bluuebunny/crossref_metadata_2025 huggingface dataset:
Characterization of LiMn0.3Co0.3Ni0.3Cr0.1O2 Cathode for an All Solid-State Thin Film Battery
Authors: Kamarulzaman Norlida , Rusdi Roshidah , Elong Kelimah , Badar Nurhanna
Published: February 2020

Thin film fabrication is very important especially for device fabrication. For an all solid-state thin film battery, very low dimensional (of the order of sub-micron), high quality thin films are needed and the fabrication technique is a key criteria for producing good quality ultra-thin films. Pulse Laser deposition (PLD) is a suitable method for producing high quality finish of metals and metal oxides. Controlling the PLD deposition parameters can affect the characteristics of thin films such as crystal orientation, thickness and roughness which in turn influence the physical and chemical properties of the thin films. Producing thin film metal oxides with simple stoichiometries such as ZnO, MgO and Al2O3, may not be such a problem to fabricate. However, producing thin films of complex metal oxides such as LiCo0.3Ni0.3Mn0.3Cr0.1O2 for Li-ion battery cathodes can be a problem. The thin film deposition technique must be appropriate so that the thin film material produced will not suffer a change of phase, stoichiometry or purity. Not all gas phase or plasma based methods are suitable for deposition of this type of material. Reactive type thin film fabrication method may not produce the needed stoichiometry or phase and may produce multiphase samples with impurities. PLD may be the choice method for producing thin films of very complex stoichiometries.

This work explores the thin film method of PLD in the fabrication of thin film LiCo0.3Ni0.3Mn0.3Cr0.1O2 material. Characteristics such as phase, stoichiometry, crystal growth orientation, and surface roughness, are studied. For this type of complex metal oxide, it is very important for the thin film to be of the right phase and stoichiometry because this will affect the electrochemical behavior of the energy device that will then be fabricated. It is found that thin films of LiCo0.3Ni0.3Mn0.3Cr0.1O2 deposited by PLD have good qualities such as mirror finish, dimensionally thin and of correct stoichiometry and high smoothness. Cyclic voltametry result shows that the cathode film is electrochemically active.
From Lab Scale to Large Volume Production: Substitution of Toxic NMP/PVDF with H2o/CMC/SBR in Lithium-Ion Cells
Authors: Noll Pascal , Hörpel Gerhard , Schroeder Melanie
Published: February 2020

Lithium-ion batteries (LIBs) are becoming more and more important for mobile energy storage devices, with respect to their energy density. For large size applications such as in electric vehicles (EVs) or hybrid electric vehicles (HEVs), both higher energy density and low-cost materials are required also taking environmental friendliness into account. In order to enhance the performance of lithium-ion batteries, researchers and battery-manufacturers are trying to create new electrode materials and new electrolyte compositions. Nevertheless, battery efficiency strongly depends on the electrode engineering and additionally on the production process with the optimization of each individual step.[1,2]

Polyvinylidene fluoride (PVDF) based electrodes on the cathode as well as on the anode side are widely used. One major drawback of PVDF based electrodes is the usage of volatile organic solvents that are often toxic (like N-methyl-2-pyrrolidone (NMP)) and are difficult to dispose at the end of the production process. Alternatively, water soluble natural and/or synthetical based binders have been proposed which also cope the increasing demand of a more environmentally-friendly production process and recycling of LIBs. Processing of active materials for negative as well as positive electrodes is possible using carboxy methyl cellulose (CMC) and/or styrene-butadiene (SBR).[3]

In our study we present the results of our experiments to substitute NMP/PVDF with a water based CMC/SBR binder solution. Moreover, the work comprises the development and adaption of mixing processes, coating techniques, and appropriate drying procedures. To optimize the mixing process for water based slurries we had to figure out ideal substitution grades, mixing ratios between CMC/SBR, and the right pH-value. With the focus on viscosity, mixer types, and shear rates we figured out an optimized slurry configuration for the adaption to our battery pilot plants including the manufacturing of different cell types. Furthermore, the adjustment of coating techniques is one essential issue towards large scale production processes. Nevertheless, we also had to pay attention to the challenging production step, the drying procedure by the combination of different drying duration and temperatures as well as the adapted drying technique.

This work demonstrates the difficulties and production steps going from lab scale to large scale manufacturing.

We kindly thank the European Regional Development Fund for the funding this project “ProLiBat” (EM-1041H) and also the project partners for support and cooperation.

[1] M. Broussely, J. Power Sources, 81-82 (1999), 140.

[2] X. Zhang, et al., J. Electrochem. Soc., 148 (2001), A463.

[3] Lux, S. F., et al J. Electrochem. Soc., 157.3 (2010), A320-A325.
Graphene/Li[Li0.2Ni0.2Mn0.6]O2 nanocomposite for Enhanced Cathode with High Rate Capability
Authors: Pyun MinHo , Park Yong Joon
Published: February 2020

Recently, solid solution system, xLi2MnO3·(1-x)LiMO2 (M = Co, Ni, Mn etc.), which has been classified as a lithium rich layered oxide, has drawn much attention due to its extraordinarily large capacity[1]. However, there are a lot of problems to overcome for commercialization such as low rate capability due to small electronic and ionic conductivities, and low cyclic performance attributed to insufficient structural stability. Over the past year, extensive effort has been made to enhance the rate capability of the lithium-rich layered oxide. As an approach, the composition with carbon-based materials with high electronic conductivity has been tried to compensate for low conductivity of the lithium-rich layered oxide [2,3]. In this study, the nanoparticles of lithium-rich layered oxide (Li[Ni0.2Li0.2Mn0.6]O2) were composited with graphene. Small particle-size of Li[Ni0.2Li0.2Mn0.6]O2 may facilitate the movement of lithium ions and electrons during cycling due to high surface area of the cathode. Graphene could be applied as a base-matrix for the composition with cathode nanoparticle because it has high electronic conductivity, wide surface area, and good mechanical flexibility. The Graphene/Li[Ni0.2Li0.2Mn0.6]O2 nanocomposite is expected to offer high rate capability because of high surface area of cathode nanoparticles and good electronic conductivity attributed to the graphene.

References

1.J. Lin, D. Mu, Y. Jin, B. Wu, Y. Ma, F. Wu. J. Power Sources 230(2013)76-80

2.A. Yamada, H. Koizumi, S.I. Nishimura, N. Sonoyama, R. Kanno, M. Yonemura, T. Nakamura,

Y. Kobayashi, Nat. Mater. 5 (2006) 357-360.

3.Y.G. Wang, Y.R. Wang, E.J. Hosono, K.X. Wang, H.S. Zhou, Angew. Chem. Int. Ed. 47 (2008)

7461-7465.
Synthesis and Characterization of Co Doped Nickel-Manganese Based Spinel-Layered Mixed Structure as Cathode Active Materials
Authors: Choi JaeMin , Choi InHyung , Hwang YunJu , Nahm KeeSuk
Published: February 2020

LiCoO2 is a most popular cathode material in lithium battery industries. But the high cost and toxicity of cobalt have drawn attention to find alternative materials. Manganese of various alternative materials has been highly considered as alternative because it is environmentally friendly and inexpensive. For the lithium ion battery applications in medium and largescale energy devices, a new active material with structural stability and high capacity is essential. So, in this study, we have synthesized spinel-layered mixed structured composite oxides based on Mn,Ni, with stable structure and high capacity for Li ion battery cathodes. The materials were synthesized and characterized for its structural and electrochemical properties. We used a batch type reactor equipped with a teflon-type impeller at a stirring speed of 150~400rpm for material synthesis. Initially, we synthesized the transition metal precursor using co-precipitation method. We then synthesized the spinel. layered mixed structure by mixing the synthesized precursor with the lithium precursor by calcination. But on battery cycling, after 50cycle, Co undoped sample exhibited very low stability with capacity maximum of approximately 90mAh/g. We also synthesized Co-doped (Co-composition x=0.05, 0.15, 0.25) transition metal precursor using solid state method. Then again by using previous method we synthesized the spinel-layered mixed structure by mixing the synthesized Co-doped precursor and lithium precursor by calcination. The transition metal precursor showed MnCO3 (rhodochrosite, R-3c, JCPDF 44-1472) structure and the final material showed spinel and layered mixed structure which was confirmed with XRD. Electrochemical properties were tested at a current density of 0.2mA/cm2within a potential range of 2.0V~4.9V using a 2032 coin type lithium cell. All samples showed the spinel-layered mixed characteristic charge-discharge curves and Co doped sample synthesized at Co composition x-0.15 showed highest stability with capacity maximum of 220mAh/g.
Invited Talk: Carbon Substrates Tuning and Improvement for Rechargeable Lithium-Oxygen Batteries
Authors: Yin Jun , Patel Bharat , Chakrapani Srinivasan , Lee Sangho , Joo Yong Lak
Published: February 2020

Notwithstanding more interests state-of-the-art rechargeable lithium oxygen batteries have attracted due to at least 4-fold increase of energy capacities in comparison with current lithium ion batteries, challenges, such as unacceptable round-trip efficiency and poor cyclability urgently demand effective cathode materials to overcome the limitations. In this report, we have utilized graphene nanoribbons (GNRs) as the cathode substrates that were partially unzipped from multi-walled carbon nanotubes (CNTs). Moreover, platinum nanoparticles were encapsulated in those two substrates in order to achieve better overpotentials, thus enhance the cyclability in the meantime. Not only the comparison of the single-cell performance between Pt/GNRs and Pt/CNTs composites, the characterizations are also carried out by an array of techniques, including SEM, TEM, XPS, XRD and Raman spectrum. Apart from charging – discharging evaluation, the electrochemical activities determined by cyclic voltammetric measurements carried out in the organic electrolytes, correlation between the carbon structure and battery performance, such as initial capacity and cyclability will also be discussed.Notwithstanding more interests state-of-the-art rechargeable lithium oxygen batteries have attracted due to at least 4-fold increase of energy capacities in comparison with current lithium ion batteries, challenges, such as unacceptable round-trip efficiency and poor cyclability urgently demand effective cathode materials to overcome the limitations. In this report, we have utilized graphene nanoribbons (GNRs) as the cathode substrates that were partially unzipped from multi-walled carbon nanotubes (CNTs). Moreover, platinum nanoparticles were synthesized and encapsulated in those two substrates in order to achieve better overpotentials, thus enhance the cyclability in the meantime. Not only the comparison of the single-cell performance between Pt/GNRs and Pt/CNTs composites, the characterizations are also carried out by an array of techniques, including SEM, TEM, XPS, XRD and Raman spectrum. Apart from charging – discharging evaluation, the electrochemical activities determined by cyclic voltammetric measurements carried out in the organic electrolytes, correlation between the carbon structure and battery performance, such as initial capacity and cyclability will also be discussed.
Slice-Selective NMR Diffusion Measurements - a Tool for the Characterization of Ion Transport Properties in Lithium Ion Battery Electrolytes
Authors: Halalay Ion C. , Krachkovskiy Sergey , Pauric Allen D. , Goward Gillian R.
Published: February 2020

The main impediments to the wide-spread acceptance of electric drive vehicles are the cost, energy storage capacity, and durability of Li-ion batteries. The first issue is best addressed within the context of materials and batteries manufacturing, the second by research on the synthesis and characterization of new materials. Successfully tacking of the third issue requires an improved understanding of battery degradation mechanisms and the development of suitable mitigation measures. In situ experimental techniques which can accurately detect and monitor performance degradation mechanisms at the nanoscale, including the identities of short-lived chemical species, or changes in materials properties as functions of temperature, position or time are emerging only gradually, due to their associated difficulties and complex challenges. We show that the combination of in situ one-dimensional imaging and slice-selective NMR diffusion measurements (Fig. 1) is a tool for spatially and temporally resolving the lithium self-diffusion coefficient in a liquid electrolyte during the application of a dc current (Fig. 2). A solution of 1M LiTFSI in propylene carbonate was used for our method development work.
Solar Photoconversion to Photovoltaic Electricity and Solar Fuels: Forty Years of History, Progress, New Concepts, and Prognosis
Authors: Nozik Arthur J.
Published: February 2020

Since the global oil crisis of 1973 that followed the Fujishima-Honda paper of 1972 showing that under certain conditions semiconductor photoelectrodes could be used to photolytically split H2O into H2 and O2, there have been large international research and development efforts to produce cost effective solar fuels, such as H2 from H2O splitting or renewable carbon-based fuels from the photoreduction of CO2 with H2O, as occurs in biological photosynthesis. Parallel efforts to develop cost effective solar electricity from photovoltaic cells were also accelerated. The intensity of both of these R&D efforts have waxed and waned over the ensuing 40 years depending upon political leadership, societal/political perceptions of the severity of the energy security problem and global climate change (and their respective relative priority), and the state of the national economy of nations funding R& D in this area. Over this rather significant time period there have been many importance advances in the associated and highly interdisciplinary science and technology, new innovations and concepts, and some persistently difficult technological barriers to penetrate that have prevented commercialization, especially in producing cost effective solar fuels. The scientific and technological history, advances, new concepts, persistent barriers, and present status of viable solar fuels and solar electricity production will be discussed.
Electrochemical Performance of Graphene/Polypyrrole Nanowire Composite for Supercapacitor Electrode
Authors: Li Jing , Li Yang , Xie Hua qing
Published: February 2020

Abstract not Available.
Effects of Nitrogen Modification on the Electrochemical Performance of Li4Ti5O12
Authors: Li Xue , Zhao Jin Bao
Published: February 2020

Abstract not Available.
Na3V2(PO4)3/C Nanocomposite As Cathode Material for Sodium Ion Batteries
Authors: Fang Yongjin , Ai Xinping , Yang Hanxi , Cao Yuliang
Published: February 2020

Abstract not Available.
Development of Laminate Type Lithium Ion Capacitors
Authors: Wang Chen , Luo Xu Fang , Yang Hong ping , Xu Yong jin
Published: February 2020

Abstract not Available.
Nanocrosses of Lead Sulphate As the Negative Active Material of Lead Acid Batteries
Authors: Yi Liu , Pengran Gao , Xianfu Bu , Guizhi Kuang , Wei Liu , Lixu Lei
Published: February 2020

Abstract not Available.
Capacity Loss of LiFePO4/Graphite Battery Induced By Lithium Loss at Graphite Anode Surface
Authors: Zheng Honghe
Published: February 2020

Abstract not Available.
Nanosized Fe2O3 on Three Dimensional Hierarchical Porous Graphene-like Network Composites As High-Performance Lithium Ion Batteries Anode Materials
Authors: Shen Pei Kang , Zhu Jinliang
Published: February 2020

Abstract not Available.
A Study of Spiro-Type Quaternary Ammonium Salt Propylene Carbonated Electrolyte for High Voltage Electric Double Layer Capacitors
Authors: Shi Zhiqiang , Yu Xuewen , Wu Changcheng , Wang Jing
Published: February 2020

Abstract not Available.
WO3 Nanorods/Graphene Nanohybrids with Excellent Lithium Storage Performance
Authors: Gou Xinglong , Li Rong , Zhang Qingqing
Published: February 2020

Abstract not Available.
Effect of Residual Lithium on Surface of Positive Electrode Material for Lithium-Ion Secondary Batteries
Authors: CHO Daehyun , Jo Chang Heum , Yashiro Hitoshi , Myung Seung-Taek
Published: February 2020

Abstract not Available.
Hierarchical Porous Carbon Fabricated from Surplus Sludge for High-Performance Supercapacitor
Authors: Weijia Zhou
Published: February 2020

Abstract not Available.
Formation of Poorly Crystalline Li2O2: Implications on RuO2 Role in Li-O2 Battery
Authors: Byon Hye Ryung , Yilmaz Eda , Yogi Chihiro , Yamanaka Keisuke , Ohta Toshiaki
Published: February 2020

Abstract not Available.
A Facile Fabrication of Lfp/Mesoporous Carbon Composite as a Superior Cathode for Lithium Ion Batteries
Authors: Wu Ruofei , Xia Guofeng , Shen Shuiyun , Zhu Fengjuan , Jiang Fengjing , Zhang Junliang
Published: February 2020

Abstract not Available.
Fabrication of Three-Dimensional Anode for Microbial Fuel Cells
Authors: Chen Shuiliang
Published: February 2020

Abstract not Available.
Facile synthesis of vanadium oxide nano-microstructures for sodium-ion battery cathode
Authors: Fei Hai Long , Wei Ming Deng
Published: February 2020

Abstract not Available.
Keynote Presentation: Using Battery Diagnostics to Analyze Degradation Modes in High-Power and High-Energy LiFePO4 Cells
Authors: Dubarry Matthieu , Devie Arnaud , Liaw Bor Yann
Published: February 2020

Abstract not Available.
Preparation of Graphene and Its Composites with MnO2 for Supercapacitors by Thermal Reduction
Authors: Dai Yu , Yan Gang , Li Jianling,
Published: February 2020

Abstract not Available.
Graphene Supported MnOx Nanoparticles As an Improved Efficient Cathode Catalyst for Oxygen Reduction Reaction in Alkaline Solution
Authors: Qin Xue , Liu Shengwei
Published: February 2020

Abstract not Available.
Electrospun Carbon Web Used As Electrode Materials for Vanadium Redox Flow Battery
Authors: Wei Guan jie , Liu Jian guo , Yan Chuan wei
Published: February 2020

Abstract not Available.
The Influence of Activated Carbon Material on the Distribution of Working Voltage at Anode and Cathode
Authors: Li Jianling, , Hou Pengfei , Yan Gang , Xue Qingrui
Published: February 2020

Abstract not Available.
Research on Anode Materials for Sodium Ion Battery
Authors: Chou Shulei , Li Weijie , Wang Yunxiao , Wang Jiazhao , Liu Hua Kun , Dou Shi Xue
Published: February 2020

Abstract not Available.
Role of Grafted Perfluorinated Moieties on Porous Carbon Cathode for the Li-O2 Battery
Authors: Thomas Morgan L. , Yamanaka Keisuke , Ohta Toshiaki , Byon Hye Ryung
Published: February 2020

Abstract not Available.
Lithium Air Batteries with Carbon Based Electrodes
Authors: Lai Bo-Yu , Chen Hsun-Yi
Published: February 2020

Abstract not Available.
Keynote Presentation: Micro/Nanostructured Electrode Materials with Multi Electron Reactions for Li Batteries
Authors: Chen Jun
Published: February 2020

Abstract not Available.
Hybrid Bio-Organic Interfaces with Matchable Nanoscale Topography for Durable High Extracellular Electron Transfer Activity
Authors: Ding Chunmei , Lv Meiling , Liu Huan , Jiang Lei
Published: February 2020

Abstract not Available.
Synthesis and Conductivity of Directly Cross-Linked Poly(vinyl alcohol)/Luviquat As Alkaline Anion-Exchange Membranes
Authors: Qiao Jinli
Published: February 2020

Abstract not Available.
Synthesis of SnO2-CuO Nanocomposite and Its High Catalytic Activity for CO2 Electroreduction
Authors: Qiao Jinli
Published: February 2020

Abstract not Available.
Facile Synthesis of Hollow Fe3O4-Co3O4 Composite for the ORR
Authors: Jie Wang , Min Wu , Fen Liu Su , Huan He , Jing Zhu , Li Wang De
Published: February 2020

Abstract not Available.
The Effect of Residual Solvent on the Morphology and Properties of Semi-Interpenetrating Polymer Network Membranes Based on Sulfonated Poly(Ether Ether Ketone) and Crosslinked Poly(2-Acrylamido-2-Methyl-1-Propanesulphonic Acid)
Authors: Liu Xin
Published: February 2020

Abstract not Available.
Electrochemical Oxidation of Ammonia Using Electrodeposited Pt on Carbon Substrate As Catalyst in Ammonia Electrolysis
Authors: Gwak Jieun
Published: February 2020

Abstract not Available.
Development of 1kW Direct Methanol Fuel Cell Stack for Portable Power Sources
Authors: Peck Dong-Hyun
Published: February 2020

Abstract not Available.
Fundamental Study on CdSe Quantum-Dot Sensitized TiO2 nanorods Based Solar Cells
Authors: Zhang Wenjun
Published: February 2020

Abstract not Available.
Keynote Presentation: Impact of Interfacial Conditions on Perfluorosulfonic-Acid (PFSA) Membranes and Thin Films
Authors: Kusoglu Ahmet , Weber Adam Z.
Published: February 2020

Abstract not Available.
A Novel Stable SrCo0.8Fe0.1Ga0.1O3-δ Pervoskite Ceramics As Cathode of Solid Oxide Fuel Cells
Authors: Shen Yichi , Meng Xiuxia , Yang Naitao , Tan Xiaoyao
Published: February 2020

Abstract not Available.
Preparation and Characterization of High Ionic Conductive SDC–sulfate Composite Electrolyte for Solid Oxide Fuel Cells
Authors: Lv Weiming , Tong Ze , Yin Jiewei , Lu Jun , Yin Yimei , Ma Zi-Feng
Published: February 2020

Abstract not Available.
Amorphous Titanium/Vanadium Oxide Composite As a High-Rate Negative Electrode Material for Lithium-Ion Batteries
Authors: Lee Jeong Beom , Chae Oh B. , Ryu Ji Heon , Oh Seung M.
Published: February 2020

Abstract not Available.
Electrochemical Properties of Sulfur-Polyacrylonitrile Composite Depending on Different States of Sulfur As Cathode Active Materials for Lithium Secondary Batteries
Authors: Kim ChangHyeon , Kim Huihoon , Park Jin-Young , Ryu Ho-suk , Kim Ki-Won , Ahn Hyo-Jun
Published: February 2020

Abstract not Available.
Invited Presentation: The Effect of Solvation on Li-O2 Redox Reactions
Authors: Kwabi David , Bryantsev Vyacheslav S , Batcho Thomas , Addison Dan , Thompson Carl V. , Shao-Horn Yang
Published: February 2020

Non-aqueous Li-O2 batteries are estimated to deliver gravimetric energies two to three times that of conventional Li-ion batteries at comparable gravimetric power. Fundamentally understanding reaction mechanisms and associated intermediates during Li-O2 cell operation is critical for implementing practical Li-O2 batteries with high reversibility and long cycle life. In particular, the role of superoxide-related reaction intermediates generated during oxygen reduction on the overall electrochemical reaction is not well understood. Such knowledge is crucial for designing highly efficient Li-O2 batteries since superoxides are thought to be potentially chemically unstable against the electrolyte solvent, reaction surface and cell components, leading to high overpotentials during charge, and short cycle life. We use the rotating disk electrode (RDE) technique coupled with theoretical calculations to probe redox potentials of superoxide formation reactions in different electrolyte solvents. These results highlight the importance of solvating ability on oxygen reactions with and without Li+ ions, and yield insights into potential criteria for selecting Li-O2 cell configurations. Implications for the growth mechanisms and chemistries of Li-O2 discharge products will also be addressed.
Invited Presentation: Fluorophosphates As High Energy Density Positive Electrodes for Li and Na Batteries
Authors: Croguennec Laurence , Bianchini Matteo , Ateba Mba Jean-Marcel , Carlier Dany , Ménétrier Michel , Suard Emmanuelle , Masquelier Christian
Published: February 2020

Development of new materials for high energy density batteries is essential as they power a wide range of devices ranging from portable electronics to transport and storage applications. Since they are still facing limitations (energy and power density, safety …), intense academic and industrial research activities are devoted to the development of better performing materials with in particular high voltage and safety. Beside the extensively studied layered and spinel oxides, polyanionic materials have aroused huge interest in the past ten years [1]. Among them, the so-called fluorophosphates, actually fluoride phosphates combining phosphate and fluoride anions in the same framework, are very attractive positive electrode materials with increased voltage versus Li and Na as compared to regular (oxide) phosphates for a given M(n+1)+/Mn+ redox couple. We will discuss results obtained recently in our groups for Tavorite-like phosphate materials LiMPO4X (M = V, Fe, Ti; X = F, OH, O) used as electrodes in Li-ion batteries, but also for Na3V2(PO4)2F3in Li and Na-ion batteries. The vanadium-rich compounds LiVPO4F and LiVPO4O have been shown to be of particular interest as V is stable at different oxidation states in similar environments (VII, VIII, VIV and VV) in these Tavorite-type structures, leading to a possible exchange of two electrons per vanadium [2-5]. Very distinct values are interestingly observed for the “same” V3+/V4+ redox couple in LiVPO4F and LiVPO4O: ~ 4.25 V vs. Li upon Li+ extraction from LiVPO4F versus ~ 2.3 V vs. Li upon Li+ insertion into LiVPO4O, showing that the potential can be tuned over a wide range moving from a V3+-rich material to a vanadyl (VO)2+-rich material. Na3V2(PO4)2F3 is also undoubtedly of high interest for the development of Na-ion batteries: it was shown recently to allow fast sodium diffusion, even at high rates (up to 20C) and despite the formation of successive intermediate phases with Na+/vacancy ordering [6]. The average potential observed for the V3+/V4+ redox couple in Na3V2(PO4)2F3 is around 3.9 V vs. Na+/Na, i.e. (as expected) significantly higher than that of the Nasicon phase Na3V2(PO4)3.

References

[1] C. Masquelier and L. Croguennec, Chem. Rev., 113, 6552 (2013)

[2] J. Barker, R.K.B. Gover, P. Burns, A. Bryan, M.Y. Saidi and J.L. Swoyer, J. Power Sources, 146, 516 (2005)

[3] J.M. Ateba Mba, C. Masquelier, E. Suard and L. Croguennec, Chem. Mater., 24, 1223 (2012)

[4] J.M. Ateba Mba, L. Croguennec, N.I. Basir, J. Barker and C. Masquelier, J. Electrochem. Soc., 159, A1171 (2012)

[5] M. Bianchini, J.M. Ateba Mba, P. Dagault, E. Bogdan, D. Carlier, E. Suard, C. Masquelier and L. Croguennec, submitted

[6] A. Ponrouch, R. Dedryvère, D. Monti, A.E. Demet, J.M. Ateba Mba, L. Croguennec, C. Masquelier, P. Johansson and M.R. Palacin, Energy and Environmental Science, 6, 2361 (2013)
Invited Presentation: Innovative Batteries for Sustainable Mobility
Authors: Iba Hideki , Yada Chihiro
Published: February 2020

The rapid economic growth, the ever-increasing populations and the increase in the number of vehicles have accelerated the consumption of fossil fuels in the world; automobile industries are now expected to tackle with reduction of CO2 emissions by developing vehicles driven by sustainable energy sources such as hybrid vehicles (HVs), plug-in hybrid vehicles (PHVs), electric vehicles (EVs) and fuel-cell hybrid vehicles (FCHVs). Since Toyota Motor Corporation introduced the first-generation Prius in 1997, we have sold more than 3 million HVs with 17 models all over the world, reducing CO2 emissions by 14 million tons (as of May 2010). And now, we are going to develop next-generation vehicles with more energy efficiency; for this reason we need to develop innovative batteries with higher energy densities than traditional batteries. Figure 1 represents a rough sketch of Ragone plots for traditional Ni-MH and Li-ion batteries together with next-generation batteries such as all-solid-state batteries and Li-air batteries. Although we have already developed prototype cells of all-solid-state batteries and Li-air batteries with energy densities of 400 Wh/L and 1000 Wh/L, respectively, it is also true that there are still many issues to be overcome until their practical application. In the presentation, we will overview our recent effort on developing innovative batteries.
Invited Presentation: Li-Ion Battery Safety Considerations during Transportation, Storage, and Disposal
Authors: Garche Juergen
Published: February 2020

The energy of a Li-ion cell is in average about 3,250 kJ/kg. About ¼ of this energy is related to electrochemical energy (chemical energy convertible into electrical energy via normal use or short circuit) and ¾ to thermal energy (chemical energy convertible only in thermal energy released at suitable stimulation; e.g. short circuit).

The main safety related events are overcharge, external heating, external and internal short circuits, and mechanical deformations of the cell/battery case. These unpredictable events may leads to a temperature increase and at T > 120 °C by internal chemical processes (SEI layer breakup, anode-electrolyte reaction) with gas development and internal pressure increase to cell container rupture at predetermined breaking points. Gas and electrolyte will escape through the rupture holes into the environment and, eventually, inflame by an external ignition source. A further temperature increase till about 200 °C triggers high rate chemical reactions (cathode decomposition with oxygen development, oxygen reaction with the electrolyte, electrolyte decomposition) leading to a very rapid temperature rise (thermal runaway) followed by flames caused by reaching the self-ignition temperature of the electrolyte (~ 450 °C) and possibly explosions. The specific occurrence of most of the above described safety related events, that may occur during the Li-ion battery life cycle phases of transportation, storage, and disposal, will be discussed in this presentation.

During transportation and storage, external heating, external and internal short circuits, and mechanical deformations, are the events most likely to happen. Measures which can prevent them (e.g. reliable and low flammable packaging, thermal barriers) and transport related standards (e.g. UN 38.3) are described.

The safety hazard in the disposal phase of the cell/battery are also associated with external heating, external and internal short circuits, and mechanical deformations. After collections it is to proof whether the battery is defective (not all functions properly) or damaged (loss of physical integrity). Defective batteries with capacity ≤ 80 % of the nominal value (end-of-life by definition) could be still used in lower demanding applications, e.g. stationary storage in PV houses. Damaged batteries and defective batteries with << 80 % capacity and other malfunctions have to be recycled. In order to reduce the safety risk before the recycling process (including transport), it is advisable to de-energize the battery by low current discharge and finally short it permanently.
Invited Presentation: Holistic Approach to Battery Materials Innovation
Authors: Fischer Andreas
Published: February 2020

Research and development of materials for lithium ion secondary batteries requires thinking across multiple disciplines and levels of complexity. The most important factor to consider is the interaction of materials in a battery cell during operation.

New active materials for the cathode may have an impact on the functionality of electrolyte, binder, and separator and might even mirror to the anode side of the cell. This can be problematic because it is time consuming to adapt other materials to e.g. a new cathode material. On the other hand it offers the chance early on to develop highly efficient optimized cell chemistries in parallel by taking possible interactions into account. A detailed understanding of cell design is a prerequisite for that challenging task. Furthermore the quality of electrode tapes and finally the test cell is crucial to distinguishing real effects from artefacts.

Research and development on high voltage cathode materials and respective electrolyte systems might serve as an example for a holistic approach. In addition to existing cell chemistries like lithium ion batteries, such an approach is of utmost importance for new cell chemistries like lithium/sulfur based systems.

In a holistic approach it is not sufficient to work only empirically. For a complete understanding, an approach from fundamental science on a molecular level to empirical development regarding cell design and resulting interaction of materials is required. A deep and scientifically profound understanding of structure / property relationship is a must. One part of that holistic approach can be accomplished by strong and trustful cooperation models of academic and industry research partners that allow open exchange of information or by industry on campus cooperation models.
Synthesis of Hollow Geo2 nanostructures, Transformation into Ge@C, and Lithium Storage Properties
Authors: Li Li , Seng Kuok Hau , Feng Chuanqi , Liu Hua Kun , Guo Zaiping
Published: February 2020

In terms of capacity, group IVA elements are the most promising as anode material for LIBs, especially silicon and germanium, which have theoretical capacities of 4200 and 1600 mAh/g, respectively. However, compared to silicon, germanium has higher lithium diffusivity and electrical conductivity, but lower volume change. In this work, we have designed mesoporous germanium@carbon hollow ellipsoids (Ge@C) through the formation of a hollow GeO2 ellipsoid precursor and subsequent simultaneous carbon coating and reduction of the GeO2 precursor. The GeO2 hollow ellipsoid precursor was firstly prepared through a facile one-pot ultrasonication method, and then after carbon coating and reduction by decomposition of acetylene and H2/Ar, the obtained mesoporous Ge@carbon exhibited excellent cycling stability at the 0.2 C and 1 C rates (1 C = 1600 mAh/g), with no significant capacity fading upon 200 cycles, indicating high reversible cycling stability. The Ge@carbon electrodes also presented a high couloumbic efficiency of 80% for the initial cycle, as well as excellent rate capability that the capacity retention value at the rate of 20 C is 66% (805 mAh/g) of the capacity at 1 C, and when the rate was returned to the 1 C rate, the capacity recorded is the same as that in the initial cycle at the 1 C rate. The excellent electrochemical performance can be ascribed to the unique hollow structure, which provides more voids and pores for accommodation of volume expansion, as well as the uniform carbon film on the surfaces of the Ge nanoparticles, which maintains their structural integrity and enhances the electronic conductivity of the whole electrode.
High Performance Na-Ion Batteries Based on Novel O3 Layered Oxide Cathode Materials
Authors: Barker Jerry , Heap Richard John , Roche Noel , Tan Chaou , Sayers Ruth , Liu Yang
Published: February 2020

Sodium-ion (Na-ion) batteries represent an attractive alternative to their lithium-ion counterparts, and are expected to offer some significant commercial advantages such as lower active material costs and improved safety characteristics [1,2]. In these systems Na-based layered oxides, NaxMO2(M = transition metal) have emerged recently as high performance and low cost cathode materials [3,4]. These oxide materials may be categorized into three main structural types using the classification proposed by Delmas and co-workers – i.e. O3, P2 and P3 types, where the alkali ions occupy either octahedral (O) or prismatic sites (P), respectively [5].

In this study single-phase O3-NaaNi(1-x-y-z)MnxMgyTixO2 materials have been prepared using conventional solid-state processing methods. In these as-made compositions nickel and magnesium are included as M2+ while manganese and titanium are present as M4+. Special attention was given to the product composition, precursor mixing and synthesis conditions to ensure no unwanted NiO impurity content. Figure 1 shows the XRD pattern for a typical O3-Na layered oxide composition and confirms that the material is essentially phase pure.

The electrochemical performance of the experimental O3-NaaNi(1-x-y-z)MnxMgyTixO2 phases was evaluated in full Na-ion test cells where the cathode materials were capacity balanced to a commercial hard carbon anode material. The electrolyte used was 0.5 M NaClO4 in propylene carbonate and testing was carried out at 30 oC.

In Figure 2 we depict the low rate (C/10) voltage profile derived from a typical constant current charge-discharge cycle. The cathode active material cycles reversibly at a specific capacity of 163 mAh/g and the Na-ion cell generates an average discharge voltage of around 3.0 V. The specific energy performance for the cathode is comparable to commercial Li-ion electrode materials.

Figure 3 shows a typical cycle life plot for a representative Na-ion cell. These data were collected at a C/10 charge/discharge rate using voltage limits of 4.2 and 1.0 V. Following 300 cycles the cell has retained over 70 % of the original discharge capacity. Most of this capacity loss is recoverable at lower discharge rates indicating importantly that the fade mechanism is associated with cell impedance changes rather than irreversible loss of active Na. Further performance data for the Na-ion system will be presented.

References:

[1] V. Palomares, P. Serras, I. Villaluenga, K. B. Hueso, J. Carretero-Gonzalez and T. Rojo, Energy Environ. Sci.
5, 5884, 2012

[2] J. Barker, M.Y. Saidi and J. Swoyer, Electrochem. Solid-State Chem.
6, A1, 2003

[3] M. Slater, D. Kim, E. Lee and C. S. Johnson, Adv. Funct. Mater.
23, 947, 2013

[4] S-W. Kim, D-H. Seo, X. Ma, G. Ceder and K. Kang, Adv. Energy Mater.
2, 710, 2012

[5] C. Delmas, C. Fouassier and P. Hagenmuller, Physica B+C, 99, 81-85, 1980.
Electrochemical Behaviours and Structure Evolution of High Capacity Li1.2Cr0.4Mn0.4O2 Cathode Material in a Wide Voltage Range
Authors: Lyu Yingchun , Xiao Dongdong , Gu Lin , Li Hong
Published: February 2020

Li-rich materials have been widely studied as high-energy cathode materials, with a high specific capacity more than 300 mAh/g when charged beyond a voltage plateau of ∼4.5 V [1]. Excess capacity at the voltage plateau has been suggested to be partly compensated by oxidation of oxide ions, causing release of oxygen from the lattice to electrolyte [2]. Electrode performance is significantly influenced by the oxygen removal process. Besides xLi2MnO3·(1−x)LiMO2 (M=Ni, Co, Mn), Li1.2Cr0.4Mn0.4O2 has also been widely studied [3, 4]. The theoretical specific capacity of Li1.2Cr0.4Mn0.4O2 reaches to 387 mAh/g by utilizing the Cr3+/Cr6+ redox, which possibly suppresses the oxygen loss associated with the voltage plateau at ∼4.5 V. The process of Cr3+/Cr6+ redox is reversible at a wide range from 4.8 to 1.5 V [5].

In this work, Li1.2Cr0.4Mn0.4O2 cathode material has been cycled in the voltage range from 4.8 to 1.0 V. The charge-discharge profiles and open circuit voltage curve of Li1.2Cr0.4Mn0.4O2 have been recorded. The low-voltage electrochemical behaviour is similar with (x)LiMn0.5Ni0.5O2·(1−x)Li2TiO3 [6]. It shows a charge capacity of 297 mAh/g during the first charge. When discharged to 1V, the discharge capacity achieved up to 387 mAh/g. It is worthwhile to note that there is a long plateau at the voltage range from 1.7 to 1.0 V, in which part the capacity is reversible during the subsequent cycles. But the voltage profile is not symmetrical; the capacity in the charging process is much less than that of the discharge process at low voltage. GITT, in situ XRD, XAS and HAADF-STEM measurements have been done to clarify the electrochemical behaviors and structure evolution of Li1.2Cr0.4Mn0.4O2 in such wide voltage range.

Acknowledgement: Financial support from CAS project (KJCX2-YW-W26), "Strategic Priority Research Program" of the Chinese Academy of Sciences,Grant No. XDA01020304 and National project 973 (2012CB932900) are appreciated.

References:

[1] M. M. Thackeray, C. S. Johnson, J. T. Vaughey, N. Li and S. A. Hackney, Journal of Materials Chemistry, 2005, 15, 2257-2267.

[2] A. R. Armstrong, M. Holzapfel, P. Novák, C. S. Johnson, S.-H. Kang, M. M. Thackeray and P. G. Bruce, Journal of the American Chemical Society, 2006, 128, 8694-8698.

[3] Z. H. Lu and J. R. Dahn, Journal of the Electrochemical Society, 2002, 149, A1454-A1459.

[4] M. Balasubramanian, J. McBreen, I. J. Davidson, P. S. Whitfield and I. Kargina, Journal of The Electrochemical Society, 2002, 149, A176-A184.

[5] N. Yabuuchi, K. Yamamoto, K. Yoshii, I. Nakai, T. Nishizawa, A. Omaru, T. Toyooka and S. Komaba, Journal of The Electrochemical Society, 2013, 160, A39-A45.

[6] C. S. Johnson, J.-S. Kim, A. Jeremy Kropf, A. J. Kahaian, J. T. Vaughey and M. M. Thackeray, Electrochemistry Communications, 2002, 4, 492-498.
Layered Lithium-Sodium Manganese Oxide As a Cathode Material for Lithium Ion Batteries
Authors: Du Ke , Hu Guorong , Huang Dianhua
Published: February 2020

Lithium-Sodium Manganese Oxide, Nax[Li0.2Mn0.8]O1.6+δ( x = 0.4, 0.5, 0.6, 0.7, 0.8),were synthesized by solid-state reaction . The physical properties and electrochemical behaviors of Nax[Li0.2Mn0.8]O1.6+δ were characterized by X-ray diffraction, scanning electron microscope, and electrochemical measurement. XRD patterns show that when the x≥0.6, the samples exhibit symmetric hexagonal space group P63/mmc, with a P2 structure. It is found that Na0.6[Li0.2Mn0.8]O1.6+δ has the high discharge capacity and good cycle performance. At a discharge rate of 0.1C in the cut off voltage range of 2.0-4.8V, Na0.6[Li0.2Mn0.8]O1.6+δ gives an initial discharge capacity of 269mAh g-1 and the capacity retention rate of 89% after 35 cycles.
Electrochemical Properties of Cu Doped Lithium Manganese Silicate/PANI Composite As Cathode Material for Lithium-Ion Batteries
Authors: Lee Sol Nip , Palanichamy Sennu , An Jae Youn , Thangavel Ranjith , Lee Yun Sung
Published: February 2020

Development of cathode materials for lithium battery application like electric vehicle (EV) and plug-in hybrid electric vehicle (PHEV) requires high capacity materials[1]. At the same time, cost, environmental concerns and safety issues cannot be excluded. Recently, lithium transition-metal silicates such as Li2MSiO4
(M=Fe, Mn and Co) have been extensively studied as cathode materials for lithium ion batteries, due to high theoretical capacity and better thermal stability than lithium transition metal oxides such as LiCoO2. Among them, Li2MnSiO4 cathode could be a better choice as a high capacity( ~330 mAh/g) cathode for lithium ion batteries than Li2FeSiO4 cathode material. Due to Mn2+/Mn3+ and Mn3+/Mn4+ redox couples, extraction of two lithium ions can be achieved from Li2MnSiO4. However, due to defects such as structure change after the first charge and low electronic conductivity(~ < 10-14S/cm), this material has poor cycle performance and lower capacity than the theoretical prediction [2-3].

In this regard, the current work is aimed on the improvement of capacity and cycle stability of Li2MnSiO4
cathode active material by applying Cu doping and poly-aniline composites. The Li2Mn0.95Cu0.05SiO4were prepared using the sol-gel synthesis. PANI was synthesized by oxidative polymerization.

XRD patterns as shown in Figure 1 exhibit that the Cu doping and PANI composite does not contribute to structure change of Li2MnSiO4. From the cycle performances as shown in Figure 2, the Li2Mn0.95Cu0.05SiO4/PANI cell shows a high discharge capacity, as well as improved cycle retention compared with pristine Li2MnSiO4 material. Synthesis methodology of Li2Mn0.95Cu0.05SiO4/PANI materials along with their physical, morphological and electrochemical characteristics will be discussed in detail.

References
:

[1] R.J. Gummow, N.Sharma, V.K.Peterson, Y.He, J. solid state chem., 188 (2012) 32–37.

[2] R. Dominko, M. Bele, A. Kokalj, M. Gaberscek, J. Jamnik , J. Power Sources., 174 (2007) 457–461.

[3] D. M. Kempaiah, D. Rangappa, I. Honma, Chem. Commun.,48 (2012) 2698–2700.
Anomalous Voltage Change in Charge and Discharge Curves for Electrode Materials Showing Plateau-like Behavior
Authors: Herrmann Matthias , Richter Frank , Riegel Bernhard
Published: February 2020

Recently T. Sasaki et al.
1 reported on a phenomenon of an anomalous voltage change that occurs when electrode materials showing a plateau-like behavior (during charge/discharge) are partially charged and/or discharged. They studied the anomalous voltage change in lithium iron phosphate (LiFePO4) as well as in lithium titanate (Li4Ti5O12). The anomalous voltage change was referred to as ‘voltage bump’ which appears already after only one cycle of partial charge and discharge. The voltage bump was explained in connection to a particle-by-particle charge/discharge model. The reported electrochemical tests were performed at room temperature in two-electrode coin-type or three-electrode cells with Li-metal as reference and counter electrode (half cell).

In this work, partial charge/discharge experiments (Fig. 1) were used to study the effect of temperature on the anomalous voltage change. The investigations were carried out on commercially available large-format cells based on LiFePO4/graphite system (full cell). Increasing the number of partial cycles leads to an interference of single voltage bumps, but the voltage rise was observed to saturate at a given voltage level (Fig. 2). An increased voltage bump was observed at smaller temperature, while an opposite effect was obtained at higher temperature (Fig. 2). Resulting voltage bumps in the range of up to 20 mV were observed, depending on temperature. The observed behavior is discussed in view of the particle-by-particle model and kinetic effects. Such a slight voltage change can lead to substantial miscalculations in estimating the state of charge of cells and batteries.

1Tsuyoshi Sasaki, Yoshio Ukyo, Petr Novák, Nature Materials, published online: 14 April 2013, DOI: 10.1038/NMAT3623.