Reversible Mn/Cr dual redox in cation-disordered Li-excess cathode materials for stable lithium ion batteries
Abstract
Cation-disordered Li-excess oxides/oxyfluorides have opened the door for designing alternative, high energy cathodes. However, achieving long cycle life and high rate capability represents a major challenge for disordered rocksalt cathodes (DRX). Herein, we develop Li2Mn3/4Cr1/4O2F (LMCOF) DRX materials through a distinct redox mechanochemical method. The LMCOF contains trivalent Cr3+ and Mn3+, which allows for simultaneously accessing stable Mn/Cr dual redox at a narrow voltage window acceptable for conventional carbonate electrolytes. Coupled with the mitigated and reversible oxygen chemical changes, the LMCOF delivers high capacity, rate capability, as well as long cycle life upon extensive 1,000 cycles at various current densities. Finally, the multiscale synchrotron and neutron scattering, spectroscopic, and imaging analyses demonstrate that the capacity originates from the Mn/Cr dual redox with minimal contribution from oxygen redox, and that the good cycle life is attributed to the stable global crystal structure and local oxygen chemical environment.
- Authors:
-
[1];
[2];
[3];
[3];
[2]
- Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Tianjin Univ. (China)
- Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Tianjin Univ. (China)
- Tianjin Univ. (China); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF); Virginia Tech University
- OSTI Identifier:
- 1807548
- Alternate Identifier(s):
- OSTI ID: 1822166
- Grant/Contract Number:
- AC02-76SF00515; DMR-2045570; AC02-06CH1357; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Acta Materialia
- Additional Journal Information:
- Journal Volume: 212; Journal ID: ISSN 1359-6454
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; disordered rocksalt; high rate capability; long cycle life; dual redox; Li ion battery
Citation Formats
Zheng, Xuerong, Xu, Zhengrui, Li, Shaofeng, Zhang, Yuxin, Zhang, Jinfeng, Kuai, Chunguang, Tao, Lei, Rahman, Muhammad Mominur, Zhang, Yan, Lee, Sang-Jun, Sun, Cheng-Jun, Li, Luxi, Hu, Wenbin, Nordlund, Dennis, Liu, Jue, Liu, Yijin, and Lin, Feng. Reversible Mn/Cr dual redox in cation-disordered Li-excess cathode materials for stable lithium ion batteries. United States: N. p., 2021.
Web. doi:10.1016/j.actamat.2021.116935.
Zheng, Xuerong, Xu, Zhengrui, Li, Shaofeng, Zhang, Yuxin, Zhang, Jinfeng, Kuai, Chunguang, Tao, Lei, Rahman, Muhammad Mominur, Zhang, Yan, Lee, Sang-Jun, Sun, Cheng-Jun, Li, Luxi, Hu, Wenbin, Nordlund, Dennis, Liu, Jue, Liu, Yijin, & Lin, Feng. Reversible Mn/Cr dual redox in cation-disordered Li-excess cathode materials for stable lithium ion batteries. United States. https://doi.org/10.1016/j.actamat.2021.116935
Zheng, Xuerong, Xu, Zhengrui, Li, Shaofeng, Zhang, Yuxin, Zhang, Jinfeng, Kuai, Chunguang, Tao, Lei, Rahman, Muhammad Mominur, Zhang, Yan, Lee, Sang-Jun, Sun, Cheng-Jun, Li, Luxi, Hu, Wenbin, Nordlund, Dennis, Liu, Jue, Liu, Yijin, and Lin, Feng. Sat .
"Reversible Mn/Cr dual redox in cation-disordered Li-excess cathode materials for stable lithium ion batteries". United States. https://doi.org/10.1016/j.actamat.2021.116935. https://www.osti.gov/servlets/purl/1807548.
@article{osti_1807548,
title = {Reversible Mn/Cr dual redox in cation-disordered Li-excess cathode materials for stable lithium ion batteries},
author = {Zheng, Xuerong and Xu, Zhengrui and Li, Shaofeng and Zhang, Yuxin and Zhang, Jinfeng and Kuai, Chunguang and Tao, Lei and Rahman, Muhammad Mominur and Zhang, Yan and Lee, Sang-Jun and Sun, Cheng-Jun and Li, Luxi and Hu, Wenbin and Nordlund, Dennis and Liu, Jue and Liu, Yijin and Lin, Feng},
abstractNote = {Cation-disordered Li-excess oxides/oxyfluorides have opened the door for designing alternative, high energy cathodes. However, achieving long cycle life and high rate capability represents a major challenge for disordered rocksalt cathodes (DRX). Herein, we develop Li2Mn3/4Cr1/4O2F (LMCOF) DRX materials through a distinct redox mechanochemical method. The LMCOF contains trivalent Cr3+ and Mn3+, which allows for simultaneously accessing stable Mn/Cr dual redox at a narrow voltage window acceptable for conventional carbonate electrolytes. Coupled with the mitigated and reversible oxygen chemical changes, the LMCOF delivers high capacity, rate capability, as well as long cycle life upon extensive 1,000 cycles at various current densities. Finally, the multiscale synchrotron and neutron scattering, spectroscopic, and imaging analyses demonstrate that the capacity originates from the Mn/Cr dual redox with minimal contribution from oxygen redox, and that the good cycle life is attributed to the stable global crystal structure and local oxygen chemical environment.},
doi = {10.1016/j.actamat.2021.116935},
journal = {Acta Materialia},
number = ,
volume = 212,
place = {United States},
year = {Sat May 01 00:00:00 EDT 2021},
month = {Sat May 01 00:00:00 EDT 2021}
}
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Works referenced in this record:
Hard X-ray fluorescence tomography—an emerging tool for structural visualization
journal, October 2010
- de Jonge, Martin D.; Vogt, Stefan
- Current Opinion in Structural Biology, Vol. 20, Issue 5
Atomic insight into electrochemical inactivity of lithium chromate (LiCrO2): Irreversible migration of chromium into lithium layers in surface regions
journal, January 2015
- Lyu, Yingchun; Ben, Liubin; Sun, Yang
- Journal of Power Sources, Vol. 273
Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials
journal, April 2018
- Lee, Jinhyuk; Kitchaev, Daniil A.; Kwon, Deok-Hwang
- Nature, Vol. 556, Issue 7700
Wavelet data analysis of EXAFS spectra
journal, June 2009
- Timoshenko, J.; Kuzmin, A.
- Computer Physics Communications, Vol. 180, Issue 6
Reversible Three-Electron Redox Reaction of Mo 3+ /Mo 6+ for Rechargeable Lithium Batteries
journal, March 2017
- Hoshino, Satoshi; Glushenkov, Alexey M.; Ichikawa, Shinnosuke
- ACS Energy Letters, Vol. 2, Issue 4
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014
- Lin, Feng; Markus, Isaac M.; Nordlund, Dennis
- Nature Communications, Vol. 5, Issue 1
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials
journal, May 2016
- Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander
- Nature Chemistry, Vol. 8, Issue 7
Improved Voltage and Cycling for Li + Intercalation in High-Capacity Disordered Oxyfluoride Cathodes
journal, June 2015
- Ren, Shuhua; Chen, Ruiyong; Maawad, Emad
- Advanced Science, Vol. 2, Issue 10
Structural and mechanistic revelations on high capacity cation-disordered Li-rich oxides for rechargeable Li-ion batteries
journal, January 2019
- Zhao, Enyue; He, Lunhua; Wang, Baotian
- Energy Storage Materials, Vol. 16
Flexible lignin carbon membranes with surface ozonolysis to host lean lithium metal anodes for nickel-rich layered oxide batteries
journal, January 2020
- Tao, Lei; Xu, Zhengrui; Kuai, Chunguang
- Energy Storage Materials, Vol. 24
First-principles prediction of redox potentials in transition-metal compounds with
journal, December 2004
- Zhou, F.; Cococcioni, M.; Marianetti, C. A.
- Physical Review B, Vol. 70, Issue 23
Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries
journal, January 2014
- Lee, J.; Urban, A.; Li, X.
- Science, Vol. 343, Issue 6170
Identifying the redox activity of cation-disordered Li–Fe–V–Ti oxide cathodes for Li-ion batteries
journal, January 2016
- Chen, Ruiyong; Witte, Ralf; Heinzmann, Ralf
- Physical Chemistry Chemical Physics, Vol. 18, Issue 11
Electrochemical Kinetics of the Li[Li 0.23 Co 0.3 Mn 0.47 ]O 2 Cathode Material Studied by GITT and EIS
journal, December 2010
- Li, Zhe; Du, Fei; Bie, Xiaofei
- The Journal of Physical Chemistry C, Vol. 114, Issue 51
Revisiting the charge compensation mechanisms in LiNi 0.8 Co 0.2−y Al y O 2 systems
journal, January 2019
- Lebens-Higgins, Zachary W.; Faenza, Nicholas V.; Radin, Maxwell D.
- Materials Horizons, Vol. 6, Issue 10
Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials
journal, April 2018
- Mu, Linqin; Lin, Ruoqian; Xu, Rong
- Nano Letters, Vol. 18, Issue 5
Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes
journal, December 2017
- Assat, Gaurav; Foix, Dominique; Delacourt, Charles
- Nature Communications, Vol. 8, Issue 1
In Situ XAFS Analysis of Li(Mn, M)2O4 (M=Cr, Co, Ni) 5V Cathode Materials for Lithium-Ion Secondary Batteries
journal, February 2001
- Terada, Yasuko; Yasaka, Kenji; Nishikawa, Fumishige
- Journal of Solid State Chemistry, Vol. 156, Issue 2
Synthesis and electrochemical properties of Li 1.3 Nb 0.3 V 0.4 O 2 as a positive electrode material for rechargeable lithium batteries
journal, January 2016
- Yabuuchi, Naoaki; Takeuchi, Mitsue; Komaba, Shinichi
- Chemical Communications, Vol. 52, Issue 10
The significance of the Li2MnO3 component in ‘composite’ xLi2MnO3·(1−x)LiMn0.5Ni0.5O2 electrodes
journal, October 2004
- Johnson, C. S.; Kim, J-S.; Lefief, C.
- Electrochemistry Communications, Vol. 6, Issue 10, p. 1085-1091
Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes
journal, January 2018
- Kitchaev, Daniil A.; Lun, Zhengyan; Richards, William D.
- Energy & Environmental Science, Vol. 11, Issue 8
Critical Role of Oxygen Evolved from Layered Li–Excess Metal Oxides in Lithium Rechargeable Batteries
journal, July 2012
- Hong, Jihyun; Lim, Hee-Dae; Lee, Minah
- Chemistry of Materials, Vol. 24, Issue 14
Tuning Redox Transitions via Inductive Effect in Metal Oxides and Complexes, and Implications in Oxygen Electrocatalysis
journal, February 2018
- Kuznetsov, Denis A.; Han, Binghong; Yu, Yang
- Joule, Vol. 2, Issue 2
A disordered rock-salt Li-excess cathode material with high capacity and substantial oxygen redox activity: Li 1.25 Nb 0.25 Mn 0.5 O 2
journal, November 2015
- Wang, Rui; Li, Xin; Liu, Lei
- Electrochemistry Communications, Vol. 60
Understanding Performance Degradation in Cation‐Disordered Rock‐Salt Oxide Cathodes
journal, July 2019
- Chen, Dongchang; Kan, Wang Hay; Chen, Guoying
- Advanced Energy Materials, Vol. 9, Issue 31
Continuous Cauchy wavelet transform analyses of EXAFS spectra: A qualitative approach
journal, April 2003
- Muñoz, Manuel; Argoul, Pierre; Farges, François
- American Mineralogist, Vol. 88, Issue 4
Iron Oxyfluorides as High Capacity Cathode Materials for Lithium Batteries
journal, January 2009
- Pereira, N.; Badway, F.; Wartelsky, M.
- Journal of The Electrochemical Society, Vol. 156, Issue 6, p. A407-A416
Electronic-Structure Origin of Cation Disorder in Transition-Metal Oxides
journal, October 2017
- Urban, Alexander; Abdellahi, Aziz; Dacek, Stephen
- Physical Review Letters, Vol. 119, Issue 17
High-capacity electrode materials for rechargeable lithium batteries: Li 3 NbO 4 -based system with cation-disordered rocksalt structure
journal, June 2015
- Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 25
Hidden structural and chemical order controls lithium transport in cation-disordered oxides for rechargeable batteries
journal, February 2019
- Ji, Huiwen; Urban, Alexander; Kitchaev, Daniil A.
- Nature Communications, Vol. 10, Issue 1
A new class of high capacity cation-disordered oxides for rechargeable lithium batteries: Li–Ni–Ti–Mo oxides
journal, January 2015
- Lee, Jinhyuk; Seo, Dong-Hwa; Balasubramanian, Mahalingam
- Energy & Environmental Science, Vol. 8, Issue 11
Calculation and interpretation of -shell x-ray absorption near-edge structure of transition metal oxides
journal, January 2003
- Modrow, H.; Bucher, S.; Rehr, J. J.
- Physical Review B, Vol. 67, Issue 3
Formation of unusual Cr 5+ charge state in CaCr 0.5 Fe 0.5 O 3 perovskite
journal, March 2018
- Dai, Jian-Hong; Zhao, Qing; Sun, Qian
- Chinese Physics B, Vol. 27, Issue 3
Reversible Oxygen Participation to the Redox Processes Revealed for Li 1.20 Mn 0.54 Co 0.13 Ni 0.13 O 2
journal, January 2013
- Koga, Hideyuki; Croguennec, Laurence; Ménétrier, Michel
- Journal of The Electrochemical Society, Vol. 160, Issue 6
Ba 3 (Cr 0.97(1) Te 0.03(1) ) 2 TeO 9 : in Search of Jahn–Teller Distorted Cr(II) Oxide
journal, September 2016
- Li, Man-Rong; Deng, Zheng; Lapidus, Saul H.
- Inorganic Chemistry, Vol. 55, Issue 20
Origin of the High Capacity Manganese-Based Oxyfluoride Electrodes for Rechargeable Batteries
journal, July 2018
- Zhang, Leiting; Dambournet, Damien; Iadecola, Antonella
- Chemistry of Materials, Vol. 30, Issue 15
Computational Investigation and Experimental Realization of Disordered High-Capacity Li-Ion Cathodes Based on Ni Redox
journal, March 2019
- Ji, Huiwen; Kitchaev, Daniil A.; Lun, Zhengyan
- Chemistry of Materials, Vol. 31, Issue 7
Reversible Li storage for nanosize cation/anion-disordered rocksalt-type oxyfluorides: LiMoO 2 – x LiF (0 ≤ x ≤ 2) binary system
journal, November 2017
- Takeda, Nanami; Hoshino, Satoshi; Xie, Lixin
- Journal of Power Sources, Vol. 367
Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials
journal, October 2017
- Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J.
- Nature Communications, Vol. 8, Issue 1
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016
- Luo, Kun; Roberts, Matthew R.; Hao, Rong
- Nature Chemistry, Vol. 8, Issue 7
Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode
journal, September 2018
- Clément, Raphaële J.; Kitchaev, Daniil; Lee, Jinhyuk
- Chemistry of Materials, Vol. 30, Issue 19
Electronic Crystallization in a Lithium Battery Material: Columnar Ordering of Electrons and Holes in the Spinel
journal, November 1998
- Rodríguez-Carvajal, J.; Rousse, G.; Masquelier, C.
- Physical Review Letters, Vol. 81, Issue 21
Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox
journal, January 2018
- House, Robert A.; Jin, Liyu; Maitra, Urmimala
- Energy & Environmental Science, Vol. 11, Issue 4
Understanding electrochemical potentials of cathode materials in rechargeable batteries
journal, March 2016
- Liu, Chaofeng; Neale, Zachary G.; Cao, Guozhong
- Materials Today, Vol. 19, Issue 2
Rock-salt-type lithium metal sulphides as novel positive-electrode materials
journal, May 2014
- Sakuda, Atsushi; Takeuchi, Tomonari; Okamura, Kazuhiro
- Scientific Reports, Vol. 4, Issue 1
Unravelling Solid-State Redox Chemistry in Li 1.3 Nb 0.3 Mn 0.4 O 2 Single-Crystal Cathode Material
journal, February 2018
- Kan, Wang Hay; Chen, Dongchang; Papp, Joseph K.
- Chemistry of Materials, Vol. 30, Issue 5
Enhanced Cycling Stability of Cation Disordered Rock-Salt Li1.2Ti0.4Mn0.4O2 Material by Surface Modification With Al2O3
journal, March 2019
- Huang, Baojun; Wang, Rui; Gong, Yansheng
- Frontiers in Chemistry, Vol. 7
Speciation of Chromium by High-Performance Thin-Layer Chromatography with Direct Determination by Laser Ablation Inductively Coupled Plasma Mass Spectrometry
journal, August 2008
- Lafleur, Josiane P.; Salin, Eric D.
- Analytical Chemistry, Vol. 80, Issue 17
The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
journal, September 2012
- Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
- Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287
In Situ X-ray Absorption Spectroscopic Study on LiNi 0.5 Mn 0.5 O 2 Cathode Material during Electrochemical Cycling
journal, August 2003
- Yoon, Won-Sub; Grey, Clare P.; Balasubramanian, Mahalingam
- Chemistry of Materials, Vol. 15, Issue 16
Fluorination of Lithium-Excess Transition Metal Oxide Cathode Materials
journal, October 2017
- Richards, William D.; Dacek, Stephen T.; Kitchaev, Daniil A.
- Advanced Energy Materials, Vol. 8, Issue 5
Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution
journal, November 2018
- Lun, Zhengyan; Ouyang, Bin; Kitchaev, Daniil A.
- Advanced Energy Materials, Vol. 9, Issue 2
Review of Recent Development of In Situ/Operando Characterization Techniques for Lithium Battery Research
journal, May 2019
- Liu, Dongqing; Shadike, Zulipiya; Lin, Ruoqian
- Advanced Materials, Vol. 31, Issue 28
A new active Li–Mn–O compound for high energy density Li-ion batteries
journal, November 2015
- Freire, M.; Kosova, N. V.; Jordy, C.
- Nature Materials, Vol. 15, Issue 2
Elucidating anionic oxygen activity in lithium-rich layered oxides
journal, March 2018
- Xu, Jing; Sun, Meiling; Qiao, Ruimin
- Nature Communications, Vol. 9, Issue 1
Wavelet analysis of extended X-ray absorption fine structure data: Theory, application
journal, August 2018
- Xia, Zhaoming; Zhang, Hao; Shen, Kongchao
- Physica B: Condensed Matter, Vol. 542
Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V
journal, June 2019
- Zhang, Jie-Nan; Li, Qinghao; Ouyang, Chuying
- Nature Energy, Vol. 4, Issue 7
Improved Electrode Performance of Lithium-Excess Molybdenum Oxyfluoride: Titanium Substitution with Concentrated Electrolyte
journal, February 2019
- Takeda, Nanami; Ikeuchi, Issei; Natsui, Ryuichi
- ACS Applied Energy Materials, Vol. 2, Issue 3
Ti -edge XANES studies of Ti coordination and disorder in oxide compounds: Comparison between theory and experiment
journal, July 1997
- Farges, François; Brown, Gordon E.; Rehr, J. J.
- Physical Review B, Vol. 56, Issue 4
A New Type of Li‐Rich Rock‐Salt Oxide Li 2 Ni 1/3 Ru 2/3 O 3 with Reversible Anionic Redox Chemistry
journal, January 2019
- Li, Xiang; Qiao, Yu; Guo, Shaohua
- Advanced Materials, Vol. 31, Issue 11
Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries
journal, December 2016
- Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue
- Nature Communications, Vol. 7, Issue 1
XPS study of coating delamination from non-rinse chromate treated steel
journal, January 1998
- Murase, Masatsugu; Watts*, John F.
- Journal of Materials Chemistry, Vol. 8, Issue 4
Structure Stabilization by Mixed Anions in Oxyfluoride Cathodes for High-Energy Lithium Batteries
journal, September 2015
- Kim, Sung-Wook; Pereira, Nathalie; Chernova, Natasha A.
- ACS Nano, Vol. 9, Issue 10
Spectroscopic Evidence for Ternary Complex Formation between Arsenate and Ferric Iron Complexes of Humic Substances
journal, November 2011
- Mikutta, Christian; Kretzschmar, Ruben
- Environmental Science & Technology, Vol. 45, Issue 22
Deciphering the Cathode-Electrolyte Interfacial Chemistry in Sodium Layered Cathode Materials
journal, October 2018
- Mu, Linqin; Feng, Xu; Kou, Ronghui
- Advanced Energy Materials, Vol. 8, Issue 34
Surface-to-Bulk Redox Coupling through Thermally Driven Li Redistribution in Li- and Mn-Rich Layered Cathode Materials
journal, July 2019
- Li, Shaofeng; Lee, Sang-Jun; Wang, Xuelong
- Journal of the American Chemical Society, Vol. 141, Issue 30