Reversible Anionic Redox Activities in Conventional LiNi1/3Co1/3Mn1/3O2 Cathodes
Abstract
Redox reactions of oxygen have been considered critical in controlling the electrochemical properties of lithium-excessive layered-oxide electrodes. However, conventional electrode materials without overlithiation remain the most practical. Typically, cationic redox reactions are believed to dominate the electrochemical processes in conventional electrodes. Herein, we show unambiguous evidence of reversible anionic redox reactions in LiNi1/3Co1/3Mn1/3O2. The typical involvement of oxygen through hybridization with transition metals is discussed, as well as the intrinsic oxygen redox process at high potentials, which is 75 % reversible during initial cycling and 63% retained after 10 cycles. Our results clarify the reaction mechanism at high potentials in conventional layered electrodes involving both cationic and anionic reactions and indicate the potential of utilizing reversible oxygen redox reactions in conventional layered oxides for high-capacity lithium-ion batteries.
- Authors:
-
- Dongguk University, Department of Energy and Materials Engineering, KOREA, REPUBLIC OF
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Kyung Hee Univ.-Global Campus, Yongin (Korea). Dept. of Mechanical Engineering
- Univ. of Texas at Dallas, Richardson, TX (United States). Dept. of Materials Science and Engineering
- Seoul National Univ. (Korea). Inst. of Advanced Machines and Design
- Dongguk Univ., Seoul (Korea). Dept. of Energy and Materials Engineering
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Research Foundation of Korea (NRF)
- OSTI Identifier:
- 1601226
- Alternate Identifier(s):
- OSTI ID: 1606068
- Grant/Contract Number:
- AC02-05CH11231; 2012R1A3A2048841; 2017R1A2B3004383
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 59; Journal Issue: 22; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electrochemistry; Mapping of resonant inelastic X-ray scattering (mRIXS); Lithium ion batteries; Redox chemistry; X-ray absorption spectroscopy
Citation Formats
Lee, Gi-Hyeok, Wu, Jinpeng, Kim, Duho, Cho, Kyeongjae, Cho, Maenghyo, Yang, Wanli, and Kang, Y. M. Reversible Anionic Redox Activities in Conventional LiNi1/3Co1/3Mn1/3O2 Cathodes. United States: N. p., 2020.
Web. doi:10.1002/anie.202001349.
Lee, Gi-Hyeok, Wu, Jinpeng, Kim, Duho, Cho, Kyeongjae, Cho, Maenghyo, Yang, Wanli, & Kang, Y. M. Reversible Anionic Redox Activities in Conventional LiNi1/3Co1/3Mn1/3O2 Cathodes. United States. https://doi.org/10.1002/anie.202001349
Lee, Gi-Hyeok, Wu, Jinpeng, Kim, Duho, Cho, Kyeongjae, Cho, Maenghyo, Yang, Wanli, and Kang, Y. M. Fri .
"Reversible Anionic Redox Activities in Conventional LiNi1/3Co1/3Mn1/3O2 Cathodes". United States. https://doi.org/10.1002/anie.202001349. https://www.osti.gov/servlets/purl/1601226.
@article{osti_1601226,
title = {Reversible Anionic Redox Activities in Conventional LiNi1/3Co1/3Mn1/3O2 Cathodes},
author = {Lee, Gi-Hyeok and Wu, Jinpeng and Kim, Duho and Cho, Kyeongjae and Cho, Maenghyo and Yang, Wanli and Kang, Y. M.},
abstractNote = {Redox reactions of oxygen have been considered critical in controlling the electrochemical properties of lithium-excessive layered-oxide electrodes. However, conventional electrode materials without overlithiation remain the most practical. Typically, cationic redox reactions are believed to dominate the electrochemical processes in conventional electrodes. Herein, we show unambiguous evidence of reversible anionic redox reactions in LiNi1/3Co1/3Mn1/3O2. The typical involvement of oxygen through hybridization with transition metals is discussed, as well as the intrinsic oxygen redox process at high potentials, which is 75 % reversible during initial cycling and 63% retained after 10 cycles. Our results clarify the reaction mechanism at high potentials in conventional layered electrodes involving both cationic and anionic reactions and indicate the potential of utilizing reversible oxygen redox reactions in conventional layered oxides for high-capacity lithium-ion batteries.},
doi = {10.1002/anie.202001349},
journal = {Angewandte Chemie (International Edition)},
number = 22,
volume = 59,
place = {United States},
year = {2020},
month = {2}
}
Web of Science
Works referenced in this record:
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
journal, July 2013
- Sathiya, M.; Rousse, G.; Ramesha, K.
- Nature Materials, Vol. 12, Issue 9
Layered Li(Ni0.5−xMn0.5−xM2x′)O2 (M′=Co, Al, Ti; x=0, 0.025) cathode materials for Li-ion rechargeable batteries
journal, October 2002
- Kang, S.
- Journal of Power Sources, Vol. 112, Issue 1
Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3
journal, February 2017
- Pearce, Paul E.; Perez, Arnaud J.; Rousse, Gwenaelle
- Nature Materials, Vol. 16, Issue 5
The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries
journal, January 2016
- Saubanère, M.; McCalla, E.; Tarascon, J. -M.
- Energy & Environmental Science, Vol. 9, Issue 3
Facile Lithium Ion Transport through Superionic Pathways Formed on the Surface of Li 3 V 2 (PO 4 ) 3 /C for High Power Li Ion Battery
journal, June 2014
- Han, Dong-Wook; Lim, Sung-Jin; Kim, Yong-Il
- Chemistry of Materials, Vol. 26, Issue 12
Atomic multiplets at the edge of 3 transition metals and the ligand K edge in x-ray absorption spectroscopy of ionic systems
journal, June 2013
- Olalde-Velasco, P.; Jiménez-Mier, J.; Denlinger, J.
- Physical Review B, Vol. 87, Issue 24
In situ analyses for ion storage materials
journal, January 2016
- Yang, Junghoon; Muhammad, Shoaib; Jo, Mi Ru
- Chemical Society Reviews, Vol. 45, Issue 20
A New Coating Method for Alleviating Surface Degradation of LiNi 0.6 Co 0.2 Mn 0.2 O 2 Cathode Material: Nanoscale Surface Treatment of Primary Particles
journal, February 2015
- Kim, Hyejung; Kim, Min Gyu; Jeong, Hu Young
- Nano Letters, Vol. 15, Issue 3
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
Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering
journal, June 2018
- Yang, Wanli; Devereaux, Thomas P.
- Journal of Power Sources, Vol. 389
Structural and Electrochemical Study of Hierarchical LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathode Material for Lithium-Ion Batteries
journal, September 2015
- Li, Li; Wang, Lecai; Zhang, Xiaoxiao
- ACS Applied Materials & Interfaces, Vol. 7, Issue 39
LiNi 1/3 Co 1/3 Mn 1/3 O 2 –Graphene Composite as a Promising Cathode for Lithium-Ion Batteries
journal, June 2011
- Venkateswara Rao, Chitturi; Leela Mohana Reddy, Arava; Ishikawa, Yasuyuki
- ACS Applied Materials & Interfaces, Vol. 3, Issue 8
Lithium and sodium battery cathode materials: computational insights into voltage, diffusion and nanostructural properties
journal, January 2014
- Islam, M. Saiful; Fisher, Craig A. J.
- Chem. Soc. Rev., Vol. 43, Issue 1
Anionic redox chemistry in Na-rich Na 2 Ru 1−y Sn y O 3 positive electrode material for Na-ion batteries
journal, April 2015
- Rozier, Patrick; Sathiya, Mariyappan; Paulraj, Alagar-Raj
- Electrochemistry Communications, Vol. 53
High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source
journal, March 2017
- Qiao, Ruimin; Li, Qinghao; Zhuo, Zengqing
- Review of Scientific Instruments, Vol. 88, Issue 3
Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries
journal, December 2015
- McCalla, E.; Abakumov, A. M.; Saubanere, M.
- Science, Vol. 350, Issue 6267
Intrinsic Origins of Crack Generation in Ni-rich LiNi0.8Co0.1Mn0.1O2 Layered Oxide Cathode Material
journal, January 2017
- Lim, Jin-Myoung; Hwang, Taesoon; Kim, Duho
- Scientific Reports, Vol. 7, Issue 1
X-ray Absorption Spectroscopy Investigation of Lithium-Rich, Cobalt-Poor Layered-Oxide Cathode Material with High Capacity
journal, November 2014
- Buchholz, Daniel; Li, Jie; Passerini, Stefano
- ChemElectroChem, Vol. 2, Issue 1
The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013
- Goodenough, John B.; Park, Kyu-Sung
- Journal of the American Chemical Society, Vol. 135, Issue 4
Electrode Materials for Rechargeable Sodium-Ion Batteries: Potential Alternatives to Current Lithium-Ion Batteries
journal, May 2012
- Kim, Sung-Wook; Seo, Dong-Hwa; Ma, Xiaohua
- Advanced Energy Materials, Vol. 2, Issue 7, p. 710-721
Lithium-Ion Transport through a Tailored Disordered Phase on the LiNi 0.5 Mn 1.5 O 4 Surface for High-Power Cathode Materials
journal, June 2014
- Jo, Mi Ru; Kim, Yong-Il; Kim, Yunok
- ChemSusChem, Vol. 7, Issue 8
Tunable-excitation soft X-ray fluorescence spectroscopy of high-Tc superconductors: an inequivalent-site seeing story
journal, October 2000
- Butorin, Sergei M.; Guo, Jinghua; Wassdahl, Nial
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 110-111
Review of the U.S. Department of Energy’s “Deep Dive” Effort to Understand Voltage Fade in Li- and Mn-Rich Cathodes
journal, October 2015
- Croy, Jason R.; Balasubramanian, Mahalingam; Gallagher, Kevin G.
- Accounts of Chemical Research, Vol. 48, Issue 11
Local structure adaptability through multi cations for oxygen redox accommodation in Li-Rich layered oxides
journal, January 2020
- Zhao, Enyue; Zhang, Minghao; Wang, Xuelong
- Energy Storage Materials, Vol. 24
A Layer-Structured Electrode Material Reformed by a PO 4 -O 2 Hybrid Framework toward Enhanced Lithium Storage and Stability
journal, January 2016
- Min, Sul Hee; Jo, Mi Ru; Choi, Si-Young
- Advanced Energy Materials, Vol. 6, Issue 7
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
journal, December 2005
- Yoon, Won-Sub; Balasubramanian, Mahalingam; Chung, Kyung Yoon
- Journal of the American Chemical Society, Vol. 127, Issue 49
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
Electron Transfer Mechanisms upon Lithium Deintercalation from LiCoO 2 to CoO 2 Investigated by XPS
journal, January 2008
- Dahéron, L.; Dedryvère, R.; Martinez, H.
- Chemistry of Materials, Vol. 20, Issue 2
Why LiFePO 4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation
journal, January 2015
- Liu, Xiaosong; Wang, Yung Jui; Barbiellini, Bernardo
- Physical Chemistry Chemical Physics, Vol. 17, Issue 39
Direct probe of Mott-Hubbard to charge-transfer insulator transition and electronic structure evolution in transition-metal systems
journal, June 2011
- Olalde-Velasco, P.; Jiménez-Mier, J.; Denlinger, J. D.
- Physical Review B, Vol. 83, Issue 24
Transition-metal redox evolution in LiNi0.5Mn0.3Co0.2O2 electrodes at high potentials
journal, August 2017
- Qiao, Ruimin; Liu, Jun; Kourtakis, Kostantinos
- Journal of Power Sources, Vol. 360
Modification of Transition-Metal Redox by Interstitial Water in Hexacyanometalate Electrodes for Sodium-Ion Batteries
journal, December 2017
- Wu, Jinpeng; Song, Jie; Dai, Kehua
- Journal of the American Chemical Society, Vol. 139, Issue 50
Oxygen 1 s x-ray-absorption edges of transition-metal oxides
journal, September 1989
- de Groot, F. M. F.; Grioni, M.; Fuggle, J. C.
- Physical Review B, Vol. 40, Issue 8
Na 3 V 2 (PO 4 ) 3 particles partly embedded in carbon nanofibers with superb kinetics for ultra-high power sodium ion batteries
journal, January 2015
- Yang, Junghoon; Han, Dong-Wook; Jo, Mi Ru
- Journal of Materials Chemistry A, Vol. 3, Issue 3
Carbon Nanofibers Heavy Laden with Li 3 V 2 (PO 4 ) 3 Particles Featuring Superb Kinetics for High-Power Lithium Ion Battery
journal, May 2017
- Shin, Jeongyim; Yang, Junghoon; Sergey, Chernov
- Advanced Science, Vol. 4, Issue 9
Oxygen Contribution on Li-Ion Intercalation−Deintercalation in LiCoO 2 Investigated by O K-Edge and Co L-Edge X-ray Absorption Spectroscopy
journal, March 2002
- Yoon, Won-Sub; Kim, Kwang-Bum; Kim, Min-Gyu
- The Journal of Physical Chemistry B, Vol. 106, Issue 10
High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions
journal, February 2019
- Dai, Kehua; Wu, Jinpeng; Zhuo, Zengqing
- Joule, Vol. 3, Issue 2
Building better batteries
journal, February 2008
- Armand, M.; Tarascon, J.-M.
- Nature, Vol. 451, Issue 7179, p. 652-657
Nanostructured materials for advanced energy conversion and storage devices
journal, May 2005
- Aricò, Antonino Salvatore; Bruce, Peter; Scrosati, Bruno
- Nature Materials, Vol. 4, Issue 5, p. 366-377
Distinction between Intrinsic and X-ray-Induced Oxidized Oxygen States in Li-Rich 3d Layered Oxides and LiAlO 2
journal, May 2019
- Lebens-Higgins, Zachary W.; Vinckeviciute, Julija; Wu, Jinpeng
- The Journal of Physical Chemistry C, Vol. 123, Issue 21
In situ x-ray absorption spectroscopic study of the Li[Ni1∕3Co1∕3Mn1∕3]O2 cathode material
journal, June 2005
- Deb, Aniruddha; Bergmann, Uwe; Cramer, Stephen P.
- Journal of Applied Physics, Vol. 97, Issue 11
Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode
journal, April 2016
- Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao
- Nature Communications, Vol. 7, Issue 1
Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi 0.5 Mn 1.5 O 4 Electrodes
journal, November 2015
- Qiao, Ruimin; Wray, L. Andrew; Kim, Jung-Hyun
- The Journal of Physical Chemistry C, Vol. 119, Issue 49
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
Soft X-ray absorption spectroscopy studies on the chemically delithiated commercial LiCoO2 cathode material
journal, December 2007
- Chen, Ching-Hsiang; Hwang, Bing-Joe; Chen, Chun-Yu
- Journal of Power Sources, Vol. 174, Issue 2
In-Situ X-ray Absorption Spectroscopic Study on Variation of Electronic Transitions and Local Structure of LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathode Material during Electrochemical Cycling
journal, June 2005
- Tsai, Y. W.; Hwang, B. J.; Ceder, G.
- Chemistry of Materials, Vol. 17, Issue 12
Band gaps and electronic structure of transition-metal compounds
journal, July 1985
- Zaanen, J.; Sawatzky, G. A.; Allen, J. W.
- Physical Review Letters, Vol. 55, Issue 4
Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy
journal, September 2016
- Li, Qinghao; Qiao, Ruimin; Wray, L. Andrew
- Journal of Physics D: Applied Physics, Vol. 49, Issue 41
Key electronic states in lithium battery materials probed by soft X-ray spectroscopy
journal, October 2013
- Yang, Wanli; Liu, Xiaosong; Qiao, Ruimin
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 190
Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries
journal, January 2017
- Xie, Y.; Saubanère, M.; Doublet, M. -L.
- Energy & Environmental Science, Vol. 10, Issue 1
Oxygen and transition metal involvement in the charge compensation mechanism of LiNi1/3Mn1/3Co1/3O2 cathodes
journal, January 2012
- Petersburg, Cole F.; Li, Zheng; Chernova, Natasha A.
- Journal of Materials Chemistry, Vol. 22, Issue 37
A comprehensive study of the role of transition metals in O3-type layered Na[Ni x Co y Mn z ]O 2 (x = 1/3, 0.5, 0.6, and 0.8) cathodes for sodium-ion batteries
journal, January 2016
- Hwang, Jang-Yeon; Yoon, Chong S.; Belharouak, Ilias
- Journal of Materials Chemistry A, Vol. 4, Issue 46
A Combined Computational/Experimental Study on LiNi 1/3 Co 1/3 Mn 1/3 O 2
journal, September 2003
- Hwang, B. J.; Tsai, Y. W.; Carlier, D.
- Chemistry of Materials, Vol. 15, Issue 19
Hierarchical Porous LiNi1/3Co1/3Mn1/3O2 Nano-/Micro Spherical Cathode Material: Minimized Cation Mixing and Improved Li+ Mobility for Enhanced Electrochemical Performance
journal, May 2016
- Chen, Zhen; Wang, Jin; Chao, Dongliang
- Scientific Reports, Vol. 6, Issue 1
Lithium and sodium battery cathode materials: computational insights into voltage, diffusion and nanostructural properties
journal, January 2014
- Islam, M. Saiful; Fisher, Craig A. J.
- Chem. Soc. Rev., Vol. 43, Issue 1
Issues and challenges facing rechargeable lithium batteries
journal, November 2001
- Tarascon, J.-M.; Armand, M.
- Nature, Vol. 414, Issue 6861, p. 359-367
Na 3 V 2 (PO 4 ) 3 particles partly embedded in carbon nanofibers with superb kinetics for ultra-high power sodium ion batteries
journal, January 2015
- Yang, Junghoon; Han, Dong-Wook; Jo, Mi Ru
- Journal of Materials Chemistry A, Vol. 3, Issue 3
In situ analyses for ion storage materials
journal, January 2016
- Yang, Junghoon; Muhammad, Shoaib; Jo, Mi Ru
- Chemical Society Reviews, Vol. 45, Issue 20
A comprehensive study of the role of transition metals in O3-type layered Na[Ni x Co y Mn z ]O 2 (x = 1/3, 0.5, 0.6, and 0.8) cathodes for sodium-ion batteries
journal, January 2016
- Hwang, Jang-Yeon; Yoon, Chong S.; Belharouak, Ilias
- Journal of Materials Chemistry A, Vol. 4, Issue 46
Layered Li(Ni0.5−xMn0.5−xM2x′)O2 (M′=Co, Al, Ti; x=0, 0.025) cathode materials for Li-ion rechargeable batteries
journal, October 2002
- Kang, S.
- Journal of Power Sources, Vol. 112, Issue 1
The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries
journal, January 2016
- Saubanère, M.; McCalla, E.; Tarascon, J. -M.
- Energy & Environmental Science, Vol. 9, Issue 3
Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries
journal, January 2017
- Xie, Y.; Saubanère, M.; Doublet, M. -L.
- Energy & Environmental Science, Vol. 10, Issue 1
Why LiFePO 4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation
journal, January 2015
- Liu, Xiaosong; Wang, Yung Jui; Barbiellini, Bernardo
- Physical Chemistry Chemical Physics, Vol. 17, Issue 39
Oxygen 1 s x-ray-absorption edges of transition-metal oxides
journal, September 1989
- de Groot, F. M. F.; Grioni, M.; Fuggle, J. C.
- Physical Review B, Vol. 40, Issue 8
Atomic multiplets at the edge of 3 transition metals and the ligand K edge in x-ray absorption spectroscopy of ionic systems
journal, June 2013
- Olalde-Velasco, P.; Jiménez-Mier, J.; Denlinger, J.
- Physical Review B, Vol. 87, Issue 24
Direct probe of Mott-Hubbard to charge-transfer insulator transition and electronic structure evolution in transition-metal systems
journal, June 2011
- Olalde-Velasco, P.; Jiménez-Mier, J.; Denlinger, J. D.
- Physical Review B, Vol. 83, Issue 24
Band gaps and electronic structure of transition-metal compounds
journal, July 1985
- Zaanen, J.; Sawatzky, G. A.; Allen, J. W.
- Physical Review Letters, Vol. 55, Issue 4
Tunable-excitation soft X-ray fluorescence spectroscopy of high-Tc superconductors: an inequivalent-site seeing story
journal, October 2000
- Butorin, Sergei M.; Guo, Jinghua; Wassdahl, Nial
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 110-111
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.
journal, March 2006
- Yoon, Won-Sub; Balasubramanian, Mahalingam; Chung, Kyung Yoon
- ChemInform, Vol. 37, Issue 13