17. Thin film and bulk investigations of LiCoBO3 as a Li-ion battery cathode

    SciTech Connect

    Bo, Shou-Hang; Veith, Gabriel M; Saccomanno, Michael; Huang, Huafeng; Burmistrova, Polina; Malingowski, Andrew; Sacci, Robert L; Grey, Clare; Khalifah, P.

    2014-01-01

    The compound LiCoBO3 is an appealing candidate for next generation Li-ion batteries based on its high theoretical specific capacity of 215 mAh/g and high expected discharge voltage (more than 4 V vs. Li+/Li). However, this level of performance has not yet been realized in experimental cells, even with nanosized particles. Reactive magnetron sputtering was therefore used to prepare thin films of LiCoBO3, allowing the influence of particle thickness on electrochemical performance to be explicitly tested. Even when ultra-thin films (~15 nm) were prepared, there was a negligible electrochemical response from LiCoBO3. Impedance spectroscopy measurements suggest that the conductivity of LiCoBO3 is many orders of magnitude worse than that of LiFeBO3, and may be severely limiting performance. The band gap and unusual blue color of LiCoBO3 were investigated by spectroscopic techniques, which allowed the determination of an optical gap of 4.2 eV and the assignment of the visible light absorption to a symmetry-allowed e a transition that occurs within the context of a particularly simple electronic configuration.

  18. Transport Properties of LiTFSI-Acetamide Room Temperature Molten Salt Electrolytes Applied in an Li-Ion Battery

    NASA Astrophysics Data System (ADS)

    Yang, Chao-Chen; Hsu, Hsin-Yi; Hsu, Chen-Ruei

    2007-11-01

    In the present work some transport properties of the binary room temperature molten salt (RTMS) lithium bis(trifluoromethane sulfone)imide (LiTFSI)-acetamide [LiN(SO2CF3)2-CH3CONH2], applied in an Li-ion battery, have been investigated. The phase diagram was determined by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The result reveals that the binary RTMS has an eutectic point at 201 K and the 30 mol% LiTFSI composition. The electric conductivity was measured using a direct current computerized method. The result shows that the conductivities of the melts increase with increasing temperature and acetamide content. The densities of all melts decrease with increasing temperature and acetamide content. The equivalent conductivities were fitted by the Arrhenius equation, where the activation energies were 18.15, 18.52, 20.35, 25.08 kJ/mol for 10, 20, 30, 40 mol% LiTFSI, respectively. Besides the relationships between conductivity, density composition and temperature, of the ion interaction is discussed.

  19. Facile Preparation of Graphene/SnO₂ Xerogel Hybrids as the Anode Material in Li-Ion Batteries.

    PubMed

    Li, Zhe-Fei; Liu, Qi; Liu, Yadong; Yang, Fan; Xin, Le; Zhou, Yun; Zhang, Hangyu; Stanciu, Lia; Xie, Jian

    2015-12-16

    SnO2 has been considered as one of the most promising anode materials for Li-ion batteries due to its theoretical ability to store up to 8.4 Li(+). However, it suffers from poor rate performance and short cycle life due to the low intrinsic electrical conductivity and particle pulverization caused by the large volume change upon lithiation/delithiation. Here, we report a facile synthesis of graphene/SnO2 xerogel hybrids as anode materials using epoxide-initiated gelation method. The synthesized hybrid materials (19% graphene/SnO2 xerogel) exhibit excellent electrochemical performance: high specific capacity, stable cyclability, and good rate capability. Even cycled at a high current density of 1 A/g for 300 cycles, the hybrid electrode can still deliver a specific capacity of about 380 mAh/g, corresponding to more than 60% capacity retention. The incorporation of graphene sheets provides fast electron transfer between the interfaces of the graphene nanosheets and the SnO2 and a short lithium ion diffusion path. The porous structure of graphene/xerogel and the strong interaction between SnO2 and graphene can effectively accommodate the volume change and tightly confine the formed Li2O and Sn nanoparticles, thus preventing the irreversible capacity degradation. PMID:26422399

  20. Design and use of multisine signals for Li-ion battery equivalent circuit modelling. Part 1: Signal design

    NASA Astrophysics Data System (ADS)

    Widanage, W. D.; Barai, A.; Chouchelamane, G. H.; Uddin, K.; McGordon, A.; Marco, J.; Jennings, P.

    2016-08-01

    The Pulse Power Current (PPC) profile is often the signal of choice for obtaining the parameters of a Lithium-ion (Li-ion) battery Equivalent Circuit Model (ECM). Subsequently, a drive-cycle current profile is used as a validation signal. Such a profile, in contrast to a PPC, is more dynamic in both the amplitude and frequency bandwidth. Modelling errors can occur when using PPC data for parametrisation since the model is optimised over a narrower bandwidth than the validation profile. A signal more representative of a drive-cycle, while maintaining a degree of generality, is needed to reduce such modelling errors. In Part 1 of this 2-part paper a signal design technique defined as a pulse-multisine is presented. This superimposes a signal known as a multisine to a discharge, rest and charge base signal to achieve a profile more dynamic in amplitude and frequency bandwidth, and thus more similar to a drive-cycle. The signal improves modelling accuracy and reduces the experimentation time, per state-of-charge (SoC) and temperature, to several minutes compared to several hours for an PPC experiment.

  1. Electrochemical properties of Sn-decorated SnO nanobranches as an anode of Li-ion battery

    NASA Astrophysics Data System (ADS)

    Shin, Jeong Ho; Song, Jae Yong

    2016-05-01

    Sn-based oxide materials as an anode of lithium ion batteries (LIBs) suffer from the unavoidable mechanical stress originated from huge volume changes during lithiation/delithiation reactions. We synthesized the hierarchical SnO nanobranches (NBs) decorated with Sn nanoparticles on Cu current collector using a vapor transport method. The Sn-decorated SnO NBs as an anode of LIB showed good electrochemical performance with high reversible capacity retention of as high as 502 mAh/g and rate capability of 455 mAh/g at a current density of 2.0 A/g after 50 cycles. Through the morphological and crystal structure analyses after the charge and discharge processes, it was found that the morphology of Sn-decorated SnO NBs was transformed to nanoporous layered-structure, composed of Sn and lithium oxide, during the repeated lithiation/delithiation reactions. The free-volume of Sn-decorated SnO NBs and nanoporous layered-structure effectively accommodate the huge volume changes and enhance the electrochemical cyclability by facilitating the diffusion of Li-ions.

  2. Li2CuVO4: A high capacity positive electrode material for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Ben Yahia, Hamdi; Shikano, Masahiro; Yamaguchi, Yoichi

    2016-07-01

    The new compound Li2CuVO4 was synthesized by a solid state reaction route, and its crystal structure was determined from single crystal X-ray diffraction data. Li2CuVO4 was characterized by galvanometric cycling, cycle voltammetry, and electrochemical impedance spectroscopy. The structure of Li2CuVO4 is isotypic to Pmn21-Li3VO4. It can be described as a disordered wurtzite structure with rows of Li1/Cu1 atoms alternating with rows of (Li2/Cu2)-V-(Li2/Cu2) atoms along [100]. All cations are tetrahedrally coordinated. The lithium and copper atoms are statistically disordered over two crystallographic sites. The electrochemical cycling between 2.0 and 4.7 V indicates that almost two lithium atoms could be extracted and re-intercalated. This delivers a maximum discharge capacity of 257 mA h g-1 at a C/50 rate (theoretical capacity = 139 mA h g-1 for one lithium). Li2CuVO4 shows also high rate capability with a capacity of 175 mA h g-1 at 1C rate. This demonstrates that Cu-based compounds can be very interesting as electrodes for Li-ion batteries if Cu-dissolution is avoided.

  3. Rice husks as a sustainable source of nanostructured silicon for high performance Li-ion battery anodes

    PubMed Central

    Liu, Nian; Huo, Kaifu; McDowell, Matthew T.; Zhao, Jie; Cui, Yi

    2013-01-01

    The recovery of useful materials from earth-abundant substances is of strategic importance for industrial processes. Despite the fact that Si is the second most abundant element in the Earth's crust, processes to form Si nanomaterials is usually complex, costly and energy-intensive. Here we show that pure Si nanoparticles (SiNPs) can be derived directly from rice husks (RHs), an abundant agricultural byproduct produced at a rate of 1.2 × 108 tons/year, with a conversion yield as high as 5% by mass. And owing to their small size (10–40 nm) and porous nature, these recovered SiNPs exhibits high performance as Li-ion battery anodes, with high reversible capacity (2,790 mA h g−1, seven times greater than graphite anodes) and long cycle life (86% capacity retention over 300 cycles). Using RHs as the raw material source, overall energy-efficient, green, and large scale synthesis of low-cost and functional Si nanomaterials is possible. PMID:23715238

  4. Thin-film and bulk investigations of LiCoBO₃ as a Li-ion battery cathode.

    PubMed

    Bo, Shou-Hang; Veith, Gabriel M; Saccomanno, Michael R; Huang, Huafeng; Burmistrova, Polina V; Malingowski, Andrew C; Sacci, Robert L; Kittilstved, Kevin R; Grey, Clare P; Khalifah, Peter G

    2014-07-23

    The compound LiCoBO3 is an appealing candidate for next-generation Li-ion batteries based on its high theoretical specific capacity of 215 mAh/g and high expected discharge voltage (more than 4 V vs Li(+)/Li). However, this level of performance has not yet been realized in experimental cells, even with nanosized particles. Reactive magnetron sputtering was therefore used to prepare thin films of LiCoBO3, allowing the influence of the particle thickness on the electrochemical performance to be explicitly tested. Even when ultrathin films (∼15 nm) were prepared, there was a negligible electrochemical response from LiCoBO3. Impedance spectroscopy measurements suggest that the conductivity of LiCoBO3 is many orders of magnitude worse than that of LiFeBO3 and may severely limit the performance. The unusual blue color of LiCoBO3 was investigated by spectroscopic techniques, which allowed the determination of a charge-transfer optical gap of 4.2 eV and the attribution of the visible light absorption peak at 2.2 eV to spin-allowed d → d transitions (assigned as overlapping (4)A2' to (4)A2″ and (4)E″ final states based on ligand-field modeling). PMID:24809458

  5. In situ scanning tunneling microscopy studies of the SEI formation on graphite electrodes for Li(+)-ion batteries.

    PubMed

    Seidl, Lukas; Martens, Slađana; Ma, Jiwei; Stimming, Ulrich; Schneider, Oliver

    2016-08-01

    The SEI-formation on graphitic electrodes operated as an Li(+)-ion battery anode in a standard 1 M LiPF6 EC/DMC (1 : 1) electrolyte has been studied in situ by EC-STM. Two different modes of in situ study were applied, one, which allowed to follow topographic and crystallographic changes (solvent cointercalation, graphite exfoliation, SEI precipitation on the HOPG basal plane) of the graphite electrode during SEI-formation, and the second, which gave an insight into the SEI precipitation on the HOPG basal plane in real time. From the in situ EC-STM studies, not only conclusions about the SEI-topography could be drawn, but also about the formation mechanism and the chemical composition, which strongly depend on the electrode potential. It was shown that above 1.0 V vs. Li/Li(+) the SEI-formation is still reversible, since the molecular structure of the solvent molecules remains intact during an initial reduction step. During further reduction, the molecular structures of the solvents are destructed, which causes the irreversible charge loss. The STM studies were completed by electrochemical methods, like cyclic voltammetry, the potentiostatic intermittent titration technique and charge/discharge tests of MCMB electrodes. PMID:27140292

  6. Silicon as a potential anode material for Li-ion batteries: where size, geometry and structure matter.

    PubMed

    Ashuri, Maziar; He, Qianran; Shaw, Leon L

    2016-01-01

    Silicon has attracted huge attention in the last decade because it has a theoretical capacity ∼10 times that of graphite. However, the practical application of Si is hindered by three major challenges: large volume expansion during cycling (∼300%), low electrical conductivity, and instability of the SEI layer caused by repeated volume changes of the Si material. Significant research efforts have been devoted to addressing these challenges, and significant breakthroughs have been made particularly in the last two years (2014 and 2015). In this review, we have focused on the principles of Si material design, novel synthesis methods to achieve such structural designs, and the synthesis-structure-performance relationships to enhance the properties of Si anodes. To provide a systematic overview of the Si material design strategies, we have grouped the design strategies into several categories: (i) particle-based structures (containing nanoparticles, solid core-shell structures, hollow core-shell structures, and yolk-shell structures), (ii) porous Si designs, (iii) nanowires, nanotubes and nanofibers, (iv) Si-based composites, and (v) unusual designs. Finally, our personal perspectives on outlook are offered with an aim to stimulate further discussion and ideas on the rational design of durable and high performance Si anodes for the next generation Li-ion batteries in the near future. PMID:26612324

  7. Identifying the redox activity of cation-disordered Li-Fe-V-Ti oxide cathodes for Li-ion batteries.

    PubMed

    Chen, Ruiyong; Witte, Ralf; Heinzmann, Ralf; Ren, Shuhua; Mangold, Stefan; Hahn, Horst; Hempelmann, Rolf; Ehrenberg, Helmut; Indris, Sylvio

    2016-03-01

    Cation-disordered oxides have recently shown promising properties on the way to explore high-performance intercalation cathode materials for rechargeable Li-ion batteries. Here, stoichiometric cation-disordered Li2FeVyTi1-yO4 (y = 0, 0.2, 0.5) nanoparticles are studied. The substitution of V for Ti in Li2FeVyTi1-yO4 increases the content of active transition metals (Fe and V) and accordingly the amount of Li(+) (about (1 + y)Li(+) capacity per formula unit) that can be reversibly intercalated. It is found that Fe(3+)/Fe(2+) and V(4+)/V(3+) redox couples contribute to the overall capacity performance, whereas Ti(4+) remains mainly inert. There is no evidence for the presence of Fe(4+) species after charging to 4.8 V, as confirmed from the ex situ(57)Fe Mössbauer spectroscopy and the Fe K-edge absorption spectra. The redox couple reactions for iron and vanadium are examined by performing in situ synchrotron X-ray absorption spectroscopy. During charging/discharging, the spectral evolution of the K-edges for Fe and V confirms the reversible Fe(3+)/Fe(2+) and V(4+)/V(3+) redox reactions during cycling between 1.5 and 4.8 V. PMID:26907961

  8. Surface structure evolution of cathode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Yingchun, Lyu; Yali, Liu; Lin, Gu

    2016-01-01

    Lithium ion batteries are important electrochemical energy storage devices for consumer electronics and the most promising candidates for electrical/hybrid vehicles. The surface chemistry influences the performance of the batteries significantly. In this short review, the evolution of the surface structure of the cathode materials at different states of the pristine, storage and electrochemical reactions are summarized. The main methods for the surface modification are also introduced. Project supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB07030200) and the National Basic Research Program of China (Grant Nos. 2014CB921002 and 2012CB921702).

  9. Multi-physics Modeling for Improving Li-Ion Battery Safety; NREL (National Renewable Energy Laboratory)

    SciTech Connect

    Pesaran, A.; Kim, G.; Santhanagopalan, S.; Yang, C.

    2015-04-21

    Battery performance, cost, and safety must be further improved for larger market share of HEVs/PEVs and penetration into the grid. Significant investment is being made to develop new materials, fine tune existing ones, improve cell and pack designs, and enhance manufacturing processes to increase performance, reduce cost, and make batteries safer. Modeling, simulation, and design tools can play an important role by providing insight on how to address issues, reducing the number of build-test-break prototypes, and accelerating the development cycle of generating products.

  10. Can Cell to Cell Thermal Runaway Propagation be Prevented in a Li-ion Battery Module?

    NASA Technical Reports Server (NTRS)

    Jeevarajan, Judith; Lopez, Carlos; Orieukwu, Josephat

    2014-01-01

    Increasing cell spacing decreased adjacent cell damage center dotElectrically connected adjacent cells drained more than physically adjacent cells center dotRadiant barrier prevents propagation when fully installed between BP cells center dotBP cells vent rapidly and expel contents at 100% SOC -Slower vent with flame/smoke at 50% -Thermal runaway event typically occurs at 160 degC center dotLG cells vent but do not expel contents -Thermal runaway event typically occurs at 200 degC center dotSKC LFP modules did not propagate; fuses on negative terminal of cell may provide a benefit in reducing cell to cell damage propagation. New requirement in NASA-Battery Safety Requirements document: JSC 20793 Rev C 5.1.5.1 Requirements - Thermal Runaway Propagation a. For battery designs greater than a 80-Wh energy employing high specific energy cells (greater than 80 watt-hours/kg, for example, lithium-ion chemistries) with catastrophic failure modes, the battery shall be evaluated to ascertain the severity of a worst-case single-cell thermal runaway event and the propensity of the design to demonstrate cell-to-cell propagation in the intended application and environment. NASA has traditionally addressed the threat of thermal runaway incidents in its battery deployments through comprehensive prevention protocols. This prevention-centered approach has included extensive screening for manufacturing defects, as well as robust battery management controls that prevent abuse-induced runaway even in the face of multiple system failures. This focused strategy has made the likelihood of occurrence of such an event highly improbable. b. The evaluation shall include all necessary analysis and test to quantify the severity (consequence) of the event in the intended application and environment as well as to identify design modifications to the battery or the system that could appreciably reduce that severity. In addition to prevention protocols, programs developing battery designs with

  11. Charactrization of a Li-ion battery based stand-alone a-Si photovoltaic system

    NASA Astrophysics Data System (ADS)

    Hamid Vishkasougheh, Mehdi; Tunaboylu, Bahadir

    2014-11-01

    The number of photovoltaic (PV) system installations is increasing rapidly. As more people learn about this versatile and often cost-effective power option, this trend will accelerate. This document presents a recommended design for a battery based stand-alone photovoltaic system (BSPV). BSPV system has the ability to be applied in different areas, including warning signals, lighting, refrigeration, communication, residential water pumping, remote sensing, and cathodic protection. The presented calculation method gives a proper idea for a system sizing technique. Based on application load, different scenarios are possible for designing a BSPV system. In this study, a battery based stand-alone system was designed. The electricity generation part is three a-Si panels, which are connected in parallel, and for the storage part LFP (lithium iron phosphate) battery was used. The high power LFP battery packs are 40 cells each 8S5P (configured 8 series 5 parallel). Each individual pack weighs 0.5 kg and is 25.6 V. In order to evaluate the efficiency of a-Si panels with respect to the temperature and the solar irradiation, cities of Istanbul, Ankara and Adana in Turkey were selected. Temperature and solar irradiation were gathered from reliable sources and by using translation equations, current and voltage output of panels were calculated. As a result of these calculations, current and energy outputs were computed by considering an average efficient solar irradiation time value per day in Turkey. The calculated power values were inserted to a battery cycler system, and the behavior of high power LFP batteries in a time sequence of 7.2 h was evaluated. The charging and discharging cycles were obtained and their behavior was discussed. According to the results, Istanbul has the lowest number of peak month's energy, it followed by Ankara, and ultimately Adana has the highest number of peak months and energy storage. It was observed during the tests that values up to 4 A was

  12. High areal capacity, micrometer-scale amorphous Si film anode based on nanostructured Cu foil for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Si, Wenping; Sun, Xiaolei; Liu, Xianghong; Xi, Lixia; Jia, Yandong; Yan, Chenglin; Schmidt, Oliver G.

    2014-12-01

    We report a feasible design to fabricate micrometer-scale Si films deposited on nanostructured Cu foil as high areal capacity anodes for Li-ion batteries with excellent cycling performance. Nanostructured copper oxides are prepared by anodic oxidation of Cu foil in alkaline solution. The resultant copper oxide nanofibers function as matrix for thick Si films (1-2 μm) loading. Metallic Cu nanofibers are obtained by in-situ electrochemical reduction at low potentials, which work as electrical highways for fast electron transport and a reliable mechanical matrix to accommodate volume changes during lithium-silicon alloy/dealloy processes. The engineered thick Si film anode exhibit both high areal capacity (0.48 mAh cm-2 for 1 μm Si film and 0.6 mAh cm-2 for 2 μm Si film after 200 cycles at 0.225 mA cm-2) and excellent rate capability (0.52 mAh cm-2 at 1.05 mA cm-2 for 2 μm Si film). The 2 μm silicon film electrode is able to recover to the initial value of 1 mAh cm-2 when the current rate is set back to 0.15 mA cm-2 even after cycling at high current rates. The reported concept can be a general method for high-loading-film electrodes, which is industrial scalable and compatible with current battery manufacturing processes.

  13. Template-free electrodeposition of AlFe alloy nanowires from a room-temperature ionic liquid as an anode material for Li-ion batteries.

    PubMed

    Chen, Gang; Chen, Yuqi; Guo, Qingjun; Wang, Heng; Li, Bing

    2016-08-15

    AlFe alloy nanowires were directly electrodeposited on copper substrates from trimethylamine hydrochloride (TMHC)-AlCl3 ionic liquids with small amounts of FeCl3 at room temperature without templates. Coin cells composed of AlFe alloy nanowire electrodes and lithium foils were assembled to characterize the alloy electrochemical properties by galvanostatic charge/discharge tests. Effects of FeCl3 concentration, potential and temperature on the alloy morphology, composition and cyclic performance were examined. Addition of Fe into the alloy changed the nanowires from a 'hill-like' bulk morphology to a free-standing morphology, and increased the coverage area of the alloy on Cu substrates. As an inactive element, Fe could also buffer the alloys' large volume changes during Li intercalation and deintercalation. AlFe alloy nanowires composed of a small amount of Fe with an average diameter of 140 nm exhibited an outstanding cyclic performance and delivered a specific capacity of about 570 mA h g(-1) after 50 cycles. This advanced template-free method for the direct preparation of high performance nanostructure AlFe alloy anode materials is quite simple and inexpensive, which presents a promising prospect for practical application in Li-ion batteries. PMID:27200436

  14. A 3D Porous Architecture of Si/graphene Nanocomposite as High-performance Anode Materials for Li-ion Batteries

    SciTech Connect

    Xin X.; Zhu Y.; Zhou, X.; Wang, F.; Yao, X.; Xu, X.; Liu, Z.

    2012-04-28

    A 3D porous architecture of Si/graphene nanocomposite has been rationally designed and constructed through a series of controlled chemical processes. In contrast to random mixture of Si nanoparticles and graphene nanosheets, the porous nanoarchitectured composite has superior electrochemical stability because the Si nanoparticles are firmly riveted on the graphene nanosheets through a thin SiO{sub x} layer. The 3D graphene network enhances electrical conductivity, and improves rate performance, demonstrating a superior rate capability over the 2D nanostructure. This 3D porous architecture can deliver a reversible capacity of {approx}900 mA h g{sup -1} with very little fading when the charge rates change from 100 mA g{sup -1} to 1 A g{sup -1}. Furthermore, the 3D nanoarchitechture of Si/graphene can be cycled at extremely high Li{sup +} extraction rates, such as 5 A g{sup -1} and 10 A g{sup -1}, for over than 100 times. Both the highly conductive graphene network and porous architecture are considered to contribute to the remarkable rate capability and cycling stability, thereby pointing to a new synthesis route to improving the electrochemical performances of the Si-based anode materials for advanced Li-ion batteries.

  15. Environmentally-friendly lithium recycling from a spent organic li-ion battery.

    PubMed

    Renault, Stéven; Brandell, Daniel; Edström, Kristina

    2014-10-01

    A simple and straightforward method using non-polluting solvents and a single thermal treatment step at moderate temperature was investigated as an environmentally-friendly process to recycle lithium from organic electrode materials for secondary lithium batteries. This method, highly dependent on the choice of electrolyte, gives up to 99% of sustained capacity for the recycled materials used in a second life-cycle battery when compared with the original. The best results were obtained using a dimethyl carbonate/lithium bis(trifluoromethane sulfonyl) imide electrolyte that does not decompose in presence of water. The process implies a thermal decomposition step at a moderate temperature of the extracted organic material into lithium carbonate, which is then used as a lithiation agent for the preparation of fresh electrode material without loss of lithium. PMID:25170568

  16. Magnetically aligned graphite electrodes for high-rate performance Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Billaud, Juliette; Bouville, Florian; Magrini, Tommaso; Villevieille, Claire; Studart, André R.

    2016-08-01

    As lithium-ion batteries become ubiquitous, the energy storage market is striving for better performance, longer lifetime and better safety of the devices. This race for performance is often focused on the search for new materials, whereas less effort has been dedicated to the electrode engineering. Enhancing the power density by increasing the amount of active material remains impractical since it impinges the transport of ions across the electrode during the charging and discharging processes. Here, we show that the electrochemical performance of a battery containing a thick (about 200 μm), highly loaded (about 10 mg cm‑2) graphite electrode can be remarkably enhanced by fabricating anodes with an out-of-plane aligned architecture using a low external magnetic field. The lower tortuosity resulting from such a simple and scalable magnetic alignment approach leads to a specific charge up to three times higher than that of non-architectured electrodes at a rate of 1C.

  17. Synthesis and Defect Structure Analysis of Complex Oxides for Li-Ion Battery Electrodes

    NASA Astrophysics Data System (ADS)

    Hao, Xiaoguang

    Lithium-ion batteries have attracted increased attention for energy storage development due to the vast demand from portable electronics, (hybrid) electric vehicles and future power grids. The research in this dissertation is focused on the development of oxide electrodes for lithium-ion batteries with high power density and improved stability. One of the promising cathodes for lithium-ion batteries is lithium manganospinel (LiMn2O4). However, this compound suffers from manganese dissolution and a Jahn-Teller distortion due to Mn3+, especially in oxygen deficient LiMn2O4-delta. Hydrothermal based synthesis methods were developed to eliminate oxygen vacancies to enable high power in cathodes composed of nano-sized spinel particles. The relationship between oxygen defects and the capacity fading mechanism was demonstrated, and collapse of the mechanical structure was identified in defect-rich LiMn 2O4-delta. Next, the nickel substituted manganospinel, LiNi0.5Mn 1.5O4 shows unexpected high voltage side reactions. To overcome this drawback, a thin and chemically inert titanate was used as an artificial SEI (solid electrolyte interface) coating to prohibit transition-metal dissolution and parasitic side reactions, which led to a 200% improvement of the capacity retention at 55°C and negligible polarization losses. Finally, the spinel-structured lithium titanate (Li 4Ti5O12) is introduced as an anode material for lithium-ion batteries due to its higher operating potential and excellent structural stability compared to current graphite anodes. However, the poor electronic conductivity and low lithium diffusion coefficient hinder its wide application. Given these advantages, a facile, low-cost solution method is explored to synthesize nano-sized titanates. Rapid charge/ discharge was achieved up to rates of 100 C (36 second charge/ discharge) due to a shorter lithium mean-free path and better contact between the active material and conductive agents.

  18. Studies on the thermal breakdown of common Li-ion battery electrolyte components

    DOE PAGESBeta

    Lamb, Joshua; Orendorff, Christopher J.; Roth, Emanuel Peter; Langendorf, Jill Louise

    2015-08-06

    While much attention is paid to the impact of the active materials on the catastrophic failure of lithium ion batteries, much of the severity of a battery failure is also governed by the electrolytes used, which are typically flammable themselves and can decompose during battery failure. The use of LiPF6 salt can be problematic as well, not only catalyzing electrolyte decomposition, but also providing a mechanism for HF production. This work evaluates the safety performance of the common components ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) in the context of the gasses producedmore » during thermal decomposition, looking at both the quantity and composition of the vapor produced. EC and DEC were found to be the largest contributors to gas production, both producing upwards of 1.5 moles of gas/mole of electrolyte. DMC was found to be relatively stable, producing very little gas regardless of the presence of LiPF6. EMC was stable on its own, but the addition of LiPF6 catalyzed decomposition of the solvent. As a result, while gas analysis did not show evidence of significant quantities of any acutely toxic materials, the gasses themselves all contained enough flammable components to potentially ignite in air.« less

  19. Studies on the thermal breakdown of common Li-ion battery electrolyte components

    SciTech Connect

    Lamb, Joshua; Orendorff, Christopher J.; Roth, Emanuel Peter; Langendorf, Jill Louise

    2015-08-06

    While much attention is paid to the impact of the active materials on the catastrophic failure of lithium ion batteries, much of the severity of a battery failure is also governed by the electrolytes used, which are typically flammable themselves and can decompose during battery failure. The use of LiPF6 salt can be problematic as well, not only catalyzing electrolyte decomposition, but also providing a mechanism for HF production. This work evaluates the safety performance of the common components ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) in the context of the gasses produced during thermal decomposition, looking at both the quantity and composition of the vapor produced. EC and DEC were found to be the largest contributors to gas production, both producing upwards of 1.5 moles of gas/mole of electrolyte. DMC was found to be relatively stable, producing very little gas regardless of the presence of LiPF6. EMC was stable on its own, but the addition of LiPF6 catalyzed decomposition of the solvent. As a result, while gas analysis did not show evidence of significant quantities of any acutely toxic materials, the gasses themselves all contained enough flammable components to potentially ignite in air.

  20. TiO2-reduced graphene oxide nanocomposites by microwave-assisted forced hydrolysis as excellent insertion anode for Li-ion battery and capacitor

    NASA Astrophysics Data System (ADS)

    Kim, Hyun-Kyung; Mhamane, Dattakumar; Kim, Myeong-Seong; Roh, Ha-Kyung; Aravindan, Vanchiappan; Madhavi, Srinivasan; Roh, Kwang Chul; Kim, Kwang-Bum

    2016-09-01

    TiO2-reduced graphene oxide (rGO) nanocomposite (TiO2-rGO) is fabricated by microwave-assisted forced hydrolysis and examined as prospective electrode for energy storage applications, especially in Li-ion battery (LIB) and Li-ion capacitor (LIC). First, the uniformly distributed nanoscopic TiO2 particulates (∼3 nm) over rGO nanosheets is evaluated as anode in half-cell assembly to ascertain the Li-insertion behavior and found that ∼0.68 mol Li (∼227 mAh g-1) is reversible. Then, "rocking-chair" type LIB is fabricated with spinel LiMn2O4 cathode, and the LiMn2O4/TiO2-rGO assembly exhibits high capacity (∼120 mAh g-1 at 0.1 C rate), good rate capability (∼53 mAh g-1 at 1 C rate), and excellent cycleability (∼90% initial reversible capacity after 1000 cycle) as well. Similarly, the LIC is also constructed with activated carbon cathode, and such configuration delivered a maximum energy density of ∼50 Wh kg-1 with ∼82% retention after 4000 cycles. The synergistic effect of both rGO and anatase nanoparticles provides excellent energy efficiency and battery performance in different kind of Li-ion based energy storage devices.

  1. Soil as an inexhaustible and high-performance anode material for Li-ion batteries.

    PubMed

    Hu, Xiaofei; Zhang, Kai; Cong, Liang; Cheng, Fangyi; Chen, Jun

    2015-11-11

    Herein, we demonstrate that by a simple treatment of heating and ball-milling, soil is endowed with a 77.2% degree of defects and acts as a high-performance anode material for soil/Li half cells and 18650-type LiNi0.915Co0.075Al0.1O2 (NCA)/soil full batteries that displayed a high and stable capacity of 3200 mA h (corresponding to 176 W h kg(-1) and 522 W h L(-1)) in the 200th cycle at a high current of 4 A. PMID:26372419

  2. Mussel inspired modification of polypropylene separators by catechol/polyamine for Li-ion batteries.

    PubMed

    Wang, Hao; Wu, Junjie; Cai, Chao; Guo, Jing; Fan, Haosen; Zhu, Caizhen; Dong, Haixia; Zhao, Ning; Xu, Jian

    2014-04-23

    Inspired by the remarkable adhesion of mussel, dopamine, a mimicking adhesive molecule, has been widely used for surface modification of various materials ranging from organic to inorganic. However, dopamine and its derivatives are expensive which impede their application in large scale. Herein, we replaced dopamine with low-cost catechol and polyamine (only 8% of the cost of dopamine), which could be polymerized in an alkaline solution and deposited on the surfaces of various materials. By using this cheap and simple modification method, polypropylene (PP) separator could be transformed from hydrophobic to hydrophilic, while the pore structure and mechanical property of the separator remained intact. The uptake of electrolyte increased from 80% to 270% after the hydrophilic modification. Electrochemical studies demonstrated that battery with the modified PP separator had a better Coulombic efficiency (80.9% to 85.3%) during the first cycle at a current density of 0.1 C, while the discharging current density increased to 15 C and the discharge capacity increased by 1.4 times compared to the battery using the bare PP separator. Additionally, the modification allowed excellent stability during manifold cycles. This study provides new insights into utilizing low-cost chemicals to mimic the mussel adhesion and has potential practical application in many fields. PMID:24684271

  3. Exploring a Li-ion battery using surface modified titania nanotubes versus high voltage cathode nanowires

    NASA Astrophysics Data System (ADS)

    Ortiz, Gregorio F.; Cabello, Marta; López, María C.; Tirado, José L.; McDonald, Matthew J.; Yang, Yong

    2016-01-01

    Novel battery architectures with improved safety, power and energy density are currently being demanded for battery miniaturization. We present a rechargeable full cell fabricated with self-organized titania nanotubes (nt-TiO2) and self-organized LiNi0.5Mn1.5O4 nanowires (LNMO). The effects of the Li3PO4-coated nt-TiO2 on the electrochemical performance of the full cell are studied. A complete (de)-intercalation of lithium into both electrodes is observed, and cells avoid the use of metallic lithium while displaying improved safety and restrained lowering of the overall cell voltage. The surface modified electrodes exhibit better rate capability and cycling performance compared to non-treated electrodes. The nt-TiO2, Li3PO4/EC:DEC LiPF6/LiNi0.5Mn1.5O4 cell could be cycled at 5C rate, with associated capacity of 125 mA h g-1, energy density of 325 W h kg-1 and power density of 637 μW cm-2 μm-1. These results give evidence to the compatibility between both nanostructured electrodes particularly when lithium phosphate exerts a stabilization effect at the electrode/electrolyte interface, facilitating improved mass transfer and Li-diffusion at high rates.

  4. Development and characterization of composite YSZ-PEI electrophoretically deposited membrane for Li-ion battery.

    PubMed

    Hadar, R; Golodnitsky, D; Mazor, H; Ripenbein, T; Ardel, G; Barkay, Z; Gladkich, A; Peled, E

    2013-02-14

    In this work, the electrophoretic-deposition (EPD) method was used to fabricate pristine and composite ceramic-polymer membranes for application in planar and 3D microbattery configurations. The major focus was on the effect of polyethyleneimine additive on the morphology, composition, and electrochemical properties of the membrane. The ionic conductivity, cycleability, and charge/discharge behavior of planar LiFePO(4)/Li cells comprising composite porous YSZ-based membrane with impregnated LiPF(6) EC:DEC electrolyte were found to be similar to the cells with commercial Celgard membrane. Conformal EPD coating of the electrode materials by a thin-film ceramic separator is advantageous for high-power operation and safety of batteries. PMID:22809387

  5. Layer cathode methods of manufacturing and materials for Li-ion rechargeable batteries

    DOEpatents

    Kang, Sun-Ho; Amine, Khalil

    2008-01-01

    A positive electrode active material for lithium-ion rechargeable batteries of general formula Li.sub.1+xNi.sub..alpha.Mn.sub..beta.A.sub..gamma.O.sub.2 and further wherein A is Mg, Zn, Al, Co, Ga, B, Zr, or Ti and 0

  6. An in situ operando MEMS platform for characterization of Li-ion battery electrodes

    NASA Astrophysics Data System (ADS)

    Jung, H.; Gerasopoulos, K.; Zhang, X.; Ghodssi, R.

    2015-12-01

    This paper presents an in situ operando approach that allows characterization of lithium-ion battery electrodes. A MEMS sensor is designed and integrated with a commercially available Raman spectroscope to enable monitoring the stress and structural changes in the electrodes. An interferometric method with an enhanced image processing algorithm is applied for analyzing the crystal phase-dependent stress changes - contributing to higher sensitivity compared to a previously reported technique - while the structural changes are monitored using Raman spectroscopy. New capabilities of our platform are highlighted, allowing visual observation of crystal phase-dependent structural changes in the electrode. Simultaneous characterization of the stress and structural changes are achieved concurrently in situ operando. The results show excellent agreement with previous literature reports on both phenomena.

  7. Electrochemical Windows of Sulfone-Based Electrolytes for High-Voltage Li-Ion Batteries

    SciTech Connect

    Shao, Nan; Sun, Xiao-Guang; Dai, Sheng; Jiang, Deen

    2011-01-01

    Further development of high-voltage lithium-ion batteries requires electrolytes with electrochemical windows greater than 5 V. Sulfone-based electrolytes are promising for such a purpose. Here we compute the electrochemical windows for experimentally tested sulfone electrolytes by different levels of theory in combination with various solvation models. The MP2 method combined with the polarizable continuum model is shown to be the most accurate method to predict oxidation potentials of sulfone-based electrolytes with mean deviation less than 0.29 V. Mulliken charge analysis shows that the oxidation happens on the sulfone group for ethylmethyl sulfone and tetramethylene sulfone, and on the ether group for ether functionalized sulfones. Large electrochemical windows of sulfone-based electrolytes are mainly contributed by the sulfone group in the molecules which helps lower the HOMO level. This study can help understand the voltage limits imposed by the sulfone-based electrolytes and aid in designing new electrolytes with greater electrochemical windows.

  8. Magnetite Nanocrystals as Anode Electrode Materials for Rechargeable Li-Ion Batteries.

    PubMed

    Ma, Xiaoling; Zeng, Guoping; Chen, Gongxuan; Huang, Yuanqiao; Wu, Tian

    2015-09-01

    Monodispersed magnetite (Fe3O4) nanocrystals were synthesized and their electrochemical properties as anode electrode materials for rechargeable lithium ion batteries were measured. The magnetite anodes, in the form of monodispersed nanospheres with average diameters (< 10 nm), show particle size effects. Specifically, the first discharge curves show that the nanocrystals can hold much more Li+ per formula unit than their counterparts in bulk before the reduction begins. The electrolyte decomposition takes place before the reduction reaction is completed. The cycling performance of the Fe3O4 nanocrystals after being heated at 300 degrees C for different lengths of time show that heating can improve the integration of the nanocrystals and increase their capacity retention in consequence. PMID:26716309

  9. Spinel materials for Li-ion batteries: new insights obtained by operando neutron and synchrotron X-ray diffraction.

    PubMed

    Bianchini, Matteo; Fauth, François; Suard, Emmanuelle; Leriche, Jean Bernard; Masquelier, Christian; Croguennec, Laurence

    2015-12-01

    In the last few decades Li-ion batteries changed the way we store energy, becoming a key element of our everyday life. Their continuous improvement is tightly bound to the understanding of lithium (de)intercalation phenomena in electrode materials. Here we address the use of operando diffraction techniques to understand these mechanisms. We focus on powerful probes such as neutrons and synchrotron X-ray radiation, which have become increasingly familiar to the electrochemical community. After discussing the general benefits (and drawbacks) of these characterization techniques and the work of customization required to adapt standard electrochemical cells to an operando diffraction experiment, we highlight several very recent results. We concentrate on important electrode materials such as the spinels Li1 + xMn2 - xO4 (0 ≤ x ≤ 0.10) and LiNi0.4Mn1.6O4. Thorough investigations led by operando neutron powder diffraction demonstrated that neutrons are highly sensitive to structural parameters that cannot be captured by other means (for example, atomic Debye-Waller factors and lithium site occupancy). Synchrotron radiation X-ray powder diffraction reveals how LiMn2O4 is subject to irreversibility upon the first electrochemical cycle, resulting in severe Bragg peak broadening. Even more interestingly, we show for the first time an ordering scheme of the elusive composition Li0.5Mn2O4, through the coexistence of Mn(3+):Mn(4+) 1:3 cation ordering and lithium/vacancy ordering. More accurately written as Li0.5Mn(3+)0.5Mn(4+)1.5O4, this intermediate phase loses the Fd\\overline 3m symmetry, to be correctly described in the P213 space group. PMID:26634725

  10. Sputtering Deposition of Sn-Mo-Based Composite Anode for Thin-Film Li-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Mani Chandran, T.; Balaji, S.

    2016-03-01

    The role of electrochemically inactive molybdenum in alleviating the anomalous volume expansion of tin anode upon charge-discharge cycling has been investigated. Tin-molybdenum thin-film composite anodes for Li-ion batteries were prepared using a direct-current sputtering method from a tin metal target incorporating molybdenum element. Results of structural and compositional analyses confirmed the presence of tin and molybdenum. The elemental ratio obtained from energy-dispersive x-ray spectroscopy confirmed the feasibility of tailoring the thin-film composition by varying the ratio of metallic elements present in the sputtering target. Scanning electron micrographs of the samples revealed the occurrence of flower-like open morphology with Mo inclusion in a Sn matrix. The gravimetric discharge capacity for pure Sn, Sn-rich, and Mo-rich samples was 733 mAh g-1, 572 mAh g-1, and 439 mAh g-1, respectively, with capacity retention after 50 cycles of 22%, 61%, and 74%, respectively. Mo inclusion reduced the surface resistivity of the Sn anode after the initial charge-discharge cycle. The charge-transfer resistance after the first cycle for pure Sn, Sn-rich, and Mo-rich samples was 17.395 Ω, 5.345 Ω, and 2.865 Ω, respectively. The lithium-ion diffusion coefficient also increased from 8.68 × 10-8 cm2S-1 for the pure Sn sample to 2.98 × 10-5 cm2S-1 for the Mo-rich sample.

  11. Sputtering Deposition of Sn-Mo-Based Composite Anode for Thin-Film Li-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Mani Chandran, T.; Balaji, S.

    2016-06-01

    The role of electrochemically inactive molybdenum in alleviating the anomalous volume expansion of tin anode upon charge-discharge cycling has been investigated. Tin-molybdenum thin-film composite anodes for Li-ion batteries were prepared using a direct-current sputtering method from a tin metal target incorporating molybdenum element. Results of structural and compositional analyses confirmed the presence of tin and molybdenum. The elemental ratio obtained from energy-dispersive x-ray spectroscopy confirmed the feasibility of tailoring the thin-film composition by varying the ratio of metallic elements present in the sputtering target. Scanning electron micrographs of the samples revealed the occurrence of flower-like open morphology with Mo inclusion in a Sn matrix. The gravimetric discharge capacity for pure Sn, Sn-rich, and Mo-rich samples was 733 mAh g-1, 572 mAh g-1, and 439 mAh g-1, respectively, with capacity retention after 50 cycles of 22%, 61%, and 74%, respectively. Mo inclusion reduced the surface resistivity of the Sn anode after the initial charge-discharge cycle. The charge-transfer resistance after the first cycle for pure Sn, Sn-rich, and Mo-rich samples was 17.395 Ω, 5.345 Ω, and 2.865 Ω, respectively. The lithium-ion diffusion coefficient also increased from 8.68 × 10-8 cm2S-1 for the pure Sn sample to 2.98 × 10-5 cm2S-1 for the Mo-rich sample.

  12. Electrochemical properties of rapidly solidified Si-Ti-Ni(-Cu) base anode for Li-ion rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Kwon, Hye Jin; Sohn, Keun Yong; Park, Won-Wook

    2013-11-01

    In this study, rapidly solidified Si-Ti-Ni-Cu alloys have been investigated as high capacity anodes for Li-ion secondary batteries. To obtain nano-sized Si particles dispersed in the inactive matrix, the alloy ribbons were fabricated using the melt spinning process. The thin ribbons were pulverized using ball-milling to make a fine powder of ˜ 4 µm average size. Coin-cell assembly was carried out under an argon gas in a glove box, in which pure lithium was used as a counter-electrode. The cells were cycled using the galvanostatic method in the potential range of 0.01 V and 1.5 V vs. Li/Li+. The microstructure and morphology were examined using an x-ray diffractometer, Field-Emission Scanning Electron Microscopy and High Resolution Transmission Electron Microscopy. Among the anode alloys, the Si70Ti15Ni15 electrodes had the highest discharge capacity (974.1 mAh/g) after the 50th cycle, and the Si60Ti16Ni16Cu8 electrode showed the best coulombic efficiency of ˜95.9% in cyclic behavior. It was revealed that the Si7Ni4Ti4 crystal phase coexisting with an amorphous phase, could more efficiently act as a buffer layer than the fully crystallized Si7Ni4Ti4 phase. Consequently, the electrochemical properties of the anode materials pronouncedly improved when the nano-sized primary Si particle was dispersed in the inactive Si7Ni4Ti4-based matrix mixed with an amorphous structure.

  13. A Yolk-Shell Design for Stabilized and Scalable Li-Ion Battery Alloy Anodes

    SciTech Connect

    Liu, Nian; Wu, Hui; McDowell, Matthew T.; Yao, Yan; Wang, Chongmin; Cui, Yi

    2012-05-02

    Silicon is regarded as one of the most promising anode materials for next generation lithium-ion batteries. For use in practical applications, a Si electrode must have high capacity, long cycle life, high efficiency, and the fabrication must be industrially scalable. Here, we design and fabricate a yolk-shell structure to meet all these needs. The fabrication is carried out without special equipment and mostly at room temperature. Commercially available Si nanoparticles are completely sealed inside conformal, thin, self-supporting carbon shells, with rationally designed void space in between the particles and the shell. Finally, the well-defined void space allows the Si particles to expand freely without breaking the outer carbon shell, therefore stabilizing the solid-electrolyte interphase on the shell surface. High capacity (~2800 mAh/g at C/10), long cycle life (1000 cycles with 74% capacity retention), and high Coulombic efficiency (99.84%) have been realized in this yolk-shell structured Si electrode.

  14. Investigation of film solidification and binder migration during drying of Li-Ion battery anodes

    NASA Astrophysics Data System (ADS)

    Jaiser, Stefan; Müller, Marcus; Baunach, Michael; Bauer, Werner; Scharfer, Philip; Schabel, Wilhelm

    2016-06-01

    The property determining micro-structure of battery electrodes essentially evolves during drying, appointing it a paramount, yet insufficiently understood processing step in cell manufacturing. The distribution of functional additives such as binder or carbon black throughout the film strongly depends on the drying process. A representative state-of-the-art model system comprising graphite, polymeric binder, carbon black and solvent is investigated to gain an insight into the underlying processes. A new experimental approach is introduced that allows for revelation of the evolution of binder concentration gradients throughout the film during drying. Binder is detected by means of energy-dispersive x-ray spectroscopy (EDS) at the top and bottom surface. Drying kinetics is investigated and the impact of the drying process on electrochemical performance is disclosed. The enrichment of binder at the surface, which is observed while applying high drying rates, is shown to depend on two fundamental processes, namely capillary action and diffusion. The findings reveal characteristic drying stages that provide fundamental insights into film solidification. Based on that, a top-down consolidation mechanism capable of explaining the experimental findings is disclosed. Adhesion of the active layer to the substrate is shown to strongly depend on the local binder concentration in the vicinity of the substrate.

  15. Electrochemical properties of cobalt hydroxychloride microspheres as a new anode material for Li-ion batteries

    PubMed Central

    Park, Gi Dae; Ko, You Na; Kang, Yun Chan

    2014-01-01

    The use of cobalt hydroxychloride [Co2(OH)3Cl] as an anode material for lithium ion batteries (LIBs) is investigated using spherical shape and ultrafine nanocrystals directly formed by spray pyrolysis from spray solution of cobalt chloride salt. Dot-mapping images of the resulting powders reveal a uniform distribution of Co, O, and Cl throughout the powder. The Co2(OH)3Cl powder prepared directly by spray pyrolysis exhibits a high thermal stability at temperatures below 220°C, as well as having superior electrochemical properties compared with those of the CoCl2(H2O)2 and CoO powders prepared by the same process. The initial discharge capacities of the Co2(OH)3Cl and CoO powders at a constant current density of 1000 mA g−1 are found to be 1570 and 1142 mA h g−1, respectively, and their initial Coulombic efficiencies are 72 and 70%. The discharge capacities of the Co2(OH)3Cl and CoO powders after 100 cycles are 955 and 632 mA h g−1, respectively. The Co2(OH)3Cl powders have a high discharge capacity of 609 mA h g−1 even after 1000 cycles at a high current density of 5000 mA g−1. PMID:25167884

  16. Functionally strain-graded nanoscoops for high power Li-ion battery anodes.

    PubMed

    Krishnan, Rahul; Lu, Toh-Ming; Koratkar, Nikhil

    2011-02-01

    Lithium-ion batteries show poor performance for high power applications involving ultrafast charging/discharging rates. Here we report a functionally strain-graded carbon-aluminum-silicon anode architecture that overcomes this drawback. It consists of an array of nanostructures each comprising an amorphous carbon nanorod with an intermediate layer of aluminum that is finally capped by a silicon nanoscoop on the very top. The gradation in strain arises from graded levels of volumetric expansion in these three materials on alloying with lithium. The introduction of aluminum as an intermediate layer enables the gradual transition of strain from carbon to silicon, thereby minimizing the mismatch at interfaces between differentially strained materials and enabling stable operation of the electrode under high-rate charge/discharge conditions. At an accelerated current density of ∼51.2 A/g (i.e., charge/discharge rate of ∼40C), the strain-graded carbon-aluminum-silicon nanoscoop anode provides average capacities of ∼412 mAh/g with a power output of ∼100 kW/kg(electrode) continuously over 100 charge/discharge cycles. PMID:21192713

  17. Regulated Breathing Effect of Silicon Negative Electrode for Dramatically Enhanced Performance of Li-Ion Battery

    SciTech Connect

    Xiao, Xingcheng; Zhou, Weidong; Kim, Youngnam; Ryu, Ill; Gu, Meng; Wang, Chong M.; Liu, Gao; Liu, Zhongyi; Gao, Huajian

    2015-03-01

    Si is an attractive negative electrode material for lithium ion batteries due to its high specifi c capacity (≈3600 mAh g –1 ). However, the huge volume swelling and shrinking during cycling, which mimics a breathing effect at the material/electrode/cell level, leads to several coupled issues including fracture of Si particles, unstable solid electrolyte interphase, and low Coulombic effi ciency. In this work, the regulation of the breathing effect is reported by using Si–C yolk–shell nanocomposite which has been well-developed by other researchers. The focus is on understanding how the nanoscaled materials design impacts the mechanical and electrochemical response at electrode level. For the fi rst time, it is possible to observe one order of magnitude of reduction on breathing effect at the electrode level during cycling: the electrode thickness variation reduced down to 10%, comparing with 100% in the electrode with Si nanoparticles as active materials. The Si–C yolk–shell nanocomposite electrode exhibits excellent capacity retention and high cycle effi ciency. In situ transmission electron microscopy and fi nite element simulations consistently reveals that the dramatically enhanced performance is associated with the regulated breathing of the Si in the new composite, therefore the suppression of the overall electrode expansion.

  18. A yolk-shell design for stabilized and scalable li-ion battery alloy anodes.

    PubMed

    Liu, Nian; Wu, Hui; McDowell, Matthew T; Yao, Yan; Wang, Chongmin; Cui, Yi

    2012-06-13

    Silicon is regarded as one of the most promising anode materials for next generation lithium-ion batteries. For use in practical applications, a Si electrode must have high capacity, long cycle life, high efficiency, and the fabrication must be industrially scalable. Here, we design and fabricate a yolk-shell structure to meet all these needs. The fabrication is carried out without special equipment and mostly at room temperature. Commercially available Si nanoparticles are completely sealed inside conformal, thin, self-supporting carbon shells, with rationally designed void space in between the particles and the shell. The well-defined void space allows the Si particles to expand freely without breaking the outer carbon shell, therefore stabilizing the solid-electrolyte interphase on the shell surface. High capacity (∼2800 mAh/g at C/10), long cycle life (1000 cycles with 74% capacity retention), and high Coulombic efficiency (99.84%) have been realized in this yolk-shell structured Si electrode. PMID:22551164

  19. Effect of Temperature on the Aging rate of Li Ion Battery Operating above Room Temperature

    NASA Astrophysics Data System (ADS)

    Leng, Feng; Tan, Cher Ming; Pecht, Michael

    2015-08-01

    Temperature is known to have a significant impact on the performance, safety, and cycle lifetime of lithium-ion batteries (LiB). However, the comprehensive effects of temperature on the cyclic aging rate of LiB have yet to be found. We use an electrochemistry-based model (ECBE) here to measure the effects on the aging behavior of cycled LiB operating within the temperature range of 25 °C to 55 °C. The increasing degradation rate of the maximum charge storage of LiB during cycling at elevated temperature is found to relate mainly to the degradations at the electrodes, and that the degradation of LCO cathode is larger than graphite anode at elevated temperature. In particular, the formation and modification of the surface films on the electrodes as well as structural/phase changes of the LCO electrode, as reported in the literatures, are found to be the main contributors to the increasing degradation rate of the maximum charge storage of LiB with temperature for the specific operating temperature range. Larger increases in the Warburg elements and cell impedance are also found with cycling at higher temperature, but they do not seriously affect the state of health (SoH) of LiB as shown in this work.

  20. Multi-Scale Correlative Tomography of a Li-Ion Battery Composite Cathode

    NASA Astrophysics Data System (ADS)

    Moroni, Riko; Börner, Markus; Zielke, Lukas; Schroeder, Melanie; Nowak, Sascha; Winter, Martin; Manke, Ingo; Zengerle, Roland; Thiele, Simon

    2016-07-01

    Focused ion beam/scanning electron microscopy tomography (FIB/SEMt) and synchrotron X-ray tomography (Xt) are used to investigate the same lithium manganese oxide composite cathode at the same specific spot. This correlative approach allows the investigation of three central issues in the tomographic analysis of composite battery electrodes: (i) Validation of state-of-the-art binary active material (AM) segmentation: Although threshold segmentation by standard algorithms leads to very good segmentation results, limited Xt resolution results in an AM underestimation of 6 vol% and severe overestimation of AM connectivity. (ii) Carbon binder domain (CBD) segmentation in Xt data: While threshold segmentation cannot be applied for this purpose, a suitable classification method is introduced. Based on correlative tomography, it allows for reliable ternary segmentation of Xt data into the pore space, CBD, and AM. (iii) Pore space analysis in the micrometer regime: This segmentation technique is applied to an Xt reconstruction with several hundred microns edge length, thus validating the segmentation of pores within the micrometer regime for the first time. The analyzed cathode volume exhibits a bimodal pore size distribution in the ranges between 0–1 μm and 1–12 μm. These ranges can be attributed to different pore formation mechanisms.

  1. Multi-Scale Correlative Tomography of a Li-Ion Battery Composite Cathode.

    PubMed

    Moroni, Riko; Börner, Markus; Zielke, Lukas; Schroeder, Melanie; Nowak, Sascha; Winter, Martin; Manke, Ingo; Zengerle, Roland; Thiele, Simon

    2016-01-01

    Focused ion beam/scanning electron microscopy tomography (FIB/SEMt) and synchrotron X-ray tomography (Xt) are used to investigate the same lithium manganese oxide composite cathode at the same specific spot. This correlative approach allows the investigation of three central issues in the tomographic analysis of composite battery electrodes: (i) Validation of state-of-the-art binary active material (AM) segmentation: Although threshold segmentation by standard algorithms leads to very good segmentation results, limited Xt resolution results in an AM underestimation of 6 vol% and severe overestimation of AM connectivity. (ii) Carbon binder domain (CBD) segmentation in Xt data: While threshold segmentation cannot be applied for this purpose, a suitable classification method is introduced. Based on correlative tomography, it allows for reliable ternary segmentation of Xt data into the pore space, CBD, and AM. (iii) Pore space analysis in the micrometer regime: This segmentation technique is applied to an Xt reconstruction with several hundred microns edge length, thus validating the segmentation of pores within the micrometer regime for the first time. The analyzed cathode volume exhibits a bimodal pore size distribution in the ranges between 0-1 μm and 1-12 μm. These ranges can be attributed to different pore formation mechanisms. PMID:27456201

  2. Multi-Scale Correlative Tomography of a Li-Ion Battery Composite Cathode

    PubMed Central

    Moroni, Riko; Börner, Markus; Zielke, Lukas; Schroeder, Melanie; Nowak, Sascha; Winter, Martin; Manke, Ingo; Zengerle, Roland; Thiele, Simon

    2016-01-01

    Focused ion beam/scanning electron microscopy tomography (FIB/SEMt) and synchrotron X-ray tomography (Xt) are used to investigate the same lithium manganese oxide composite cathode at the same specific spot. This correlative approach allows the investigation of three central issues in the tomographic analysis of composite battery electrodes: (i) Validation of state-of-the-art binary active material (AM) segmentation: Although threshold segmentation by standard algorithms leads to very good segmentation results, limited Xt resolution results in an AM underestimation of 6 vol% and severe overestimation of AM connectivity. (ii) Carbon binder domain (CBD) segmentation in Xt data: While threshold segmentation cannot be applied for this purpose, a suitable classification method is introduced. Based on correlative tomography, it allows for reliable ternary segmentation of Xt data into the pore space, CBD, and AM. (iii) Pore space analysis in the micrometer regime: This segmentation technique is applied to an Xt reconstruction with several hundred microns edge length, thus validating the segmentation of pores within the micrometer regime for the first time. The analyzed cathode volume exhibits a bimodal pore size distribution in the ranges between 0–1 μm and 1–12 μm. These ranges can be attributed to different pore formation mechanisms. PMID:27456201

  3. Thermomechanical analysis and durability of commercial micro-porous polymer Li-ion battery separators

    NASA Astrophysics Data System (ADS)

    Love, Corey T.

    2011-03-01

    Static and dynamic thermomechanical analysis was performed with a dynamic mechanical analyzer (DMA) to identify thermal and mechanical transitions for commercially available polymer separators under mechanical loading. Clear transitions in deformation mode were observed at elevated temperatures. These transitions identified the onset of separator "shutdown" which occurred at temperatures below the polymer melting point. Mechanical loading direction was critical to the overall integrity of the separator. Anisotropic separators (Celgard 2320, 2400 and 2500) were mechanically limited when pulled in tensile in the transverse direction. The anisotropy of these separators is a result of the dry technique used to manufacture the micro-porous membranes. Separators prepared using the wet technique (Entek Gold LP) behaved more uniformly, or biaxially, where all mechanical properties were nearly identical within the separator plane. The information provided by the DMA can also be useful for predicting the long-term durability of polymer separators in lithium-ion batteries exposed to electrolyte (solvent and salt), thermal fluctuations and electrochemical cycling. Small losses in mechanical integrity were observed for separators exposed to the various immersion environments over the 4-week immersion time.

  4. Effect of Temperature on the Aging rate of Li Ion Battery Operating above Room Temperature

    PubMed Central

    Leng, Feng; Tan, Cher Ming; Pecht, Michael

    2015-01-01

    Temperature is known to have a significant impact on the performance, safety, and cycle lifetime of lithium-ion batteries (LiB). However, the comprehensive effects of temperature on the cyclic aging rate of LiB have yet to be found. We use an electrochemistry-based model (ECBE) here to measure the effects on the aging behavior of cycled LiB operating within the temperature range of 25 °C to 55 °C. The increasing degradation rate of the maximum charge storage of LiB during cycling at elevated temperature is found to relate mainly to the degradations at the electrodes, and that the degradation of LCO cathode is larger than graphite anode at elevated temperature. In particular, the formation and modification of the surface films on the electrodes as well as structural/phase changes of the LCO electrode, as reported in the literatures, are found to be the main contributors to the increasing degradation rate of the maximum charge storage of LiB with temperature for the specific operating temperature range. Larger increases in the Warburg elements and cell impedance are also found with cycling at higher temperature, but they do not seriously affect the state of health (SoH) of LiB as shown in this work. PMID:26245922

  5. Grid indentation analysis of mechanical properties of composite electrodes in Li-ion batteries

    DOE PAGESBeta

    Vasconcelos, Luize Scalco de; Xu, Rong; Li, Jianlin; Zhao, Kejie

    2016-03-09

    We report that electrodes in commercial rechargeable batteries are microscopically heterogeneous materials. The constituent components, including active materials, polymeric binders, and porous conductive matrix, often have large variation in their mechanical properties, making the mechanical characterization of composite electrodes a challenging task. In a model system of LiNi0.5Mn0.3Co0.2O2 cathode, we employ the instrumented grid indentation to determine the elastic modulus and hardness of the constituent phases. The approach relies on a large array of nanoindentation experiments and statistical analysis of the resulting data provided that the maximum indentation depth is carefully chosen. The statistically extracted properties of the active particlesmore » and the surrounding medium are in good agreement with the tests of targeted indentation at selected sites. Lastly, the combinatory technique of grid indentation and statistical deconvolution represents a fast and reliable route to quantify the mechanical properties of composite electrodes that feed the parametric input for the mechanics models.« less

  6. Effect of water on solid electrolyte interphase formation in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Saito, M.; Fujita, M.; Aoki, Y.; Yoshikawa, M.; Yasuda, K.; Ishigami, R.; Nakata, Y.

    2016-03-01

    Time-of-flight-elastic recoil detection analysis (TOF-ERDA) with 20 MeV Cu ions has been applied to measure the depth profiles of solid electrolyte interphase (SEI) layers on the negative electrode of lithium ion batteries (LIB). In order to obtain quantitative depth profiles, the detector efficiency was first assessed, and the test highlighted a strong mass and energy dependence of the recoiled particles, especially H and He. Subsequently, we prepared LIB cells with different water contents in the electrolyte, and subjected them to different charge-discharge cycle tests. TOF-ERDA, X-ray photoelectron spectrometry (XPS), gas chromatography (GC), ion chromatography (IC), and 1H nuclear magnetic resonance (1H NMR) were applied to characterize the SEI region of the negative electrode. The results showed that the SEI layer is formed after 300 cycle tests, and a 500 ppm water concentration in the electrolyte does not appear to cause significant differences in the elemental and organic content of the SEI.

  7. Influence of constraints on axial growth reduction of cylindrical Li-ion battery electrode particles

    NASA Astrophysics Data System (ADS)

    Chakraborty, Jeevanjyoti; Please, Colin P.; Goriely, Alain; Chapman, S. Jonathan

    2015-04-01

    Volumetric expansion of silicon anode particles in a lithium-ion battery during charging may lead to the generation of undesirable internal stresses. For a cylindrical particle such growth may also lead to failure by buckling if the expansion is constrained in the axial direction due to other particles or supporting structures. To mitigate this problem, the possibility of reducing axial growth is investigated theoretically by studying simple modifications of the solid cylinder geometry. First, an annular cylinder is considered with lithiation either from the inside or from the outside. In both cases, the reduction of axial growth is not found to be significant. Next, explicit physical constraints are studied by addition of a non-growing elasto-plastic material: first, an outer annular constraint on a solid silicon cylinder, and second a rod-like inner constraint for an annular silicon cylinder. In both cases, it is found that axial growth can be reduced if the yield stress of the constraining material is significantly higher than that of silicon and/or the thickness of the constraint is relatively high. Phase diagrams are presented for both the outer and the inner constraint cases to identify desirable operating zones. Finally, to interpret the phase diagrams and isolate the key physical principles two different simplified models are presented and are shown to recover important qualitative trends of the numerical simulation results.

  8. Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries.

    PubMed

    Huang, Yiqing; Lin, Yuh-Chieh; Jenkins, David M; Chernova, Natasha A; Chung, Youngmin; Radhakrishnan, Balachandran; Chu, Iek-Heng; Fang, Jin; Wang, Qi; Omenya, Fredrick; Ong, Shyue Ping; Whittingham, M Stanley

    2016-03-23

    The thermal stability of electrochemically delithiated Li0.1Ni0.8Co0.15Al0.05O2 (NCA), FePO4 (FP), Mn0.8Fe0.2PO4 (MFP), hydrothermally synthesized VOPO4, LiVOPO4, and electrochemically lithiated Li2VOPO4 is investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis, coupled with mass spectrometry (TGA-MS). The thermal stability of the delithiated materials is found to be in the order of NCA < VOPO4 < MFP < FP. Unlike the layered oxides and MFP, VOPO4 does not evolve O2 on heating. Thus, VOPO4 is less likely to cause a thermal run-away phenomenon in batteries at elevated temperature and so is inherently safer. The lithiated materials LiVOPO4, Li2VOPO4, and LiNi0.8Co0.15Al0.05O2 are found to be stable in the presence of electrolyte, but sealed-capsule high-pressure experiments show a phase transformation of VOPO4 → HVOPO4 → H2VOPO4 when VOPO4 reacts with electrolyte (1 M LiPF6 in EC/DMC = 1:1) between 200 and 300 °C. Using first-principles calculations, we confirm that the charged VOPO4 cathode is indeed predicted to be marginally less stable than FP but significantly more stable than NCA in the absence of electrolyte. An analysis of the reaction equilibria between VOPO4 and EC using a multicomponent phase diagram approach yields products and reaction enthalpies that are highly consistent with the experiment results. PMID:26915096

  9. Computational characterization of lightweight multilayer MXene Li-ion battery anodes

    NASA Astrophysics Data System (ADS)

    Ashton, Michael; Hennig, Richard G.; Sinnott, Susan B.

    2016-01-01

    MXenes, a class of two-dimensional transition metal carbides and nitrides, have shown promise experimentally and computationally for use in energy storage applications. In particular, the most lightweight members of the monolayer MXene family (M = Sc, Ti, V, or Cr) are predicted to have gravimetric capacities above 400 mAh/g, higher than graphite. Additionally, intercalation of ions into multilayer MXenes can be accomplished at low voltages, and low diffusion barriers exist for Li diffusing across monolayer MXenes. However, large discrepancies have been observed between the calculated and experimental reversible capacities of MXenes. Here, dispersion-corrected density functional theory calculations are employed to predict reversible capacities and other battery-related properties for six of the most promising members of the MXene family (O-functionalized Ti- and V-based carbide MXenes) as bilayer structures. The calculated reversible capacities of the V2CO2 and Ti2CO2 bilayers agree more closely with experiment than do previous calculations for monolayers. Additionally, the minimum energy paths and corresponding energy barriers along the in-plane [1000] and [0100] directions for Li travelling between neighboring MXene layers are determined. V4C3O2 exhibits the lowest diffusion barrier of the compositions considered, at 0.42 eV, but its reversible capacity (148 mAh/g) is dragged down by its heavy formula unit. Conversely, the V2CO2 MXene shows good reversible capacity (276 mAh/g), but a high diffusion barrier (0.82 eV). We show that the diffusion barriers of all bilayer structures are significantly higher than those calculated for the corresponding monolayers, advocating the use of dispersed monolayer MXenes instead of multilayers in high performance anodes.

  10. Original implementation of Electrochemical Impedance Spectroscopy (EIS) in symmetric cells: Evaluation of post-mortem protocols applied to characterize electrode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Gordon, Isabel Jiménez; Genies, Sylvie; Si Larbi, Gregory; Boulineau, Adrien; Daniel, Lise; Alias, Mélanie

    2016-03-01

    Understanding ageing mechanisms of Li-ion batteries is essential for further optimizations. To determine performance loss causes, post-mortem analyses are commonly applied. For each type of post-mortem test, different sample preparation protocols are adopted. However, reports on the reliability of these protocols are rare. Herein, Li-ion pouch cells with LiNi1/3Mn1/3Co1/3O2 - polyvinylidene fluoride positive electrode, graphite-carboxymethyl cellulose-styrene rubber negative electrode and LiPF6 - carbonate solvents mixture electrolyte, are opened and electrodes are recovered following a specified protocol. Negative and positive symmetric cells are assembled and their impedances are recorded. A signal analysis is applied to reconstruct the Li-ion pouch cell impedance from the symmetric cells, then comparison against the pouch cell true impedance allows the evaluation of the sample preparation protocols. The results are endorsed by Transmission Electronic Microscopy (TEM) and Gas Chromatography - Mass Spectrometry (GC-MS) analyses. Carbonate solvents used to remove the salt impacts slightly the surface properties of both electrodes. Drying electrodes under vacuum at 25 °C produces an impedance increase, particularly very marked for the positive electrode. Drying at 50 °C under vacuum or/and exposition to the anhydrous room atmosphere is very detrimental.

  11. Amorphous Zn₂GeO₄ Nanoparticles as Anodes with High Reversible Capacity and Long Cycling Life for Li-ion Batteries

    SciTech Connect

    Yi, Ran; Feng, Jinkui; Lv, Dongping; Gordin, Mikhail; Chen, Shuru; Choi, Daiwon; Wang, Donghai

    2013-07-30

    Amorphous and crystalline Zn₂GeO₄ nanoparticles were prepared and characterized as anode materials for Li-ion batteries. A higher reversible specific capacity of 1250 mAh/g after 500 cycles and excellent rate capability were obtained for amorphous Zn₂GeO₄ nanoparticles, compared to that of crystalline Zn₂GeO₄ nanoparticles. Small particle size, amorphous phase and incorporation of zinc and oxygen contribute synergetically to the improved performance by effectively mitigating the huge volume variations during lithiation and delithiation process.

  12. SnO2 nanocrystals deposited on multiwalled carbon nanotubes with superior stability as anode material for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Ren, Jianguo; Yang, Junbing; Abouimrane, Ali; Wang, Dapeng; Amine, Khalil

    2011-10-01

    We report a novel ethylene glycol-mediated solvothermal-polyol route for synthesis of SnO2-CNT nanocomposites, which consist of highly dispersed 3-5 nm SnO2 nanocrystals on the surface of multiwalled carbon nanotubes (CNTs). As anode materials for Li-ion batteries, the nanocomposites showed high rate capability and superior cycling stability with specific capacity of 500 mAh g-1 for up to 300 cycles. The CNTs served as electron conductors and volume buffers in the nanocomposites. This strategy could be extended to synthesize other metal oxides composites with other carbon materials.

  13. Si/Ag composite with bimodal micro-nano porous structure as a high-performance anode for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Hao, Qin; Zhao, Dianyun; Duan, Huimei; Zhou, Qiuxia; Xu, Caixia

    2015-03-01

    A one-step dealloying method is employed to conveniently fabricate a bimodal porous (BP) Si/Ag composite in high throughput under mild conditions. Upon dealloying the carefully designed SiAgAl ternary alloy in HCl solution at room temperature, the obtained Si/Ag composite has a uniform bicontinuous porous structure in three dimensions with micro-nano bimodal pore size distribution. Compared with the traditional preparation methods for porous Si and Si-based composites, this dealloying route is easily operated and environmentally benign. More importantly, it is convenient to realize the controllable components and uniform distribution of Si and Ag in the product. Owing to the rich porosity of the unique BP structure and the incorporation of highly conductive Ag, the as-made Si/Ag composite possesses the improved conductivity and alleviated volume changes of the Si network during repeated charging and discharging. As expected, the BP Si/Ag anode exhibits high capacity, excellent cycling reversibility, long cycling life and good rate capability for lithium storage. When the current rate is up to 1 A g-1, BP Si/Ag can deliver a stable reversible capacity above 1000 mA h g-1, and exhibits a capacity retention of up to 89.2% against the highest capacity after 200 cycles. With the advantages of unique performance and easy preparation, the BP Si/Ag composite holds great application potential as an advanced anode material for Li-ion batteries.A one-step dealloying method is employed to conveniently fabricate a bimodal porous (BP) Si/Ag composite in high throughput under mild conditions. Upon dealloying the carefully designed SiAgAl ternary alloy in HCl solution at room temperature, the obtained Si/Ag composite has a uniform bicontinuous porous structure in three dimensions with micro-nano bimodal pore size distribution. Compared with the traditional preparation methods for porous Si and Si-based composites, this dealloying route is easily operated and environmentally benign

  14. Non-uniform temperature distribution in Li-ion batteries during discharge - A combined thermal imaging, X-ray micro-tomography and electrochemical impedance approach

    NASA Astrophysics Data System (ADS)

    Robinson, James B.; Darr, Jawwad A.; Eastwood, David S.; Hinds, Gareth; Lee, Peter D.; Shearing, Paul R.; Taiwo, Oluwadamilola O.; Brett, Dan J. L.

    2014-04-01

    Thermal runaway is a major cause of failure in Li-ion batteries (LIBs), and of particular concern for high energy density transport applications, where safety concerns have hampered commercialisation. A clear understanding of electro-thermal properties and how these relate to structure and operation is vital to improving thermal management of LIBs. Here a combined thermal imaging, X-ray tomography and electrochemical impedance spectroscopy (EIS) approach was applied to commercially available 18650 cells to study their thermal characteristics. Thermal imaging was used to characterise heterogeneous temperature distributions during discharge above 0.75C; the complementary information provided by 3D X-ray tomography was utilised to evaluate the internal structure of the battery and identify the regions causing heating, specifically the components of the battery cap.

  15. A novel surface-sensitive X-ray absorption spectroscopic detector to study the thermal decomposition of cathode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Nonaka, Takamasa; Okuda, Chikaaki; Oka, Hideaki; Nishimura, Yusaku F.; Makimura, Yoshinari; Kondo, Yasuhito; Dohmae, Kazuhiko; Takeuchi, Yoji

    2016-09-01

    A surface-sensitive conversion-electron-yield X-ray absorption fine structure (CEY-XAFS) detector that operates at elevated temperatures is developed to investigate the thermal decomposition of cathode materials for Li-ion batteries. The detector enables measurements with the sample temperature controlled from room temperature up to 450 °C. The detector is applied to the LiNi0.75Co0.15Al0.05Mg0.05O2 cathode material at 0% state of charge (SOC) and 50% SOC to examine the chemical changes that occur during heating in the absence of an electrolyte. The combination of surface-sensitive CEY-XAFS and bulk-sensitive transmission-mode XAFS shows that the reduction of Ni and Co ions begins at the surface of the cathode particles at around 150 °C, and propagates inside the particle upon further heating. These changes with heating are irreversible and are more obvious at 50% SOC than at 0% SOC. The fraction of reduced Ni ions is larger than that of reduced Co ions. These results demonstrate the capability of the developed detector to obtain important information for the safe employment of this cathode material in Li-ion batteries.

  16. Study of poly(acrylonitrile-methyl methacrylate) as binder for graphite anode and LiMn 2O 4 cathode of Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, S. S.; Jow, T. R.

    We evaluated poly(acrylonitrile-methyl methacrylate) (AMMA, AN/MMA=94:6) as a binder for the graphite anode and the LiMn 2O 4 cathode of Li-ion batteries by studying the cycling performance of lithium half-cells. The results showed that, using AMMA binder, both graphite and LiMn 2O 4 could be cycled well in 1 m LiPF 6 3:3:4 (weight) PC/EC/EMC electrolyte with less capacity fading. AMMA is chemically more stable than poly(vinylidene fluoride) (PVDF) against the lithiated graphite. More importantly, AMMA can help graphite to form a stable solid electrolyte interface (SEI) film. An impedance study showed that the SEI film formed with AMMA is more stable than the one formed with PVDF. Therefore, self-delithiation of the lithiated graphite can be reduced by use of AMMA instead of PVDF, which improves the storage performance of Li-ion batteries.

  17. Sphere-Shaped Hierarchical Cathode with Enhanced Growth of Nanocrystal Planes for High-Rate and Cycling-Stable Li-Ion Batteries

    DOE PAGESBeta

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

    2015-01-14

    High-energy and high-power Li-ion batteries have been intensively pursued as power sources in electronic vehicles and renewable energy storage systems in smart grids. With this purpose, developing high-performance cathode materials is urgently needed. Here we report an easy and versatile strategy to fabricate high-rate and cycling-stable hierarchical sphered cathode Li1.2Ni0.13Mn0.54Co0.13O2, by using an ionic interfusion method. The sphere-shaped hierarchical cathode is assembled with primary nanoplates with enhanced growth of nanocrystal planes in favor of Li+ intercalation/deintercalation, such as (010), (100), and (110) planes. This material with such unique structural features exhibits outstanding rate capability, cyclability, and high discharge capacities, achievingmore » around 70% (175 mAhg–1) of the capacity at 0.1 C rate within about 2.1 min of ultrafast charging. Such cathode is feasible to construct high-energy and high-power Li-ion batteries.« less

  18. Current density and state of charge inhomogeneities in Li-ion battery cells with LiFePO4 as cathode material due to temperature gradients

    NASA Astrophysics Data System (ADS)

    Fleckenstein, Matthias; Bohlen, Oliver; Roscher, Michael A.; Bäker, Bernard

    2011-05-01

    Current density distributions and local state of charge (SoC) differences that are caused by temperature gradients inside actively cooled Li-ion battery cells are discussed and quantified. As an example, a cylindrical Li-ion cell with LiFePO4 as cathode material (LiFePO4-cell) is analyzed in detail both experimentally and by means of spatial electro-thermal co-simulations. The reason for current density inhomogeneities is found to be the local electrochemical impedance varying with temperature in different regions of the jelly roll. For the investigated cell, high power cycling and the resulting temperature gradient additionally cause SoC-gradients inside the jelly roll. The local SoCs inside one cell diverge firstly because of asymmetric current density distributions during charge and discharge inside the cell and secondly because of the temperature dependence of the local open circuit potential. Even after long relaxation periods, the SoC distribution in cycled LiFePO4-cells remains inhomogeneous across the jelly roll as a result of hysteresis in the open circuit voltage. The occurring thermal electrical inhomogeneities are expected to influence local aging differences and thus, global cell aging. Additionally the occurrence of inhomogeneous current flow and SoC-development inside non-uniformly cooled battery packs of parallel connected LiFePO4-cells is measured and discussed.

  19. Amorphous silicon-carbon nanospheres synthesized by chemical vapor deposition using cheap methyltrichlorosilane as improved anode materials for Li-ion batteries.

    PubMed

    Zhang, Zailei; Zhang, Meiju; Wang, Yanhong; Tan, Qiangqiang; Lv, Xiao; Zhong, Ziyi; Li, Hong; Su, Fabing

    2013-06-21

    We report the preparation and characterization of amorphous silicon-carbon (Si-C) nanospheres as anode materials in Li-ion batteries. These nanospheres were synthesized by a chemical vapor deposition at 900 °C using methyltrichlorosilane (CH3SiCl3) as both the Si and C precursor, which is a cheap byproduct in the organosilane industry. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, nitrogen adsorption, thermal gravimetric analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy. It was found that the synthesized Si-C nanospheres composed of amorphous C (about 60 wt%) and Si (about 40 wt%) had a diameter of 400-600 nm and a surface area of 43.8 m(2) g(-1). Their charge capacities were 483.6, 331.7, 298.6, 180.6, and 344.2 mA h g(-1) at 50, 200, 500, 1000, and 50 mA g(-1) after 50 cycles, higher than that of the commercial graphite anode. The Si-C amorphous structure could absorb a large volume change of Si during Li insertion and extraction reactions and hinder the cracking or crumbling of the electrode, thus resulting in the improved reversible capacity and cycling stability. The work opens a new way to fabricate low cost Si-C anode materials for Li-ion batteries. PMID:23652614

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

    PubMed

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

    2015-01-14

    High-energy and high-power Li-ion batteries have been intensively pursued as power sources in electronic vehicles and renewable energy storage systems in smart grids. With this purpose, developing high-performance cathode materials is urgently needed. Here we report an easy and versatile strategy to fabricate high-rate and cycling-stable hierarchical sphered cathode Li(1.2)Ni(0.13)Mn(0.54)Co(0.13)O2, by using an ionic interfusion method. The sphere-shaped hierarchical cathode is assembled with primary nanoplates with enhanced growth of nanocrystal planes in favor of Li(+) intercalation/deintercalation, such as (010), (100), and (110) planes. This material with such unique structural features exhibits outstanding rate capability, cyclability, and high discharge capacities, achieving around 70% (175 mAh g(-1)) of the capacity at 0.1 C rate within about 2.1 min of ultrafast charging. Such cathode is feasible to construct high-energy and high-power Li-ion batteries. PMID:25513887

  1. Sphere-Shaped Hierarchical Cathode with Enhanced Growth of Nanocrystal Planes for High-Rate and Cycling-Stable Li-Ion Batteries

    SciTech Connect

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

    2015-01-14

    High-energy and high-power Li-ion batteries have been intensively pursued as power sources in electronic vehicles and renewable energy storage systems in smart grids. With this purpose, developing high-performance cathode materials is urgently needed. Here we report an easy and versatile strategy to fabricate high-rate and cycling-stable hierarchical sphered cathode Li1.2Ni0.13Mn0.54Co0.13O2, by using an ionic interfusion method. The sphere-shaped hierarchical cathode is assembled with primary nanoplates with enhanced growth of nanocrystal planes in favor of Li+ intercalation/deintercalation, such as (010), (100), and (110) planes. This material with such unique structural features exhibits outstanding rate capability, cyclability, and high discharge capacities, achieving around 70% (175 mAhg–1) of the capacity at 0.1 C rate within about 2.1 min of ultrafast charging. Such cathode is feasible to construct high-energy and high-power Li-ion batteries.

  2. Preliminary studies of biominerals-coated spinel LiMn2 O4 as a cathode material on electrochemical performances for Li-ion rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Vediappan, Kumaran; Lee, Chang Woo

    2010-05-01

    Lithium manganese oxide (LiMn2O4) is an inexpensive and pollution-free cathode material for Li-ion rechargeable batteries. In this study, spinel LiMn2O4 cathode material was coated with biomineral powders by the mechano-chemical method. In the course of the material synthesis, citric acid and acryl amide were added to serve as a complexing agent and a gelling agent, respectively, followed by a calcination process at 700 °C for 6 h in a high-purity argon atmosphere. The spinel LiMn2O4 and biominerals-coated spinel LiMn2O4 cathode materials were, from diverse viewpoints, characterized by x-ray diffraction, field emission-scanning electron microscopy, Fourier transform infrared spectroscopy and the electrochemical cycling method to understand the mechanism of improvements in electrochemical performances. We suggest that the biominerals-coated spinel LiMn2O4 is a good candidate as a low cost and environmentally friendly cathode material showing the enlarged capacity characteristic of Li-ion rechargeable batteries.

  3. The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Byles, B. W.; Palapati, N. K. R.; Subramanian, A.; Pomerantseva, E.

    2016-04-01

    Single nanowires of two manganese oxide polymorphs (α-MnO2 and todorokite manganese oxide), which display a controlled size variation in terms of their square structural tunnels, were isolated onto nanofabricated platforms using dielectrophoresis. This platform allowed for the measurement of the electronic conductivity of these manganese oxides, which was found to be higher in α-MnO2 as compared to that of the todorokite phase by a factor of ˜46. Despite this observation of substantially higher electronic conductivity in α-MnO2, the todorokite manganese oxide exhibited better electrochemical rate performance as a Li-ion battery cathode. The relationship between this electrochemical performance, the electronic conductivities of the manganese oxides, and their reported ionic conductivities is discussed for the first time, clearly revealing that the rate performance of these materials is limited by their Li+ diffusivity, and not by their electronic conductivity. This result reveals important new insights relevant for improving the power density of manganese oxides, which have shown promise as a low-cost, abundant, and safe alternative for next-generation cathode materials. Furthermore, the presented experimental approach is suitable for assessing a broader family of one-dimensional electrode active materials (in terms of their electronic and ionic conductivities) for both Li-ion batteries and for electrochemical systems utilizing charge-carrying ions beyond Li+.

  4. SEI Formation and Interfacial Stability of a Si Electrode in a LiTDI-Salt Based Electrolyte with FEC and VC Additives for Li-Ion Batteries.

    PubMed

    Lindgren, Fredrik; Xu, Chao; Niedzicki, Leszek; Marcinek, Marek; Gustafsson, Torbjörn; Björefors, Fredrik; Edström, Kristina; Younesi, Reza

    2016-06-22

    An electrolyte based on the new salt, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI), is evaluated in combination with nano-Si composite electrodes for potential use in Li-ion batteries. The additives fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are also added to the electrolyte to enable an efficient SEI formation. By employing hard X-ray photoelectron spectroscopy (HAXPES), the SEI formation and the development of the active material is probed during the first 100 cycles. With this electrolyte formulation, the Si electrode can cycle at 1200 mAh g(-1) for more than 100 cycles at a coulombic efficiency of 99%. With extended cycling, a decrease in Si particle size is observed as well as an increase in silicon oxide amount. As opposed to LiPF6 based electrolytes, this electrolyte or its decomposition products has no side reactions with the active Si material. The present results further acknowledge the positive effects of SEI forming additives. It is suggested that polycarbonates and a high LiF content are favorable components in the SEI over other kinds of carbonates formed by ethylene carbonate (EC) and dimethyl carbonate (DMC) decomposition. This work thus confirms that LiTDI in combination with the investigated additives is a promising salt for Si electrodes in future Li-ion batteries. PMID:27220376

  5. Silicon on conductive self-organized TiO2 nanotubes - A high capacity anode material for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Brumbarov, Jassen; Kunze-Liebhäuser, Julia

    2014-07-01

    The study of high energy density electrode materials is central to the development of Li+-ion batteries. Si is among the most promising anode materials for next generation Li+-ion batteries. Model composite electrodes of self-organized, conductive titania (TiO2-x-C) nanotubes coated with silicon (Si) via plasma enhanced chemical vapor deposition (PECVD) are produced and studied in terms of their lithiation/delithiation characteristics. The nanotube array provides direct one dimensional electron transport to the current collector, without the need of adding binders or conductive additives. Both components of the composite can be lithiated delivering 120 μAh cm-2 total capacity for a film thickness of 1 μm and a Si loading of ∼10 wt.%. 86% capacity retention upon 88 cycles at a rate of C/5 and 60 μAh cm-2 total capacity at a rate of 10 C are achieved owing to the low lateral expansion and thus good adhesion of the thin Si coating to the TiO2-x-C nanotubes, and due to the formation of a stable solid electrolyte interface (SEI) in ethylene-carbonate (EC), dimethyl-carbonate (DMC), vinylene-carbonate (VC) electrolyte with 1 M LiPF6.

  6. The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries

    DOE PAGESBeta

    Byles, B. W.; Palapati, N. K. R.; Subramanian, A.; Pomerantseva, E.

    2016-04-29

    Single nanowires of two manganese oxide polymorphs (α-MnO2 and todorokite manganese oxide), which display a controlled size variation in terms of their square structural tunnels, were isolated onto nanofabricated platforms using dielectrophoresis. This platform allowed for the measurement of the electronic conductivity of these manganese oxides, which was found to be higher in α-MnO2 as compared to that of the todorokite phase by a factor of similar to 46. Despite this observation of substantially higher electronic conductivity in α-MnO2, the todorokite manganese oxide exhibited better electrochemical rate performance as a Li-ion battery cathode. The relationship between this electrochemical performance, themore » electronic conductivities of the manganese oxides, and their reported ionic conductivities is discussed for the first time, clearly revealing that the rate performance of these materials is limited by their Li+ diffusivity, and not by their electronic conductivity. This result reveals important new insights relevant for improving the power density of manganese oxides, which have shown promise as a low-cost, abundant, and safe alternative for next-generation cathode materials. Moreover, the presented experimental approach is suitable for assessing a broader family of one-dimensional electrode active materials (in terms of their electronic and ionic conductivities) for both Li-ion batteries and for electrochemical systems utilizing charge-carrying ions beyond Li+.« less

  7. FeF3@Thin Nickel Ammine Nitrate Matrix: Smart Configurations and Applications as Superior Cathodes for Li-Ion Batteries.

    PubMed

    Jiang, Jian; Li, Linpo; Xu, Maowen; Zhu, Jianhui; Li, Chang Ming

    2016-06-29

    Iron fluorides (FeFx) for Li-ion battery cathodes are still in the stage of intensive research due to their low delivery capacity and limited lifetime. One critical reason for cathode degradation is the severe aggregation of FeFx nanocrystals upon long-term cycling. To maximize the capacity and cyclability of these cathodes, we propose herein a novel and applicable method using a thin-layered nickel ammine nitrate (NAN) matrix as a feasible encapsulation material to disperse the FeF3 nanoparticles. Such core-shell hybrids with smart configurations are constructed via a green, scalable, in situ encapsulation approach. The outer thin-film NAN matrix with prominent electrochemical stability can keep the FeF3 nanoactives encapsulated throughout the cyclic testing, protecting them from adverse aggregation into bulk crystals and thus leading to drastic improvements of electrode behaviors (e.g., high electrode capacity up to ∼423 mA h g(-1), greatly prolonged cyclic period, and promoted rate capabilities). This present work may set up a new and general platform to develop intriguing core-shell hybrid cathodes for Li-ion batteries, not only for FeFx but also for a wide spectrum of other cathode materials. PMID:27269361

  8. Percolation threshold of graphene nanosheets as conductive additives in Li4Ti5O12 anodes of Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Biao; Yu, Yang; Liu, Yusi; Huang, Zhen-Dong; He, Yan-Bing; Kim, Jang-Kyo

    2013-02-01

    Graphene nanosheets (GNSs) have been considered as potential conductive additives for electrodes in Li-ion batteries to replace the existing carbon black (CB). Graphene has exceptionally high aspect ratio and excellent electrical conductivity, enabling the formation of extensive conductive networks at a much lower content than CB. This paper reports the beneficial effects of GNSs with a low percolation threshold on electrochemical performance of Li4Ti5O12 (LTO) anodes. The experimental results show that the GNSs with a diameter of 46 μm and a thickness of 4.5 nm have a percolation threshold of 1.8 wt%. The prediction based on the interparticle distance concept gives a percolation threshold of 0.54 wt% for GNSs, which is almost an order of magnitude lower than that for CB particles. The substantially low percolation along with a high electrical conductivity of GNSs explains why the LTO anodes containing only 5 wt% GNSs deliver a much better rate capability than those with 15 wt% CB. However, a higher GNS content of 10 wt% results in re-stacking GNSs, deteriorating the diffusion of Li ions through the thickness of GNSs. The parametric study indicates that the percolation threshold of GNSs is inversely proportional to the aspect ratio of GNSs.Graphene nanosheets (GNSs) have been considered as potential conductive additives for electrodes in Li-ion batteries to replace the existing carbon black (CB). Graphene has exceptionally high aspect ratio and excellent electrical conductivity, enabling the formation of extensive conductive networks at a much lower content than CB. This paper reports the beneficial effects of GNSs with a low percolation threshold on electrochemical performance of Li4Ti5O12 (LTO) anodes. The experimental results show that the GNSs with a diameter of 46 μm and a thickness of 4.5 nm have a percolation threshold of 1.8 wt%. The prediction based on the interparticle distance concept gives a percolation threshold of 0.54 wt% for GNSs, which is almost

  9. Mesocarbon Microbead Carbon-Supported Magnesium Hydroxide Nanoparticles: Turning Spent Li-ion Battery Anode into a Highly Efficient Phosphate Adsorbent for Wastewater Treatment.

    PubMed

    Zhang, Yan; Guo, Xingming; Wu, Feng; Yao, Ying; Yuan, Yifei; Bi, Xuanxuan; Luo, Xiangyi; Shahbazian-Yassar, Reza; Zhang, Cunzhong; Amine, Khalil

    2016-08-24

    Phosphorus in water eutrophication has become a serious problem threatening the environment. However, the development of efficient adsorbents for phosphate removal from water is lagging. In this work, we recovered the waste material, graphitized carbon, from spent lithium ion batteries and modified it with nanostructured Mg(OH)2 on the surface to treat excess phosphate. This phosphate adsorbent shows one of the highest phosphate adsorption capacities to date, 588.4 mg/g (1 order of magnitude higher than previously reported carbon-based adsorbents), and exhibits decent stability. A heterogeneous multilayer adsorption mechanism was proposed on the basis of multiple adsorption results. This highly efficient adsorbent from spent Li-ion batteries displays great potential to be utilized in industry, and the mechanism study paved a way for further design of the adsorbent for phosphate adsorption. PMID:27463402

  10. Assessment of Various Low Temperature Electrolytes in Prototype Li-Ion Cells Developed for ESMD Applications

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Whitcanack, L. D.

    2008-01-01

    Due to their attractive properties and proven success, Li-ion batteries have become identified as the battery chemistry of choice for a number of future NASA missions. A number of these applications would be greatly benefited by improved performance of Li-ion technology over a wider operating temperature range, especially at low temperatures, such as future ESMD missions. In many cases, these technology improvements may be mission enabling, and at the very least mission enhancing. In addition to aerospace applications, the DoE has interest in developing advanced Li-ion batteries that can operate over a wide temperature range to enable terrestrial HEV applications. Thus, our focus at JPL in recent years has been to extend the operating temperature range of Li-ion batteries, especially at low temperatures. To accomplish this, the main focus of the research has been devoted to developing improved lithium-ion conducting electrolytes. In the present paper, we would like to present some of the results we have obtained with six different ethylene carbonate-based electrolytes optimized for low temperature. In addition to investigating the behavior in experimental cells initially, the performance of these promising low temperature electrolytes was demonstrated in large capacity, aerospace quality Li-ion prototype cells, manufactured by Yardney Technical Products and Saft America, Inc. These cells were subjected to a number of performance tests, including discharge rate characterization, charge rate characterization, cycle life performance at various temperatures, and power characterization tests.

  11. Nanocarbon networks for advanced rechargeable lithium batteries.

    PubMed

    Xin, Sen; Guo, Yu-Guo; Wan, Li-Jun

    2012-10-16

    Carbon is one of the essential elements in energy storage. In rechargeable lithium batteries, researchers have considered many types of nanostructured carbons, such as carbon nanoparticles, carbon nanotubes, graphene, and nanoporous carbon, as anode materials and, especially, as key components for building advanced composite electrode materials. Nanocarbons can form efficient three-dimensional conducting networks that improve the performance of electrode materials suffering from the limited kinetics of lithium storage. Although the porous structure guarantees a fast migration of Li ions, the nanocarbon network can serve as an effective matrix for dispersing the active materials to prevent them from agglomerating. The nanocarbon network also affords an efficient electron pathway to provide better electrical contacts. Because of their structural stability and flexibility, nanocarbon networks can alleviate the stress and volume changes that occur in active materials during the Li insertion/extraction process. Through the elegant design of hierarchical electrode materials with nanocarbon networks, researchers can improve both the kinetic performance and the structural stability of the electrode material, which leads to optimal battery capacity, cycling stability, and rate capability. This Account summarizes recent progress in the structural design, chemical synthesis, and characterization of the electrochemical properties of nanocarbon networks for Li-ion batteries. In such systems, storage occurs primarily in the non-carbon components, while carbon acts as the conductor and as the structural buffer. We emphasize representative nanocarbon networks including those that use carbon nanotubes and graphene. We discuss the role of carbon in enhancing the performance of various electrode materials in areas such as Li storage, Li ion and electron transport, and structural stability during cycling. We especially highlight the use of graphene to construct the carbon conducting

  12. Percolation threshold of graphene nanosheets as conductive additives in Li4Ti5O12 anodes of Li-ion batteries.

    PubMed

    Zhang, Biao; Yu, Yang; Liu, Yusi; Huang, Zhen-Dong; He, Yan-bing; Kim, Jang-Kyo

    2013-03-01

    Graphene nanosheets (GNSs) have been considered as potential conductive additives for electrodes in Li-ion batteries to replace the existing carbon black (CB). Graphene has exceptionally high aspect ratio and excellent electrical conductivity, enabling the formation of extensive conductive networks at a much lower content than CB. This paper reports the beneficial effects of GNSs with a low percolation threshold on electrochemical performance of Li(4)Ti(5)O(12) (LTO) anodes. The experimental results show that the GNSs with a diameter of 46 μm and a thickness of 4.5 nm have a percolation threshold of 1.8 wt%. The prediction based on the interparticle distance concept gives a percolation threshold of 0.54 wt% for GNSs, which is almost an order of magnitude lower than that for CB particles. The substantially low percolation along with a high electrical conductivity of GNSs explains why the LTO anodes containing only 5 wt% GNSs deliver a much better rate capability than those with 15 wt% CB. However, a higher GNS content of 10 wt% results in re-stacking GNSs, deteriorating the diffusion of Li ions through the thickness of GNSs. The parametric study indicates that the percolation threshold of GNSs is inversely proportional to the aspect ratio of GNSs. PMID:23381093

  13. Percolation-tunneling modeling for the study of the electric conductivity in LiFePO 4 based Li-ion battery cathodes

    NASA Astrophysics Data System (ADS)

    Awarke, Ali; Lauer, Sven; Pischinger, Stefan; Wittler, Michael

    In this work a percolation-tunneling based model is developed and used to study the electrical conductivity of LiFePO 4 composite Li-ion battery cathodes. The active and conductive additive particles are explicitly represented using a random hybrid geometric-mechanical packing algorithm, while the inter-particle electric transport is achieved by including electron tunneling effects. The model is adjusted to the experimental data of a PVDF/C composite with different mixing ratios. The performed study aims to capture the variation of the conductivity of the LiFePO 4 cathode with particle sizes, carbon black particles wt.% and carbon coating wt.%. It is found that ultra fine carbon-free nanosized particles (∼50 nm), which are favorable for improved diffusion, would require a relatively high amount of carbon black (15 wt.%) putting at risk the gravimetric capacity of the cell. On the other hand, particles with 1 wt.% continuous carbon coating delivers already sufficient conductivity for all particle sizes without any additives. The further addition of conductive phases is at the risk of redundancy in view of conductivity enhancements. Although continuous carbon coating with loading as low as 1 wt.% is thought to be the most efficient way to achieve electric conductivity, its manufacturability and effect on Li ion diffusion remain to be assessed.

  14. Enhancing the energy density of safer Li-ion batteries by combining high-voltage lithium cobalt fluorophosphate cathodes and nanostructured titania anodes

    PubMed Central

    Ortiz, Gregorio F.; López, María C.; Li, Yixiao; McDonald, Matthew J.; Cabello, Marta; Tirado, José L.; Yang, Yong

    2016-01-01

    Recently, Li-ion batteries have been heavily scrutinized because of the apparent incompatibility between safety and high energy density. This work report a high voltage full battery made with TiO2/Li3PO4/Li2CoPO4F. The Li2CoPO4F cathode and TiO2 anode materials are synthesized by a sol–gel and anodization methods, respectively. X-ray diffraction (XRD) analysis confirmed that Li2CoPO4F is well-crystallized in orthorhombic crystal structure with Pnma space group. The Li3PO4-coated anode was successfully deposited as shown by the (011) lattice fringes of anatase TiO2 and (200) of γ-Li3PO4, as detected by HRTEM. The charge profile of Li2CoPO4F versus lithium shows a plateau at 5.0 V, revealing its importance as potentially high-voltage cathode and could perfectly fit with the plateau of anatase anode (1.8–1.9 V). The full cell made with TiO2/Li3PO4/Li2CoPO4F delivered an initial reversible capacity of 150 mA h g−1 at C rate with good cyclic performance at an average potential of 3.1–3.2 V. Thus, the full cell provides an energy density of 472 W h kg−1. This full battery behaves better than TiO2/Li2CoPO4F. The introduction of Li3PO4 as buffer layer is expected to help the cyclability of the electrodes as it allows a rapid Li-ion transport. PMID:26879916

  15. Enhancing the energy density of safer Li-ion batteries by combining high-voltage lithium cobalt fluorophosphate cathodes and nanostructured titania anodes

    NASA Astrophysics Data System (ADS)

    Ortiz, Gregorio F.; López, María C.; Li, Yixiao; McDonald, Matthew J.; Cabello, Marta; Tirado, José L.; Yang, Yong

    2016-02-01

    Recently, Li-ion batteries have been heavily scrutinized because of the apparent incompatibility between safety and high energy density. This work report a high voltage full battery made with TiO2/Li3PO4/Li2CoPO4F. The Li2CoPO4F cathode and TiO2 anode materials are synthesized by a sol-gel and anodization methods, respectively. X-ray diffraction (XRD) analysis confirmed that Li2CoPO4F is well-crystallized in orthorhombic crystal structure with Pnma space group. The Li3PO4-coated anode was successfully deposited as shown by the (011) lattice fringes of anatase TiO2 and (200) of γ-Li3PO4, as detected by HRTEM. The charge profile of Li2CoPO4F versus lithium shows a plateau at 5.0 V, revealing its importance as potentially high-voltage cathode and could perfectly fit with the plateau of anatase anode (1.8-1.9 V). The full cell made with TiO2/Li3PO4/Li2CoPO4F delivered an initial reversible capacity of 150 mA h g-1 at C rate with good cyclic performance at an average potential of 3.1-3.2 V. Thus, the full cell provides an energy density of 472 W h kg-1. This full battery behaves better than TiO2/Li2CoPO4F. The introduction of Li3PO4 as buffer layer is expected to help the cyclability of the electrodes as it allows a rapid Li-ion transport.

  16. Enhancing the energy density of safer Li-ion batteries by combining high-voltage lithium cobalt fluorophosphate cathodes and nanostructured titania anodes.

    PubMed

    Ortiz, Gregorio F; López, María C; Li, Yixiao; McDonald, Matthew J; Cabello, Marta; Tirado, José L; Yang, Yong

    2016-01-01

    Recently, Li-ion batteries have been heavily scrutinized because of the apparent incompatibility between safety and high energy density. This work report a high voltage full battery made with TiO2/Li3PO4/Li2CoPO4F. The Li2CoPO4F cathode and TiO2 anode materials are synthesized by a sol-gel and anodization methods, respectively. X-ray diffraction (XRD) analysis confirmed that Li2CoPO4F is well-crystallized in orthorhombic crystal structure with Pnma space group. The Li3PO4-coated anode was successfully deposited as shown by the (011) lattice fringes of anatase TiO2 and (200) of γ-Li3PO4, as detected by HRTEM. The charge profile of Li2CoPO4F versus lithium shows a plateau at 5.0 V, revealing its importance as potentially high-voltage cathode and could perfectly fit with the plateau of anatase anode (1.8-1.9 V). The full cell made with TiO2/Li3PO4/Li2CoPO4F delivered an initial reversible capacity of 150 mA h g(-1) at C rate with good cyclic performance at an average potential of 3.1-3.2 V. Thus, the full cell provides an energy density of 472 W h kg(-1). This full battery behaves better than TiO2/Li2CoPO4F. The introduction of Li3PO4 as buffer layer is expected to help the cyclability of the electrodes as it allows a rapid Li-ion transport. PMID:26879916

  17. Electrolyte Mixtures Based on Ethylene Carbonate and Dimethyl Sulfone for Li-Ion Batteries with Improved Safety Characteristics.

    PubMed

    Hofmann, Andreas; Migeot, Matthias; Thißen, Eva; Schulz, Michael; Heinzmann, Ralf; Indris, Sylvio; Bergfeldt, Thomas; Lei, Boxia; Ziebert, Carlos; Hanemann, Thomas

    2015-06-01

    In this study, novel electrolyte mixtures for Li-ion cells are presented with highly improved safety features. The electrolyte formulations are composed of ethylene carbonate/dimethyl sulfone (80:20 wt/wt) as the solvent mixture and LiBF4 , lithium bis(trifluoromethanesulfonyl)azanide, and lithium bis(oxalato)borate as the conducting salts. Initially, the electrolytes are characterized with regard to their physical properties, their lithium transport properties, and their electrochemical stability. The key advantages of the electrolytes are high flash points of >140 °C, which enhance significantly the intrinsic safety of Li-ion cells containing these electrolytes. This has been quantified by measurements in an accelerating rate calorimeter. By using the newly developed electrolytes, which are liquid down to T=-10 °C, it is possible to achieve C-rates of up to 1.5 C with >80 % of the initial specific capacity. During 100 cycles in cell tests (graphite||LiNi1/3 Co1/3 Mn1/3 O2 ), it is proven that the retention of the specific capacity is >98 % of the third discharge cycle with dependence on the conducting salt. The best electrolyte mixture yields a capacity retention of >96 % after 200 cycles in coin cells. PMID:25950145

  18. Eutectic Nano-Droplet Template Injection into Bulk Silicon to Construct Porous Frameworks with Concomitant Conformal Coating as Anodes for Li-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Qu, Fei; Li, Chilin; Wang, Zumin; Wen, Yuren; Richter, Gunther; Strunk, Horst P.

    2015-05-01

    Building porosity in monolithic materials is highly desired to design 3D electrodes, however ex-situ introduction or in-situ generation of nano-scale sacrificial template is still a great challenge. Here Al-Si eutectic droplet templates are uniformly injected into bulk Si through Al-induced solid-solid convection to construct a highly porous Si framework. This process is concomitant with process-inherent conformal coating of ion-conductive oxide. Such an all-in-one method has generated a (continuously processed) high-capacity Si anode integrating longevity and stable electrolyte-anode diaphragm for Li-ion batteries (e.g. a reversible capacity as large as ~1800 mAh/g or ~350 μAh/cm2-μm with a CE of ~99% at 0.1 C after long-term 400 cycles).

  19. From Dispersed Microspheres to Interconnected Nanospheres: Carbon-Sandwiched Monolayered MoS2 as High-Performance Anode of Li-Ion Batteries.

    PubMed

    Shao, Jie; Qu, Qunting; Wan, Zhongming; Gao, Tian; Zuo, Zhichen; Zheng, Honghe

    2015-10-21

    Hierarchical structured carbon@MoS2 (C@MoS2) microspheres and nanospheres composed of carbon-sandwiched monolayered MoS2 building blocks are synthesized through a facile one-pot polyvinylpyrrolidone (PVP) micelle-assisted hydrothermal route. The dimension and carbon content of C@MoS2 spheres are effectively controlled by singly adjusting the concentration of PVP, which plays the dual functions of soft-template and carbon source. As the anode materials of Li-ion batteries, C@MoS2 nanospheres present considerably higher capacity, better rate behavior and cycling stability than C@MoS2 microspheres. The reasons are attributed to the unique interconnected nanospherical morphology and the internal hierarchical construction of C@MoS2 nanospheres with expanded MoS2/carbon interlayer spacing. PMID:26426361

  20. CuO single crystal with exposed {001} facets - A highly efficient material for gas sensing and Li-ion battery applications

    PubMed Central

    Su, Dawei; Xie, Xiuqiang; Dou, Shixue; Wang, Guoxiu

    2014-01-01

    Single crystal copper oxide nanoplatelets with a high percentage of {001} facets were synthesized by a facile hydrothermal approach. The as-prepared materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, and high resolution transmission microscopy. Via density functional theory calculations, it was found that the {001} facets are active crystal planes. When the single crystal CuO nanoplatelets were applied as an anode material in Li-ion batteries, they demonstrated outstanding electrochemical performance with high lithium storage capacity, satisfactory cyclability, and excellent high rate capacity. When used as a sensing material in gas sensors, they exhibited a superior sensitivity towards toxic and flammable gases. PMID:25169039

  1. High-rate aluminium yolk-shell nanoparticle anode for Li-ion battery with long cycle life and ultrahigh capacity

    NASA Astrophysics Data System (ADS)

    Li, Sa; Niu, Junjie; Zhao, Yu Cheng; So, Kang Pyo; Wang, Chao; Wang, Chang An; Li, Ju

    2015-08-01

    Alloy-type anodes such as silicon and tin are gaining popularity in rechargeable Li-ion batteries, but their rate/cycling capabilities should be improved. Here by making yolk-shell nanocomposite of aluminium core (30 nm in diameter) and TiO2 shell (~3 nm in thickness), with a tunable interspace, we achieve 10 C charge/discharge rate with reversible capacity exceeding 650 mAh g-1 after 500 cycles, with a 3 mg cm-2 loading. At 1 C, the capacity is approximately 1,200 mAh g-1 after 500 cycles. Our one-pot synthesis route is simple and industrially scalable. This result may reverse the lagging status of aluminium among high-theoretical-capacity anodes.

  2. A dimensionally stable and fast-discharging graphite-silicon composite Li-ion battery anode enabled by electrostatically self-assembled multifunctional polymer-blend coating.

    PubMed

    Li, Fu-Sheng; Wu, Yu-Shiang; Chou, Jackey; Wu, Nae-Lih

    2015-05-18

    A high-performance graphite-Si composite anode for Li-ion batteries containing Si nanoparticles (NPs) attached onto graphite microparticles was synthesized by adopting a polymer-blend of poly(diallyl dimethyl-ammonium chloride) and poly(sodium 4-styrenesulfonate). The polymer-blend enabled uniform distribution of Si NPs during synthesis and served as a robust artificial solid-electrolyte interphase that substantially enhanced the cycle stability and rate performance of the composite electrode. The electrode exhibited a specific capacity of 450 mA h g(-1), 96% capacity retention at a 10 C-rate, 95% retention after 200 cycles, and the same electrode expansion behavior as a pristine graphite electrode. PMID:25656469

  3. High-rate aluminium yolk-shell nanoparticle anode for Li-ion battery with long cycle life and ultrahigh capacity

    PubMed Central

    Li, Sa; Niu, Junjie; Zhao, Yu Cheng; So, Kang Pyo; Wang, Chao; Wang, Chang An; Li, Ju

    2015-01-01

    Alloy-type anodes such as silicon and tin are gaining popularity in rechargeable Li-ion batteries, but their rate/cycling capabilities should be improved. Here by making yolk-shell nanocomposite of aluminium core (30 nm in diameter) and TiO2 shell (∼3 nm in thickness), with a tunable interspace, we achieve 10 C charge/discharge rate with reversible capacity exceeding 650 mAh g−1 after 500 cycles, with a 3 mg cm−2 loading. At 1 C, the capacity is approximately 1,200 mAh g−1 after 500 cycles. Our one-pot synthesis route is simple and industrially scalable. This result may reverse the lagging status of aluminium among high-theoretical-capacity anodes. PMID:26243004

  4. Mesoporous anatase TiO2 nanorods as thermally robust anode materials for Li-ion batteries: detailed insight into the formation mechanism.

    PubMed

    Seisenbaeva, Gulaim A; Nedelec, Jean-Marie; Daniel, Geoffrey; Tiseanu, Carmen; Parvulescu, Vasile; Pol, Vilas G; Abrego, Luis; Kessler, Vadim G

    2013-12-16

    Uniformly mesoporous and thermally robust anatase nanorods were produced with quantitative yield by a simple and efficient one-step approach. The mechanism of this process was revealed by insertion of Eu(3+) cations from the reaction medium as luminescent probes. The obtained structure displays an unusually high porosity, an active surface area of about 300 m(2) g(-1) and a specific capacity of 167 mA h g(-1) at a C/3 rate, making it attractive as an anode electrode for Li-ion batteries. An additional attractive feature is its remarkable thermal stability; heating to 400 °C results in a decrease in the active surface area to a still relatively high value of 110 m(2) g(-1) with conservation of open mesoporosity. Thermal treatment at 800 °C or higher, however, causes transformation into a non-porous rutile monolith, as commonly observed with nanoscale titania. PMID:24243542

  5. Eutectic Nano-Droplet Template Injection into Bulk Silicon to Construct Porous Frameworks with Concomitant Conformal Coating as Anodes for Li-Ion Batteries

    PubMed Central

    Qu, Fei; Li, Chilin; Wang, Zumin; Wen, Yuren; Richter, Gunther; Strunk, Horst P.

    2015-01-01

    Building porosity in monolithic materials is highly desired to design 3D electrodes, however ex-situ introduction or in-situ generation of nano-scale sacrificial template is still a great challenge. Here Al-Si eutectic droplet templates are uniformly injected into bulk Si through Al-induced solid-solid convection to construct a highly porous Si framework. This process is concomitant with process-inherent conformal coating of ion-conductive oxide. Such an all-in-one method has generated a (continuously processed) high-capacity Si anode integrating longevity and stable electrolyte-anode diaphragm for Li-ion batteries (e.g. a reversible capacity as large as ~1800 mAh/g or ~350 μAh/cm2-μm with a CE of ~99% at 0.1 C after long-term 400 cycles). PMID:25988370

  6. Eutectic nano-droplet template injection into bulk silicon to construct porous frameworks with concomitant conformal coating as anodes for Li-ion batteries.

    PubMed

    Qu, Fei; Li, Chilin; Wang, Zumin; Wen, Yuren; Richter, Gunther; Strunk, Horst P

    2015-01-01

    Building porosity in monolithic materials is highly desired to design 3D electrodes, however ex-situ introduction or in-situ generation of nano-scale sacrificial template is still a great challenge. Here Al-Si eutectic droplet templates are uniformly injected into bulk Si through Al-induced solid-solid convection to construct a highly porous Si framework. This process is concomitant with process-inherent conformal coating of ion-conductive oxide. Such an all-in-one method has generated a (continuously processed) high-capacity Si anode integrating longevity and stable electrolyte-anode diaphragm for Li-ion batteries (e.g. a reversible capacity as large as ~1800 mAh/g or ~350 μAh/cm(2)-μm with a CE of ~99% at 0.1 C after long-term 400 cycles). PMID:25988370

  7. Ternary Cu2SnS3 cabbage-like nanostructures: large-scale synthesis and their application in Li-ion batteries with superior reversible capacity

    NASA Astrophysics Data System (ADS)

    Qu, Baihua; Li, Hongxing; Zhang, Ming; Mei, Lin; Chen, Libao; Wang, Yanguo; Li, Qiuhong; Wang, Taihong

    2011-10-01

    In this paper, novel ternary Cu2SnS3 cabbage-like nanostructures are synthesized on a large scale via a facile solvothermal route. The individual Cu2SnS3 cabbage-like hierarchitecture is constructed from 2D nanosheets with thickness of about 15.6 nm. The Cu2SnS3 electrodes exhibit an initial reversible capacity of 842 mAh g-1 and still reach 621 mAh g-1 after 50 cycles. Such an admirable performance could be related to their 3D porous structural features as well as the high electrical conductivity induced by Cu. The electrochemical properties of the 3D hierarchical nanostructures imply its potential application in high energy density Li-ion batteries.

  8. High-rate aluminium yolk-shell nanoparticle anode for Li-ion battery with long cycle life and ultrahigh capacity.

    PubMed

    Li, Sa; Niu, Junjie; Zhao, Yu Cheng; So, Kang Pyo; Wang, Chao; Wang, Chang An; Li, Ju

    2015-01-01

    Alloy-type anodes such as silicon and tin are gaining popularity in rechargeable Li-ion batteries, but their rate/cycling capabilities should be improved. Here by making yolk-shell nanocomposite of aluminium core (30 nm in diameter) and TiO2 shell (∼3 nm in thickness), with a tunable interspace, we achieve 10 C charge/discharge rate with reversible capacity exceeding 650 mAh g(-1) after 500 cycles, with a 3 mg cm(-2) loading. At 1 C, the capacity is approximately 1,200 mAh g(-1) after 500 cycles. Our one-pot synthesis route is simple and industrially scalable. This result may reverse the lagging status of aluminium among high-theoretical-capacity anodes. PMID:26243004

  9. Pomegranate-Structured Conversion-Reaction Cathode with a Built-in Li Source for High-Energy Li-Ion Batteries.

    PubMed

    Fan, Xiulin; Zhu, Yujie; Luo, Chao; Suo, Liumin; Lin, Yan; Gao, Tao; Xu, Kang; Wang, Chunsheng

    2016-05-24

    Transition metal fluorides (such as FeF3 or CoF2) promise significantly higher theoretical capacities (>571 mAh g(-1)) than the cathode materials currently used in Li-ion batteries. However, their practical application faces major challenges that include poor electrochemical reversibility induced by the repeated bond-breaking and formation and the accompanied volume changes and the difficulty of building an internal Li source within the material so that a full Li-ion cell could be assembled at a discharged state without inducing further technical risk and cost issues. In this work, we effectively addressed these challenges by designing and synthesizing, via an aerosol-spray pyrolysis technique, a pomegranate-structured nanocomposite FeM/LiF/C (M = Co, Ni), in which 2-3 nm carbon-coated FeM nanoparticles (∼10 nm in diameter) and LiF nanoparticles (∼20 nm) are uniformly embedded in a porous carbon sphere matrix (100-1000 nm). This uniquely architectured nanocomposite was made possible by the extremely short pyrolysis time (∼1 s) and carbon coating in a high-temperature furnace, which prevented the overgrowth of FeM and LiF in the primordial droplet that serves as the carbon source. The presence of Ni or Co in FeM/LiF/C effectively suppresses the formation of Fe3C and further reduces the metallic particle size. The pomegranate architecture ensures the intimate contact among FeM, LiF, and C, thus significantly enhancing the conversion-reaction kinetics, while the nanopores inside the pomegranate-like carbon matrix, left by solvent evaporation during the pyrolysis, effectively accommodate the volume change of FeM/LiF during charge/discharge. Thus, the FeM/LiF/C nanocomposite shows a high specific capacity of >300 mAh g(-1) for more than 100 charge/discharge cycles, which is one of the best performances among all of the prelithiated metal fluoride cathodes ever reported. The pomegranate-structured FeM/LiF/C with its built-in Li source provides an inspiration to the

  10. Original electrochemical mechanisms of CaSnO{sub 3} and CaSnSiO{sub 5} as anode materials for Li-ion batteries

    SciTech Connect

    Mouyane, M.; Womes, M.; Jumas, J.C.; Olivier-Fourcade, J.; Lippens, P.E.

    2011-11-15

    Calcium stannate (CaSnO{sub 3}) and malayaite (CaSnSiO{sub 5}) were synthesized by means of a high temperature solid-state reaction. Their crystal structures and morphologies were characterized by X-ray diffraction (XRD) and Scanning Electron Microscopy; their electrochemical properties were analyzed by galvanostatic tests. The amorphization of the initial electrode materials was followed by XRD. The first discharge of the oxides CaSnO{sub 3} and CaSnSiO{sub 5} shows a plateau at low potential, which is due to the progressive formation of Li-Ca-Sn and/or Li-Sn alloys as shown by {sup 119}Sn Moessbauer spectroscopy. The results reveal similar electrochemical mechanisms for CaSnO{sub 3} and CaSnSiO{sub 5} but they completely differ from those related to SnO{sub 2}. - Graphical abstract: {sup 119}Sn Moessbauer spectra at the end of the first discharge of CaSnO{sub 3} (dashed line) and CaSnSiO{sub 5} (solid line) anodes for Li-ion batteries. Inset shows that relative amounts of Sn(0) based alloys formed during the first discharge are similar for CaSnO{sub 3} and CaSnSiO{sub 5} pristine materials. Highlights: > CaSnSiO{sub 5} and CaSnO{sub 3} as anode materials for Li-ion batteries. > X-ray diffraction and Moessbauer spectroscopy, to explain the electrochemical mechanisms. > Similar mechanisms for the two compounds but different from those of SnO{sub 2} due to Ca.

  11. A facile approach to nanoarchitectured three-dimensional graphene-based Li–Mn–O composite as high-power cathodes for Li-ion batteries

    PubMed Central

    Zhang, Wenyu; Zeng, Yi; Xu, Chen; Xiao, Ni; Gao, Yiben; Li, Lain-Jong; Chen, Xiaodong; Hng, Huey Hoon

    2012-01-01

    Summary We report a facile method to prepare a nanoarchitectured lithium manganate/graphene (LMO/G) hybrid as a positive electrode for Li-ion batteries. The Mn2O3/graphene hybrid is synthesized by exfoliation of graphene sheets and deposition of Mn2O3 in a one-step electrochemical process, which is followed by lithiation in a molten salt reaction. There are several advantages of using the LMO/G as cathodes in Li-ion batteries: (1) the LMO/G electrode shows high specific capacities at high gravimetric current densities with excellent cycling stability, e.g., 84 mAh·g−1 during the 500th cycle at a discharge current density of 5625 mA·g−1 (~38.01 C capacity rating) in the voltage window of 3–4.5 V; (2) the LMO/G hybrid can buffer the Jahn–Teller effect, which depicts excellent Li storage properties at high current densities within a wider voltage window of 2–4.5 V, e.g., 93 mAh·g−1 during the 300th cycle at a discharge current density of 5625 mA·g−1 (~38.01 C). The wider operation voltage window can lead to increased theoretical capacity, e.g., 148 mAh·g−1 between 3 and 4.5 V and 296 mAh·g−1 between 2 and 4.5 V; (3) more importantly, it is found that the attachment of LMO onto graphene can help to reduce the dissolution of Mn2+ into the electrolyte, as indicated by the inductively coupled plasma (ICP) measurements, and which is mainly attributed to the large specific surface area of the graphene sheets. PMID:23019546

  12. Nanoscale coating of LiMO2 (M = Ni, Co, Mn) nanobelts with Li+-conductive Li2TiO3: toward better rate capabilities for Li-ion batteries.

    PubMed

    Lu, Jun; Peng, Qing; Wang, Weiyang; Nan, Caiyun; Li, Lihong; Li, Yadong

    2013-02-01

    By using a novel coating approach based on the reaction between MC(2)O(4)·xH(2)O and Ti(OC(4)H(9))(4), a series of nanoscale Li(2)TiO(3)-coated LiMO(2) nanobelts with varied Ni, Co, and Mn contents was prepared for the first time. The complete, thin Li(2)TiO(3) coating layer strongly adheres to the host material and has a 3D diffusion path for Li(+) ions. It is doped with Ni(2+) and Co(3+) ions in addition to Ti(4+) in LiMO(2), both of which were found to favor Li(+)-ion transfer at the interface. As a result, the coated nanobelts show improved rate, cycling, and thermal capabilities when used as the cathode for Li-ion battery. PMID:23301844

  13. A study of lithium ion intercalation induced fracture of silicon particles used as anode material in Li-ion battery

    SciTech Connect

    Daniel, Claus; Kalnaus, Sergiy; Rhodes, Kevin

    2011-01-01

    The fracture of Si particles due to internal stresses formed during the intercalation of lithium ions was described by means of thermal analogy model and brittle fracture damage parameter. The stresses were calculated following the diffusion equation and equations of elasticity with appropriate volumetric expansion term. The damage parameter takes into account triaxiality of the stress state and change in elasticity upon tension and compression, and represents the probability of fracture under given stress state, - an approach suitable for brittle materials. The results were compared with the acoustic emission data from the experiments on electrochemical cycling of Li ion half-cells with silicon electrodes. A good correlation between experiment and prediction was observed.

  14. Tailored Oxygen Framework of Li4Ti5O12 Nanorods for High-Power Li Ion Battery.

    PubMed

    Song, Kyeongse; Seo, Dong-Hwa; Jo, Mi Ru; Kim, Yong-Il; Kang, Kisuk; Kang, Yong-Mook

    2014-04-17

    Here we designed the kinetically favored Li4Ti5O12 by modifying its crystal structure to improve intrinsic Li diffusivity for high power density. Our first-principles calculations revealed that the substituted Na expanded the oxygen framework of Li4Ti5O12 and facilitated Li ion diffusion in Li4Ti5O12 through 3-D high-rate diffusion pathway secured by Na ions. Accordingly, we synthesized sodium-substituted Li4Ti5O12 nanorods having not only a morphological merit from 1-D nanostructure engineering but also sodium substitution-induced open framework to attain ultrafast Li diffusion. The new material exhibited an outstanding cycling stability and capacity retention even at 200 times higher current density (20 C) compared with the initial condition (0.1 C). PMID:26269981

  15. Combinatorial Study of the Li-Ni-Mn-Co Oxide Pseudoquaternary System for Use in Li-Ion Battery Materials Research.

    PubMed

    Brown, Colby R; McCalla, Eric; Watson, Cody; Dahn, J R

    2015-06-01

    Combinatorial synthesis has proven extremely effective in screening for new battery materials for Li-ion battery electrodes. Here, a study in the Li-Ni-Mn-Co-O system is presented, wherein samples with nearly 800 distinct compositions were prepared using a combinatorial and high-throughput method to screen for single-phase materials of high interest as next generation positive electrode materials. X-ray diffraction is used to determine the crystal structure of each sample. The Gibbs' pyramid representing the pseudoquaternary system was studied by making samples within three distinct pseudoternary planes defined at fractional cobalt metal contents of 10%, 20%, and 30% within the Li-Ni-Mn-Co-O system. Two large single-phase regions were observed in the system: the layered region (ordered rocksalt) and cubic spinel region; both of which are of interest for next-generation positive electrodes in lithium-ion batteries. These regions were each found to stretch over a wide range of compositions within the Li-Ni-Mn-Co-O pseudoquaternary system and had complex coexistence regions existing between them. The sample cooling rate was found to have a significant effect on the position of the phase boundaries of the single-phase regions. The results of this work are intended to guide further research by narrowing the composition ranges worthy of study and to illustrate the broad range of applications where solution-based combinatorial synthesis can have significant impact. PMID:25970448

  16. Role of Ce and In doping in the performance of LiFePO4 cathode material for Li ion Batteries

    NASA Astrophysics Data System (ADS)

    Mandal, Balaji; Nazri, Mariam; Vaishnava, Prem P.; Naik, Vaman M.; Nazri, Gholam A.; Naik, Ratna

    2012-02-01

    Recently, the olivine LiFePO4 has attracted attention as a promising cathode material for Li ion batteries. However, its poor electronic conductivity is a major challenge for its industrial applications. Different approaches have been taken to address this problem. Here, we report a method of improving its conductivity by doping In and Ce ions at the Fe site. We prepared the samples by sol-gel method followed by annealing at 650 C in Ar (95%) +H2(5%) atmosphere for 5 hrs. XRD and Raman spectroscopy confirm that the olivine structure remains unchanged upon doping with In and Ce up to 5 wt%. XRD analysis shows the values of the lattice parameters increase with doping as the ionic radii of Ce and In ions are larger than that of the Fe^2+ ion. This observation also suggests that both Ce and In ions replace Fe ions and not the Li ions in the material. Upon doping, ionic conductivity was found to increase from 10-9 to 10-4 Ohm-1cm-1. Interestingly, Ce doped LiFePO4 showed a higher conductivity than In doped LiFePO4. SEM measurements show a bigger grain size of ˜300-500 nm in doped LiFePO4 which decreased to ˜50 nm when the materials were synthesized using 0.25M lauric acid as a precursor. The electrochemical characteristics of the doped LiFePO4 along with conductivity and Raman data will be presented.

  17. Platform Li-Ion Battery Risk Assessment Tool: Cooperative Research and Development Final Report, CRADA Number CRD-01-406

    SciTech Connect

    Santhanagopalan, S.

    2012-07-01

    The pressure within a lithium-ion cell changes due to various chemical reactions. When a battery undergoes an unintended short circuit, the pressure changes are drastic - and often lead to uncontrolled failure of the cells. As part of work for others with Oceanit Laboratories Inc. for the NAVY STTR, NREL built Computational Fluid Dynamic (CFD) simulations that can identify potential weak spots in the battery during such events, as well as propose designs to control violent failure of batteries.

  18. Platform Li-Ion Battery Risk Assessment Tool: Cooperative Research and Development Final Report, CRADA Number CRD-10-407

    SciTech Connect

    Smith, K.

    2012-01-01

    Creare was awarded a Phase 1 STTR contract from the US Office of Naval Research, with a seven month period of performance from 6/28/2010 to 1/28/2011. The objectives of the STTR were to determine the feasibility of developing a software package for estimating reliability of battery packs, and develop a user interface to allow the designer to assess the overall impact on battery packs and host platforms for cell-level faults. NREL served as sub-tier partner to Creare, providing battery modeling and battery thermal safety expertise.

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

    PubMed

    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. PMID:27303957

  20. Synthesis and extreme rate capability of Si-Al-C-N functionalized carbon nanotube spray-on coatings as Li-ion battery electrode.

    PubMed

    David, Lamuel; Asok, Deepu; Singh, Gurpreet

    2014-09-24

    Silicon-based precursor derived glass-ceramics or PDCs have proven to be an attractive alternative anode material for Li ion batteries. Main challenges associated with PDC anodes are their low electrical conductivity, first cycle loss, and meager C-rate performance. Here, we show that thermal conversion of single source aluminum-modified polysilazane on the surfaces of carbon nanotubes (CNTs) results in a robust Si-Al-C-N/CNT shell/core composite that offers extreme C-rate capability as battery electrode. Addition of Al to the molecular network of Si-C-N improved electrical conductivity of Si-C-N by 4 orders of magnitude, while interfacing with CNTs showed 7-fold enhancement. Further, we present a convenient spray-coating technique for PDC composite electrode preparation that eliminates polymeric binder and conductive agent there-by reducing processing steps and eradicating foreign material in the electrode. The Si-Al-C-N/CNT electrode showed stable charge capacity of 577 mAh g(-1) at 100 mA g(-1) and a remarkable 400 mAh g(-1) at 10,000 mA g(-1), which is the highest reported value for a silazane derived glass-ceramic or nanocomposite electrode. Under symmetric cycling conditions, a high charge capacity of ∼350 mA g(-1) at 1600 mA g(-1) was continuously observed for over 1000 cycles. PMID:25178109

  1. In situ analysis of capacity fade in thin-film anodes for high performance Li-ion all-solid-state batteries

    NASA Astrophysics Data System (ADS)

    Leite, Marina S.; Gong, Chen; Ruzmetov, Dmitry; Talin, A. Alec

    There is still a pressing need to understand how the solid-interfaces in Li-ion all-solid-batteries form, including their chemical composition and electrical characteristics. In order to resolve the origin of the degradation mechanism in Al anodes, we combine in situ scanning electron microscopy in ultra-high vacuum with electrochemical cycling, in addition to ex situ characterization of the morphological, chemical, and electrical changes of the Al anodes upon lithiation. An AlLi alloy capped by a stable Al-Li-O is formed on the top surface of the anode, trapping Li, which results in the capacity fade, from 48.0 to 41.5 μ.Ah/cm2 in two cycles. The addition of a Cu capping layer is insufficient to prevent the device degradation because of the fast Li diffusion within Al. Yet, Si present extremely stable cycling: >92% of capacity retention after 100 cycles, with average Coulombic efficiency of 98%. Our in situ measurements represent a new platform for probing the real-time degradation of electrodes in all-solid-state batteries for energy storage devices.

  2. A morphology, porosity and surface conductive layer optimized MnCo2O4 microsphere for compatible superior Li(+) ion/air rechargeable battery electrode materials.

    PubMed

    Yun, Young Jun; Kim, Jin Kyu; Ju, Ji Young; Unithrattil, Sanjith; Lee, Sun Sook; Kang, Yongku; Jung, Ha-Kyun; Park, Jin-Seong; Im, Won Bin; Choi, Sungho

    2016-03-15

    Uniform surface conductive layers with porous morphology-conserved MnCo2O4 microspheres are successfully synthesized, and their electrochemical performances are thoroughly investigated. It is found that the microwave-assisted hydrothermally grown MnCo2O4 using citric acid as the carbon source shows a maximum Li(+) ion lithiation/delithiation capacity of 501 mA h g(-1) at 500 mA g(-1) with stable capacity retention. Besides, the given microsphere compounds are effectively activated as air cathode catalysts in Li-O2 batteries with reduced charge overpotentials and improved cycling performance. We believe that such an affordable enhanced performance results from the appropriate quasi-hollow nature of MnCo2O4 microspheres, which can effectively mitigate the large volume change of electrodes during Li(+) migration and/or enhance the surface transport of the LiOx species in Li-air batteries. Thus, the rationally designed porous media for the improved Li(+) electrochemical reaction highlight the importance of the 3D macropores, the high specific area and uniformly overcoated conductive layer for the promising Li(+) redox reaction platforms. PMID:26877264

  3. Commercialization of advanced batteries

    SciTech Connect

    Mader, J.

    1996-11-01

    Mader and Associates has been working as a contractor for the South Coast Air Quality Management District (District) for the past several years. During this period it has performed various assessments of advanced battery technology as well as established the Advanced Battery Task Force. The following paper is Mader`s view of the status of battery technologies that are competing for the electric vehicle (EV) market being established by the California Air Resources Board`s Zero Emission Vehicle (ZEV) Mandate. The ZEV market is being competed for by various advanced battery technologies. And, given the likelihood of modifications to the Mandate, the most promising technologies should capture the following market share during the initial 10 years: Lead-Acid--8.4%, Nickel Metal Hydride--50.8%, Sodium Sulfur--7.8%, Lithium Ion 33.0%.

  4. Cathodically induced antimony for rechargeable Li-ion and Na-ion batteries: The influences of hexagonal and amorphous phase

    NASA Astrophysics Data System (ADS)

    Yang, Yingchang; Yang, Xuming; Zhang, Yan; Hou, Hongshuai; Jing, Mingjun; Zhu, Yirong; Fang, Laibing; Chen, Qiyuan; Ji, Xiaobo

    2015-05-01

    Cathodic corrosion, a green electrochemical method, has been employed to obtain Sb nanomaterials utilized as anode material for lithium-ion batteries and sodium-ion batteries. Interestingly, two different corrosion mechanisms are found, coming from the impact of electrolyte, resulting in the formation of hexagonal and amorphous Sb in aqueous and organic solution, respectively. With the help of water-soluble carboxymethyl cellulose binder and the electrolyte additive fluoroethylene carbonate, both hexagonal and amorphous Sb electrodes exhibit good cycling stability when utilized as anode materials for lithium-ion batteries and sodium-ion batteries. Additionally, both the hexagonal and amorphous Sb electrodes show very good rate capability in lithium-ion batteries. Even at high current density (2000 mA g-1), the hexagonal and amorphous Sb give reversible capacities of 422 and 379 mA h g-1, respectively. Surprisingly, when used as anode materials for sodium-ion batteries, the hexagonal Sb electrode exhibits a good rate performance of 632, 625, 569, 515 and 426 mA h g-1 at a current density of 100, 200, 500, 1000, and 2000 mA g-1, respectively. However, limited rate performance is observed from the amorphous Sb electrode in case of sodium-ion battery due to the large impedance.

  5. Effets du vieillisement de la batterie Li-ion sur les performances d'un vehicule recreatif hybride branchable a trois roues

    NASA Astrophysics Data System (ADS)

    Nadeau, Jonathan

    La prediction de l'evolution du vieillissement de la batterie lithium-ion est source d'un grand defi, dans les applications liees aux vehicules electriques et hybrides. Sa meconnaissance est un risque considerable compromettant la viabilite d'un tel systeme. Invoquant les couts substantiels de la densite d'energie, liee a la degradation considerable des performances de la batterie au cours de sa duree de vie, il devient important d'en tenir compte des le processus de conception. La dependance de la strategie de controle du vehicule aux parametres de la batterie justifie aussi la necessite d'une telle prediction. Il est connu que le vieillissement, sensible aux facteurs tels que le courant, la temperature et la profondeur de decharge, a un impact considerable sur la perte de capacite de la batterie ainsi que sur l'augmentation de la resistance interne. Le premier est directement lie a l'autonomie electrique du vehicule, alors que le second mene a une surchauffe de la batterie, a une augmentation des pertes en puissance qui se manifeste par une diminution de la tension de bus. A cet egard, implique dans la conception d'un vehicule recreatif hybride branchable a trois roues, le Centre de Technologies Avancees s'interesse a l'etude du vieillissement de la batterie Li-ion pour une telle application. Pour ce faire, au contraire de la plupart des estimations empiriques de la duree de vie, basees sur des profils de decharge a courant constant, un profil de courant plus approprie pour l'application donnee, base sur un cycle de vitesse representatif de la conduite d'une motocyclette, a ete utilise. Par le biais d'un simulateur complet du vehicule, le cycle de courant a ete extrait du cycle de vitesse. Ainsi, les travaux menes impliquent l'analyse experimentale de la decharge cyclique de quatre cellules LiFePO 4. Pendant plus de 1400 cycles, un banc d'essai complet a permis l'acquisition de la capacite, de la resistance interne, du courant, de la tension ainsi que de la

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

    SciTech Connect

    Gu, Meng; Yan, Pengfei; Wang, Chongmin; Shi, Wei; Zheng, Jianming; Zhang, Ji-guang

    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.

  7. PHEV/EV Li-Ion Battery Second-Use Project, NREL (National Renewable Energy Laboratory) (Poster)

    SciTech Connect

    Newbauer, J.; Pesaran, A.

    2010-05-01

    Plug-in hybrid electric vehicles (PHEVs) and full electric vehicles (Evs) have great potential to reduce U.S. dependence on foreign oil and emissions. Battery costs need to be reduced by ~50% to make PHEVs cost competitive with conventional vehicles. One option to reduce initial costs is to reuse the battery in a second application following its retirement from automotive service and offer a cost credit for its residual value.

  8. Electrolytes for advanced batteries

    NASA Astrophysics Data System (ADS)

    Blomgren, George E.

    The choices of the components of the electrolyte phase for advanced batteries (lithium and lithium ion batteries) are very sensitive to the electrodes which are used. There are also a number of other requirements for the electrolyte phase, which depend on the cell design and the materials chosen for the battery. The difficulty of choice is compounded when the cell is a rechargeable one. This paper looks at each of these requirements and the degree to which they are met for lithium and lithium ion batteries. The discussion is broken into sections on anode or negative electrode stability requirements, cathode or positive electrode stability requirements, conductivity needs, viscosity and wetting requirements. The effects of these properties and interactions on the performance of batteries are also discussed.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Energy-savvy solid-state and sonochemical synthesis of lithium sodium titanate as an anode active material for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Ghosh, Swatilekha; Kee, Yongho; Okada, Shigeto; Barpanda, Prabeer

    2015-11-01

    Lithium sodium titanate insertion-type anode has been synthesized by classical solid-state (dry) and an alternate solution-assisted (wet) sonochemical synthesis routes. Successful synthesis of the target compound has been realized using simple Na- and Li-hydroxide salts along with titania. In contrast to the previous reports, these energy-savvy synthesis routes can yield the final product by calcination at 650-750 °C for limited duration of 1-10 h. Owing to the restricted calcination duration (dry route for 1-2 h and wet route for 1-5 h), they yield homogeneous nanoscale lithium sodium titanate particles. Sonochemical synthesis reduces the lithium sodium titanate particle size down to 80-100 nm vis-à-vis solid-state method delivering larger (200-500 nm) particles. Independent of the synthetic methods, the end products deliver reversible electrochemical performance with reversible capacity exceeding 80 mAh·g-1 acting as a 1.3 V anode for Li-ion batteries.

  11. Free-standing Fe2O3 nanomembranes enabling ultra-long cycling life and high rate capability for Li-ion batteries

    PubMed Central

    Liu, Xianghong; Si, Wenping; Zhang, Jun; Sun, Xiaolei; Deng, Junwen; Baunack, Stefan; Oswald, Steffen; Liu, Lifeng; Yan, Chenglin; Schmidt, Oliver G.

    2014-01-01

    With Fe2O3 as a proof-of-concept, free-standing nanomembrane structure is demonstrated to be highly advantageous to improve the performance of Li-ion batteries. The Fe2O3 nanomembrane electrodes exhibit ultra-long cycling life at high current rates with satisfactory capacity (808 mAh g−1 after 1000 cycles at 2 C and 530 mAh g−1 after 3000 cycles at 6 C) as well as repeatable high rate capability up to 50 C. The excellent performance benefits particularly from the unique structural advantages of the nanomembranes. The mechanical feature can buffer the strain of lithiation/delithiation to postpone the pulverization. The two-dimensional transport pathways in between the nanomembranes can promote the pseudo-capacitive type storage. The parallel-laid nanomembranes, which are coated by polymeric gel-like film and SEI layer with the electrolyte in between layers, electrochemically behave like numerous “mini-capacitors” to provide the pseudo-capacitance thus maintain the capacity at high rate. PMID:25503055

  12. Understanding of Surface Redox Behaviors of Li2MnO3 in Li-Ion Batteries: First-Principles Prediction and Experimental Validation.

    PubMed

    Kim, Duho; Lim, Jin-Myoung; Lim, Young-Geun; Park, Min-Sik; Kim, Young-Jun; Cho, Maenghyo; Cho, Kyeongjae

    2015-10-12

    Critical degradation mechanism of many cathode materials for Li-ion batteries is closely related to phase transformations at the surface/interface. Li2MnO3 in x Li2MnO3 ⋅(1-x) LiMO2 (M=Ni, Co, Mn) provides high capacity, but the Li2MnO3 phase is known to degrade during cycling through phase transformation and O2 evolution. To resolve such degradation problems, it is critical to develop a fundamental understanding of the underlying mechanism. Using first-principles calculations, we identified the surface delithiation potential (<4.5 V vs. Li/Li(+) ) of Li2MnO3, which is significantly lower than the bulk redox potential. A lower Mn oxidation state at the surface would reduce the delithiation potential compared with the fully oxidized Mn(4+) in the bulk. As a result, the delithiation would be initiated from the surface, which induces a phase transformation of Li2MnO3 into a spinel-like structure from the surface. These theoretical findings have been confirmed by experimental analyses. Based on these detailed mechanistic understanding, it would be possible to develop rational approaches to modify and coat the surface to suppress degradation mechanisms. PMID:26289748

  13. Metal-organic framework derived Fe2O3@NiCo2O4 porous nanocages as anode materials for Li-ion batteries.

    PubMed

    Huang, Gang; Zhang, Leilei; Zhang, Feifei; Wang, Limin

    2014-05-21

    Metal-organic frameworks (MOFs) with high surface areas and uniform microporous structures have shown potential application in many fields. Here we report a facial strategy to synthesize Fe2O3@NiCo2O4 porous nanocages by annealing core-shell Co3[Fe(CN)6]2@Ni3[Co(CN)6]2 nanocubes in air. The obtained samples have been systematically characterized by XRD, SEM, TEM and N2 adsorption-desorption analysis. The results show that the Fe2O3@NiCo2O4 porous nanocages have an average diameter of 213 nm and a shell thickness of about 30 nm. As anode materials for Li-ion batteries, the Fe2O3@NiCo2O4 porous nanocages exhibit a high initial discharge capacity of 1311.4 mA h g(-1) at a current density of 100 mA g(-1) (about 0.1 C). The capacity is retained at 1079.6 mA h g(-1) after 100 cycles. The synergistic effect of the different components and the porous hollow structure contributes to the outstanding performance of the composite electrode. PMID:24730026

  14. Free-standing Fe2O3 nanomembranes enabling ultra-long cycling life and high rate capability for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Liu, Xianghong; Si, Wenping; Zhang, Jun; Sun, Xiaolei; Deng, Junwen; Baunack, Stefan; Oswald, Steffen; Liu, Lifeng; Yan, Chenglin; Schmidt, Oliver G.

    2014-12-01

    With Fe2O3 as a proof-of-concept, free-standing nanomembrane structure is demonstrated to be highly advantageous to improve the performance of Li-ion batteries. The Fe2O3 nanomembrane electrodes exhibit ultra-long cycling life at high current rates with satisfactory capacity (808 mAh g-1 after 1000 cycles at 2 C and 530 mAh g-1 after 3000 cycles at 6 C) as well as repeatable high rate capability up to 50 C. The excellent performance benefits particularly from the unique structural advantages of the nanomembranes. The mechanical feature can buffer the strain of lithiation/delithiation to postpone the pulverization. The two-dimensional transport pathways in between the nanomembranes can promote the pseudo-capacitive type storage. The parallel-laid nanomembranes, which are coated by polymeric gel-like film and SEI layer with the electrolyte in between layers, electrochemically behave like numerous ``mini-capacitors'' to provide the pseudo-capacitance thus maintain the capacity at high rate.

  15. Li-ion diffusion in Li4Ti5O12 and LiTi2O4 battery materials detected by muon spin spectroscopy

    NASA Astrophysics Data System (ADS)

    Sugiyama, Jun; Nozaki, Hiroshi; Umegaki, Izumi; Mukai, Kazuhiko; Miwa, Kazutoshi; Shiraki, Susumu; Hitosugi, Taro; Suter, Andreas; Prokscha, Thomas; Salman, Zaher; Lord, James S.; Mânsson, Martin

    2015-07-01

    Lithium diffusion in spinel Li4Ti5O12 and LiTi2O4 compounds for future battery applications has been studied with muon spin relaxation (μ+SR ) . Measurements were performed on both thin-film and powder samples in the temperature range between 25 and 500 K. For Li4Ti5O12 and above about ˜200 K , the field distribution width (Δ ) is found to decrease gradually, while the field fluctuation rate (ν ) increases exponentially with temperature. For LiTi2O4 , on the contrary, the Δ (T ) curve shows a steplike decrease at ˜350 K , around which the ν (T ) curve exhibits a local maximum. These behaviors suggest that Li+ starts to diffuse above around 200 K for both spinels. Assuming a jump diffusion of Li+ at the tetrahedral 8 a site to the vacant octahedral 16 c site, diffusion coefficients of Li+ at 300 K in the film samples are estimated as (3.2 ±0.8 ) ×10-11 cm2/s for Li4Ti5O12 and (3.6 ±1.1 ) ×10-11 cm2/s for LiTi2O4 . Further, some small differences are found in both thermal activation energies and Li-ion diffusion coefficients between the powder and thin-film samples.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    The stannides CuLi2Sn (CSD-427095) and Cu2LiSn (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 Cu2Sn lattices form channels which host Cu and Li atoms at partly mixed occupied positions exhibiting extensive vacancies. For CuLi2Sn, the space group F-43m. was verified (structure type CuHg2Ti; a=6.295(2) Å; wR2(F²)=0.0355 for 78 unique reflections). The 4(c) and 4(d) positions are occupied by Cu atoms and Cu+Li atoms, respectively. For Cu2LiSn, the space group P63/mmc was confirmed (structure type InPt2Gd; a=4.3022(15) Å, c=7.618(3) Å; wR2(F²)=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.

  17. The design of a Li-ion full cell battery using a nano silicon and nano multi-layer graphene composite anode

    NASA Astrophysics Data System (ADS)

    Eom, KwangSup; Joshi, Tapesh; Bordes, Arnaud; Do, Inhwan; Fuller, Thomas F.

    2014-03-01

    In this study, a Si-graphene composite, which is composed of nano Si particles and nano-sized multi-layer graphene particles, and micro-sized multi-layer graphene plate conductor, was used as the anode for Li-ion battery. The Si-graphene electrode showed the high capacity and stable cyclability at charge/discharge rate of C/2 in half cell tests. Nickel cobalt aluminum material (NCA) was used as a cathode in the full cell to evaluate the practicality of the new Si-graphene material. Although the Si-graphene anode has more capacity than the NCA cathode in this designed full cell, the Si-graphene anode had a greater effect on the full-cell performance due to its large initial irreversible capacity loss and continuous SEI formation during cycling. When fluoro-ethylene carbonate was added to the electrolyte, the cyclability of the full cell was much improved due to less SEI formation, which was confirmed by the decreases in the 1st irreversible capacity loss, overpotential for the 1st lithiation, and the resistance of the SEI.

  18. Template Free and Binderless NiO Nanowire Foam for Li-ion Battery Anodes with Long Cycle Life and Ultrahigh Rate Capability

    NASA Astrophysics Data System (ADS)

    Liu, Chueh; Li, Changling; Ahmed, Kazi; Mutlu, Zafer; Ozkan, Cengiz S.; Ozkan, Mihrimah

    2016-07-01

    Herein, NiO-decorated Ni nanowires with diameters ca. 30–150 nm derived from Ni wire backbone (ca. 2 μm in diameter) is directly synthesized on commercially available Ni foam as a renovated anode for Li-ion batteries. Excellent stability with capacity 680 mAh g‑1 at 0.5C (1C = 718 mA g‑1) is achieved after 1000 cycles. Superior rate capability is exhibited by cycling at extremely high current rates, such as 20C and 50C with capacities ca. 164 and 75 mAh g‑1, respectively. The capacity can be recovered back to ca. 430 mAh g‑1 in 2 cycles when lowered to 0.2C and stably cycled for 430 times with capacity 460 mAh g‑1. The NiO nanowire foam anode possesses low equivalent series resistance ca. 3.5 Ω, resulting in superior power performance and low resistive losses. The NiO nanowire foam can be manufactured with bio-friendly chemicals and low temperature processes without any templates, binders and conductive additives, which possesses the potential transferring from lab scale to industrial production.

  19. Silicon Diphosphide: A Si-Based Three-Dimensional Crystalline Framework as a High-Performance Li-Ion Battery Anode.

    PubMed

    Kwon, Hyuk-Tae; Lee, Churl Kyoung; Jeon, Ki-Joon; Park, Cheol-Min

    2016-06-28

    The development of an electrode material for rechargeable Li-ion batteries (LIBs) and the understanding of its reaction mechanism play key roles in enhancing the electrochemical characteristics of LIBs for use in various portable electronics and electric vehicles. Here, we report a three-dimensional (3D) crystalline-framework-structured silicon diphosphide (SiP2) and its interesting electrochemical behaviors for superior LIBs. During Li insertion in the SiP2, a three-step electrochemical reaction mechanism, sequentially comprised of a topotactic transition (0.55-2 V), an amorphization (0.25-2 V), and a conversion (0-2 V), was thoroughly analyzed. On the basis of the three-step electrochemical reaction mechanism, excellent electrochemical properties, such as high initial capacities, high initial Coulombic efficiencies, stable cycle behaviors, and fast-rate capabilities, were attained from the preparation of a nanostructured SiP2/C composite. This 3D crystalline-framework-structured SiP2 compound will be a promising alternative anode material in the realization and mass production of excellent, rechargeable LIBs. PMID:27243799

  20. Template Free and Binderless NiO Nanowire Foam for Li-ion Battery Anodes with Long Cycle Life and Ultrahigh Rate Capability.

    PubMed

    Liu, Chueh; Li, Changling; Ahmed, Kazi; Mutlu, Zafer; Ozkan, Cengiz S; Ozkan, Mihrimah

    2016-01-01

    Herein, NiO-decorated Ni nanowires with diameters ca. 30-150 nm derived from Ni wire backbone (ca. 2 μm in diameter) is directly synthesized on commercially available Ni foam as a renovated anode for Li-ion batteries. Excellent stability with capacity 680 mAh g(-1) at 0.5C (1C = 718 mA g(-1)) is achieved after 1000 cycles. Superior rate capability is exhibited by cycling at extremely high current rates, such as 20C and 50C with capacities ca. 164 and 75 mAh g(-1), respectively. The capacity can be recovered back to ca. 430 mAh g(-1) in 2 cycles when lowered to 0.2C and stably cycled for 430 times with capacity 460 mAh g(-1). The NiO nanowire foam anode possesses low equivalent series resistance ca. 3.5 Ω, resulting in superior power performance and low resistive losses. The NiO nanowire foam can be manufactured with bio-friendly chemicals and low temperature processes without any templates, binders and conductive additives, which possesses the potential transferring from lab scale to industrial production. PMID:27426433

  1. Template Free and Binderless NiO Nanowire Foam for Li-ion Battery Anodes with Long Cycle Life and Ultrahigh Rate Capability

    PubMed Central

    Liu, Chueh; Li, Changling; Ahmed, Kazi; Mutlu, Zafer; Ozkan, Cengiz S.; Ozkan, Mihrimah

    2016-01-01

    Herein, NiO-decorated Ni nanowires with diameters ca. 30–150 nm derived from Ni wire backbone (ca. 2 μm in diameter) is directly synthesized on commercially available Ni foam as a renovated anode for Li-ion batteries. Excellent stability with capacity 680 mAh g−1 at 0.5C (1C = 718 mA g−1) is achieved after 1000 cycles. Superior rate capability is exhibited by cycling at extremely high current rates, such as 20C and 50C with capacities ca. 164 and 75 mAh g−1, respectively. The capacity can be recovered back to ca. 430 mAh g−1 in 2 cycles when lowered to 0.2C and stably cycled for 430 times with capacity 460 mAh g−1. The NiO nanowire foam anode possesses low equivalent series resistance ca. 3.5 Ω, resulting in superior power performance and low resistive losses. The NiO nanowire foam can be manufactured with bio-friendly chemicals and low temperature processes without any templates, binders and conductive additives, which possesses the potential transferring from lab scale to industrial production. PMID:27426433

  2. Connecting the irreversible capacity loss in Li-ion batteries with the electronic insulating properties of solid electrolyte interphase (SEI) components.

    DOE PAGESBeta

    Leung, Kevin; Lin, Yu -Xiao; Liu, Zhe; Chen, Long -Qing; Lu, Peng; Qi, Yue

    2016-01-01

    The formation and continuous growth of a solid electrolyte interphase (SEI) layer are responsible for the irreversible capacity loss of batteries in the initial and subsequent cycles, respectively. In this article, the electron tunneling barriers from Li metal through three insulating SEI components, namely Li2CO3, LiF and Li3PO4, are computed by density function theory (DFT) approaches. Based on electron tunneling theory, it is estimated that sufficient to block electron tunneling. It is also found that the band gap decreases under tension while the work function remains the same, and thus the tunneling barrier decreases under tension and increases under compression.more » A new parameter, η, characterizing the average distances between anions, is proposed to unify the variation of band gap with strain under different loading conditions into a single linear function of η. An analytical model based on the tunneling results is developed to connect the irreversible capacity loss, due to the Li ions consumed in forming these SEI component layers on the surface of negative electrodes. As a result, the agreement between the model predictions and experimental results suggests that only the initial irreversible capacity loss is due to the self-limiting electron tunneling property of the SEI.« less

  3. Connecting the irreversible capacity loss in Li-ion batteries with the electronic insulating properties of solid electrolyte interphase (SEI) components.

    SciTech Connect

    Leung, Kevin; Lin, Yu -Xiao; Liu, Zhe; Chen, Long -Qing; Lu, Peng; Qi, Yue

    2016-01-01

    The formation and continuous growth of a solid electrolyte interphase (SEI) layer are responsible for the irreversible capacity loss of batteries in the initial and subsequent cycles, respectively. In this article, the electron tunneling barriers from Li metal through three insulating SEI components, namely Li2CO3, LiF and Li3PO4, are computed by density function theory (DFT) approaches. Based on electron tunneling theory, it is estimated that sufficient to block electron tunneling. It is also found that the band gap decreases under tension while the work function remains the same, and thus the tunneling barrier decreases under tension and increases under compression. A new parameter, η, characterizing the average distances between anions, is proposed to unify the variation of band gap with strain under different loading conditions into a single linear function of η. An analytical model based on the tunneling results is developed to connect the irreversible capacity loss, due to the Li ions consumed in forming these SEI component layers on the surface of negative electrodes. As a result, the agreement between the model predictions and experimental results suggests that only the initial irreversible capacity loss is due to the self-limiting electron tunneling property of the SEI.

  4. Synthesis and Electrochemical Characterization of Li2FeSiO4/Carbon Nanofiber Composite Cathode Material for Li Ion Batteries

    NASA Astrophysics Data System (ADS)

    Kumar, Ajay; Nazri, Gholam Abbas; Naik, Ratna; Naik, Vaman M.

    2014-03-01

    Lithium transition metal silicates (Li2MSiO4) , where, M =Ni, Mn, Fe, and Co with a theoretical capacity of ~ 330 mAh/g have attracted great interest as possible replacements for cathode material in rechargeable batteries. However, this class of materials exhibit very low electronic conductivity and low lithium diffusivity. In order to enhance the electronic conductivity and reduce the diffusion length for lithium ion, we have synthesized Li2FeSiO4/carbon nanofiber (15 % wt) composites by sol-gel method. The composite materials were characterized by x-ray diffraction and scanning electron microscopy. The XRD data confirmed the formation of Li2FeSiO4 crystallites with size ~ 25 nm for composites annealed at 600 °C under argon atmosphere. The composite material was used as positive electrode in a coin cell configuration and the cells were characterized by AC impedance spectroscopy, cyclic voltammetry, and galvanostatic charge/discharge cycling. The cells showed a discharge capacity of ~ 230 mAh/g in the initial cycles, which suggests that more than one Li ion is extracted from the electrode. The effect of annealing at higher temperature on the electrochemical performance of Li2FeSiO4/carbon nanofiber composites will be presented.

  5. Effect of Transition Metal Ordering on the Electronic Properties of LiNi1 - y - xCoyMnxO2 Cathode Materials for Li-ion Batteries

    NASA Astrophysics Data System (ADS)

    Longo, Roberto; Kong, Fantai; Kc, Santosh; Yeon, Dong-Hee; Yoon, Jaegu; Park, Jin-Hwan; Doo, Seok-Kwang; Cho, Kyeongjae; MSL Team; SAIT Team

    2015-03-01

    Current Li-ion batteries use layered oxides as cathode materials, specially LiCoO2 or LiNi1 - y - xCoyMnxO2(NCM), and graphite as anode. Co layered oxides suffer from the high cost and toxicity of cobalt, together with certain instability at high operational temperatures. To overcome these difficulties, the synthesis of novel materials composed of layered oxides with different sets of Transition Metals (TM) has become the most successful way to solve the particular drawbacks of every single-oxide family. Although layered materials can deliver larger capacity than other families of cathode materials, the energy density has yet to be increased in order to match the expectations deposited on the NCM oxides. To acquire a high capacity, they need to be cycled at high operational voltages, resulting in voltage and capacity fading over a large number of cycles. In this work, we examine the phase diagram of the Li-Ni-Co-Mn-O system and the effect of TM ordering on the electronic properties of NCM cathode materials, using density-functional theory. Our findings will provide conceptual guidance in the experimental search for the mechanisms driving the voltage and capacity fading of the NCM family of cathode materials, in an attempt to solve such structural instability problems and, thus, improving the performance of the NCM cathode materials. This work was supported by Samsung GRO project.

  6. A high pressure x-ray photoelectron spectroscopy experimental method for characterization of solid-liquid interfaces demonstrated with a Li-ion battery system

    NASA Astrophysics Data System (ADS)

    Maibach, Julia; Xu, Chao; Eriksson, Susanna K.; Åhlund, John; Gustafsson, Torbjörn; Siegbahn, Hans; Rensmo, Hâkan; Edström, Kristina; Hahlin, Maria

    2015-04-01

    We report a methodology for a direct investigation of the solid/liquid interface using high pressure x-ray photoelectron spectroscopy (HPXPS). The technique was demonstrated with an electrochemical system represented by a Li-ion battery using a silicon electrode and a liquid electrolyte of LiClO4 in propylene carbonate (PC) cycled versus metallic lithium. For the first time the presence of a liquid electrolyte was realized using a transfer procedure where the sample was introduced into a 2 mbar N2 environment in the analysis chamber without an intermediate ultrahigh vacuum (UHV) step in the load lock. The procedure was characterized in detail concerning lateral drop gradients as well as stability of measurement conditions over time. The X-ray photoelectron spectroscopy (XPS) measurements demonstrate that the solid substrate and the liquid electrolyte can be observed simultaneously. The results show that the solid electrolyte interphase (SEI) composition for the wet electrode is stable within the probing time and generally agrees well with traditional UHV studies. Since the methodology can easily be adjusted to various high pressure photoelectron spectroscopy systems, extending the approach towards operando solid/liquid interface studies using liquid electrolytes seems now feasible.

  7. Separators for Li-ion and Li-metal battery including ionic liquid based electrolytes based on the TFSI- and FSI- anions.

    PubMed

    Kirchhöfer, Marija; von Zamory, Jan; Paillard, Elie; Passerini, Stefano

    2014-01-01

    The characterization of separators for Li-ion or Li-metal batteries incorporating hydrophobic ionic liquid electrolytes is reported herein. Ionic liquids made of N-butyl-N-methylpyrrolidinium (PYR14+) or N-methoxyethyl-N-methylpyrrolidinium (PYR12O1+), paired with bis(trifluoromethanesulfonyl)imide (TFSI-) or bis(fluorosulfonyl)imide (FSI-) anions, were tested in combination with separators having different chemistries and morphologies in terms of wetting behavior, Gurley and McMullin number, as well as Li/(Separator+Electrolyte) interfacial properties. It is shown that non-functionalized microporous polyolefin separators are poorly wetted by FSI--based electrolytes (contrary to TFSI--based electrolytes), while the ceramic coated separator Separion® allows good wetting with all electrolytes. Furthermore, by comparing the lithium solid electrolyte interphase (SEI) resistance evolution at open circuit and during cycling, depending on separator morphologies and chemistries, it is possible to propose a scale for SEI forming properties in the order: PYR12O1FSI>PYR14FSI>PYR14TFSI>PYR12O1TFSI. Finally, the impact the separator morphology is evidenced by the SEI resistance evolution and by comparing Li electrodes cycled using separators with two different morphologies. PMID:25153637

  8. Multi-layer electrode with nano-Li4Ti5O12 aggregates sandwiched between carbon nanotube and graphene networks for high power Li-ion batteries

    PubMed Central

    Choi, Jin-Hoon; Ryu, Won-Hee; Park, Kyusung; Jo, Jeong-Dai; Jo, Sung-Moo; Lim, Dae-Soon; Kim, Il-Doo

    2014-01-01

    Self-aggregated Li4Ti5O12 particles sandwiched between graphene nanosheets (GNSs) and single-walled carbon nanotubes (SWCNTs) network are reported as new hybrid electrodes for high power Li-ion batteries. The multi-layer electrodes are fabricated by sequential process comprising air-spray coating of GNSs layer and the following electrostatic spray (E-spray) coating of well-dispersed colloidal Li4Ti5O12 nanoparticles, and subsequent air-spray coating of SWCNTs layer once again. In multi-stacked electrodes of GNSs/nanoporous Li4Ti5O12 aggregates/SWCNTs networks, GNSs and SWCNTs serve as conducting bridges, effectively interweaving the nanoporous Li4Ti5O12 aggregates, and help achieve superior rate capability as well as improved mechanical stability of the composite electrode by holding Li4Ti5O12 tightly without a binder. The multi-stacked electrodes deliver a specific capacity that maintains an impressively high capacity of 100 mA h g−1 at a high rate of 100C even after 1000 cycles. PMID:25476980

  9. Separators for Li-Ion and Li-Metal Battery Including Ionic Liquid Based Electrolytes Based on the TFSI− and FSI− Anions

    PubMed Central

    Kirchhöfer, Marija; von Zamory, Jan; Paillard, Elie; Passerini, Stefano

    2014-01-01

    The characterization of separators for Li-ion or Li-metal batteries incorporating hydrophobic ionic liquid electrolytes is reported herein. Ionic liquids made of N-butyl-N-methylpyrrolidinium (PYR14+) or N-methoxyethyl-N-methylpyrrolidinium (PYR12O1+), paired with bis(trifluoromethanesulfonyl)imide (TFSI−) or bis(fluorosulfonyl)imide (FSI−) anions, were tested in combination with separators having different chemistries and morphologies in terms of wetting behavior, Gurley and McMullin number, as well as Li/(Separator + Electrolyte) interfacial properties. It is shown that non-functionalized microporous polyolefin separators are poorly wetted by FSI−-based electrolytes (contrary to TFSI−-based electrolytes), while the ceramic coated separator Separion® allows good wetting with all electrolytes. Furthermore, by comparing the lithium solid electrolyte interphase (SEI) resistance evolution at open circuit and during cycling, depending on separator morphologies and chemistries, it is possible to propose a scale for SEI forming properties in the order: PYR12O1FSI > PYR14FSI > PYR14TFSI > PYR12O1TFSI. Finally, the impact the separator morphology is evidenced by the SEI resistance evolution and by comparing Li electrodes cycled using separators with two different morphologies. PMID:25153637

  10. A high pressure x-ray photoelectron spectroscopy experimental method for characterization of solid-liquid interfaces demonstrated with a Li-ion battery system

    SciTech Connect

    Maibach, Julia; Xu, Chao; Gustafsson, Torbjörn; Edström, Kristina; Eriksson, Susanna K.; Åhlund, John; Siegbahn, Hans; Rensmo, Håkan; Hahlin, Maria

    2015-04-15

    We report a methodology for a direct investigation of the solid/liquid interface using high pressure x-ray photoelectron spectroscopy (HPXPS). The technique was demonstrated with an electrochemical system represented by a Li-ion battery using a silicon electrode and a liquid electrolyte of LiClO{sub 4} in propylene carbonate (PC) cycled versus metallic lithium. For the first time the presence of a liquid electrolyte was realized using a transfer procedure where the sample was introduced into a 2 mbar N{sub 2} environment in the analysis chamber without an intermediate ultrahigh vacuum (UHV) step in the load lock. The procedure was characterized in detail concerning lateral drop gradients as well as stability of measurement conditions over time. The X-ray photoelectron spectroscopy (XPS) measurements demonstrate that the solid substrate and the liquid electrolyte can be observed simultaneously. The results show that the solid electrolyte interphase (SEI) composition for the wet electrode is stable within the probing time and generally agrees well with traditional UHV studies. Since the methodology can easily be adjusted to various high pressure photoelectron spectroscopy systems, extending the approach towards operando solid/liquid interface studies using liquid electrolytes seems now feasible.

  11. Multi-layer electrode with nano-Li4Ti5O12 aggregates sandwiched between carbon nanotube and graphene networks for high power Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Choi, Jin-Hoon; Ryu, Won-Hee; Park, Kyusung; Jo, Jeong-Dai; Jo, Sung-Moo; Lim, Dae-Soon; Kim, Il-Doo

    2014-12-01

    Self-aggregated Li4Ti5O12 particles sandwiched between graphene nanosheets (GNSs) and single-walled carbon nanotubes (SWCNTs) network are reported as new hybrid electrodes for high power Li-ion batteries. The multi-layer electrodes are fabricated by sequential process comprising air-spray coating of GNSs layer and the following electrostatic spray (E-spray) coating of well-dispersed colloidal Li4Ti5O12 nanoparticles, and subsequent air-spray coating of SWCNTs layer once again. In multi-stacked electrodes of GNSs/nanoporous Li4Ti5O12 aggregates/SWCNTs networks, GNSs and SWCNTs serve as conducting bridges, effectively interweaving the nanoporous Li4Ti5O12 aggregates, and help achieve superior rate capability as well as improved mechanical stability of the composite electrode by holding Li4Ti5O12 tightly without a binder. The multi-stacked electrodes deliver a specific capacity that maintains an impressively high capacity of 100 mA h g-1 at a high rate of 100C even after 1000 cycles.

  12. Nanospheres of a New Intermetalic FeSn5 Phase: Synthesis Magnetic Properties and Anode Performance in Li-ion Batteries

    SciTech Connect

    X Wang; M Feygenson; H Chen; C Lin; W Ku; J Bai; M Aronson; T Tyson; W Han

    2011-12-31

    We synthesized monodisperse nanospheres of an intermetallic FeSn{sub 5} phase via a nanocrystal-conversion protocol using preformed Sn nanospheres as templates. This tetragonal phase in P4/mcc space group, along with the defect structure Fe{sub 0.74}Sn{sub 5} of our nanospheres, has been resolved by synchrotron X-ray diffraction and Rietveld refinement. Importantly, FeSn{sub 5}, which is not yet established in the Fe-Sn phase diagram, exhibits a quasi-one dimensional crystal structure along the c-axis, thus leading to interesting anisotropic thermal expansion and magnetic properties. Magnetization measurements indicate that nanospheres are superparamagnetic above the blocking temperature T{sub B} = 300 K, which is associated with the higher magnetocrystalline anisotropy constant K = 3.33 kJ m{sup -3}. The combination of the magnetization measurements and first-principles density functional theory calculations reveals the canted antiferromagnetic nature with significant spin fluctuation in lattice a-b plane. The low Fe concentration also leads Fe{sub 0.74}Sn{sub 5} to enhanced capacity as an anode in Li ion batteries.

  13. Highly Efficient Storage of Pulse Energy Produced by Triboelectric Nanogenerator in Li3V2(PO4)3/C Cathode Li-Ion Batteries.

    PubMed

    Nan, Xihui; Zhang, Changkun; Liu, Chaofeng; Liu, Mengmeng; Wang, Zhong Lin; Cao, Guozhong

    2016-01-13

    Triboelectric nanogenerator (TENG) has been considered as a new type of energy harvesting technology, which employs the coupling effects of triboelectrification and electrostatic induction. One key factor having limited its application is the energy storage. In this work, a high performance Li3V2(PO4)3/C material synthesized by low-cost hydrothermal method followed with subsequent annealing treatment was studied to efficiently store the power generated by a radial-arrayed rotary TENG. Not only does the Li3V2(PO4)3/C exhibit a discharge capacity of 128 mAh g(-1) at 1 C with excellent cyclic stability (capacity retention is 90% after 1000 cycles at a rate of 5 C) in Li-ion battery, but also shows outstanding energy conversion efficiency (83.4%) compared with the most popular cathodic materials: LiFePO4 (74.4%), LiCoO2 (66.1%), and LiMn2O4 (73.6%) when it was charged by high frequency and large current electricity directly from by TENG. PMID:26681671

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

    PubMed Central

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

    2014-01-01

    The stannides CuLi2Sn (CSD-427095) and Cu2LiSn (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 Cu2Sn lattices form channels which host Cu and Li atoms at partly mixed occupied positions exhibiting extensive vacancies. For CuLi2Sn, the space group F-43m. was verified (structure type CuHg2Ti; a=6.295(2) Å; wR2(F²)=0.0355 for 78 unique reflections). The 4(c) and 4(d) positions are occupied by Cu atoms and Cu+Li atoms, respectively. For Cu2LiSn, the space group P63/mmc was confirmed (structure type InPt2Gd; a=4.3022(15) Å, c=7.618(3) Å; wR2(F²)=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. PMID:25473128

  15. The effect of pH on the interlayer distances of elongated titanate nanotubes and their use as a Li-ion battery anode.

    PubMed

    Yarali, Miad; Biçer, Emre; Gürsel, Selmiye Alkan; Yürüm, Alp

    2016-01-01

    Titanate nanotubes are promising materials for Li-ion battery anodes because of their special morphology and high specific surface areas. These titanates provide high rate capability and low volume expansion upon lithiation. More importantly, their tubular structure helps the transport of ions through the crystal. In this study, we synthesized elongated titanate nanotubes and modified their interlayer distances by changing the pH (2-13). For the structural characterization XRD, BET, SEM and TEM techniques were used. In addition, the effect of interlayer distance on energy capacity and rate capability was investigated. The highest interlayer distance was obtained at pH 10 and with decreasing pH, the interlayer distance dropped until reaching a pH value of 4. Conversely, the specific surface area reached its maximum value of 204 m(2) g(-1) at a pH of 4. Different from anatase (TiO2), titanate nanotubes had broad peaks in cyclic voltammograms suggesting a pseudocapacitive behavior. The sloping profiles of potential-capacity results also supported the pseudocapacitive property. For the titanate nanotubes obtained at pH 10, an initial discharge capacity of 980 mAh g(-1) was achieved. More importantly, titanate nanotubes showed exceptional rate capabilities and the capacities stayed almost constant at high current rates because of their elongated structure. It was found that the interlayer distance and the elongated structure play an important role in the electrochemical performance of the material. PMID:26597213

  16. Understanding conversion mechanism of NiO anodic materials for Li-ion battery using in situ X-ray absorption near edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Jang, Jue-Hyuk; Chae, Byung-Mok; Oh, Hyun-Jung; Lee, Yong-Kul

    2016-02-01

    Nano-scaled NiO particles (nano-NiO) are prepared by a ligand stabilization method and compared with micron-sized NiO particles (micro-NiO) as anodic material of Li-ion battery. The structural and physical properties are characterized by N2 physisorption, transmission electron microscopy, and X-ray diffraction. The nano-NiO shows uniform spheres with an average particle size of 9 nm with high and stable discharge capacity of 637 mAh g-1, while the micro-NiO forms irregularly shaped particles with an average particle size of 750 nm with low capacity of 431 mAh g-1 at 0.5C. In situ X-ray absorption near edge structure (XANES) analysis reveals that the capacity and reversibility of the NiO anode is highly affected by the particle size of the NiO. The micro-NiO exhibits a low capacity with absence of phase transformation upon the discharge/charge cycles. In contrast, the nano-NiO exhibits a high capacity with reversible phase transformation between NiO and Ni metal upon the cycle test.

  17. Performance Testing of Lithium Li-ion Cells and Batteries in Support of JPL's 2003 Mars Exploration Rover Mission

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Ratnakumar, B. V.; Ewell, R. C.; Whitcanack, L. D.; Surampudi, S.; Puglia, F.; Gitzendanner, R.

    2007-01-01

    In early 2004, JPL successfully landed two Rovers, named Spirit and Opportunity, on the surface of Mars after traveling > 300 million miles over a 6-7 month period. In order to operate for extended duration on the surface of Mars, both Rovers are equipped with rechargeable Lithium-ion batteries, which were designed to aid in the launch, correct anomalies during cruise, and support surface operations in conjunction with a triple-junction deployable solar arrays. The requirements of the Lithium-ion battery include the ability to provide power at least 90 sols on the surface of Mars, operate over a wide temperature range (-20(super 0)C to +40(super 0)C), withstand long storage periods (e.g., including pre-launch and cruise period), operate in an inverted position, and support high currents (e.g., firing pyro events). In order to determine the inability of meeting these requirements, ground testing was performed on a Rover Battery Assembly Unit RBAU), consisting of two 8-cell 8 Ah lithium-ion batteries connected in parallel. The RBAU upon which the performance testing was performed is nearly identical to the batteries incorporated into the two Rovers currently on Mars. The primary focus of this paper is to communicate the latest results regarding Mars surface operation mission simulation testing, as well as, the corresponding performance capacity loss and impedance characteristics as a function of temperature and life. As will be discussed, the lithium-ion batteries (fabricated by Yardney Technical Products, Inc.) have been demonstrated to far exceed the requirements defined by the mission, being able to support the operation of the rovers for over three years, and are projected to support an even further extended mission.

  18. Ground testing of the Li-ion batteries in support of JPL's 2003 Mars Exploration Rover Mission

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Ewell, R. C.; Whitcanack, L. D.; Chin, K. B.; Surampudi, S.; Puglia, F.; Gitzendanner, R.

    2005-01-01

    In early 2004, JPL successfully landed two Rovers, named Spirit and Opportunity, on the surface of Mars after traveling > 300 million miles over a 6-7 month period. In order to operate for extended duration on the surface of Mars, both Rovers are equipped with rechargeable Lithium-ion batteries, which were designed to aid in the launch, correct anomalies during cruise, and support surface operations in conjunction with a triple-junction deployable solar arrays. The requirements of the Lithium-ion battery include the ability to provide power at least 90 sols on the surface of Mars, operate over a wide temperature range (-20(deg)C to +4O(deg)C), withstand long storage periods (e.g., cruise period), operate in an inverted position, and support high currents (e.g., firing pyro events). In order to determine the viability of meeting these requirements, ground testing was performed on a Rover Battery Assembly Unit (RBAU), consisting of two 8-cell 8 Ah lithium-ion batteries connected in parallel. The RBAU upon which the performance testing was performed is nearly identical to the batteries incorporated into the two Rovers currently on Mars. The testing performed includes, (a) performing initial characterization tests (discharge capacity at different temperatures), (b) simulating the launch conditions, (c) simulating the cruise phase conditions (including trajectory corrections), (d) simulating the entry, decent, and landing pulse load profile (if required to support the pyros) (e) simulating the Mars surface operation mission simulation conditions, as well as, (f) assessing performance capacity loss and impedance characteristics as a function of temperature and life. As will be discussed, the lithium-ion batteries (fabricated by LithiodYardney, Inc.) were demonstrated to far exceed the requirements defined by the mission, and are projected to support an extended mission (> 2 years) with margin to spare.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    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 LiFePO4 composite electrodes were obtained with PIXE and PIGE by scanning the proton microbeam for various charged states of the electrodes. Lithium concentration in LiFePO4 composite electrodes was decreased from the contact interface between LiFePO4 electrode and liquid electrolyte during the charge reaction.

  20. State-space representation of Li-ion battery porous electrode impedance model with balanced model reduction

    NASA Astrophysics Data System (ADS)

    Jun, Myungsoo; Smith, Kandler; Graf, Peter

    2015-01-01

    This paper presents an approximate time-domain solution for physics-based electrochemical lithium-ion cell battery models. The time-domain solution is represented in state-space form and can be easily used for the design of a state estimator or controller. It uses an interconnection-of-system approach to derive a state-space representation of a battery impedance model and provides a reduced order model based via the balanced truncation method. Simulation results are also provided to show the performance of the proposed model in the frequency domain.

  1. Physical characterization of the charging process of a Li-ion battery and prediction of Li plating by electrochemical modelling

    NASA Astrophysics Data System (ADS)

    Legrand, N.; Knosp, B.; Desprez, P.; Lapicque, F.; Raël, S.

    2014-01-01

    This paper deals with occurrence of lithium plating on the negative electrode of lithium-ion batteries, a significant ageing phenomenon known to damage lithium-ion battery performances. Charge transfer process, one of the two different steps of the process of Li insertion in the negative active material being the cause of this ageing, was considered here to be the limiting process. This transfer occurs at short-time scales. The second process, the diffusion of lithium in the solid insertion compound, occurring at relatively long-time scales, has not been fully examined here. The aim of this paper was to develop a new method to evaluate the maximal rate of a charge pulse solicitation to prevent this ageing phenomenon. The approach relies on the use of a fundamental model of lithium ion battery with coupled mass and charge transfer. To validate the method, 2 s microcycles have been performed on a commercial VL41M SAFT cell. Theoretical and experimental works led to the maximum current density to be applied without undesired Li deposition, depending on the state of charge (SOC). The abacus established for the cell of interest can orient further specifications for suitable use of the battery.

  2. Design, Fabrication and Testing of Silicon-integrated Li-ion Secondary Micro Batteries with Side-by-Side Electrodes

    NASA Astrophysics Data System (ADS)

    Hoeppner, K.; Ferch, M.; Eisenreich, M.; Marquardt, K.; Hahn, R.; Mackowiak, P.; Mukhopadhyay, B.; Ngo, H.-D.; Gernhardt, R.; Toepper, M.; Lang, K.-D.

    2013-12-01

    This paper reports the design, fabrication, and testing of silicon-integrated lithium ion secondary micro batteries with a side-by-side electrode setup. Two cavities separated by a narrow silicon spacer served as a containment for the electrodes and were etched into <110>-Si by wet chemical etching using aqueous KOH solution. The etched silicon battery containment was passivated by a stress-compensated layer of SiO2/Si3N4. Ti/Pt-current collectors were applied by E-beam evaporation and lift-off structuring. A volumetric dispenser served to fill the cavities with slurries of the active materials - lithium cobalt oxide (LiCoO2) as the anode and graphite as the cathode material. Encapsulation, electrolyte filling, and electrochemical characterisation of the finished cells took place in an Ar-filled glove box. The fabricated batteries have shown a rate capability of up to 5C and a linear capacity loss rate of <1 % per cycle over 30 full-cycles. Battery containments with different cavity and spacer widths have been fabricated.

  3. Considerations for Estimating Electrode Performance in Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Bennett, William R.

    2012-01-01

    Advanced electrode materials with increased specific capacity and voltage performance are critical to the development of Li-ion batteries with increased specific energy and energy density. Although performance metrics for individual electrodes are critically important, a fundamental understanding of the interactions of electrodes in a full cell is essential to achieving the desired performance, and for establishing meaningful goals for electrode performance. This paper presents practical design considerations for matching positive and negative electrodes in a viable design. Methods for predicting cell-level discharge voltage, based on laboratory data for individual electrodes, are presented and discussed.

  4. Recycling of cobalt from spent Li-ion batteries as β-Co(OH)2 and the application of Co3O4 as a pseudocapacitor

    NASA Astrophysics Data System (ADS)

    Barbieri, E. M. S.; Lima, E. P. C.; Lelis, M. F. F.; Freitas, M. B. J. G.

    2014-12-01

    This work has investigated recycling cobalt from the cathodes of spent Li-ion batteries as β-Co(OH)2, obtaining Co3O4. β-Co(OH)2 with a hexagonal structure by using chemical precipitation (CP) or electrochemical precipitation (EP). In addition, the study has investigated whether the charge density applied directly affects the β-Co(OH)2 morphology. Co3O4 is formed by heat-treating β-Co(OH)2 at 450 °C for 3 h (h) in an air atmosphere. After calcining, the Co3O4 shows a cubic structure and satisfactory purity grade, regardless of the route used for preparation via which it was obtained. Cyclic voltammetry (CV) is then used for electrochemical characterization of the Co3O4 composite electrodes. In the cathodic process, CoO2 undergoes reduction to CoOOH, which undergoes further reduction to Co3O4. In the anodic process, Co3O4 undergoes oxidation to CoOOH, which simultaneously undergoes further oxidation to CoO2. The composite electrodes containing Co3O4, carbon black, and epoxy resin show great reversibility, charge efficiency, and a specific capacitance of 13.0 F g-1 (1.0 mV s-1). The synthesis method of Co(OH)2 influences the charge efficiency of Co3O4 composite electrodes at a scan rate of 10.0 mV s-1. Therefore, in addition to presenting an alternative use for exhausted batteries, Co3O4 composites exhibit favorable characteristics for use as pseudocapacitors.

  5. Pre-Lithiation of Li(Ni1-x-yMnxCoy)O2 Materials Enabling Enhancement of Performance for Li-Ion Battery.

    PubMed

    Wu, Zhongzhen; Ji, Shunping; Hu, Zongxiang; Zheng, Jiaxin; Xiao, Shu; Lin, Yuan; Xu, Kang; Amine, Khalil; Pan, Feng

    2016-06-22

    Transition metal oxide materials Li(NixMnyCoz)O2 (NMCxyz) based on layered structure are potential cathode candidates for automotive Li-ion batteries because of their high specific capacities and operating potentials. However, the actual usable capacity, cycling stability, and first-cycle Coulombic efficiency remain far from practical. Previously, we reported a combined strategy consisting of depolarization with embedded carbon nanotube (CNT) and activation through pre-lithiation of the NMC host, which significantly improved the reversible capacity and cycling stability of NMC532-based material. In the present work we attempt to understand how pre-lithiation leads to these improvements on an atomic level with experimental investigation and ab initio calculations. By lithiating a series of NMC materials with varying chemical compositions prepared via a conventional approach, we identified the Ni in the NMC lattice as the component responsible for accommodating a double-layered Li structure. Specifically, much better improvements in the cycling stability and capacity can be achieved with the NMC lattices populated with Ni(3+) than those populated with only Ni(2+). Using the XRD we also found that the emergence of a double-layer Li structure is not only reversible during the pre-lithiation and the following delithiation, but also stable against elevated temperatures up to 320 °C. These new findings regarding the mechanism of pre-lithiation as well as how it affects the reversibility and stability of NMC-based cathode materials prepared by the conventional slurry approach will promote the possibility of their application in the future battery industry. PMID:27237226

  6. Research and analysis on electrochemical performances of α-Fe{sub 2}O{sub 3} electrode in Li-ion battery with different current collectors

    SciTech Connect

    Huang, Lihong Min, Zhonghua; Zhang, Qinyong

    2015-06-15

    Highlights: • We achieved a reversible capacity of 415 mAh g{sup −1} after 30 cycles for α-Fe{sub 2}O{sub 3} electrode in Li-ion battery. • Better electrical performance was obtained when using Cu foam as current collector. • As current collector for α-Fe{sub 2}O{sub 3} electrode, Cu foam is better than Cu foil and Ni foam. • It could avoid the active materials falling off from the current collector during cycling. • It is owe to smaller surface film resistance, charge-transfer resistance, etc. - Abstract: In this work, we reported a simple synthesis of submicron α-Fe{sub 2}O{sub 3} with rod-like structure. When it evaluated as electrode material for lithium ion battery, comparing with Cu foil and Ni foam, the as-prepared α-Fe{sub 2}O{sub 3} electrodes with Cu foam current collector exhibited higher reversible capacity of 415 mAh g{sup −1} and more stable cycle performance after 30 cycles. Comparative researches on electrochemical performances of the α-Fe{sub 2}O{sub 3} employing different current collectors (Cu foil, Cu foam and Ni foam) were discussed here in detail. According to our results, the improved electrochemical behaviors of α-Fe{sub 2}O{sub 3} electrode with Cu foam current collector could be attributed to its particular electrode structure, i.e., porous, good electric conductivity, closed adhere to the electrode materials. Just because of that, it may make sure an easy accessibility of electrolytes and fast transportation of lithium ions, importantly, it could avoid the active materials falling off from the current collector on account of volume expansion.

  7. Sandwich nanoarchitecture of Si/reduced graphene oxide bilayer nanomembranes for Li-ion batteries with long cycle life.

    PubMed

    Liu, Xianghong; Zhang, Jun; Si, Wenping; Xi, Lixia; Eichler, Barbara; Yan, Chenglin; Schmidt, Oliver G

    2015-02-24

    The large capacity loss and huge volume change of silicon anodes severely restricts their practical applications in lithium ion batteries. In this contribution, the sandwich nanoarchitecture of rolled-up Si/reduced graphene oxide bilayer nanomembranes was designed via a strain released strategy. Within this nanoarchitecture, the inner void space and the mechanical feature of nanomembranes can help to buffer the strain during lithiation/delithiation; the alternately stacked conductive rGO layers can protect the Si layers from excessive formation of SEI layers. As anodes for lithium-ion batteries, the sandwiched Si/rGO nanoarchitecture demonstrates long cycling life of 2000 cycles at 3 A g(-1) with a capacity degradation of only 3.3% per 100 cycles. PMID:25646575

  8. Ultra-fast dry microwave preparation of SnSb used as negative electrode material for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Antitomaso, P.; Fraisse, B.; Sougrati, M. T.; Morato-Lallemand, F.; Biscaglia, S.; Aymé-Perrot, D.; Girard, P.; Monconduit, L.

    2016-09-01

    Tin antimonide alloy was obtained for the first time using a very simple dry microwave route. Up to 1 g of well crystallized SnSb can be easily prepared in 90 s under air in an open crucible. A full characterization by X-ray diffraction and 119Sn Mössbauer spectroscopy demonstrated the benefit of carbon as susceptor, which avoid any oxide contamination. The microwave-prepared SnSb was tested as negative electrode material in Li batteries. Interesting results in terms of capacity and rate capability were obtained with up to 700 mAh/g sustained after 50 cycles at variable current. These results pave the way for the introduction of microwave synthesis as realistic route for a rapid, low cost and up-scalable production of electrode material for Li batteries or other large scale application types.

  9. Mesoscale Origin of the Enhanced Cycling-Stability of the Si-Conductive Polymer Anode for Li-ion Batteries

    SciTech Connect

    Gu, Meng; Xiao, Xingcheng; Liu, Gao; Thevuthasan, Suntharampillai; Baer, Donald R.; Zhang, Jiguang; Liu, Jun; Browning, Nigel D.; Wang, Chong M.

    2014-01-14

    Electrode used in lithium-ion battery is invariably a composite of multifunctional components. The performance of the electrode is controlled by the interactive function of all components at mesoscale. Fundamental understanding of mesoscale phenomenon sets the basis for innovative designing of new materials. Here we report the achievement and origin of a significant performance enhancement of electrode for lithium ion batteries based on Si nanoparticles wrapped with conductive polymer. This new material is in marked contrast with conventional material, which exhibit fast capacity fade. In-situ TEM unveils that the enhanced cycling stability of the conductive polymer-Si composite is associated with mesoscale concordant function of Si nanoparticles and the conductive polymer. Reversible accommodation of the volume changes of Si by the conductive polymer allows good electrical contact between all the particles during the cycling process. In contrast, the failure of the conventional Si-electrode is probed to be the inadequate electrical contact.

  10. Cr, N-Codoped TiO2 Mesoporous Microspheres for Li-ion Rechargeable Batteries with Enhanced Electrochemical Performance

    SciTech Connect

    Bi, Zhonghe; Paranthaman, Mariappan Parans; Guo, Bingkun; Unocic, Raymond R; Meyer III, Harry M; Bridges, Craig A; Sun, Xiao-Guang; Dai, Sheng

    2014-01-01

    Cr,N-codoped TiO2 mesoporous microspheres synthesized using hydrothermal and subsequent nitridation treatment, exhibited higher solubility of nitrogen, and improved electrical conductivity than N-doped TiO2, as anode for Lithium-ion rechargeable batteries, which led to improving charge-discharge capacity at 0.1 C and twice higher rate capability compared to that of nitrogen-doped TiO2 mesoporous microsphere at 10 C

  11. Three-Phase Model for the Reversible Lithiation-Delithiation of SnO Anodes in Li-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Pedersen, Andreas; Khomyakov, Petr A.; Luisier, Mathieu

    2015-09-01

    A high reversible capacity is a key feature for any rechargeable battery. In lithium-ion battery technology, tin-oxide anodes do fulfill this requirement, but a fast loss of capacity hinders a full commercialization. Using first-principles calculations, we propose a microscopic model that sheds light on the reversible lithiation-delithiation of SnO and reveals that a sintering of Sn causes a strong degradation of SnO-based anodes. When the initial irreversible transformation ends, active anode grains consist of Li-oxide layers separated by Sn bilayers. During the following reversible lithiation, the Li oxide undergoes two phase transformations that give rise to a Li enrichment of the oxide and the formation of a layered SnLi composite. We find that the model-predicted anode volume expansion and voltage profile agree well with experiments, and a layered anode grain is highly conductive and has a theoretical reversible capacity of 4.5 Li atoms per a SnO host unit. The model suggests that the grain structure has to remain layered to sustain its reversible capacity and a thin-film design of battery anodes could be a remedy for the capacity loss.

  12. Design, Fabrication, and Testing of Silicon-integrated Li-ion Secondary Micro Batteries with Interdigital Electrodes

    NASA Astrophysics Data System (ADS)

    Hoeppner, K.; Ferch, M.; Froebe, A.; Gernhardt, R.; Hahn, R.; Mackowiak, P.; Mukhopadhyay, B.; Roder, S.; Saalhofen, I.; Lang, K.-D.

    2015-12-01

    This paper reports the design, fabrication, and testing of silicon-integrated lithium ion secondary micro batteries with a side-by-side electrode setup. Cavities separated by narrow silicon spacers served as containments for two interdigitally arranged electrodes and were etched into <110>-Si by wet chemical etching. The etched silicon battery containments were passivated by a layer of SiOx/SixNy. Al current collectors were applied by sputtering and back etching. A volumetric micro dispenser served to fill the cavities with slurries of the active materials - lithium cobalt manganese oxide (Liy(Ni1/2Co1/5Mn3/10)O2) as the cathode and lithium titanate (Li4Ti5O12) as the anode material. Filling with electrolyte, encapsulation, and electrochemical characterization of the finished cells took place in an Ar-filled glove box. The fabricated batteries with IDE show considerably lower impedances than cells with single side by side electrodes and are capable of constant current loads up to 10 C. A linear capacity loss rate of <0.1% per cycle was observed over 30 full cycles at 0.2C.

  13. Advanced battery development

    NASA Astrophysics Data System (ADS)

    In order to promote national security by ensuring that the United States has an adequate supply of safe, assured, affordable, and environmentally acceptable energy, the Storage Batteries Division at Sandia National Laboratories (SNL), Albuquerque, is responsible for engineering development of advanced rechargeable batteries for energy applications. This effort is conducted within the Exploratory Battery Technology Development and Testing (ETD) Lead center, whose activities are coordinated by staff within the Storage Batteries Division. The ETD Project, directed by SNL, is supported by the U.S. Department of Energy, Office of Energy Systems Research, Energy Storage and Distribution Division (DOE/OESD). SNL is also responsible for technical management of the Electric Vehicle Advanced Battery Systems (EV-ABS) Development Project, which is supported by the U.S. Department of Energy's Office of Transportation Systems (OTS). The ETD Project is operated in conjunction with the Technology Base Research (TBR) Project, which is under the direction of Lawrence Berkeley Laboratory. Together these two projects seek to establish the scientific feasibility of advanced electrochemical energy storage systems, and conduct the initial engineering development on systems suitable for mobile and stationary commercial applications.

  14. Bamboo leaf derived ultrafine Si nanoparticles and Si/C nanocomposites for high-performance Li-ion battery anodes.

    PubMed

    Wang, Lei; Gao, Biao; Peng, Changjian; Peng, Xiang; Fu, Jijiang; Chu, Paul K; Huo, Kaifu

    2015-09-01

    Silicon-based nanomaterials are promising anode materials in lithium-ion batteries (LIBs) due to their high theoretical capacity of 4200 mA h g(-1), more than 10 times that of commercial graphite. Si nanoparticles (NPs) with a diameter of or below 10 nm generally exhibit enhanced lithium storage properties due to their small size and large surface area. However, it is challenging to generate such ultrafine Si NPs by a facile and scalable method. This paper reports a scalable method to fabricate ultrafine Si NPs 5-8 nm in size from dead bamboo leaves (BLs) by thermally decomposing the organic matter, followed by magnesiothermic reduction in the presence of NaCl as a heat scavenger. The ultrafine Si NPs show a high capacity of 1800 mA h g(-1) at a 0.2 C (1 C = 4200 mA g(-1)) rate and are thus promising anode materials in lithium-ion batteries. To achieve better rate capability, the BLs-derived ultrafine Si NPs are coated with a thin amorphous carbon layer (Si@C) and then dispersed and embedded in a reduced graphene oxide (RGO) network to produce Si@C/RGO nanocomposites by a layer-by-layer assembly method. The double protection rendered by the carbon shell and RGO network synergistically yield structural stability, high electrical conductivity and a stable solid electrolyte interface during Li insertion/extraction. The Si@C/RGO nanocomposites show excellent battery properties with a high capacity of 1400 mA h g(-1) at a high current density of 2 C and remarkable rate performance with a capacity retention of 60% when the current density is increased 20 times from 0.2 to 4 C. This work provides a simple, low cost, and scalable approach enabling the use of BL waste as a sustainable source for the production of ultrafine Si NPs towards high-performance LIBs. PMID:26098990

  15. Chemical Bonding In Amorphous Si Coated-carbon Nanotube As Anodes For Li ion Batteries: A XANES Study

    SciTech Connect

    Zhou, Jigang; Hu, Yongfeng; Li, Xiaolin; Wang, Chong M.; Zuin, Lucia

    2014-03-11

    The chemical bonding nature and its evolution upon electrochemical cycling in amorphous Si coated-carbon nanotube (Si-CNT) anode has been investigated using comprehensive X-ray absorption spectroscopy (XANES) at Si L- and K-edges along with C and O K-edges. The Si nanolayer on CNT is found to be anchored to CNT via Si-O-C bonding. This bond weakens upon electrochemical cycling accompanied with generation of Li2CO3 on the surface of Si-CNT. Those findings are crucial in designing further improved Si-C composite anode for lithium ion battery.

  16. Materials for advanced batteries

    SciTech Connect

    Murphy, D.W.; Broadhead, J.

    1980-01-01

    The requirements of battery systems are considered along with some recent studies of materials of importance in aqueous electrochemical energy-storage systems, lithium-aluminum/iron sulfide batteries, solid electrolytes, molten salt electrolytes in secondary batteries, the recharging of the lithium electrode in organic electrolytes, intercalation electrodes, and interface phenomena in advanced batteries. Attention is given to a lead-acid battery overview, the design and development of micro-reference electrodes for the lithium/metal-sulfide cell system, molten salt electrochemical studies and high energy density cell development, a selenium (IV) cathode in molten chloroaluminates, and the behavior of hard and soft ions in solid electrolytes. Other topics explored are related to the use of the proton conductor hydrogen uranyl phosphate tetrahydrate as the solid electrolyte in hydride-air batteries and hydrogen-oxygen fuel cells, the behavior of the passivating film in Li/SOCl2 cells under various conditions, and the analysis of surface insulating films in lithium nitride crystals.

  17. Supercritical Carbon Dioxide-Assisted Process for Well-Dispersed Silicon/Graphene Composite as a Li ion Battery Anode

    PubMed Central

    Lee, Sang Ha; Park, Sengyoen; Kim, Min; Yoon, Dohyeon; Chanthad, Chalathorn; Cho, Misuk; Kim, Jaehoon; Park, Jong Hyeok; Lee, Youngkwan

    2016-01-01

    The silicon (Si)/graphene composite has been touted as one of the most promising anode materials for lithium ion batteries. However, the optimal fabrication method for this composite remains a challenge. Here, we developed a novel method using supercritical carbon dioxide (scCO2) to intercalate Si nanoparticles into graphene nanosheets. Silicon was modified with a thin layer of polyaniline, which assisted the dispersion of graphene sheets by introducing π-π interaction. Using scCO2, well-dispersed Si/graphene composite was successfully obtained in a short time under mild temperature. The composite showed high cycle performance (1,789 mAh/g after 250 cycles) and rate capability (1,690 mAh/g at a current density of 4,000 mA/g). This study provides a new approach for cost-effective and scalable preparation of a Si/graphene composite using scCO2 for a highly stable lithium battery anode material. PMID:27535108

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

    PubMed

    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. PMID:27031918

  19. Supercritical Carbon Dioxide-Assisted Process for Well-Dispersed Silicon/Graphene Composite as a Li ion Battery Anode.

    PubMed

    Lee, Sang Ha; Park, Sengyoen; Kim, Min; Yoon, Dohyeon; Chanthad, Chalathorn; Cho, Misuk; Kim, Jaehoon; Park, Jong Hyeok; Lee, Youngkwan

    2016-01-01

    The silicon (Si)/graphene composite has been touted as one of the most promising anode materials for lithium ion batteries. However, the optimal fabrication method for this composite remains a challenge. Here, we developed a novel method using supercritical carbon dioxide (scCO2) to intercalate Si nanoparticles into graphene nanosheets. Silicon was modified with a thin layer of polyaniline, which assisted the dispersion of graphene sheets by introducing π-π interaction. Using scCO2, well-dispersed Si/graphene composite was successfully obtained in a short time under mild temperature. The composite showed high cycle performance (1,789 mAh/g after 250 cycles) and rate capability (1,690 mAh/g at a current density of 4,000 mA/g). This study provides a new approach for cost-effective and scalable preparation of a Si/graphene composite using scCO2 for a highly stable lithium battery anode material. PMID:27535108

  20. Spray drying method for large-scale and high-performance silicon negative electrodes in Li-ion batteries.

    PubMed

    Jung, Dae Soo; Hwang, Tae Hoon; Park, Seung Bin; Choi, Jang Wook

    2013-05-01

    Nanostructured silicon electrodes have shown great potential as lithium ion battery anodes because they can address capacity fading mechanisms originating from large volume changes of silicon alloys while delivering extraordinarily large gravimetric capacities. Nonetheless, synthesis of well-defined silicon nanostructures in an industrially adaptable scale still remains as a challenge. Herein, we adopt an industrially established spray drying process to enable scalable synthesis of silicon-carbon composite particles in which silicon nanoparticles are embedded in porous carbon particles. The void space existing in the porous carbon accommodates the volume expansion of silicon and thus addresses the chronic fading mechanisms of silicon anodes. The composite electrodes exhibit excellent electrochemical performance, such as 1956 mAh/g at 0.05C rate and 91% capacity retention after 150 cycles. Moreover, the spray drying method requires only 2 s for the formation of each particle and allows a production capability of ~10 g/h even with an ultrasonic-based lab-scale equipment. This investigation suggests that established industrial processes could be adaptable to the production of battery active materials that require sophisticated nanostructures as well as large quantity syntheses. PMID:23537321

  1. The microstructure matters: breaking down the barriers with single crystalline silicon as negative electrode in Li-ion batteries.

    PubMed

    Sternad, M; Forster, M; Wilkening, M

    2016-01-01

    Silicon-based microelectronics forms a major foundation of our modern society. Small lithium-ion batteries act as the key enablers of its success and have revolutionised portable electronics used in our all everyday's life. While large-scale LIBs are expected to help establish electric vehicles, on the other end of device size chip-integrated Si-based μ-batteries may revolutionise microelectronics once more. In general, Si is regarded as one of the white hopes since it offers energy densities being ten times higher than conventional anode materials. The use of monocrystalline, wafer-grade Si, however, requires several hurdles to be overcome since it its volume largely expands during lithiation. Here, we will show how 3D patterned Si wafers, prepared by the sophisticated techniques from semiconductor industry, are to be electrochemically activated to overcome these limitations and to leverage their full potential being reflected in stable charge capacities (>1000 mAhg(-1)) and high Coulomb efficiencies (98.8%). PMID:27531589

  2. Succinic acid-based leaching system: A sustainable process for recovery of valuable metals from spent Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Li, Li; Qu, Wenjie; Zhang, Xiaoxiao; Lu, Jun; Chen, Renjie; Wu, Feng; Amine, Khalil

    2015-05-01

    A hydrometallurgical method involving natural organic acid leaching has been developed for recovery of lithium and cobalt from the cathode active materials in spent lithium-ion batteries. Succinic acid is employed as leaching agent and H2O2 as reductant. The cobalt and lithium contents from the succinic acid-based treatment of spent batteries are determined by inductively coupled plasma-optical emission spectroscopy to calculate the leaching efficiency. The spent LiCoO2 samples after calcination and the residues after leaching are characterized by X-ray diffraction and scanning electron microscopy. The results show that nearly 100% of cobalt and more than 96% of lithium are leached under optimal conditions: succinic acid concentration of 1.5 mol L-1, H2O2 content of 4 vol.%, solid-to-liquid ratio of 15 g L-1, temperature of 70 °C, and reaction time of 40 min. Results are also given for fitting of the experimental data to acid leaching kinetic models.

  3. The microstructure matters: breaking down the barriers with single crystalline silicon as negative electrode in Li-ion batteries

    PubMed Central

    Sternad, M.; Forster, M.; Wilkening, M.

    2016-01-01

    Silicon-based microelectronics forms a major foundation of our modern society. Small lithium-ion batteries act as the key enablers of its success and have revolutionised portable electronics used in our all everyday’s life. While large-scale LIBs are expected to help establish electric vehicles, on the other end of device size chip-integrated Si-based μ-batteries may revolutionise microelectronics once more. In general, Si is regarded as one of the white hopes since it offers energy densities being ten times higher than conventional anode materials. The use of monocrystalline, wafer-grade Si, however, requires several hurdles to be overcome since it its volume largely expands during lithiation. Here, we will show how 3D patterned Si wafers, prepared by the sophisticated techniques from semiconductor industry, are to be electrochemically activated to overcome these limitations and to leverage their full potential being reflected in stable charge capacities (>1000 mAhg–1) and high Coulomb efficiencies (98.8%). PMID:27531589

  4. Influence of conductivity on the capacity retention of NiO anodes in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Spinner, Neil S.; Palmieri, Alessandro; Beauregard, Nicole; Zhang, Lichun; Campanella, James; Mustain, William E.

    2015-02-01

    The roles of conductivity and structure in the reversibility, rate capability, capacity and capacity retention of nickel oxide anodes for lithium-ion batteries were investigated. Conductivity was controlled by the systematic addition of non-intercalating carbon. The NiO nanostructure was controlled through four different preparation procedures. Overall, the top-performing electrodes were made from tetrahedral-shaped particles with a broad particle size distribution that were derived from a simple direct calcination of nickel nitrate salt. Capacity values >700 mA h/g after 100 cycles at 1C were observed, and a rate capability >400 mA h/g at 5C was achieved for electrodes with 40% carbon added. The addition of carbon universally improved anode performance by influencing the charge transferability, as evidenced by SEI peak shifts and reduced resistances seen via EIS. Reversibility was greatly enhanced as the conductivity was improved through carbon addition, which enabled otherwise inactive anode particles to maintain activity after many cycles. This work suggests that improved conductivity, as opposed to the conventional opinion regarding nanostructure, is the key to creating high performance anodes for next generation lithium-ion batteries.

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

    NASA Astrophysics Data System (ADS)

    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

  6. Performance of Low Temperature Electrolytes in Experimental and Prototype Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Whitcanack, L. D.

    2007-01-01

    Due to their attractive properties and proven success, Li-ion batteries have become identified as the battery chemistry of choice for a number of future NASA missions. A number of these applications would be greatly benefited by improved performance of Li-ion technology over a wider operating temperature range, especially at low temperatures, such as future ESMD missions. In many cases, these technology improvements may be mission enabling, and at the very least mission enhancing. In addition to aerospace applications, the DoE has interest in developing advanced Li-ion batteries that can operate over a wide temperature range to enable terrestrial HEV applications. Thus, our focus at JPL in recent years has been to extend the operating temperature range of Li-ion batteries, especially at low temperatures. To accomplish this, the main focus of the research has been devoted to developing improved lithium-ion conducting electrolytes. In the present paper, we would like to present some of the results we have obtained with ethylene carbonate-based electrolytes optimized for low temperature in experimental MCMB-LiNixCo1_x0 2 cells. In addition to obtaining discharge and charge rate performance data at various temperatures, electrochemical measurements were performed on individual electrodes (made possible by the incorporation of Li reference electrodes), including EIS, linear polarization and Tafel polarization measurements. The combination of techniques enables the elucidation of various trends associated with electrolyte composition. In addition to investigating the behavior in experimental cells, the performance of many promising low temperature electrolytes was demonstrated in large capacity, aerospace quality Li-ion prototype cells. These cells were subjected to a number of performance tests, including discharge rate characterization, charge rate characterization, cycle life performance at various temperatures, and power characterization tests.

  7. Binder-free Ge-three dimensional graphene electrodes for high-rate capacity Li-ion batteries

    SciTech Connect

    Wang, C. D.; Chui, Y. S.; Chen, X. F. E-mail: apwjzh@cityu.edu.hk; Zhang, W. J. E-mail: apwjzh@cityu.edu.hk; Li, Y.

    2013-12-16

    A binder-free, high-rate Ge-three dimensional (3D) graphene composite was synthesized by directly depositing Ge film atop 3D graphene grown by microwave plasma chemical vapor deposition on Ni substrate. The Ge-3D graphene structure demonstrates excellent electrochemical performance as a lithium ion battery (LIB) anode with a reversible capacity of 1140 mAh g{sup −1} at 1/3C over 100 cycles and 835 mAh g{sup −1} at 8C after 60 cycles, and significantly a discharge capacity of 186 mAh g{sup −1} was still achieved at 32C. The high capacity and outstanding stability of the Ge-3D graphene composite propose it as a promising electrode in high-performance thin film LIBs.

  8. Effects of cell positive cans and separators on the performance of high-voltage Li-ion batteries

    SciTech Connect

    Chen, Xilin; Xu, Wu; Xiao, Jie; Engelhard, Mark H.; Ding, Fei; Mei, Donghai; Hu, Dehong; Zhang, Jian; Zhang, Jiguang

    2012-09-01

    The effects of different cell cans and separators on the first-cycle Coulombic efficiency and long-term cycling stability of high voltage spinel cathode were investigated systematically. Compared to stainless steel (SS) positive-cans, aluminum (Al)-clad SS-316 positive-cans have a much better resistance to oxidation at high voltages thus improving the initial Coulombic efficiency of the batteries by more than 13%. Among the five separators studied in this work, polyethylene (PE) separator shows the best electrochemical stability. The cells using LiCr0.05Ni0.45Mn1.5O4 as cathode, Al-clad positive-can, and PE separator exhibit the first-cycle Columbic efficiency of about 90% and a capacity fading of only 0.01% per cycle.

  9. Chemical synthesis of porous hierarchical Ge-Sn binary composites using metathesis reaction for rechargeable Li-ion batteries.

    PubMed

    Lin, Ning; Zhou, Jie; Han, Ying; Zhang, Kailong; Zhu, Yongchun; Qian, Yitai

    2015-12-14

    Direct metathesis reaction between Mg2Ge and SnCl4 is introduced to prepare porous hierarchical Ge-Sn binary composites, in which the Ge and Sn components are distributed uniformly, with a tap density of 2.3 g cm(-3). As an anode for LIBs, the Ge-Sn composite displays a specific capacity of 980 mA h g(-1) at 0.5 A g(-1) after 250 cycles, and 890 mA h g(-1) at 3 A g(-1) over 1700 cycles. When paired with a commercial LiCoO2 cathode, a 3.6 V full battery with a capacity of 830 mA h g(-1) is obtained. PMID:26455516

  10. Si nanoparticles encapsulated in elastic hollow carbon fibres for Li-ion battery anodes with high structural stability.

    PubMed

    Fang, Shan; Shen, Laifa; Tong, Zhenkun; Zheng, Hao; Zhang, Fang; Zhang, Xiaogang

    2015-04-28

    Silicon has a large specific capacity which is an order of magnitude beyond that of conventional graphite, making it a promising anode material for lithium ion batteries. However, the large volume changes (∼ 300%) during cycling caused material pulverization and instability of the solid-electrolyte interphase resulting in poor cyclability which prevented its commercial application. Here, we have prepared a novel one-dimensional core-shell nanostructure in which the Si nanoparticles have been confined within hollow carbon nanofibres. Such a unique nanostructure exhibits high conductivity and facile ion transport, and the uniform pores within the particles which are generated during magnesiothermic reduction can serve as a buffer zone to accommodate the large volume changes of Si during electrochemical lithiation. Owing to these advantages, the composite shows high rate performance and good cycling stability. The optimum design of the core-shell nanostructure shows promise for the synthesis of a variety of high-performance electrode materials. PMID:25826238

  11. Surface/Interface Effects on High-Performance Thin-Film All-Solid-State Li-Ion Batteries.

    PubMed

    Gong, Chen; Ruzmetov, Dmitry; Pearse, Alexander; Ma, Dakang; Munday, Jeremy N; Rubloff, Gary; Talin, A Alec; Leite, Marina S

    2015-12-01

    The further development of all-solid-state batteries is still limited by the understanding/engineering of the interfaces formed upon cycling. Here, we correlate the morphological, chemical, and electrical changes of the surface of thin-film devices with Al negative electrodes. The stable Al-Li-O alloy formed at the stress-free surface of the electrode causes rapid capacity fade, from 48.0 to 41.5 μAh/cm(2) in two cycles. Surprisingly, the addition of a Cu capping layer is insufficient to prevent the device degradation. Nevertheless, Si electrodes present extremely stable cycling, maintaining >92% of its capacity after 100 cycles, with average Coulombic efficiency of 98%. PMID:26436529

  12. Remarkable performance improvement of inexpensive ball-milled Si nanoparticles by carbon-coating for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Kasukabe, Takatoshi; Nishihara, Hirotomo; Iwamura, Shinichiroh; Kyotani, Takashi

    2016-07-01

    Si nanoparticles prepared by ball-milling (BM-Si) are expected as practical negative-electrode materials for lithium-ion batteries, but their performance is much lower than those of more expensive Si nanomaterials, such as chemical-vapor-deposition derived Si nanoparticles (CVD-Si) having a tight network structure. It is found that carbon-coating of aggregations of BM-Si forms a quasi-network structure, thereby making the performance comparable to that of CVD-Si under capacity restriction (to 1500 mAh g-1). In this case, the structural transition of BM-Si during charge/discharge cycling is characterized by the formation of a specific 'wrinkled structure', which is very similar to that formed in CVD-Si.

  13. Li-ion Battery Separators, Mechanical Integrity and Failure Mechanisms Leading to Soft and Hard Internal Shorts.

    PubMed

    Zhang, Xiaowei; Sahraei, Elham; Wang, Kai

    2016-01-01

    Separator integrity is an important factor in preventing internal short circuit in lithium-ion batteries. Local penetration tests (nail or conical punch) often produce presumably sporadic results, where in exactly similar cell and test set-ups one cell goes to thermal runaway while the other shows minimal reactions. We conducted an experimental study of the separators under mechanical loading, and discovered two distinct deformation and failure mechanisms, which could explain the difference in short circuit characteristics of otherwise similar tests. Additionally, by investigation of failure modes, we provided a hypothesis about the process of formation of local "soft short circuits" in cells with undetectable failure. Finally, we proposed a criterion for predicting onset of soft short from experimental data. PMID:27581185

  14. Effects of cell positive cans and separators on the performance of high-voltage Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Chen, Xilin; Xu, Wu; Xiao, Jie; Engelhard, Mark H.; Ding, Fei; Mei, Donghai; Hu, Dehong; Zhang, Jian; Zhang, Ji-Guang

    2012-09-01

    The effects of different cell positive cans and separators on first-cycle Coulombic efficiency and long-term cycling stability of a high-voltage spinel cathode are investigated systematically. Compared to stainless steel (SS) positive cans, aluminum (Al)-clad SS-316 positive cans are much more resistant to oxidation at high voltages; therefore, the initial Coulombic efficiency of the batteries with Al-clad can is improved by more than 13%. Among the five separators studied in this work, the polyethylene (PE) separator exhibits the best electrochemical stability. The cells using LiCr0.05Ni0.45Mn1.5O4 as the cathode, an Al-clad positive can, and a PE separator exhibits a first-cycle Coulombic efficiency of about 90% and a capacity fading of only 0.01% per cycle.

  15. Fabrication of Sn-Ni/MWCNT composite coating for Li-ion batteries by pulse electrodeposition: Effects of duty cycle

    NASA Astrophysics Data System (ADS)

    Uysal, Mehmet; Cetinkaya, Tugrul; Alp, Ahmet; Akbulut, Hatem

    2015-04-01

    Nanocrystalline Sn-Ni/MWCNT composite was prepared by ultrasonic-pulse electrodeposition on a copper substrate in a pyrophosphate bath at different duty cycles. Surface morphology of produced Sn-Ni/MWCNT composites were characterized by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) was conducted to understand the elemental surface composition of composites. X-ray diffraction analysis (XRD) was carried out to investigate structure of Sn-Ni/MWCNT composites. The electrochemical performance of Sn-Ni/MWCNT composite electrodes were investigated by charge/discharge tests and cyclic voltammetric experiments. The cells discharge capacities were determined by cyclic testing by a battery tester at a constant current in voltage range between 0.02 V and 1.5 V. The duty cycle was shown to be a crucial factor to improve Sn-Ni/MWCNT composite anodes for cyclability and reversible capacity.

  16. Li-ion Battery Separators, Mechanical Integrity and Failure Mechanisms Leading to Soft and Hard Internal Shorts

    PubMed Central

    Zhang, Xiaowei; Sahraei, Elham; Wang, Kai

    2016-01-01

    Separator integrity is an important factor in preventing internal short circuit in lithium-ion batteries. Local penetration tests (nail or conical punch) often produce presumably sporadic results, where in exactly similar cell and test set-ups one cell goes to thermal runaway while the other shows minimal reactions. We conducted an experimental study of the separators under mechanical loading, and discovered two distinct deformation and failure mechanisms, which could explain the difference in short circuit characteristics of otherwise similar tests. Additionally, by investigation of failure modes, we provided a hypothesis about the process of formation of local “soft short circuits” in cells with undetectable failure. Finally, we proposed a criterion for predicting onset of soft short from experimental data. PMID:27581185

  17. A siloxane-incorporated copolymer as an in situ cross-linkable binder for high performance silicon anodes in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Jeena, M. T.; Bok, Taesoo; Kim, Si Hoon; Park, Sooham; Kim, Ju-Young; Park, Soojin; Ryu, Ja-Hyoung

    2016-04-01

    The electrochemical performance of Li-ion batteries (LIBs) can be highly tuned by various factors including the morphology of the anode material, the nature of the electrolyte, the binding material, and the percentage of conducting materials. Binding materials have been of particular interest to researchers over the decades as a means to further improve the cycle durability and columbic efficiency of LIBs. Such approaches include the introduction of different polymeric binders such as poly(acrylic acid) (PAA), carboxymethyl cellulose (CMC), and alginic acid (Alg) into the Si anode of LIBs. To achieve a better efficiency of LIBs, herein, we introduce a novel copolymer, poly(tert-butyl acrylate-co-triethoxyvinylsilane) (TBA-TEVS), as an efficient binder with stable cycle retention and excellent specific capacity. The binder forms a highly interconnected three-dimensional network upon thermal treatment as a result of de-protection of the tert-butyl group and the consequent inter-intra condensation reaction, which minimizes pulverization of the Si nanoparticles. Moreover, the siloxane group is expected to promote the formation of stable solid-electrolyte-interface (SEI) layers. A series of random copolymers were synthesized by varying the molar ratio of tert-butyl acrylate and triethoxyvinylsilane. Twenty-one percent of TEVS in the TBS-TEVS copolymer gave rise to a superior performance as a binder for Si anodes, where the anodes showed a stable specific capacity of 2551 mA h g-1 over hundreds of cycles and an initial columbic efficiency (ICE) of 81.8%.The electrochemical performance of Li-ion batteries (LIBs) can be highly tuned by various factors including the morphology of the anode material, the nature of the electrolyte, the binding material, and the percentage of conducting materials. Binding materials have been of particular interest to researchers over the decades as a means to further improve the cycle durability and columbic efficiency of LIBs. Such approaches

  18. Bamboo leaf derived ultrafine Si nanoparticles and Si/C nanocomposites for high-performance Li-ion battery anodes

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Gao, Biao; Peng, Changjian; Peng, Xiang; Fu, Jijiang; Chu, Paul K.; Huo, Kaifu

    2015-08-01

    Silicon-based nanomaterials are promising anode materials in lithium-ion batteries (LIBs) due to their high theoretical capacity of 4200 mA h g-1, more than 10 times that of commercial graphite. Si nanoparticles (NPs) with a diameter of or below 10 nm generally exhibit enhanced lithium storage properties due to their small size and large surface area. However, it is challenging to generate such ultrafine Si NPs by a facile and scalable method. This paper reports a scalable method to fabricate ultrafine Si NPs 5-8 nm in size from dead bamboo leaves (BLs) by thermally decomposing the organic matter, followed by magnesiothermic reduction in the presence of NaCl as a heat scavenger. The ultrafine Si NPs show a high capacity of 1800 mA h g-1 at a 0.2 C (1 C = 4200 mA g-1) rate and are thus promising anode materials in lithium-ion batteries. To achieve better rate capability, the BLs-derived ultrafine Si NPs are coated with a thin amorphous carbon layer (Si@C) and then dispersed and embedded in a reduced graphene oxide (RGO) network to produce Si@C/RGO nanocomposites by a layer-by-layer assembly method. The double protection rendered by the carbon shell and RGO network synergistically yield structural stability, high electrical conductivity and a stable solid electrolyte interface during Li insertion/extraction. The Si@C/RGO nanocomposites show excellent battery properties with a high capacity of 1400 mA h g-1 at a high current density of 2 C and remarkable rate performance with a capacity retention of 60% when the current density is increased 20 times from 0.2 to 4 C. This work provides a simple, low cost, and scalable approach enabling the use of BL waste as a sustainable source for the production of ultrafine Si NPs towards high-performance LIBs.Silicon-based nanomaterials are promising anode materials in lithium-ion batteries (LIBs) due to their high theoretical capacity of 4200 mA h g-1, more than 10 times that of commercial graphite. Si nanoparticles (NPs) with a

  19. Analysis of Heat Dissipation in Li-Ion Cells & Modules for Modeling of Thermal Runaway (Presentation)

    SciTech Connect

    Kim, G.-H.; Pesaran, A.

    2007-05-15

    The objectives of this study are: (1) To develop 3D Li-Ion battery thermal abuse ''reaction'' models for cell and module analysis; (2) To understand the mechanisms and interactions between heat transfer and chemical reactions during thermal runaway for Li-Ion cells and modules; (3) To develop a tool and methodology to support the design of abuse-tolerant Li-Ion battery systems for PHEVs/HEVs; and (4) To help battery developers accelerate delivery of abuse-tolerant Li-Ion battery systems in support of the FreedomCAR's Energy Storage Program.

  20. Synthesis of hierarchically porous SnO(2) microspheres and performance evaluation as li-ion battery anode by using different binders.

    PubMed

    Gurunathan, P; Ette, Pedda Masthanaiah; Ramesha, K

    2014-10-01

    We have prepared nanoporous SnO2 hollow microspheres (HMS) by employing the resorcinol-formaldehyde (RF) gel method. Further, we have investigated the electrochemical property of SnO2-HMS as negative electrode material in rechargeable Li-ion batteries by employing three different binders-polyvinylidene difluoride (PVDF), Na salt of carboxy methyl cellulose (Na-CMC), and Na-alginate. At 1C rate, SnO2 electrode with Na-alginate binder exhibits discharge capacity of 800 mA h g(-1), higher than when Na-CMC (605 mA h g(-1)) and PVDF (571 mA h g(-1)) are used as binders. After 50 cycles, observed discharge capacities were 725 mA h g(-1), 495 mA h g(-1), and 47 mA h g(-1), respectively, for electrodes with Na-alginate, Na-CMC, and PVDF binders that amounts to a capacity retention of 92%, 82%, and 8% . Electrochemical impedance spectroscopy (EIS) results confirm that the SnO2 electrode with Na-alginate as binder had much lower charge transfer resistance than the electrode with Na-CMC and PVDF binders. The superior electrochemical property of the SnO2 electrode containing Na-alginate can be attributed to the cumulative effects arising from integration of nanoarchitecture with a suitable binder; the hierarchical porous structure would accommodate large volume changes during the Li interaclation-deintercalation process, and the Na-alginate binder provides a stronger adhesion betweeen electrode film and current collector. PMID:25203752

  1. Novel binary deep eutectic electrolytes for rechargeable Li-ion batteries based on mixtures of alkyl sulfonamides and lithium perfluoroalkylsulfonimide salts

    NASA Astrophysics Data System (ADS)

    Geiculescu, O. E.; DesMarteau, D. D.; Creager, S. E.; Haik, O.; Hirshberg, D.; Shilina, Y.; Zinigrad, E.; Levi, M. D.; Aurbach, D.; Halalay, I. C.

    2016-03-01

    Ionic liquids (IL's) were proposed for use in Li-ion batteries (LIBs), in order to mitigate some of the well-known drawbacks of LiPF6/mixed organic carbonates solutions. However, their large cations seriously decrease lithium transference numbers and block lithium insertion sites at electrode-electrolyte interfaces, leading to poor LIB rate performance. Deep eutectic electrolytes (DEEs) (which share some of the advantages of ILs but possess only one cation, Li+), were then proposed, in order to overcome the difficulties associated with ILs. We report herein on the preparation, thermal properties (melting, crystallization, and glass transition temperatures), transport properties (specific conductivity and viscosity) and thermal stability of binary DEEs based on mixtures of lithium bis(trifluoromethane)sulfonimide or lithium bis(fluoro)sulfonimide salts with an alkyl sulfonamide solvent. Promise for LIB applications is demonstrated by chronoamperometry on Al current collectors, and cycling behavior of negative and positive electrodes. Residual current densities of 12 and 45 nA cm-2 were observed at 5 V vs. Li/Li+ on aluminum, 1.5 and 16 nA cm-2 at 4.5 V vs. Li/Li+, respectively for LiFSI and LiTFSI based DEEs. Capacities of 220, 130, and 175 mAh· g-1 were observed at low (C/13 or C/10) rates, respectively for petroleum coke, LiMn1/3Ni1/3Co1/3O2 (a.k.a. NMC 111) and LiAl0.05Co0.15Ni0.8O2 (a.k.a. NCA).

  2. A siloxane-incorporated copolymer as an in situ cross-linkable binder for high performance silicon anodes in Li-ion batteries.

    PubMed

    Jeena, M T; Bok, Taesoo; Kim, Si Hoon; Park, Sooham; Kim, Ju-Young; Park, Soojin; Ryu, Ja-Hyoung

    2016-04-28

    The electrochemical performance of Li-ion batteries (LIBs) can be highly tuned by various factors including the morphology of the anode material, the nature of the electrolyte, the binding material, and the percentage of conducting materials. Binding materials have been of particular interest to researchers over the decades as a means to further improve the cycle durability and columbic efficiency of LIBs. Such approaches include the introduction of different polymeric binders such as poly(acrylic acid) (PAA), carboxymethyl cellulose (CMC), and alginic acid (Alg) into the Si anode of LIBs. To achieve a better efficiency of LIBs, herein, we introduce a novel copolymer, poly(tert-butyl acrylate-co-triethoxyvinylsilane) (TBA-TEVS), as an efficient binder with stable cycle retention and excellent specific capacity. The binder forms a highly interconnected three-dimensional network upon thermal treatment as a result of de-protection of the tert-butyl group and the consequent inter-intra condensation reaction, which minimizes pulverization of the Si nanoparticles. Moreover, the siloxane group is expected to promote the formation of stable solid-electrolyte-interface (SEI) layers. A series of random copolymers were synthesized by varying the molar ratio of tert-butyl acrylate and triethoxyvinylsilane. Twenty-one percent of TEVS in the TBS-TEVS copolymer gave rise to a superior performance as a binder for Si anodes, where the anodes showed a stable specific capacity of 2551 mA h g(-1) over hundreds of cycles and an initial columbic efficiency (ICE) of 81.8%. PMID:27087685

  3. Enhancing phase stability and kinetics of lithium-rich layered oxide for an ultra-high performing cathode in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Lee, Sung Hoon; Moon, Jong-Seok; Lee, Mi-Sun; Yu, Tae-Hwan; Kim, Hyunbin; Park, Bong Mo

    2015-05-01

    To achieve a higher capacity and rate capability, the electrochemical performance of doped Li-rich layered oxide (LLO), in which Co and O ions are substituted with various dopants (Ti, Zr, Ce, Mo, W, and F), is investigated using first-principles calculations. W and Mo are candidate dopants to enhance the phase stability but are excluded due to the decreased average cell voltage of 2.5-5.4 %, lowering the energy density of a battery. Instead, F is selected as a promising dopant because F-doped LLO can achieve high structural stability without a reduction in the average cell voltage compared with un-doped LLO. The Li slab distance in F-doped LLO expands approximately 3-8% depending on the Li concentration, and the activation energy for Li hopping is reduced about 30%, suggesting faster Li ion diffusion. The enthalpy of formation of F-doped LLO is reduced to 5.3-12.4 kJ mol-1 during de-lithiation, implying an increase in phase stability. Based on the DFT prediction, we experimentally demonstrate F-doped LLO (Li1.17Ni0.17Co0.17Mn0.50O1.96F0.04) exhibits a high capacity of 252.2 mAh g-1 at 0.33C rate in the cut-off voltage range of 3.0-4.6 V. The rate capability is enhanced, and the capacity is retained up to 83% at 3C compared with the 0.33C rate.

  4. Overview of Computer-Aided Engineering of Batteries and Introduction to Multi-Scale, Multi-Dimensional Modeling of Li-Ion Batteries (Presentation)

    SciTech Connect

    Pesaran, A.; Kim, G. H.; Smith, K.; Santhanagopalan, S.; Lee, K. J.

    2012-05-01

    This 2012 Annual Merit Review presentation gives an overview of the Computer-Aided Engineering of Batteries (CAEBAT) project and introduces the Multi-Scale, Multi-Dimensional model for modeling lithium-ion batteries for electric vehicles.

  5. Core-shell Si@TiO2 nanosphere anode by atomic layer deposition for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Bai, Ying; Yan, Dong; Yu, Caiyan; Cao, Lina; Wang, Chunlei; Zhang, Jinshui; Zhu, Huiyuan; Hu, Yong-Sheng; Dai, Sheng; Lu, Junling; Zhang, Weifeng

    2016-03-01

    Silicon (Si) has been regarded as next-generation anode for high-energy lithium-ion batteries (LIBs) due to its high Li storage capacity (4200 mA h g-1). However, the mechanical degradation and resultant capacity fade critically hinder its practical application. In this regard, we demonstrate that nanocoating of Si spheres with a 3 nm titanium dioxide (TiO2) layer via atomic layer deposition (ALD) can utmostly balance the high conductivity and the good structural stability to improve the cycling stability of Si core material. The resultant sample, Si@TiO2-3 nm core-shell nanospheres, exhibits the best electrochemical performance of all with a highest initial Coulombic efficiency and specific charge capacity retention after 50 cycles at 0.1C (82.39% and 1580.3 mA h g-1). In addition to making full advantage of the ALD technique, we believe that our strategy and comprehension in coating the electrode and the active material could provide a useful pathway towards enhancing Si anode material itself and community of LIBs.

  6. Graphene Folding in Si Rich Carbon Nanofibers for Highly Stable, High Capacity Li-Ion Battery Anodes.

    PubMed

    Fei, Ling; Williams, Brian P; Yoo, Sang H; Kim, Jangwoo; Shoorideh, Ghazal; Joo, Yong Lak

    2016-03-01

    Silicon nanoparticles (Si NPs) wrapped by graphene in carbon nanofibers were obtained via electrospinning and subsequent thermal treatment. In this study, water-soluble poly(vinyl alcohol) (PVA) with low carbon yield is selected to make the process water-based and to achieve a high silicon yield in the composite. It was also found that increasing the amount of graphene helps keep the PVA fiber morphology after carbonization, while forming a graphene network. The fiber SEM and HRTEM images reveal that micrometer graphene is heavily folded into sub-micron scale fibers during electrospinning, while Si NPs are incorporated into the folds with nanospace in between. When applied to lithium-ion battery anodes, the Si/graphene/carbon nanofiber composites show a high reversible capacity of ∼2300 mAh g(-1) at a charging rate of 100 mA/g and a stable capacity of 1191 mAh g(-1) at 1 A/g after more than 200 cycles. The interconnected graphene network not only ensures the excellent conductivity but also serves as a buffering matrix for the mechanic stress caused by volume change; the nanospace between Si NPs and folded graphene provides the space needed for volume expansion. PMID:26853163

  7. Poly(isobutylene-alt-maleic anhydride) binders containing lithium for high-performance Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Ku, Jun-Hwan; Hwang, Seung-Sik; Ham, Dong-Jin; Song, Min-Sang; Shon, Jeong-Kuk; Ji, Sang-Min; Choi, Jae-Man; Doo, Seok-Gwang

    2015-08-01

    Anode materials including graphite are known to be thermodynamically unstable toward organic solvents and salts and become covered by a passivating film (Solid electrolyte interphase, SEI) which retards the kinetics because of the high electronic resistivity. To achieve high performance in lithium ion batteries (LIBs), the SEIs are required to be mechanically stable during repeated cycling and possess highly ion-conductive. In this work, we have investigated an artificial pre-SEI on graphite electrode using a polymer binder containing lithium (i.e., a Li-copolymer of isobutylene and maleic anhydride, Li-PIMA) and its effect on the anode performances. During charging, the polymer binder with the functional group (-COOLi) acts as a SEI component, reducing the electrolyte decomposition and providing a stable passivating layer for the favorable penetration of lithium ions. Hence, by using the binder containing lithium, we have been able to obtain the first Coulombic efficiency of 84.2% (compared to 77.2% obtained using polyvinylidene fluoride as the binder) and a capacity retention of 99% after 100 cycles. The results of our study demonstrate that binder containing lithium we have used is a favorable candidate for the development of high-performance LIBs.

  8. Water based processing of LiFePO4/C cathode material for Li-ion batteries utilizing freeze granulation

    NASA Astrophysics Data System (ADS)

    Orlenius, J.; Lyckfeldt, O.; Kasvayee, K. A.; Johander, P.

    2012-09-01

    A water based solid state synthesis of LiFePO4 has been conducted by utilizing freeze granulation. Various processing conditions were tested and achieved powder properties were characterized by density, XRD, specific surface area, carbon content, conductivity and SEM. Freeze granulation, a novel method for precursor preparation was shown to be an effective method to provide high degree of homogeneity prior to calcination and high ultimate yield of pure LiFePO4. Cathodes were manufactured by water based as well as NMP system based tape casting. A commercial LiFePO4/C powder was also characterized and used to manufacture cathodes as comparison in this study. Charge cycling tests showed promising results with high capacity and long term stability, well in the range of what the commercial powder provided. Post-milling of calcined powder prior to paste preparation for tape casting tended, however, to retard the capacity owing to disturbed carbon distribution and loss of conductivity of the LiFePO4/C. In comparison with the solvent system for cathode manufacturing, the water based system gave similar cell performance, illustrating the possibility to apply a more environmentally sustainable processing of Li-battery cells.

  9. Rational Design of Graphene-Reinforced MnO Nanowires with Enhanced Electrochemical Performance for Li-Ion Batteries.

    PubMed

    Sun, Qi; Wang, Zhijie; Zhang, Zijiao; Yu, Qian; Qu, Yan; Zhang, Jingyu; Yu, Yan; Xiang, Bin

    2016-03-01

    Recently, transition metal oxides (TMOs) mixed with carbon materials have attracted attention as lithium-ion battery (LIB) anode materials. However, the aggregation issue in TMOs hinders the development of an ideal encapsulation structure with carbon materials. In this paper, we report graphene reinforced MnO nanowires with enhanced electrochemical performance as an anode in LIB. The graphene nanosheets (GNs)/MnO feature was confirmed by transmission electron microscopy, X-ray diffraction, Raman scattering, and X-ray photoelectron spectroscopy. The GNs/MnO nanowires delivered a highly stable discharge capacity of ∼815 mAh g(-1) at a current density of 100 mA g(-1) after 200 cycles, which is 1.5 times higher than that of pure MnO nanowires. This GNs/MnO structure with a specific capacity of ∼995 mAh g(-1) at a current density of 50 mA g(-1) also exhibited excellent Li storage properties. The superior cycling and high rate capability were attributed to the intimate incorporation between the MnO and GNs. The structure of the GNs/MnO nanowires effectively accommodated the volume change of the MnO nanowires and prevented structure collapse during cycling. PMID:26894410

  10. Comprehensive Understanding of High Polar Polyacrylonitrile as an Effective Binder for Li-Ion Battery Nano-Si Anodes.

    PubMed

    Luo, Lei; Xu, Yunlong; Zhang, Huang; Han, Xiaona; Dong, Hui; Xu, Xing; Chen, Chao; Zhang, Yang; Lin, Jiahao

    2016-03-01

    Well-defined polyacrylonitriles (PANs) with different molecular weights were synthesized through an activator regenerated by electron-transfer atom-transfer radical polymerization method and employed as binders in silicon negative electrode for lithium-ion batteries. Compared with poly(vinylidene fluoride) and carboxyl methyl cellulose as binders, the electrode performance of PANs is well-improved. Specifically, at 100 mA g(-1) from 0.01 to 1.5 V, the initial discharge capacity of PAN100-based electrode is 4147.8 mA h g(-1) and still remains about 1639.6 mA h g(-1) over 50 cycles. A comprehensive understanding on the improvement mechanism is preliminarily discussed. The results indicate that the superior performance largely depends on the higher lithium ion diffusion efficiency in PAN which results from the weak interaction between lithium ions and PAN polymer chain, and the hydrogen bonds among the nitrile group (C≡N) of PAN, Si nanoparticles, and the current collector, which will lead to an efficient coating of PAN with the Si particles and well-improved adhesion strength, synergistically depressing the structural deterioration of silicon electrodes. PMID:26978186

  11. Novel pyrolyzed polyaniline-grafted silicon nanoparticles encapsulated in graphene sheets as Li-ion battery anodes.

    PubMed

    Li, Zhe-Fei; Zhang, Hangyu; Liu, Qi; Liu, Yadong; Stanciu, Lia; Xie, Jian

    2014-04-23

    A simple method to fabricate graphene-encapsulated pyrolyzed polyaniline-grafted Si nanoparticles has been developed. Instead of using Si nanoparticles with a native oxide layer, HF-treated Si nanoparticles were employed in this work. The uniqueness of this method is that, first, a PANI layer over the Si nanoparticles was formed via the surface-initiated polymerization of aniline on the surface of aniline-functionalized Si nanoparticles; then, the PANI-grafted Si nanoparticles were wrapped by the GO sheets via π-π interaction and electrostatic attraction between the GO and the PANI. Finally, the GO and PANI were pyrolyzed, and this pyrolyzed PANI layer tightly binds the graphene sheets and the Si nanoparticles together in the composite. The composite materials exhibit better cycling stability and Coulombic efficiency as anodes in lithium ion batteries, as compared to pure Si nanoparticles and physically mixed graphene/Si composites. After 300 cycles at a current density of 2 A/g, the composite electrodes can still deliver a specific capacity of about 900 mAh/g, which corresponds to ∼76% capacity retention. The enhanced performance can be attributed to the absence of surface oxides, the better electronic conductivity, faster ion diffusion rate, and the strong interaction between the graphene sheets and the tightly bound carbon-coated Si nanoparticles. PMID:24703375

  12. Probing the Degradation Mechanism of Li2MnO3 Cathode for Li-Ion Batteries

    SciTech Connect

    Yan, Pengfei; Xiao, Liang; Zheng, Jianming; Zhou, Yungang; He, Yang; Zu, Xiaotao; Mao, Scott X.; Xiao, Jie; Gao, Fei; Zhang, Jiguang; Wang, Chong M.

    2015-02-10

    Capacity and voltage fading of Li2MnO3 is a major challenge for the application of this category of material, which is believed to be associated with the structural and chemical evolution of the materials. This paper reports the detailed structural and chemical evolutions of Li2MnO3 cathode captured by using aberration corrected scanning/transmission electron microscope (S/TEM) after certain numbers of charge-discharge cycling of the batteries. It is found that structural degradation occurs from the very first cycle and is spatially initiated from the surface of the particle and propagates towards the inner bulk as cyclic number increase, featuring the formation of the surface phase transformation layer and gradual thickening of this layer. The structure degradation is found to follow a sequential phase transformation: monoclinic C2/m → tetragonal I41 → cubic spinel, which is consistently supported by the decreasing lattice formation energy based on DFT calculations. For the first time, high spatial resolution quantitative chemical analysis reveals that 20% oxygen in the surface phase transformation layer is removed and such newly developed surface layer is a Li-depleted layer with reduced Mn cations. This work demonstrates a direct correlation between structural degradation and cell’s electrochemical degradation, which enhances our understanding of Li-Mn-rich (LMR) cathode materials.

  13. LiFePO4 - 3D carbon nanofiber composites as cathode materials for Li-ions batteries

    NASA Astrophysics Data System (ADS)

    Dimesso, L.; Spanheimer, C.; Jaegermann, W.; Zhang, Y.; Yarin, A. L.

    2012-03-01

    The characterization of carbon nanofiber 3D nonwovens, prepared by electrospinning process, coated with olivine structured lithium iron phosphate is reported. The LiFePO4 as cathode material for lithium ion batteries was prepared by a Pechini-assisted reversed polyol process. The coating has been successfully performed on carbon nanofiber 3D nonwovens by soaking in aqueous solution containing lithium, iron salts and phosphates at 70 °C for 2-4 h. After drying-out, the composites were annealed at 600 °C for 5 h under nitrogen. The surface investigation of the prepared composites showed a uniform coating of the carbon nonwoven nanofibers as well as the formation of cauliflower-like crystalline structures which are uniformly distributed all over the surface area of the carbon nanofibers. The electrochemical measurements on the composites showed good performances delivering a discharge specific capacity of 156 mAhg- 1 at a discharging rate of C/25 and 152 mAhg- 1 at a discharging rate of C/10 at room temperature.

  14. Electrochemical characteristics of Li 2- xVTiO 4 rock salt phase in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Dominko, R.; Garrido, C. Vidal-Abraca; Bele, M.; Kuezma, M.; Arcon, I.; Gaberscek, M.

    Li 2- xVTiO 4/C sample with a disordered rock salt structure was successfully prepared by annealing at a temperature of 850 °C. The electrochemical oxidation in the first cycle occurs at voltages above 4 V vs. metallic lithium, while the shapes of the electrochemical curves in consequent reduction-oxidation processes show a monotonous change of the potential between the selected cut-off voltages. A linear combination fit of individual XANES spectra was used for the determination of the oxidation states of as prepared sample and intermediate states during oxidation and reduction. In the as-prepared sample, vanadium was found to be in the average oxidation state of V 3.5+ and was additionally oxidized to V 3.8+ by the electrochemical charging. During the discharge process, the vanadium oxidation state was reduced to V 3.0+. In situ X-ray diffraction patterns and EXAFS analysis suggest good structural stability during oxidation and reduction, which is also reflected in the cycling stability if batteries were cycled in the voltage window between 2.0 V and 4.4 V. Extension of the lower cut-off voltage to 1.0 V doubles the capacity retention with the improved capacity stability if compared with several high capacity vanadium based materials.

  15. LiFePO 4: From molten ingot to nanoparticles with high-rate performance in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zaghib, K.; Charest, P.; Dontigny, M.; Guerfi, A.; Lagacé, M.; Mauger, A.; Kopec, M.; Julien, C. M.

    LiFePO 4 (LFP) particles were obtained by grinding ingot synthesized in the molten state. This process, followed by jet milling, and then wet milling, provides a simple way to obtain powders with controlled particle size in the range from macroscopic to 25 nm. However, at this time, we find that these particles tend to agglomerate to form secondary particles of size ∼100 nm. The particles obtained by this process are characterized by X-ray diffraction (XRD). In situ and ex situ scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The effect of milling was also investigated by analysis of physical properties using infrared spectroscopy (FTIR) and magnetic measurements. The electrochemical performance was evaluated in cells containing Li/1 M LiPF 6 in EC:DEC (1:1)/C-LiFePO 4. After carbon coating, the LFP particles which are free of impurities, exhibit high-rate capability. Even with a limited amount of carbon (2 wt.%) appropriate for commercial batteries, the capacity is 157 mAh g -1 at 0.1 C, 120 mAh g -1 at 10 C, without capacity fading after 60 cycles.

  16. A comparison of the electrode/electrolyte reaction at elevated temperatures for various Li-ion battery cathodes

    NASA Astrophysics Data System (ADS)

    MacNeil, D. D.; Lu, Zhonghua; Chen, Zhaohui; Dahn, J. R.

    Differential scanning calorimetry (DSC) was used to compare the thermal stability of charged cathodes in 1 M LiPF 6 EC/DEC electrolyte. Seven possible cathode materials for lithium-ion batteries (LiCoO 2, LiNiO 2, LiNi 0.8Co 0.2O 2, Li 1+ xMn 2- xO 4, LiNi 0.7Co 0.2Ti 0.05Mg 0.05O 2, Li[Ni 3/8Co 1/4Mn 3/8]O 2, and LiFePO 4) were tested under the same conditions. Welded stainless steel DSC sample tubes, that ensured no weight loss during analysis, were used for these measurements, making them reliable. A consideration of these DSC results and the known electrochemical properties of the cathodes may assist the selection of the most suitable lithium-ion cathode material for use in a particular application.

  17. Atomic/Molecular Layer Deposition of Lithium Terephthalate Thin Films as High Rate Capability Li-Ion Battery Anodes.

    PubMed

    Nisula, Mikko; Karppinen, Maarit

    2016-02-10

    We demonstrate the fabrication of high-quality electrochemically active organic lithium electrode thin films by the currently strongly emerging combined atomic/molecular layer deposition (ALD/MLD) technique using lithium terephthalate, a recently found anode material for lithium-ion battery (LIB), as a proof-of-the-concept material. Our deposition process for Li-terephthalate is shown to well comply with the basic principles of ALD-type growth including the sequential self-saturated surface reactions, a necessity when aiming at micro-LIB devices with three-dimensional architectures. The as-deposited films are found crystalline across the deposition temperature range of 200-280 °C, which is a trait highly desired for an electrode material but rather unusual for hybrid inorganic-organic thin films. Excellent rate capability is ascertained for the Li-terephthalate films with no conductive additives required. The electrode performance can be further enhanced by depositing a thin protective LiPON solid-state electrolyte layer on top of Li-terephthalate; this yields highly stable structures with capacity retention of over 97% after 200 charge/discharge cycles at 3.2 C. PMID:26812433

  18. Core-shell Si@TiO2 nanosphere anode by atomic layer deposition for Li-ion batteries

    DOE PAGESBeta

    Dai, Sheng

    2016-01-28

    Silicon (Si) is regarded as next-generation anode for high-energy lithium-ion batteries (LIBs) due to its high Li storage capacity (4200 mA h g-1). However, the mechanical degradation and resultant capacity fade critically hinder its practical application. In this regard, we demonstrate that nanocoating of Si spheres with a 3 nm titanium dioxide (TiO2) layer via atomic layer deposition (ALD) can utmostly balance the high conductivity and the good structural stability to improve the cycling stability of Si core material. The resultant sample, Si@TiO2-3 nm core–shell nanospheres, exhibits the best electrochemical performance of all with a highest initial Coulombic efficiency andmore » specific charge capacity retention after 50 cycles at 0.1C (82.39% and 1580.3 mA h g-1). In addition to making full advantage of the ALD technique, we believe that our strategy and comprehension in coating the electrode and the active material could provide a useful pathway towards enhancing Si anode material itself and community of LIBs.« less

  19. Caramel popcorn shaped silicon particle with carbon coating as a high performance anode material for Li-ion batteries.

    PubMed

    He, Meinan; Sa, Qina; Liu, Gao; Wang, Yan

    2013-11-13

    Silicon is a very promising anode material for lithium ion batteries. It has a 4200 mAh/g theoretical capacity, which is ten times higher than that of commercial graphite anodes. However, when lithium ions diffuse to Si anodes, the volume of Si will expand to almost 400% of its initial size and lead to the crack of Si. Such a huge volume change and crack cause significant capacity loss. Meanwhile, with the crack of Si particles, the conductivity between the electrode and the current collector drops. Moreover, the solid electrolyte interphase (SEI), which is generated during the cycling, reduces the discharge capacity. These issues must be addressed for widespread application of this material. In this work, caramel popcorn shaped porous silicon particles with carbon coating are fabricated by a set of simple chemical methods as active anode material. Si particles are etched to form a porous structure. The pores in Si provide space for the volume expansion and liquid electrolyte diffusion. A layer of amorphous carbon is formed inside the pores, which gives an excellent isolation between the Si particle and electrolyte, so that the formation of the SEI layer is stabilized. Meanwhile, this novel structure enhances the mechanical properties of the Si particles, and the crack phenomenon caused by the volume change is significantly restrained. Therefore, an excellent cycle life under a high rate for the novel Si electrode is achieved. PMID:24111737

  20. Co3O4-reduced graphene oxide nanocomposite synthesized by microwave-assisted hydrothermal process for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Park, Sang-Hoon; Kim, Hyun-Kyung; Roh, Kwang Chul; Kim, Kwang-Bum

    2015-03-01

    A nanocomposite of Co3O4 and reduced graphene oxide (Co3O4-rGO) was successfully synthesized as an anode material for lithium-ion batteries by a one-pot microwave-assisted hydrothermal process. In the nanocomposite, Co3O4 nanoparticles with narrow size distribution in the range of 10-30 nm uniformly decorated the surface of rGO, indicating that rGO could act as a two-dimensional template for the heterogeneous precipitation of Co3O4 nanoparticles. To investigate the effect of mass ratios of Co3O4 and rGO on the electrochemical properties, the Co3O4 loading in the nanocomposite was controlled during the microwave-assisted hydrothermal synthesis. The resulting nanocomposite electrode exhibited high electrochemical performance in terms of specific capacity and cyclability, indicating that rGO served as an efficient template material to provide a highly conducting and buffering network for Co3O4 nanoparticles. [Figure not available: see fulltext.