Long-term chemothermal stability of delithiated NCA in polymer solid-state batteries

Besli, Münir M.; Usubelli, Camille; Metzger, Michael; Hellstrom, Sondra; Sainio, Sami; Nordlund, Dennis; Christensen, Jake; Schneider, Gerhard; Doeff, Marca M.; Kuppan, Saravanan

doi:10.1039/C9TA11103D

Title: Long-term chemothermal stability of delithiated NCA in polymer solid-state batteries

Journal Article · 17 November 2019 · Journal of Materials Chemistry. A

DOI: https://doi.org/10.1039/C9TA11103D · OSTI ID:1582225

^[1]; Usubelli, Camille ^[2]; Metzger, Michael ^[3]; Hellstrom, Sondra ^[3]; Sainio, Sami ^[4]; Nordlund, Dennis ^[4];

^[3]; Schneider, Gerhard ^[5];

^[6];

^[3]

Robert Bosch LLC, Sunnyvale, CA (United States); Karlsruhe Inst. of Technology (KIT) (Germany)
Robert Bosch LLC, Sunnyvale, CA (United States); Univ. of Strasbourg (France)
Robert Bosch LLC, Sunnyvale, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Karlsruhe Inst. of Technology (KIT) (Germany); Aalen Univ. (Germany)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

Here, the long-term chemothermal stability of chemically delithiated Li_0.3Ni_0.8Co_0.15Al_0.05O₂ (Li_0.3NCA) was systematically investigated at relevant operating temperatures of polymer solid-state batteries using ex situ synchrotron-based hard and soft X-ray absorption spectroscopy. The reduction of nickel on the surface, subsurface, and in the bulk of secondary NCA particles was studied and directly related to aging time, temperature, the presence of polymeric electrolyte (poly(ethylene oxide) or polycaprolactone), and lithium salt (lithium tetrafluoroborate or lithium bis(trifluoromethanesulfonyl)imide). Depending on the polymer and/or lithium salt accompanying the delithiated Li_0.3NCA, reduction of nickel at the surface, subsurface, and bulk occurs to varying extents, starting at the surface and propagating into the bulk material. Our findings predict how degradation (reduction of nickel) is strongly correlated to temperature, time, and the presence of blended polymer and/or lithium salt in the cathode. The relative stability of the NCA material in cathodes having different polymer and lithium salt combinations identified in the ex situ spectroscopy study is directly demonstrated in solid-state polymer batteries.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1582225

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 47 Vol. 7; ISSN JMCAET; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (63)

Combining In Situ Synchrotron X-Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium-Ion Batteries Nam, Kyung-Wan; Bak, Seong-Min; Hu, Enyuan Advanced Functional Materials, Vol. 23, Issue 8 https://doi.org/10.1002/adfm.201200693	journal	June 2012
Persistent State-of-Charge Heterogeneity in Relaxed, Partially Charged Li ₁₋ _x Ni _1/3 Co _1/3 Mn _1/3 O ₂ Secondary Particles Gent, William E.; Li, Yiyang; Ahn, Sungjin Advanced Materials, Vol. 28, Issue 31 https://doi.org/10.1002/adma.201601273	journal	May 2016
Understanding the Degradation Mechanisms of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ Cathode Material in Lithium Ion Batteries Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun Advanced Energy Materials, Vol. 4, Issue 1 https://doi.org/10.1002/aenm.201300787	journal	August 2013
Simultaneous Electronic and Ionic Conduction in a Block Copolymer: Application in Lithium Battery Electrodes Javier, Anna E.; Patel, Shrayesh N.; Hallinan, Daniel T. Angewandte Chemie, Vol. 123, Issue 42 https://doi.org/10.1002/ange.201102953	journal	September 2011
Simultaneous Electronic and Ionic Conduction in a Block Copolymer: Application in Lithium Battery Electrodes Javier, Anna E.; Patel, Shrayesh N.; Hallinan, Daniel T. Angewandte Chemie International Edition, Vol. 50, Issue 42 https://doi.org/10.1002/anie.201102953	journal	September 2011
Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li1-xCo1/3Ni1/3Mn1/3O2 Electrode System by Combination of Soft and Hard X-Ray Absorption Spectroscopy. Yoon, Won-Sub; Balasubramanian, Mahalingam; Chung, Kyung Yoon ChemInform, Vol. 37, Issue 13 https://doi.org/10.1002/chin.200613019	journal	March 2006
Recent progress in solid oxide and lithium ion conducting electrolytes research Thangadurai, V.; Weppner, W. Ionics, Vol. 12, Issue 1 https://doi.org/10.1007/s11581-006-0013-7	journal	April 2006
K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites Baker, Michael L.; Mara, Michael W.; Yan, James J. Coordination Chemistry Reviews, Vol. 345 https://doi.org/10.1016/j.ccr.2017.02.004	journal	August 2017
Safety characteristics of Li(Ni0.8Co0.15Al0.05)O2 and Li(Ni1/3Co1/3Mn1/3)O2 Belharouak, Ilias; Lu, Wenquan; Vissers, Donald Electrochemistry Communications, Vol. 8, Issue 2 https://doi.org/10.1016/j.elecom.2005.12.007	journal	February 2006
The reactivity of delithiated Li(Ni1/3Co1/3Mn1/3)O2, Li(Ni0.8Co0.15Al0.05)O2 or LiCoO2 with non-aqueous electrolyte Wang, Yadong; Jiang, Junwei; Dahn, J. R. Electrochemistry Communications, Vol. 9, Issue 10 https://doi.org/10.1016/j.elecom.2007.07.033	journal	October 2007
A rechargeable lithium/quinone battery using a commercial polymer electrolyte Lécuyer, Margaud; Gaubicher, Joël; Barrès, Anne-Lise Electrochemistry Communications, Vol. 55 https://doi.org/10.1016/j.elecom.2015.03.010	journal	June 2015
A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries Manthiram, Arumugam; Song, Bohang; Li, Wangda Energy Storage Materials, Vol. 6 https://doi.org/10.1016/j.ensm.2016.10.007	journal	January 2017
The application of synchrotron X-ray techniques to the study of rechargeable batteries Gong, Zhengliang; Yang, Yong Journal of Energy Chemistry, Vol. 27, Issue 6 https://doi.org/10.1016/j.jechem.2018.03.020	journal	November 2018
Thermal behavior and decomposition kinetics of six electrolyte salts by thermal analysis Lu, Zhenrong; Yang, Li; Guo, Yaju Journal of Power Sources, Vol. 156, Issue 2 https://doi.org/10.1016/j.jpowsour.2005.05.085	journal	June 2006
An improved electrolyte for the LiFePO4 cathode working in a wide temperature range Zhang, S. S.; Xu, K.; Jow, T. R. Journal of Power Sources, Vol. 159, Issue 1 https://doi.org/10.1016/j.jpowsour.2005.11.042	journal	September 2006
Review on electrode–electrolyte solution interactions, related to cathode materials for Li-ion batteries Aurbach, Doron; Markovsky, Boris; Salitra, Gregory Journal of Power Sources, Vol. 165, Issue 2 https://doi.org/10.1016/j.jpowsour.2006.10.025	journal	March 2007
Ceramic and polymeric solid electrolytes for lithium-ion batteries Fergus, Jeffrey W. Journal of Power Sources, Vol. 195, Issue 15, p. 4554-4569 https://doi.org/10.1016/j.jpowsour.2010.01.076	journal	August 2010
Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries Noh, Hyung-Joo; Youn, Sungjune; Yoon, Chong Seung Journal of Power Sources, Vol. 233 https://doi.org/10.1016/j.jpowsour.2013.01.063	journal	July 2013
Recent progress in cathode materials research for advanced lithium ion batteries Xu, Bo; Qian, Danna; Wang, Ziying Materials Science and Engineering: R: Reports, Vol. 73, Issue 5-6 https://doi.org/10.1016/j.mser.2012.05.003	journal	May 2012
Recent advances in all-solid-state rechargeable lithium batteries Sun, Chunwen; Liu, Jin; Gong, Yudong Nano Energy, Vol. 33 https://doi.org/10.1016/j.nanoen.2017.01.028	journal	March 2017
Synthesis, Structure, and Electrochemical Performance of High Capacity Li ₂ Cu _0.5 Ni _0.5 O ₂ Cathodes Ruther, Rose E.; Zhou, Hui; Dhital, Chetan Chemistry of Materials, Vol. 27, Issue 19 https://doi.org/10.1021/acs.chemmater.5b02843	journal	September 2015
Surface Reconstruction in Li-Rich Layered Oxides of Li-Ion Batteries Jarvis, Karalee; Wang, Chih-Chieh; Varela, Maria Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b00120	journal	September 2017
Mesoscale Chemomechanical Interplay of the LiNi _0.8 Co _0.15 Al _0.05 O ₂ Cathode in Solid-State Polymer Batteries Besli, Münir M.; Xia, Sihao; Kuppan, Saravanan Chemistry of Materials, Vol. 31, Issue 2 https://doi.org/10.1021/acs.chemmater.8b04418	journal	December 2018
Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries Lin, Feng; Liu, Yijin; Yu, Xiqian Chemical Reviews, Vol. 117, Issue 21 https://doi.org/10.1021/acs.chemrev.7b00007	journal	September 2017
Atomic Insight into the Layered/Spinel Phase Transformation in Charged LiNi _0.80 Co _0.15 Al _0.05 O ₂ Cathode Particles Zhang, Hanlei; Karki, Khim; Huang, Yiqing The Journal of Physical Chemistry C, Vol. 121, Issue 3 https://doi.org/10.1021/acs.jpcc.6b10220	journal	January 2017
Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials Mu, Linqin; Lin, Ruoqian; Xu, Rong Nano Letters, Vol. 18, Issue 5 https://doi.org/10.1021/acs.nanolett.8b01036	journal	April 2018
Mechanisms of LiCoO ₂ Cathode Degradation by Reaction with HF and Protection by Thin Oxide Coatings Tebbe, Jonathon L.; Holder, Aaron M.; Musgrave, Charles B. ACS Applied Materials & Interfaces, Vol. 7, Issue 43 https://doi.org/10.1021/acsami.5b07887	journal	October 2015
Are All-Solid-State Lithium-Ion Batteries Really Safe?–Verification by Differential Scanning Calorimetry with an All-Inclusive Microcell Inoue, Takao; Mukai, Kazuhiko ACS Applied Materials & Interfaces, Vol. 9, Issue 2 https://doi.org/10.1021/acsami.6b13224	journal	January 2017
Superior Blends Solid Polymer Electrolyte with Integrated Hierarchical Architectures for All-Solid-State Lithium-Ion Batteries Zhang, Dechao; Zhang, Long; Yang, Kun ACS Applied Materials & Interfaces, Vol. 9, Issue 42 https://doi.org/10.1021/acsami.7b12186	journal	October 2017
Accelerated Evolution of Surface Chemistry Determined by Temperature and Cycling History in Nickel-Rich Layered Cathode Materials Steiner, James D.; Mu, Linqin; Walsh, Julia ACS Applied Materials & Interfaces, Vol. 10, Issue 28 https://doi.org/10.1021/acsami.8b06399	journal	June 2018
Correlating Structural Changes and Gas Evolution during the Thermal Decomposition of Charged Li _x Ni _0.8 Co _0.15 Al _0.05 O ₂ Cathode Materials Bak, Seong-Min; Nam, Kyung-Wan; Chang, Wonyoung Chemistry of Materials, Vol. 25, Issue 3 https://doi.org/10.1021/cm303096e	journal	January 2013
Electronic Structure and Symmetry in Nickel L Edge X-ray Absorption Spectroscopy: Application to a Nickel Protein van Elp, J.; Peng, G.; Searle, B. G. Journal of the American Chemical Society, Vol. 116, Issue 5 https://doi.org/10.1021/ja00084a036	journal	March 1994
Mechanism of anodic cleavage of benzyl ethers Boyd, Jean W.; Schmalzl, Paul W.; Miller, Larry L. Journal of the American Chemical Society, Vol. 102, Issue 11 https://doi.org/10.1021/ja00531a030	journal	May 1980
Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li ₁ _- _x Co _1/3 Ni _1/3 Mn _1/3 O ₂ Electrode System by Combination of Soft and Hard X-ray Absorption Spectroscopy Yoon, Won-Sub; Balasubramanian, Mahalingam; Chung, Kyung Yoon Journal of the American Chemical Society, Vol. 127, Issue 49 https://doi.org/10.1021/ja0530568	journal	December 2005
Effect of AlF ₃ Coating on Thermal Behavior of Chemically Delithiated Li _0.35 [Ni _1/3 Co _1/3 Mn _1/3 ]O ₂ Myung, Seung-Taek; Lee, Ki-Soo; Yoon, Chong Seung The Journal of Physical Chemistry C, Vol. 114, Issue 10 https://doi.org/10.1021/jp9082322	journal	March 2010
X-ray Absorption Spectroscopic Study of Chemically and Electrochemically Li Ion Extracted Li _y Co _0.85 Al _0.15 O ₂ Compounds Kim, Min Gyu; Yo, Chul Hyun The Journal of Physical Chemistry B, Vol. 103, Issue 31 https://doi.org/10.1021/jp990753b	journal	August 1999
Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes Panday, Ashoutosh; Mullin, Scott; Gomez, Enrique D. Macromolecules, Vol. 42, Issue 13 https://doi.org/10.1021/ma900451e	journal	July 2009
High-throughput computational design of cathode coatings for Li-ion batteries Aykol, Muratahan; Kim, Soo; Hegde, Vinay I. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13779	journal	December 2016
Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy Kuppan, Saravanan; Xu, Yahong; Liu, Yijin Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14309	journal	February 2017
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries Lin, Feng; Markus, Isaac M.; Nordlund, Dennis Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4529	journal	March 2014
In situ soft XAS study on nickel-based layered cathode material at elevated temperatures: A novel approach to study thermal stability Yoon, Won-Sub; Haas, Otto; Muhammad, Shoaib Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep06827	journal	October 2014
A study of room-temperature LixMn1.5Ni0.5O4 solid solutions Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep08027	journal	January 2015
Profiling the nanoscale gradient in stoichiometric layered cathode particles for lithium-ion batteries Lin, Feng; Nordlund, Dennis; Markus, Isaac M. Energy & Environmental Science, Vol. 7, Issue 9 https://doi.org/10.1039/C4EE01400F	journal	January 2014
Controlling side reactions and self-discharge in high-voltage spinel cathodes: the critical role of surface crystallographic facets Kuppan, Saravanan; Duncan, Hugues; Chen, Guoying Physical Chemistry Chemical Physics, Vol. 17, Issue 39 https://doi.org/10.1039/C5CP04899K	journal	January 2015
Future generations of cathode materials: an automotive industry perspective Andre, Dave; Kim, Sung-Jin; Lamp, Peter Journal of Materials Chemistry A, Vol. 3, Issue 13 https://doi.org/10.1039/C5TA00361J	journal	January 2015
Thermally driven mesoscale chemomechanical interplay in Li _0.5 Ni _0.6 Mn _0.2 Co _0.2 O ₂ cathode materials Wei, Chenxi; Zhang, Yan; Lee, Sang-Jun Journal of Materials Chemistry A, Vol. 6, Issue 45 https://doi.org/10.1039/C8TA08973F	journal	January 2018
Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles Besli, Münir M.; Shukla, Alpesh Khushalchand; Wei, Chenxi Journal of Materials Chemistry A, Vol. 7, Issue 20 https://doi.org/10.1039/C9TA01720H	journal	January 2019
Li₂MnO₃-stabilized LiMO₂ (M = Mn, Ni, Co) electrodes for lithium-ion batteries Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S. Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125 https://doi.org/10.1039/b702425h	journal	January 2007
Material/element-dependent fluorescence-yield modes on soft X-ray absorption spectroscopy of cathode materials for Li-ion batteries Asakura, Daisuke; Hosono, Eiji; Nanba, Yusuke AIP Advances, Vol. 6, Issue 3 https://doi.org/10.1063/1.4943673	journal	March 2016
CoO₂, The End Member of the Li_xCoO₂ Solid Solution Amatucci, G. G.; Tarascon, J. M.; Klein, L. C. Journal of The Electrochemical Society, Vol. 143, Issue 3, p. 1114-1123 https://doi.org/10.1149/1.1836594	journal	January 1996
Thermal Stability of the Li(Ni[sub 0.8]Co[sub 0.15]Al[sub 0.05])O[sub 2] Cathode in the Presence of Cell Components Belharouak, I.; Vissers, D.; Amine, K. Journal of The Electrochemical Society, Vol. 153, Issue 11 https://doi.org/10.1149/1.2336994	journal	January 2006
Structural and Electrochemical Investigation of Li(Ni[sub 0.4]Co[sub 0.15]Al[sub 0.05]Mn[sub 0.4])O[sub 2] Cathode Material Rumble, C.; Conry, T. E.; Doeff, Marca Journal of The Electrochemical Society, Vol. 157, Issue 12 https://doi.org/10.1149/1.3494211	journal	January 2010
Ambient Storage Derived Surface Contamination of NCM811 and NCM111: Performance Implications and Mitigation Strategies Sicklinger, Johannes; Metzger, Michael; Beyer, Hans Journal of The Electrochemical Society, Vol. 166, Issue 12 https://doi.org/10.1149/2.0011912jes	journal	January 2019
Oxygen Release and Its Effect on the Cycling Stability of LiNi _x Mn _y Co _z O ₂ (NMC) Cathode Materials for Li-Ion Batteries Jung, Roland; Metzger, Michael; Maglia, Filippo Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.0021707jes	journal	January 2017
Discharge Characteristics of Lithium Battery Electrodes with a Semiconducting Polymer Studied by Continuum Modeling and Experiment Wu, Shao-Ling; Javier, Anna E.; Devaux, Didier Journal of The Electrochemical Society, Vol. 161, Issue 12 https://doi.org/10.1149/2.0261412jes	journal	January 2014
LiBF ₄ -Based Concentrated Electrolyte Solutions for Suppression of Electrolyte Decomposition and Rapid Lithium-Ion Transfer at LiNi _0.5 Mn _1.5 O ₄ /Electrolyte Interface Doi, Takayuki; Shimizu, Yusuke; Hashinokuchi, Michihiro Journal of The Electrochemical Society, Vol. 163, Issue 10 https://doi.org/10.1149/2.0331610jes	journal	January 2016
Stability and Rate Capability of Al Substituted Lithium-Rich High-Manganese Content Oxide Materials for Li-Ion Batteries Li, Zheng; Chernova, Natasha A.; Feng, Jijun Journal of The Electrochemical Society, Vol. 159, Issue 2 https://doi.org/10.1149/2.044202jes	journal	January 2011
Dilution of Highly Concentrated LiBF ₄ /Propylene Carbonate Electrolyte Solution with Fluoroalkyl Ethers for 5-V LiNi _0.5 Mn _1.5 O ₄ Positive Electrodes Doi, Takayuki; Shimizu, Yusuke; Hashinokuchi, Michihiro Journal of The Electrochemical Society, Vol. 164, Issue 1 https://doi.org/10.1149/2.0611701jes	journal	January 2017
Lithium Tetrafluoroborate as an Electrolyte Additive to Improve the High Voltage Performance of Lithium-Ion Battery Zuo, Xiaoxi; Fan, Chengjie; Liu, Jiansheng Journal of The Electrochemical Society, Vol. 160, Issue 8 https://doi.org/10.1149/2.066308jes	journal	January 2013
Synergistic Effect of LiPF ₆ and LiBF ₄ as Electrolyte Salts in Lithium-Ion Cells Ellis, L. D.; Hill, I. G.; Gering, Kevin L. Journal of The Electrochemical Society, Vol. 164, Issue 12 https://doi.org/10.1149/2.0811712jes	journal	January 2017
Effect of Substituting LiBF ₄ for LiPF ₆ in High Voltage Lithium-Ion Cells Containing Electrolyte Additives Ellis, L. D.; Xia, J.; Louli, A. J. Journal of The Electrochemical Society, Vol. 163, Issue 8 https://doi.org/10.1149/2.0851608jes	journal	January 2016
Using the Charge-Discharge Cycling of Positive Electrode Symmetric Cells to Find Electrolyte/Electrode Combinations with Minimum Reactivity Shen, Chongheng; Xiong, Deijun; Ellis, L. D. Journal of The Electrochemical Society, Vol. 164, Issue 13 https://doi.org/10.1149/2.1711713jes	journal	January 2017
SIXPack a Graphical User Interface for XAS Analysis Using IFEFFIT Webb, S. M. Physica Scripta https://doi.org/10.1238/Physica.Topical.115a01011	journal	January 2005

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