Xiaolin Li, Pacific Northwest National Lab
Liangbing Hu, Univ of Maryland
Teofilo Rojo, CIC Energigune Energy Cooperative Research Centre
Husam Alshareef, King Abdullah University of Science and Technology
ACS Energy Letters | ACS Publications, Bio-Logic, USA, Contemporary Amperex Technology Co., Limited (CATL), Materials for Renewable and Sustainable Energy | SpringerMaterials, MilliporeSigma (Sigma-Aldrich Materials Science), Pacific Northwest National Laboratory
ES1.1: Li-Ion Battery I
Monday AM, November 28, 2016
Sheraton, 2nd Floor, Republic B
8:30 AM - *ES1.1.01
On the Role of Power Electronics and Power Conversion Systems in Grid Energy Storage
Babu Chalamala 1 , Stanley Atcitty 1 , Adam Morgan 1
1 Sandia National Laboratories Albuquerque United StatesShow Abstract
Grid-tied energy storage systems (ESS) are becoming more prevalent in the electricity infrastructure and are seen as critical to improve grid stability and reliability, and to accommodate large scale integration of renewables. When properly integrated, energy storage will improve the quality, flexibility, reliability, resiliency, and cost effectiveness of the existing electric utility systems. The enabling technology for grid-tied energy storage systems is the power conversion system (PCS). The PCS provides the bi-directional power conversion necessary to connect energy storage devices, such as batteries, flywheels, and other storage devices, to the grid. An optimized system would provide for maximum power transfer and control to and from the grid, while maintaining reliable and safe operation of the storage device. The integral part of the PCS is power electronics, which dominates the overall cost, and determines the overall reliability and performance of the converter. Most PCSs currently used in energy storage systems utilize silicon-based power semiconductor devices. PCSs using wide-bandgap (WBG) power semiconductors, such as Silicon Carbide and Gallium Nitride, are beginning to find greater use. SiC and GaN power modules allow for higher switching frequencies, higher breakdown voltages, and higher junction temperatures, while reducing the size of power modules enabled by advanced packaging techniques. Utilizing these types of switches will improve system performance by increasing the power density and efficiency by an order of magnitude, compared to traditional silicon-based designs. This presentation will give an overview of power electronics and power conversion systems, and highlight recent advances in associated component technologies, such as solid state transformers (SSTs) and high-frequency converters and advanced magnetics; along with their impact on the development of lower cost, high performance PCS for grid energy systems.
9:00 AM - ES1.1.02
Designing Aqueous Lithium Ion Batteries from a Catalysis Vision
Yuhang Wang 1 , Gengfeng Zheng 1
1 Laboratory of Advanced Materials Fudan University Shanghai ChinaShow Abstract
Aqueous energy storage systems, e.g. aqueous lithium ion batteries (ARLIBs), are becoming increasingly important for its high theoretical specific power and safety, while the practical performance has been critically constrained by its narrow voltage window due to the electrochemical water splitting side reactions.[1, 2] Although the sluggish oxygen evolution usually requires a large overpotential, the hydrogen evolution reaction (HER) can easily take place when the applied potential increases, and critically constrains the battery voltage window as well as the Coulombic efficiency. The rational design of anode materials, where the hydrogen evolution also takes place, may suggest a new avenue for developing ARLIB with enhanced voltage window and power density.
Inspired by the high efficient hydrogen evolution catalysts,[4, 5] we designed an opposite strategy instead, aiming to create a large HER overpotential for inhibiting water reduction and subsequently boosting both the battery output voltage and Coulombic efficiency in aqueous solutions. Moreover, the electrode surface passivated with hydrogen evolution further enables high current density during battery cycling, leading to both an ultrahigh power density and an excellent energy density. Density functional theory calculations indicate polyimide nanosheets provide limited sites for hydrogen atom binding and large activation barriers for HER, especially for Li+ associated polyimides. After improving their electronic conductivity by carbon nanotube (CNT) networks, the polyimides/CNT aqueous lithium-ion battery anode exhibits hydrogen evolution onset overpotential as large as 820 mV in neutral aqueous electrolytes, an outstanding reversible capacity of 133.0 mA h g-1, and ultrafast charge-discharge capability (13.6 sec per cycle at 128C). Moreover, an aqueous polyimide-CNT//LiMn2O4 battery exhibits top-level performance, including a wide voltage window (> 2 V), exceptional capacity (68.8 mA h g-1), energy density (76.1 W h kg-1) and power density (12,610 W kg-1), and excellent cycling stability over 1000 cycles when fast operated within ~ 5 min.
1. Luo, J.; Cui, W.; He, P.; Xia, Y. Nat. Chem. 2010, 2, 760-765.
2. Kim, H.; Hong, J.; Park, K.; Kim, H.; Kim, S.; Kang, K. Chem. Rev. 2014, 114, 11788-11827.
3. Suo, L.; Borodin, O; Gao, T; Olguin, M; Ho, J; Fan, X; Luo, C; Wang, C; Xu, K. Science 2015, 350, 938-943.
4. Zhang, X.; Meng, F.; Mao, S.; Ding, Q.; Shearer, M. J.; Faber, M. S.; Chen, J.; Hamers, R. J.; Jin, S. Energy Environ. Sci. 2015, 8, 862-868.
5. Wang, D.; Gong, M.; Chou, H.; Pan, C.; Chen, H.; Wu, Y.; Lin, M. C.; Guan, M.; Yang, J.; Chen, C.; Wang, Y.; Hwang, B.; Chen, C.; Dai, H. J. Am. Chem. Soc. 2015, 137, 1587-1592.
9:15 AM - ES1.1.03
Exploring Bio-Inspired Organic-Based Liquid Batteries towards Sustainable Energy Storage
Yu Ding 1 , Guihua Yu 1
1 University of Texas at Austin Austin United StatesShow Abstract
As an alternative to metal-based electroactive materials, quinone-based organic redox species represent one of the most promising electrode materials owing to features including material sustainability and tailorable properties. Here we systematically study quinones for liquid batteries in both aqueous and non-aqueous electrolyte. As an emerging battery technology, this organic liquid battery inherits the advantageous features of modular design of flow batteries and high voltage and energy efficiency of Li ion batteries. With the help of rotating disk electrode and cyclic voltammetry measurements, the redox chemistries of quinones are investigated comprehensively. Moreover, a combined experimental and computational study reveals that the redox properties of quinones are strongly dependent on the molecular aromaticity and electronic structures. As quinones play a pivotal role in bioelectrochemical process, a fundamental understanding of their reaction mechanisms in electrochemical energy storage devices can pave the path towards bio-inspired sustainable energy technologies.
9:30 AM - ES1.1.04
Low-Cost Tire-Derived Carbon/Metal Oxide Composite Electrodes for Lithium Ion Batteries
Yunchao Li 2 1 , Alan Levine 3 , Richard Lee 3 , Kokouvi Akato 1 , Amit Naskar 4 1 , Sheng Dai 2 , M. Paranthaman 2 1
2 Chemical Sciences Division Oak Ridge National Laboratory Oak Ridge United States, 1 The Bredesen Center University of Tennessee Knoxville United States, 3 RJ Lee Group Monroeville United States, 4 Materials Science and Technology Division Oak Ridge National Laboratory Oak Ridge United StatesShow Abstract
With the growth of sustainable energy generation, there is an increased demand for large-scale energy storage to secure the grid system. Lithium-ion battery is considered as one of the most attractive energy storage solution due to its high energy density and efficiency. However, the high cost of the electrode materials hinders its application in such price sensitive market. Here, we report a low-cost, large-scalable waste tire-derived carbon and metal oxide composite anode for lithium ion batteries. Carbon composite powders were prepared with carbon recovered from used tire powders and 25 wt. % of the select metal oxides to form composite electrodes. With such controlled amount of the metal oxide and the unique pore size distribution of the tire-derived carbon as the absorbing matrix, the volume change and the degradation of the electrodes are minimized. The composite anode shows a very stable electrochemical performance with a capacity of over 650 mAh g-1 after 300 cycles at a current density of 40 mA g-1. We will report in detail about the synthesis and characterization of the carbon composite electrodes. This study provides a new pathway for inexpensive, environmentally benign and value-added waste tire-derived products towards large-scale energy storage applications.
9:45 AM - ES1.1.05
SnO2-Reduced Graphene Oxide Aerogels as High Energy Anodes for Lithium-Ion Batteries
Cristina Botas 1 , Daniel Carriazo 1 2 , Gurpreet Singh 1 , Teofilo Rojo 1 3
1 CICenergiGUNE Miñano Spain, 2 Basque Foundation for Science IKERBASQUE Miñano Spain, 3 Departamento de Química Inorgánica Universidad Del País Vasco UPV/EHU Bilbao SpainShow Abstract
Lithium-ion batteries (LIBs) are the key components of portable electronic devices and electric vehicles. High energy density lithium ion batteries are required for their future applications in electronic market, as the needs of the market are more demanding. Graphene and graphene based materials have gained the interest due to their good properties such as mechanical flexibility and high electrical conductivity, surface area and chemical diffusivity of Li. Graphene has been studied in the batteries in the past and their challenge has been demonstrated over the past couple of years [1, 2]. On the other hand metallic Tin based materials have also attracted great attention due to their good electrochemical properties when used as anode for LIBs, mainly due to theoretical specific capacity (993 mAh g-1) of Sn, low cost and low toxicity . However, Sn shows several problems: i) large volume changes during the lithiation/delithiation process (which can be up to 300 %); ii) high degradation and low cyclability due to these volume changes; iii) high decomposition of the electrolyte due to high reactivity of Sn nanoparticles. Different Sn/C composites have been developed to overcome these problems and improve the stability of Sn anodes. These carbon matrixes are reported to buffer the volume change of Sn during charge/discharge. 
The aim of this work, was to evaluate reduce graphene oxide (rGO) and a novel composite of SnO2@rGO (binder free) aerogels as self-standing anodes for LIBs. SnO2@rGO composites were synthesized in two steps: i) freeze-drying and ii) thermal reduction of a mixture of SnSO4 and graphene oxide suspension, previously prepared by modified Hummer method.  The pure rGO was prepared following the same procedure. The materials have been characterized by XRD, XPS and SEM. Homogeneous distribution of 50–200 nm particles of SnO2 in the graphene matrix has been observed.
CR2032 type coin cells were used to analyze the electrochemical properties of the composite cathode. Cells were fabricated inside a glove box under Argon atmosphere with H2O and O2 level < 0.1 ppm. 1.2 M LiPF6 solution in ethylene carbonate and dimethyl carbonate 1:1 (v/v) solution with VC as additive was used as electrolyte. Lithium metal foil was used as counter/reference and glass fiber as separator. Self-standing rGO and Sn/SnO2@rGO composite (without any binder and any support) were used as anodes. The reversible specific capacity of Sn/SnO2@rGO was 650 mAh g-1 at 50 mA g-1 after 40 cycles and 420 mAh g-1 at 1A g-1. The pure rGO specific capacity was 298 mAh g-1 after 40 cycles at 50 mA g-1.
 Z. Wu, G. Zhoua, L.Yina, W. R., F. Lia, H. Cheng. Nano Energy, 1 (2012) 107.
 J. Qin, C. He, N. Zhao, Z. Wang, C. Shi, E. Liu, J. Li. ACS Nano, 8 (2014) 1728.
 C. Botas, P. Álvarez, C. Blanco, R. Santamaría, M. Granda, et al. Carbon, 50 (2012) 275.
 C. Botas, D. Carriazo, G. Singh, T. Rojo, J. Mater. Chem. A, 3 (2015) 13402.
10:00 AM - *ES1.1.06
Designing Electrolytes for Post Lithium-Ion Batteries
Wladyslaw Wieczorek 1
1 Faculty of Chemistry Warsaw University of Technology Warszawa PolandShow Abstract
In this presentation novel ambient temperature electrolytes for application inn lithium-ion and post lithium-ion (e.g. sodium, magnesium, Li-S etc.) batteries will be presented. New fluorine and fluorine free salts which can easily be synthesized in the form required for various applications will be presented and their properties discussed from the viewpoint of particular applications. Some examples of the performance of batteries with electrolytes based on newly developed salts will also be included. In particular we would like to highlight some new ideas of the preparation of polymer solid, gel and ionic liquid electrolytes leading to their superior properties compared with currently commercially available electrolytes.
10:30 AM -
10:30 AM -
10:45 AM - ES1.1.08
Elastic and Stretchable Gel Polymer Electrolyte Coating to Improve Long-Term Cycling Stability of High-Areal-Capacity SiO Electrode for Lithium-Ion Battery
Qingquan Huang 1 , Jiangxuan Song 1 , Donghai Wang 1
1 The Pennsylvania State University State College United StatesShow Abstract
High-capacity Si-based anode is an advanced anode material to improve the energy density of Li-ion battery. In order to pair with commercial cathode, the areal capacity of Si-based anode should be increased to 3-4 mAh/cm2. However, high-areal-capacity Si-based anode still encounters fast capacity fading issue and poor cycling stability, because huge volume change of Si active material upon repeated charge/discharge cycles will lead to damage of electrode structure integrity (like particle pulverization, electrode cracking/delamination, and loss of conducive network) and accumulative growth of SEI (solid electrolyte interface) layer. Here we develop an elastic and stretchable gel polymer electrolyte (GPE) coating strategy to improve the long-term cycling stability of high-areal-capacity SiO electrode. The polymer coating can swell and uptake 75 w% carbonate electrolyte, providing a moderate ionic conductivity of 2.4*10-4 S/cm at room temperature. The GPE shows great chemical and electrochemical stability with lithium metal. At the electrode level, the GPE coating is elastic and stretchable, and it can improve electrode adhesion strength and alleviate electrode thickness change during charge/discharge process. For long-term cycling, the GPE coating can restrict the pulverized particles in a localized space to prevent loss of conductive network and maintain the electrode structure integrity. In half cell test, the SiO electrode with GPE coating shows a reversible capacity of 3.0 mAh/cm2 (or specific capacity of 1200 mAh/g) for 280 cycles. In full cell test, the cell of NCM/prelithiated SiO electrode with GPE coating has a reversible capacity of 2.1 mAh/cm2 (or specific capacity of 150 mAh/g) for 300 cycles, with an improved Coulombic efficiency of above 99.9%.
11:00 AM - ES1.1.09
Microstructurally Tuned Si/TiFeSi2 Nanocomposite as a Highly Stable Lithium Storage Material
Hyeong-Il Park 1 , Myungbeom Sohn 1 , Jeong-Hee Choi 2 , Cheolho Park 3 , Jae-Hun Kim 4 , Hansu Kim 1
1 Department of Energy Engineering Hanyang University Seoul Korea (the Republic of), 2 Korea Electro-Technology Research Institute Changwon Korea (the Republic of), 3 Next-G Institute of Technology, Iljin Electric Co., Ltd. Ansan Korea (the Republic of), 4 School of Advanced Materials Engineering Kookmin University Seoul Korea (the Republic of)Show Abstract
Although silicon has higher reversible capacity than graphite as a lithium storage material, its large volume expansion during lithium insertion causes poor capacity retention. To address this technical issue, melt-spun Si based alloy materials have been suggested as a promising materials for lithium ion batteries because of their high capacity and relatively low production cost. However, their long-term cycle performance should be further improved for the commercial success. In this work, it was demonstrated that mechanical deformation can improve the electrochemical performances of melt-spun Si alloy material. With the help of high-energy mechanical milling, Si/TiFeSi2 nanocomposite was successfully tuned with a size of few nanometers based on the results of X-ray diffraction analysis and transmission electron microscopy observation. As a result, the microstructurally tuned Si/TiFeSi2 showed a reversible capacity of more than 1000 mAh g-1 with stable capacity retention up to 100 cycles. More detailed studies on the reasons for better cycle performance of milled Si/TiFeSi2 will be discussed in this presentation.
11:15 AM - ES1.1.10
The Influence of Pre-Lithiation on Li
12/Activated Carbon Hybrid Battery
Jun Feng 1 , Fredrick Omenya 1 , Natalya Chernova 1 , Linyue Tong 1 , Wayne Jones 1 , Alok Rastogi 1 , M. Stanley Whittingham 1
1 Binghamton University Binghamton United StatesShow Abstract
The increasing demand for energy storage nowadays requires both high power and high energy density devices. Hybrid batteries are good candidates to meet the requirements by marrying battery and super-capacitor electrodes. In this work, Li4Ti5O12 (LTO), as battery electrode, and activated carbon (AC), as supercapacitor electrode, are combined into one hybrid battery. Prior to the hybrid battery assembly, LTO electrodes were cycled three times against lithium chip in a Swagelok cells and then charged or discharged to non-lithiated or pre-lithiated states. We compared the charge/discharge capacity, cyclic voltammetry graphs, impedance, diffusion efficiency and other characteristic to discuss the impact of the pre-lithiation on the LTO/AC hybrid batteries. From charge/discharge and cyclic voltammetry tests, both kinds of hybrid batteries exhibit physical-absorption-domain CV curves and have similar performance. However, with the pre-lithation process, the hybrid battery has higher specific capacity, reduced electrode resistance and higher capacitive reactance.
This research is supported by NSF, a US government agency which supports fundamental research and education in all the non-medical fields of science and engineering, under Award Number 1318202.
11:30 AM - ES1.1.11
A High Power, Fast-Charging and Long-Life Li-Ion Battery for High Energy Storage Application
Marco Agostini 1 , Priscilla Reale 3 , Sergio Brutti 2 , Aleksandar Matic 1
1 Chalmers University of Technology Göteborg Sweden, 3 Agenzia nazionale per le nuove tecnologie, L'energia e lo sviluppo economico sostenibile, ENEA, Centro Ricerche Casaccia Rome Italy, 2 Dipartimento di Scienze Università della Basilicata Potenza ItalyShow Abstract
The urgent need to increase the share of renewable sources in the energy scenario, as well as of environmentally compatible vehicles, either hybrid electric vehicles (HEVs) or electric (EVs), requests the fast development of improved energy storage systems. Lithium Ion Batteries (LiBs) are presently viewed as the most promising candidates due to their high specific energy density. However, the current LiB technology based on a C/LiCoO2 chemistry is not yet at such a level to meet the requirements for HEVs and, in particularly EVs. Therefore, the development of alternative chemistries assuring decrease in cost and enhancement in energy density is a mandatory step. A promising example of a cathode alternative to the high cost and partially toxic LiCoO2 is the LiNi0.5Mn1.5O4 (LNMO) spinel, since it is characterized by higher theoretical energy density, about 660 Wh kg-1, environmental compatibility and lower cost. However, several issues still prevent the practical implementation of LNMO cathodes in lithium batteries. Furthermore, the severe requirements of the battery manufacturers triggered the replacement of the metallic anode by alternative materials characterized by higher safety. In this contribution we present Li-ion batteries (LiBs) exploiting spinel cathodes and TiO2-nanotubes anodes. The LiBs showed outstanding properties in terms of fast charge (about 5 minutes), high energy (230 Wh kg-1) and long cycle life (extending to over 400 cycles). Moreover, by the addition of an ionic liquid to the carbonate-based electrolyte solution we demonstrated an enhanced safety content of the LiBs developed.
11:45 AM - ES1.1.12
Flexible,Three-Dimensional Ordered Macroporous TiO
2 Electrode with Enhanced Electrode–Electrolyte Interaction in High-Power Li-Ion Batteries
Gregory Lui 1 , Ge Li 1 , Xiaolei Wang 1 , Gaopeng Jiang 1 , Edric Lin 1 , Michael Fowler 1 , Aiping Yu 1 , Zhongwei Chen 1
1 Chemical Engineering University of Waterloo Waterloo CanadaShow Abstract
A simple methodology is developed for the in-situ preparation of flexible, three-dimensional ordered macroporous (3DOM) TiO2 electrodes with greatly enhanced mass transfer. The 3DOM electrode is fabricated using a polystyrene colloidal crystal templated carbon cloth, and provides significant improvements over conventional nanoparticle electrodes without the use of binder or other additive. When evaluated as an anode in a Li-ion battery, the 3DOM electrode provides outstanding high rate performance. The electrode provides a specific capacity of 174 mAh g-1 at a current density of 2 A g-1, which is 2.6 times greater than that achieved with a nanoparticle electrode (68 mAh g-1). The 3DOM electrode also achieves excellent cycling stability, with a capacity retention of 94.8% (181 mAh g-1) over 1000 cycles at 10C (1.7 A g-1) compared to 93.7% (67 mAh g-1) for the nanoparticle electrode. To the best of our knowledge, the performance of our 3DOM electrode is among the highest of binder-free, flexible TiO2 electrodes. We believe that this methodology is highly useful and is easily transferable to other materials and applications.
ES1.2: Li-Ion Battery II
Monday PM, November 28, 2016
Sheraton, 2nd Floor, Republic B
2:00 PM - *ES1.2.01
Quantifying Defects in Electrode Materials—Coupling Microstructure and Battery Performance
Montse Casas-Cabanas 1 , Marine Reynaud 1 , Jon Serrano 1 , Morgane Giner 1 , Montserrat Galceran-Mestres 1 , Chunjoong Kim 1 , Jokin Rikarte 1 , Jordi Cabana 1 , Juan Rodriguez-Carvajal 1
1 CIC EnergiGUNE Minano SpainShow Abstract
Disruptions in periodicity are extremely common in all kinds of solid materials and can manifest in multiple ways. Indeed solids often exhibit point defects (such as antisites, interstitials or vacancies), stacking faults, grain boundaries, pores, intergrowths or microstrains, just to name a few. While some technologies require the use of crystals that are nearly perfect, polycrystalline solids are usually the norm in most applications. This is the case of electrochemical storage systems, for which a proper understanding of the underlying thermodynamics and kinetics unavoidably requires the framework of both structure and microstructure.
Diffraction techniques (XRD, NPD) are typically used to characterize average structural features of functional materials. Thanks to the recent development of advanced tools for diffraction data treatment (either implemented in Rietveld refinement programs such as FullProf, or available as independent refinement programs such as FAULTS), powder diffraction can now be also used for the quantitative characterization of extended defects. Several examples corresponding to different battery materials will be shown to illustrate how, besides classic structural determination, quantitative information regarding microstructural features such as anti-phase domains, stacking faults, twinning or intergrowths or microstrains can now be extracted from diffraction data to establish correlations with materials’ properties and monitor their evolution upon cycling through the use of in situ or operando data.
2:30 PM - ES1.2.03
Minimize the Voltage Degradation in Li-Rich Layered Oxide Cathode Materials by Morphology Control
Minghao Zhang 1 , Haodong Liu 1 , Chengcheng Fang 1 , Ying Shirley Meng 1
1 NanoEngineering University of California, San Diego La Jolla United StatesShow Abstract
Li-rich layered oxides, either as a solid solution or as a nano-composite of layered Li2MnO3 and Li(TM)O2 (TM=Ni, Co, Mn), draw significant attention as the next-generation cathode materials for high-energy-density lithium ion batteries in electric vehicles. Over the past twenty years, the discharge capacity at room temperature of these cathode materials has been improved from 200 mAh g-1 to over 320 mAh g-1 today, even higher at elevated temperatures. While the research has continued to push the limit of the available capacity of the materials throughout the years, there are many issues still unclear. And numerous scientific challenges, especially voltage degradation during cycling of these materials, that must be overcome to realize their utilization in commercial lithium ion batteries.
Here, we report a design of modified co-precipitation method without ammonia addition to synthesize morphology controlled Li-rich material Li1.2Ni0.2Mn0.6O2 as high energy density cathode for lithium ion batteries. The obtained material has spherical secondary particles with uniform dispersion. The secondary particles are dense, and have an average diameter of approximately 3 μm. These secondary spherical particles consist of primary particles with particle size approximately 150 nm. The morphology controlled sample can minimize voltage decay as well as improve capacity retention during cycling. The successful implementation of this morphology controlled Li-rich material as the cathode for lithium ion batteries can increase the overall energy density of the state-of-the-art lithium ion batteries by 20-25%. And furthermore, the influence of morphology control on the cycling performance has been investigated through Transmission X-ray Microscope.
2:45 PM - ES1.2.04
Enhanced Cycling Stability of Nickel-Rich Cathode Materials via an Artificial Solid Electrolyte Interface Layer
Jianming Zheng 1 , Pengfei Yan 1 , Jian Liu 1 , Xueliang Sun 2 , Chongmin Wang 1 , Ji-Guang Zhang 1
1 Pacific Northwest National Lab Richland United States, 2 Western University London CanadaShow Abstract
Recently, Ni-rich layered structure cathode materials LiNixMnyCozO2 (NMC, x ≥ 0.6) have received great attention as a promising cathode due to their high achievable discharge capacity (200~220 mAh g-1), representing a significant enhancement in energy density (~800 Wh kg-1) in comparison with traditional LiCoO2 (~570 Wh kg-1) and spinel LiMn2O4 (~440 Wh kg-1). Ni-rich cathode materials also have much higher lithium ion diffusion coefficients, indicating a superior power capability as compared to other NMC cathodes with lower Ni contents. The other advantage of Ni-rich cathode materials is the reduction of production cost due to the reduced Co content. However, there are still some technical challenges hindering the mass applications of Ni-rich cathode materials, mainly including (i) micro strain and crack formation because of the significant volume variation during lithium ion de/intercalation processes, (ii) safety concern ascribed to the aggressive thermal reactions between the delithiated Ni-rich NMC materials and the organic carbonate electrolyte.
A lot of effort has been dedicated to improving the electrochemical performances and thermal stability of the Ni-rich NMC cathode materials. Representative approaches include lattice doping, surface treatment/modification, tuning the material compositions, a smart design of core-shell or concentration gradient structures, structural stabilization with a low content of Li2MnO3, and so on. In addition to the solution-based coating method, surface coating via atomic layer deposition (ALD) has attracted increasing attention in the development of high performance electrode materials for LIBs, due to its exclusive advantages including low deposition temperature and extremely uniform and conformal deposition of thin films with precisely controlled thickness. ALD surface coating of various oxide has proved to be effective in improving the long-term cycle life of a variety of cathode materials. Herein, we report for the first time ALD coating of a new solid-state electrolyte Li3PO4 on a Ni-rich cathode material LiNi0.76Mn0.14Co0.10O2 with. Coating with solid-state electrolyte Li3PO4 gives rise to a significant enhancement in the interfacial and structural stability, and the electrochemical performances of LiNi0.76Mn0.14Co0.10O2 even under harsh testing conditions of charge cut-off 4.5 V and at 60 oC. The functioning mechanism of solid electrolyte coating was investigated in detail by electrochemical measurements, impedance analysis in conjunction with systematic electron microscopic observations.
3:30 PM - ES1.2.05
Solvent-Free Dry Powder Coating Process for Low-Cost Manufacturing of LiNi
2 Cathodes in Lithium-Ion Batteries
Mohanad Al-shroofy 1 , Susan Odom 2 , Yang-Tse Cheng 1
1 Department of Chemical amp; Materials Engineering University of Kentucky Lexington United States, 2 Department of Chemistry University of Kentucky Lexington United StatesShow Abstract
We report a solvent-free dry powder coating process for making a LiNi1/3Mn1/3Co1/3O2 (NMC) cathodes in lithium-ion batteries. Comparing with the conventional wet slurry-based electrode manufacturing method, the dry powder coating method is a lower cost, higher throughput, and more environmentally friendly manufacturing process. This process lowers electrode fabrication cost by 90%, eliminates volatile organic compound emission, and reduces electrode drying time from hours to minutes. A dry mixture of NMC, carbon black, and poly(vinylidene difluoride) was sprayed onto an aluminum current collector to form a uniformly distributed electrode of controlled thickness and porosity. The composition, structure, thermal stability, and electrochemical performance of the electrodes were analyzed. Excellent electrochemical performance was obtained with a discharge specific capacity of 155 mAh g-1 and capacity retention of 96% over 80 cycles from 3 to 4.3 V at 0.2 C/5 charging rate in lithium half cells. The electrodes have similar long-term cycling performance and durability to those made by the conventional web slurry process.
3:45 PM - ES1.2.05.5
One-Step Fabrication of Fe-Si- O/Carbon Nanotube Composite Anode Material with Excellent High-Rate Long-Term Cycling Stability
Yunkai Sun 1 , Xue Bai 1 , Tao Li 1 , Gui-Xia Lu 1 , Yong-Xin Qi 1 , Ning Lun 1 , Yun Tian 1 , Yu-Jun Bai 1
1 Key Laboratory for Liquid−Solid Structural Evolution and Processing of Materials Shandong University Jinan ChinaShow Abstract
The composite of Fe2SiO4 with carbon nanotubes and Fe3O4 (Fe-Si-O/CNT) are fabricated by a simple one-step pyrolysis of ferrocene and tetraethyl orthosilicate mixture. The composite utilized as anode material for Li-ion storage exhibits ever-increasing capacities when cycled at a current density of 100 mA g-1, and after 280 cycles, a stable capacity of 588 mAh g-1 is achieved. When cycled at 200, 400, 800 and 1600 mA g-1, the reversible capacities are 364, 323, 281, 235, and 186 mAh g-1, respectively. Even cycled at 500 mA g-1, a reversible capacity of 350 mAh g-1 is retained after 600 cycles. The excellent performance is much superior to that of the carbon-coated Fe3O4 prepared under the similar conditions and mechanically mixed Carbon Nanotube@Fe3O4. The Fe-Si-O/CNT active material is characterized by structural analysis, such as XRD, TEM, Raman and FTIR, and electrochemical tests, such as Cyclic Voltammetry and Electrochemical Impedance Spectra. Outstanding performance of Fe-Si-O/CNT could be ascribed to improved conductivity by CNTs, stable structure of Fe2SiO4, enhanced capacity by Fe3O4 and significant activation effect during cycling.
4:00 PM - ES1.2.06
Identifying the Link between Active Particle Fracture and Impedance Growth in LiXMn2O4
Frank McGrogan 1 , Sean Bishop 1 , Yet-Ming Chiang 1 , Krystyn Van Vliet 1
1 Massachusetts Institute of Technology Cambridge United StatesShow Abstract
Energy storage designs that include lithium-ion transport between electrodes require increased understanding of basic materials science that promotes mechanical degradation of the electrodes and reduced charge storage capacity of the energy storage device. Chemically induced stress in Li-ion battery (LIB) electrodes often leads to fracture of electrode particles during cycling and is commonly believed to be a key origin of decreased LIB lifetime and late-life performance. Here we identify the role of fracture on capacity and impedance in LiXMn2O4 cathodes using a novel electrochemical shock approach combined with detailed analysis of impedance spectra and post-test microscopy and spectroscopic analysis. Specific charge-time cycles and conditions were used to induce discrete fracture events verified by in situ monitoring of acoustic emissions and post-test microscopy. We find that the discrete fracture events correlate with increased impedance, consistent with surface film growth and active particle-carbon contact resistance. Among the myriad number of potential LIB degradation mechanisms, this study demonstrates directly the relationship between electrochemically driven electrode fracture and performance loss, critical for well-informed design of Li-ion batteries with improved longevity and late-life performance required of expanded applications including grid-scale energy storage.
4:15 PM - ES1.2.07
Magnetic Field Processing of High-Capacity Low-Tortuosity Thick Electrodes for Lithium-Ion Batteries
Linsen Li 1 , Jonathan Sander 1 , Randall Erb 2 , Anvesh Gurijala 2 , Yet-Ming Chiang 1
1 Materials Science amp; Engineering Massachusetts Institute of Technology Cambridge United States, 2 Northeastern University Boston United StatesShow Abstract
The high inactive materials content (e. g., separators, current collectors, conductive additives, binder and packaging) of current battery designs leads to high materials and manufacturing cost and reduces the overall energy density (both gravimetric and volumetric) of the battery. Increasing battery electrode thickness and/or density would be a simple and straightforward approach to increasing energy density and reducing cost, but is limited by transport limitations. In the limit of high density and large thickness, lithium salt depletion within the electrolyte-filled porosity typically becomes rate-limiting. To overcome this limitation and deliver high energy density at practical C-rates, it is critical to lower tortuosity through rational design and tailoring of the topology of the electrode pore structure.
We report magnetic alignment methods that produce low tortuosity porosity from sacrificial pore formers, and that are rapid, scalable, and naturally produce aligned porosity favorably oriented normal to the electrode plane. These methods are not limited to certain electrode materials and can be generally used to make both battery cathode and anode. We also report electrochemical measurement results of the low-tortuosity electrodes under both standard galvanostatic and model EV duty cycle tests. The low-tortuosity electrodes show overall faster charge transport kinetics and deliver more than threefold higher areal-capacity (e.g., >12 mAh/cm2 vs <4 mAh/cm2 in conventional electrodes) at practical charge-discharge rates.
Acknowledgement: This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, Subcontract No. 7056592 under the Batteries for Advanced Transportation Technologies (BATT) Program. J.S Sander thanks the Swiss National Science Foundation for financial Support (Grant Number P300P2_154584 and P2EZP2_148768).
4:30 PM - ES1.2.08
A Universal Capacity Fading Mechanism of Lithium Transition Metal Oxide Cathodes for Lithium Ion Batteries
Sanghan Lee 1 , Wooyoung Jin 1 , Jaephil Cho 1
1 UNIST Ulsan Korea (the Republic of)Show Abstract
Nowadays, Lithium-ion batteries are not only used in simple portable devices, but also its usage has been expanded into large scale applications such as electronic vehicle (EV) and hybrid electronic vehicle (HEV) owing to its high economic feasibility and high energy density compared to other types of energy storage devices. Currently, commercialized LIBs can maintain 80% of its initial capacity after 500 cycles in proper usage, which corresponds to a cycle efficiency of 99.93% per cycle. The irreversible capacity of 0.07% at every 1 cycle seems to be trivial but the small difference in cycle efficiency brings out a big difference upon cycles; reducing the irreversible capacity of cells by half (0.07% to 0.03%) corresponds to extending lifespans by double. Therefore, deeper understandings of the capacity fading mechanism of LIBs are necessary to realize the next generation LIBs.
In this study, the relationship between oxygen vacancy and structure degradation of lithium transition metal oxides is investigated. Herein, we have demonstrated that the cathode degradation process can be started from the inside of a single crystal due to an inevitable existence of oxygen vacancies and their diffusion in metal oxides, which is an opposite idea to the conventional fading mechanisms where the fading starts from the particle surface.
4:45 PM - ES1.2.09
Investigating the Effects of Al2O3 Coating on the Electrochemical Performance of High-Voltage NMC-532/Graphite Cell
Xuemin Li 1 , Yongan Yang 1 , Seoung-Bum Son 2 , Robert Tenent 2 , Chunmei Ban 2
1 Chemistry Colorado School of Mines Golden United States, 2 National Renewable Energy Laboratory Golden United StatesShow Abstract
With the increasing demands of rechargeable batteries in electric vehicles and grid storage, the layer-structured ternary material LiNixCoyMn(1−x−y)O2 (0 < x, y < 1) has been one of the most promising cathode materials in the market. Li1.03(Ni0.5Mn0.35Co0.2)0.97O2 (NMC-532) is a representative ternary material for the nickel rich layered structure and is expected to be promising due to its high discharge capacity and low cost, compared to those of LiCoO2 and LiMn2O4. However, cycling at high working voltage accelerates the inferior side reactions between the electrode surface and the organic electrolyte, which leads to decomposition of the organic electrolyte, reconstruction of the surface of cathode, and finally capacity and cell voltage degradation. Aluminum oxide (Al2O3) atomic layer deposition (ALD) has been proven effective in protecting electrode surfaces and mitigating the unwanted interfacial reactions in many circumstances. This research focuses on the investigation of ALD Al2O3 coating effects on the electrochemical performance of NMC-532/graphite full cells. Both NMC-532 powder and the laminated electrodes made from NMC-532 powder have been used for ALD Al2O3 coating experiments, and characterized through complex electrochemical analysis methods. Moreover, the laminated electrodes with different porosity have also been studied to identify the coating effect on high-voltage cycling performance. Initial results show negligible effect of coating on the cycling behavior of thick electrodes after calendering. However, improvement in cycling performance has been observed for the porous electrodes without calendering. The divergent impacts of ALD coating are attributed to the coating coverage and quality for different electrode architectures. In addition, this presentation will compare the results from the coated NMC powder and the coated laminated-electrodes, systematically analyze the impact of coating on the electrochemical properties, and determine the most effective electrode structure for improved performance.