Evolution of the Electrode–Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress

Lebens-Higgins, Zachary W.; Sallis, Shawn; Faenza, Nicholas V.; Badway, Fadwa; Pereira, Nathalie; Halat, David M.; Wahila, Matthew; Schlueter, Christoph; Lee, Tien-Lin; Yang, Wanli; Grey, Clare P.; Amatucci, Glenn G.; Piper, Louis F.  J.

doi:10.1021/acs.chemmater.7b04782

Title: Evolution of the Electrode–Electrolyte Interface of LiNi_0.8Co_0.15Al_0.05O₂ Electrodes Due to Electrochemical and Thermal Stress

Journal Article · Wed Jan 10 00:00:00 EST 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.7b04782· OSTI ID:1470192

^[1]; Sallis, Shawn ^[1];

^[2]; Badway, Fadwa ^[2]; Pereira, Nathalie ^[2];

^[3]; Wahila, Matthew ^[1]; Schlueter, Christoph ^[4]; Lee, Tien-Lin ^[5];

^[6];

^[3]; Amatucci, Glenn G. ^[2];

^[1]

Binghamton Univ., NY (United States)
Rutgers Univ., New Brunswick, NJ (United States)
Univ. of Cambridge (United Kingdom)
Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.; Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

For layered oxide cathodes, impedance growth and capacity fade related to reactions at the cathode–electrolyte interface (CEI) are particularly prevalent at high voltage and high temperatures. At a minimum, the CEI layer consists of Li₂CO₃, LiF, reduced (relative to the bulk) metal-ion species, and salt decomposition species, but conflicting reports exist regarding their progression during (dis)charging. Utilizing transport measurements in combination with X-ray and nuclear magnetic resonance spectroscopy techniques in our work, we study the evolution of these CEI species as a function of electrochemical and thermal stress for LiNi_0.8Co_0.15Al_0.05O₂ (NCA) particle electrodes using a LiPF₆ ethylene carbonate:dimethyl carbonate (1:1 volume ratio) electrolyte. Although initial surface metal reduction does correlate with surface Li₂CO₃ and LiF, these species are found to decompose upon charging and are absent above 4.25 V. While there is trace LiPF₆ breakdown at room temperature above 4.25 V, thermal aggravation is found to strongly promote salt breakdown and contributes to surface degradation even at lower voltages (4.1 V). An interesting finding of our work was the partial reformation of LiF upon discharge, which warrants further consideration for understanding CEI stability during cycling.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: SC0001294; SC0012583; AC02-05CH11231; SI12764; SI16005

OSTI ID:: 1470192

Journal Information:: Chemistry of Materials, Vol. 30, Issue 3; Related Information: NECCES partners with Stony Brook University (lead); Argonne National Laboratory; Binghamton University; Brookhaven National University; University of California, San Diego; University of Cambridge, UK; Lawrence Berkeley National Laboratory; Massachusetts Institute of Technology; University of Michigan; Rutgers University; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 62 works

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References (43)

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Electrode–Electrolyte Interface in Li-Ion Batteries: Current Understanding and New Insights Gauthier, Magali; Carney, Thomas J.; Grimaud, Alexis The Journal of Physical Chemistry Letters, Vol. 6, Issue 22 https://doi.org/10.1021/acs.jpclett.5b01727	journal	October 2015
A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate-Dimethyl Carbonate Mixtures Aurbach, D. Journal of The Electrochemical Society, Vol. 143, Issue 12 https://doi.org/10.1149/1.1837300	journal	January 1996
Surface film formation on a graphite electrode in Li-ion batteries: AFM and XPS study Leroy, S.; Blanchard, F.; Dedryvère, R. Surface and Interface Analysis, Vol. 37, Issue 10 https://doi.org/10.1002/sia.2072	journal	January 2005
Studies of Lithium Intercalation into Carbons Using Nonaqueous Electrochemical Cells Fong, Rosamaría Journal of The Electrochemical Society, Vol. 137, Issue 7 https://doi.org/10.1149/1.2086855	journal	January 1990
Cobalt dissolution in LiCoO₂-based non-aqueous rechargeable batteries Amatucci, G. G.; Tarascon, J. M.; Klein, L. C. Solid State Ionics, Vol. 83, Issue 1-2, p. 167-173 https://doi.org/10.1016/0167-2738(95)00231-6	journal	January 1996
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
Improving the High Voltage Cycling of Li[Ni _0.42 Mn _0.42 Co _0.16 ]O ₂ (NMC442)/Graphite Pouch Cells Using Electrolyte Additives Ma, Lin; Xia, Jian; Dahn, J. R. Journal of The Electrochemical Society, Vol. 161, Issue 14 https://doi.org/10.1149/2.1041414jes	journal	January 2014
Surface degradation of Li1–xNi0.80Co0.15Al0.05O2 cathodes: Correlating charge transfer impedance with surface phase transformations Sallis, S.; Pereira, N.; Mukherjee, P. Applied Physics Letters, Vol. 108, Issue 26 https://doi.org/10.1063/1.4954800	journal	June 2016
Cycle-Life Characterization of Automotive Lithium-Ion Batteries with LiNiO[sub 2] Cathode Zhang, Yancheng; Wang, Chao-Yang Journal of The Electrochemical Society, Vol. 156, Issue 7 https://doi.org/10.1149/1.3126385	journal	January 2009
Effects of manganese and cobalt on the electrochemical and thermal properties of layered Li[Ni0.52Co0.16+xMn0.32−x]O2 cathode materials Kim, Hyoung-Geun; Myung, Seung-Taek; Lee, Jung Kyu Journal of Power Sources, Vol. 196, Issue 16 https://doi.org/10.1016/j.jpowsour.2010.11.045	journal	August 2011
Surface Characterization of Electrodes from High Power Lithium-Ion Batteries Andersson, A. M.; Abraham, D. P.; Haasch, R. Journal of The Electrochemical Society, Vol. 149, Issue 10 https://doi.org/10.1149/1.1505636	journal	January 2002
Investigation of positive electrodes after cycle testing of high-power Li-ion battery cells II Shikano, M.; Kobayashi, H.; Koike, S. Journal of Power Sources, Vol. 174, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.06.138	journal	December 2007
Microscopy and Spectroscopy of Lithium Nickel Oxide-Based Particles Used in High Power Lithium-Ion Cells Abraham, D. P.; Twesten, R. D.; Balasubramanian, M. Journal of The Electrochemical Society, Vol. 150, Issue 11 https://doi.org/10.1149/1.1613291	journal	January 2003
Investigating Local Degradation and Thermal Stability of Charged Nickel-Based Cathode Materials through Real-Time Electron Microscopy Hwang, Sooyeon; Kim, Seung Min; Bak, Seong-Min ACS Applied Materials & Interfaces, Vol. 6, Issue 17 https://doi.org/10.1021/am503278f	journal	August 2014
XPS Study on Al[sub 2]O[sub 3]- and AlPO[sub 4]-Coated LiCoO[sub 2] Cathode Material for High-Capacity Li Ion Batteries Verdier, S.; El Ouatani, L.; Dedryvère, R. Journal of The Electrochemical Society, Vol. 154, Issue 12 https://doi.org/10.1149/1.2789299	journal	January 2007
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
Surface Analysis of LiMn[sub 2]O[sub 4] Electrodes in Carbonate-Based Electrolytes Eriksson, Tom; Andersson, Anna M.; Bishop, Andrea G. Journal of The Electrochemical Society, Vol. 149, Issue 1 https://doi.org/10.1149/1.1426398	journal	January 2002
The cathode–electrolyte interface in the Li-ion battery Edström, K.; Gustafsson, T.; Thomas, J. O. Electrochimica Acta, Vol. 50, Issue 2-3 https://doi.org/10.1016/j.electacta.2004.03.049	journal	November 2004
Understanding Transition-Metal Dissolution Behavior in LiNi _0.5 Mn _1.5 O ₄ High-Voltage Spinel for Lithium Ion Batteries Pieczonka, Nicholas P. W.; Liu, Zhongyi; Lu, Peng The Journal of Physical Chemistry C, Vol. 117, Issue 31 https://doi.org/10.1021/jp405158m	journal	July 2013
XPS Studies of Surface Chemistry Changes of LiNi _0.5 Mn _0.5 O ₂ Electrodes during High-Voltage Cycling Quinlan, Ronald A.; Lu, Yi-Chun; Shao-Horn, Yang Journal of The Electrochemical Society, Vol. 160, Issue 4 https://doi.org/10.1149/2.069304jes	journal	January 2013
Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi _0.8 Co _0.15 Al _0.05 O ₂ Faenza, Nicholas V.; Lebens-Higgins, Zachary W.; Mukherjee, Pinaki Langmuir, Vol. 33, Issue 37 https://doi.org/10.1021/acs.langmuir.7b00863	journal	June 2017
Influence of the PVdF binder on the stability of LiCoO2 electrodes Markevich, E.; Salitra, G.; Aurbach, D. Electrochemistry Communications, Vol. 7, Issue 12 https://doi.org/10.1016/j.elecom.2005.09.010	journal	December 2005
Capacity fade of LiAlyNi1−x−yCoxO2 cathode for lithium-ion batteries during accelerated calendar and cycle life tests (surface analysis of LiAlyNi1−x−yCoxO2 cathode after cycle tests in restricted depth of discharge ranges) Watanabe, Shoichiro; Kinoshita, Masahiro; Hosokawa, Takashi Journal of Power Sources, Vol. 258 https://doi.org/10.1016/j.jpowsour.2014.02.018	journal	July 2014
Looking 100 Å deep into spatially inhomogeneous dilute systems with hard x-ray photoemission Dallera, C.; Duò, L.; Braicovich, L. Applied Physics Letters, Vol. 85, Issue 19 https://doi.org/10.1063/1.1814441	journal	January 2004
Probing the Origin of Enhanced Stability of “AlPO₄” Nanoparticle Coated LiCoO₂ during Cycling to High Voltages: Combined XRD and XPS Studies Lu, Yi-Chun; Mansour, Azzam N.; Yabuuchi, Naoaki Chemistry of Materials, Vol. 21, Issue 19, p. 4408-4424 https://doi.org/10.1021/cm900862v	journal	October 2009
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
Surface chemistry of metal oxide coated lithium manganese nickel oxide thin film cathodes studied by XPS Baggetto, Loïc; Dudney, Nancy J.; Veith, Gabriel M. Electrochimica Acta, Vol. 90 https://doi.org/10.1016/j.electacta.2012.11.120	journal	February 2013
X-ray absorption and dichroism of transition metals and their compounds de Groot, F. M. F. Journal of Electron Spectroscopy and Related Phenomena, Vol. 67, Issue 4 https://doi.org/10.1016/0368-2048(93)02041-J	journal	August 1994
Electronic structural changes of the electrochemically Li-ion deintercalated LiNi0.8Co0.15Al0.05O2 cathode material investigated by X-ray absorption spectroscopy Yoon, Won-Sub; Chung, Kyung Yoon; McBreen, James Journal of Power Sources, Vol. 174, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.06.214	journal	December 2007
Soft X-Ray Irradiation Effects of Li2O2, Li2CO3 and Li2O Revealed by Absorption Spectroscopy Qiao, Ruimin; Chuang, Yi-De; Yan, Shishen PLoS ONE, Vol. 7, Issue 11 https://doi.org/10.1371/journal.pone.0049182	journal	November 2012
Activation Mechanism of LiNi _0.80 Co _0.15 Al _0.05 O ₂ : Surface and Bulk Operando Electrochemical, Differential Electrochemical Mass Spectrometry, and X-ray Diffraction Analyses Robert, Rosa; Bünzli, Christa; Berg, Erik J. Chemistry of Materials, Vol. 27, Issue 2 https://doi.org/10.1021/cm503833b	journal	January 2015
Structural and Chemical Evolution of Amorphous Nickel Iron Complex Hydroxide upon Lithiation/Delithiation Niu, Kai-Yang; Lin, Feng; Fang, Liang Chemistry of Materials, Vol. 27, Issue 5 https://doi.org/10.1021/cm5041375	journal	February 2015
Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange Shkrob, Ilya A.; Gilbert, James A.; Phillips, Patrick J. Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.0861707jes	journal	January 2017
Stability of Li ₂ CO ₃ in cathode of lithium ion battery and its influence on electrochemical performance Bi, Yujing; Wang, Tao; Liu, Meng RSC Advances, Vol. 6, Issue 23 https://doi.org/10.1039/C6RA00648E	journal	January 2016
Soft X-ray XANES studies of various phases related to LiFePO4 based cathode materials Yang, Songlan; Wang, Dongniu; Liang, Guoxian Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee03445j	journal	January 2012
Thermal Decomposition of LiPF[sub 6]-Based Electrolytes for Lithium-Ion Batteries Campion, Christopher L.; Li, Wentao; Lucht, Brett L. Journal of The Electrochemical Society, Vol. 152, Issue 12 https://doi.org/10.1149/1.2083267	journal	January 2005
Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni Biesinger, Mark C.; Payne, Brad P.; Grosvenor, Andrew P. Applied Surface Science, Vol. 257, Issue 7, p. 2717-2730 https://doi.org/10.1016/j.apsusc.2010.10.051	journal	January 2011
Fluoroethylene Carbonate as an Important Component in Electrolyte Solutions for High-Voltage Lithium Batteries: Role of Surface Chemistry on the Cathode Markevich, Elena; Salitra, Gregory; Fridman, Katia Langmuir, Vol. 30, Issue 25 https://doi.org/10.1021/la501368y	journal	June 2014
Study of the LiMn1.5Ni0.5O4∕Electrolyte Interface at Room Temperature and 60°C Duncan, Hugues; Duguay, Dominique; Abu-Lebdeh, Yaser Journal of The Electrochemical Society, Vol. 158, Issue 5 https://doi.org/10.1149/1.3567954	journal	January 2011
Effect of Residual Lithium Compounds on Layer Ni-Rich Li[Ni _0.7 Mn _0.3 ]O ₂ Cho, Dae-Hyun; Jo, Chang-Heum; Cho, Woosuk Journal of The Electrochemical Society, Vol. 161, Issue 6 https://doi.org/10.1149/2.042406jes	journal	January 2014
Solubility of Lithium Salts Formed on the Lithium-Ion Battery Negative Electrode Surface in Organic Solvents Tasaki, Ken; Goldberg, Alex; Lian, Jian-Jie Journal of The Electrochemical Society, Vol. 156, Issue 12 https://doi.org/10.1149/1.3239850	journal	January 2009
Reaction Heterogeneity in LiNi _0.8 Co _0.15 Al _0.05 O ₂ Induced by Surface Layer Grenier, Antonin; Liu, Hao; Wiaderek, Kamila M. Chemistry of Materials, Vol. 29, Issue 17 https://doi.org/10.1021/acs.chemmater.7b02236	journal	August 2017

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Effects of Charge Cutoff Potential on an Electrolyte Additive for LiNi _0.6 Co _0.2 Mn _0.2 O ₂ –Mesocarbon Microbead Full Cells Deng, Bangwei; Wang, Hao; Li, Xiang Energy Technology, Vol. 7, Issue 4 https://doi.org/10.1002/ente.201800981	journal	March 2019
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Title: Evolution of the Electrode–Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress

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Title: Evolution of the Electrode–Electrolyte Interface of LiNi_0.8Co_0.15Al_0.05O₂ Electrodes Due to Electrochemical and Thermal Stress