Understanding Performance Degradation in Cation‐Disordered Rock‐Salt Oxide Cathodes

Chen, Dongchang; Kan, Wang Hay; Chen, Guoying

doi:10.1002/aenm.201901255

Understanding Performance Degradation in Cation‐Disordered Rock‐Salt Oxide Cathodes

Journal Article · Thu Jul 11 00:00:00 EDT 2019 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.201901255· OSTI ID:1558720

Chen, Dongchang ^[1]; Kan, Wang Hay ^[2]; ^[1]

Energy Storage and Distributed Resources Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
Energy Storage and Distributed Resources Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA, Institute of High Energy Physics Chinese Academy of Sciences (CAS) Beijing 100049 China

Abstract

The collective redox activities of transition‐metal (TM) cations and oxygen anions have been shown to increase charge storage capacity in both Li‐rich layered and cation‐disordered rock‐salt cathodes. Repeated cycling involving anionic redox is known to trigger TM migration and phase transformation in layered Li‐ and Mn‐rich (LMR) oxides, however, detailed mechanistic understanding on the recently discovered Li‐rich rock‐salt cathodes is largely missing. The present study systematically investigates the effect of oxygen redox on a Li _1.3 Nb _0.3 Mn _0.4 O ₂ cathode and demonstrates that performance deterioration is directly correlated to the extent of oxygen redox. It is shown that voltage fade and hysteresis begin only after initiating anionic redox at high voltages, which grows progressively with either deeper oxidation of oxygen at higher potential or extended cycling. In contrast to what is reported on layered LMR oxides, extensive TM reduction is observed but phase transition is not detected in the cycled oxide. A densification/degradation mechanism is proposed accordingly which elucidates how a unique combination of extensive chemical reduction of TM and reduced quality of the Li percolation network in cation‐disordered rock‐salts can lead to performance degradation in these newer cathodes with 3D Li migration pathways. Design strategies to achieve balanced capacity and stability are also discussed.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1558720

Alternate ID(s):: OSTI ID: 1569862

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 31 Vol. 9; ISSN 1614-6832

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (71)

Lithium- and Manganese-Rich Oxide Cathode Materials for High-Energy Lithium Ion Batteries Wang, Jun; He, Xin; Paillard, Elie Advanced Energy Materials, Vol. 6, Issue 21 https://doi.org/10.1002/aenm.201600906	journal	August 2016
Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides Qiao, Ruimin; Chin, Timothy; Harris, Stephen J. Current Applied Physics, Vol. 13, Issue 3 https://doi.org/10.1016/j.cap.2012.09.017	journal	May 2013
The significance of the Li₂MnO₃ component in ‘composite’ xLi₂MnO₃·(1−x)LiMn_0.5Ni_0.5O₂ electrodes Johnson, C. S.; Kim, J-S.; Lefief, C. Electrochemistry Communications, Vol. 6, Issue 10, p. 1085-1091 https://doi.org/10.1016/j.elecom.2004.08.002	journal	October 2004
Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes Gallagher, Kevin G.; Croy, Jason R.; Balasubramanian, Mahalingam Electrochemistry Communications, Vol. 33 https://doi.org/10.1016/j.elecom.2013.04.022	journal	August 2013
The first cycle characteristics of Li[Ni1/3Co1/3Mn1/3]O2 charged up to 4.7 V Kim, Jung-Min; Chung, Hoon-Taek Electrochimica Acta, Vol. 49, Issue 6 https://doi.org/10.1016/j.electacta.2003.10.005	journal	March 2004
In situ X-ray absorption spectroscopic study of Li-rich layered cathode material Li[Ni0.17Li0.2Co0.07Mn0.56]O2 Ito, Atsushi; Sato, Yuichi; Sanada, Takashi Journal of Power Sources, Vol. 196, Issue 16 https://doi.org/10.1016/j.jpowsour.2010.09.105	journal	August 2011
Direct observation of reversible charge compensation by oxygen ion in Li-rich manganese layered oxide positive electrode material, Li1.16Ni0.15Co0.19Mn0.50O2 Oishi, Masatsugu; Yogi, Chihiro; Watanabe, Iwao Journal of Power Sources, Vol. 276 https://doi.org/10.1016/j.jpowsour.2014.11.104	journal	February 2015
Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering Yang, Wanli; Devereaux, Thomas P. Journal of Power Sources, Vol. 389 https://doi.org/10.1016/j.jpowsour.2018.04.018	journal	June 2018
Singlet oxygen evolution from layered transition metal oxide cathode materials and its implications for lithium-ion batteries Wandt, Johannes; Freiberg, Anna T. S.; Ogrodnik, Alexander Materials Today, Vol. 21, Issue 8 https://doi.org/10.1016/j.mattod.2018.03.037	journal	October 2018
Revealing and suppressing surface Mn(II) formation of Na0.44MnO2 electrodes for Na-ion batteries Qiao, Ruimin; Dai, Kehua; Mao, Jing Nano Energy, Vol. 16 https://doi.org/10.1016/j.nanoen.2015.06.024	journal	September 2015
Resolving the degradation pathways in high-voltage oxides for high-energy-density lithium-ion batteries; Alternation in chemistry, composition and crystal structures Mohanty, Debasish; Mazumder, Baishakhi; Devaraj, Arun Nano Energy, Vol. 36 https://doi.org/10.1016/j.nanoen.2017.04.008	journal	June 2017
Review of the U.S. Department of Energy’s “Deep Dive” Effort to Understand Voltage Fade in Li- and Mn-Rich Cathodes Croy, Jason R.; Balasubramanian, Mahalingam; Gallagher, Kevin G. Accounts of Chemical Research, Vol. 48, Issue 11 https://doi.org/10.1021/acs.accounts.5b00277	journal	October 2015
Unravelling Solid-State Redox Chemistry in Li _1.3 Nb _0.3 Mn _0.4 O ₂ Single-Crystal Cathode Material Kan, Wang Hay; Chen, Dongchang; Papp, Joseph K. Chemistry of Materials, Vol. 30, Issue 5 https://doi.org/10.1021/acs.chemmater.7b05036	journal	February 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
In Situ L-Edge XAS Study of a Manganese Oxide Water Oxidation Catalyst Xi, Lifei; Schwanke, Christoph; Xiao, Jie The Journal of Physical Chemistry C, Vol. 121, Issue 22 https://doi.org/10.1021/acs.jpcc.7b02331	journal	May 2017
Design of Nickel-Based Cation-Disordered Rock-Salt Oxides: The Effect of Transition Metal (M = V, Ti, Zr) Substitution in LiNi _0.5 M _0.5 O ₂ Binary Systems Cambaz, Musa Ali; Vinayan, Bhaghavathi P.; Euchner, Holger ACS Applied Materials & Interfaces, Vol. 10, Issue 26 https://doi.org/10.1021/acsami.8b02266	journal	June 2018
Evolution of Strategies for Modern Rechargeable Batteries Goodenough, John B. Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar2002705	journal	June 2012
Oxygen-Release-Related Thermal Stability and Decomposition Pathways of Li _x Ni _0.5 Mn _1.5 O ₄ Cathode Materials Hu, Enyuan; Bak, Seong-Min; Liu, Jue Chemistry of Materials, Vol. 26, Issue 2 https://doi.org/10.1021/cm403400y	journal	December 2013
Probing the Degradation Mechanism of Li ₂ MnO ₃ Cathode for Li-Ion Batteries Yan, Pengfei; Xiao, Liang; Zheng, Jianming Chemistry of Materials, Vol. 27, Issue 3 https://doi.org/10.1021/cm504257m	journal	January 2015
Structural and Chemical Evolution of Li- and Mn-Rich Layered Cathode Material Zheng, Jianming; Xu, Pinghong; Gu, Meng Chemistry of Materials, Vol. 27, Issue 4 https://doi.org/10.1021/cm5045978	journal	February 2015
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
Positive Electrode Materials for Li-Ion and Li-Batteries ^† Ellis, Brian L.; Lee, Kyu Tae; Nazar, Linda F. Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm902696j	journal	February 2010
Lithium Batteries and Cathode Materials Whittingham, M. Stanley Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302 https://doi.org/10.1021/cr020731c	journal	October 2004
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
Phase Transformation and Lithiation Effect on Electronic Structure of Li _x FePO ₄ : An In-Depth Study by Soft X-ray and Simulations Liu, Xiaosong; Liu, Jun; Qiao, Ruimin Journal of the American Chemical Society, Vol. 134, Issue 33 https://doi.org/10.1021/ja303225e	journal	August 2012
The Li-Ion Rechargeable Battery: A Perspective Goodenough, John B.; Park, Kyu-Sung Journal of the American Chemical Society, Vol. 135, Issue 4 https://doi.org/10.1021/ja3091438	journal	January 2013
Manganese L-Edge X-ray Absorption Spectroscopy of Manganese Catalase from Lactobacillus plantarum and Mixed Valence Manganese Complexes Grush, M. M.; Chen, J.; Stemmler, T. L. Journal of the American Chemical Society, Vol. 118, Issue 1 https://doi.org/10.1021/ja951614k	journal	January 1996
Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li _0.2 Ni _0.2 Mn _0.6 ]O ₂ Luo, Kun; Roberts, Matthew R.; Guerrini, Niccoló Journal of the American Chemical Society, Vol. 138, Issue 35 https://doi.org/10.1021/jacs.6b05111	journal	August 2016
Exploring Oxygen Activity in the High Energy P2-Type Na _0.78 Ni _0.23 Mn _0.69 O ₂ Cathode Material for Na-Ion Batteries Ma, Chuze; Alvarado, Judith; Xu, Jing Journal of the American Chemical Society, Vol. 139, Issue 13 https://doi.org/10.1021/jacs.7b00164	journal	March 2017
Theoretical Fingerprints of Transition Metal L _2,3 XANES and ELNES for Lithium Transition Metal Oxides by ab Initio Multiplet Calculations Ikeno, Hidekazu; Mizoguchi, Teruyasu; Koyama, Yukinori The Journal of Physical Chemistry C, Vol. 115, Issue 23 https://doi.org/10.1021/jp202383n	journal	May 2011
Operando X-ray Absorption Study of the Redox Processes Involved upon Cycling of the Li-Rich Layered Oxide Li _1.20 Mn _0.54 Co _0.13 Ni _0.13 O ₂ in Li Ion Batteries Koga, H.; Croguennec, L.; Ménétrier, M. The Journal of Physical Chemistry C, Vol. 118, Issue 11 https://doi.org/10.1021/jp412197z	journal	March 2014
Insight into the Atomic Structure of Cycled Lithium-Rich Layered Oxide Li _1.20 Mn _0.54 Co _0.13 Ni _0.13 O ₂ Using HAADF STEM and Electron Nanodiffraction Genevois, Cécile; Koga, Hideyuki; Croguennec, Laurence The Journal of Physical Chemistry C, Vol. 119, Issue 1 https://doi.org/10.1021/jp509388j	journal	December 2014
First Evidence of Manganese–Nickel Segregation and Densification upon Cycling in Li-Rich Layered Oxides for Lithium Batteries Boulineau, Adrien; Simonin, Loïc; Colin, Jean-François Nano Letters, Vol. 13, Issue 8 https://doi.org/10.1021/nl4019275	journal	July 2013
Designing New Lithium-Excess Cathode Materials from Percolation Theory: Nanohighways in Li _x Ni _{2–4 x /3} Sb _{x /3} O ₂ Twu, Nancy; Li, Xin; Urban, Alexander Nano Letters, Vol. 15, Issue 1 https://doi.org/10.1021/nl5040754	journal	December 2014
Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries Gu, Meng; Belharouak, Ilias; Zheng, Jianming ACS Nano, Vol. 7, Issue 1 https://doi.org/10.1021/nn305065u	journal	December 2012
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen Luo, Kun; Roberts, Matthew R.; Hao, Rong Nature Chemistry, Vol. 8, Issue 7 https://doi.org/10.1038/nchem.2471	journal	March 2016
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander Nature Chemistry, Vol. 8, Issue 7 https://doi.org/10.1038/nchem.2524	journal	May 2016
Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2 Maitra, Urmimala; House, Robert A.; Somerville, James W. Nature Chemistry, Vol. 10, Issue 3 https://doi.org/10.1038/nchem.2923	journal	January 2018
Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13814	journal	December 2016
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes Sathiya, M.; Rousse, G.; Ramesha, K. Nature Materials, Vol. 12, Issue 9 https://doi.org/10.1038/nmat3699	journal	July 2013
Origin of voltage decay in high-capacity layered oxide electrodes Sathiya, M.; Abakumov, A. M.; Foix, D. Nature Materials, Vol. 14, Issue 2 https://doi.org/10.1038/nmat4137	journal	December 2014
A new active Li–Mn–O compound for high energy density Li-ion batteries Freire, M.; Kosova, N. V.; Jordy, C. Nature Materials, Vol. 15, Issue 2 https://doi.org/10.1038/nmat4479	journal	November 2015
Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01115-0	journal	October 2017
Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides Gent, William E.; Lim, Kipil; Liang, Yufeng Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-02041-x	journal	December 2017
Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes Assat, Gaurav; Foix, Dominique; Delacourt, Charles Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-02291-9	journal	December 2017
Understanding voltage decay in lithium-excess layered cathode materials through oxygen-centred structural arrangement Myeong, Seungjun; Cho, Woongrae; Jin, Wooyoung Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05802-4	journal	August 2018
Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries Assat, Gaurav; Tarascon, Jean-Marie Nature Energy, Vol. 3, Issue 5 https://doi.org/10.1038/s41560-018-0097-0	journal	April 2018
Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials Lee, Jinhyuk; Kitchaev, Daniil A.; Kwon, Deok-Hwang Nature, Vol. 556, Issue 7700 https://doi.org/10.1038/s41586-018-0015-4	journal	April 2018
Uncovering the roles of oxygen vacancies in cation migration in lithium excess layered oxides Qian, Danna; Xu, Bo; Chi, Miaofang Phys. Chem. Chem. Phys., Vol. 16, Issue 28 https://doi.org/10.1039/C4CP01799D	journal	January 2014
A new class of high capacity cation-disordered oxides for rechargeable lithium batteries: Li–Ni–Ti–Mo oxides Lee, Jinhyuk; Seo, Dong-Hwa; Balasubramanian, Mahalingam Energy & Environmental Science, Vol. 8, Issue 11 https://doi.org/10.1039/C5EE02329G	journal	January 2015
The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries Saubanère, M.; McCalla, E.; Tarascon, J. -M. Energy & Environmental Science, Vol. 9, Issue 3 https://doi.org/10.1039/C5EE03048J	journal	January 2016
The origins and mechanism of phase transformation in bulk Li ₂ MnO ₃ : first-principles calculations and experimental studies Lim, Jin-Myoung; Kim, Duho; Lim, Young-Geun Journal of Materials Chemistry A, Vol. 3, Issue 13 https://doi.org/10.1039/C5TA00944H	journal	January 2015
High-voltage positive electrode materials for lithium-ion batteries Li, Wangda; Song, Bohang; Manthiram, Arumugam Chemical Society Reviews, Vol. 46, Issue 10 https://doi.org/10.1039/C6CS00875E	journal	January 2017
Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox House, Robert A.; Jin, Liyu; Maitra, Urmimala Energy & Environmental Science, Vol. 11, Issue 4 https://doi.org/10.1039/C7EE03195E	journal	January 2018
Nanostructured Li ₂ MnO ₃ : a disordered rock salt type structure for high energy density Li ion batteries Freire, M.; Lebedev, O. I.; Maignan, A. J. Mater. Chem. A, Vol. 5, Issue 41 https://doi.org/10.1039/C7TA07476J	journal	January 2017
Fine Li(4 ? x)/3Ti(2 ? 2x)/3FexO2 (0.18 ? x ? 0.67) powder with cubic rock-salt structure as a positive electrode material for rechargeable lithium batteries Tabuchi, Mitsuharu; Nakashima, Akiko; Shigemura, Hikari Journal of Materials Chemistry, Vol. 13, Issue 7 https://doi.org/10.1039/b209569f	journal	January 2003
High-capacity lithium insertion materials of lithium nickel manganese oxides for advanced lithium-ion batteries: toward rechargeable capacity more than 300 mA h g−1 Ohzuku, Tsutomu; Nagayama, Masatoshi; Tsuji, Kyoji Journal of Materials Chemistry, Vol. 21, Issue 27 https://doi.org/10.1039/c0jm04325g	journal	January 2011
Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study Xu, Bo; Fell, Christopher R.; Chi, Miaofang Energy & Environmental Science, Vol. 4, Issue 6 https://doi.org/10.1039/c1ee01131f	journal	January 2011
High-capacity electrode materials for rechargeable lithium batteries: Li ₃ NbO ₄ -based system with cation-disordered rocksalt structure Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu Proceedings of the National Academy of Sciences, Vol. 112, Issue 25 https://doi.org/10.1073/pnas.1504901112	journal	June 2015
Oxygen 1 s x-ray-absorption edges of transition-metal oxides de Groot, F. M. F.; Grioni, M.; Fuggle, J. C. Physical Review B, Vol. 40, Issue 8 https://doi.org/10.1103/PhysRevB.40.5715	journal	September 1989
Electronic-Structure Origin of Cation Disorder in Transition-Metal Oxides Urban, Alexander; Abdellahi, Aziz; Dacek, Stephen Physical Review Letters, Vol. 119, Issue 17 https://doi.org/10.1103/PhysRevLett.119.176402	journal	October 2017
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries Lee, J.; Urban, A.; Li, X. Science, Vol. 343, Issue 6170 https://doi.org/10.1126/science.1246432	journal	January 2014
Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries McCalla, E.; Abakumov, A. M.; Saubanere, M. Science, Vol. 350, Issue 6267 https://doi.org/10.1126/science.aac8260	journal	December 2015
Lithium Extraction and Insertion Behavior of Nanocrystalline Li[sub 2]TiO[sub 3]-LiFeO[sub 2] Solid Solution with Cubic Rock Salt Structure Shigemura, Hikari; Tabuchi, Mitsuharu; Sakaebe, Hikari Journal of The Electrochemical Society, Vol. 150, Issue 5 https://doi.org/10.1149/1.1565135	journal	January 2003
Synthesis and Electrochemical Characteristics of Li[Co[sub x]Li[sub (1/3−x/3)]Mn[sub (2/3−2x/3)]]O[sub 2] Compounds Park, Yong Joon; Hong, Young-Sik; Wu, Xianglan Journal of The Electrochemical Society, Vol. 151, Issue 5 https://doi.org/10.1149/1.1690781	journal	January 2004
Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries Assat, Gaurav; Delacourt, Charles; Corte, Daniel Alves Dalla Journal of The Electrochemical Society, Vol. 163, Issue 14 https://doi.org/10.1149/2.0531614jes	journal	January 2016
Electrochemical Property of Li-Mn Cation Disordered Li-Rich Li ₂ MnO ₃ with NaCl Type Structure Kataoka, R.; Kojima, T.; Takeichi, N. Journal of The Electrochemical Society, Vol. 165, Issue 2 https://doi.org/10.1149/2.1041802jes	journal	January 2018
Materials Challenges Facing Electrical Energy Storage Whittingham, M. Stanley MRS Bulletin, Vol. 33, Issue 4 https://doi.org/10.1557/mrs2008.82	journal	April 2008

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