Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode
Abstract
Increasing interest in high-energy lithium-ion batteries has triggered the demand to clarify the reaction mechanism in battery cathodes during high-potential operation. Yet, the reaction mechanism often involves both transition-metal and oxygen activities that remain elusive. Here we report a comprehensive study of both cationic and anionic redox mechanisms of LiNiO2 nearly full delithiation. Selection of pure LiNiO2 removes the complication of multiple transition metals. Using combined X-ray absorption spectroscopy, resonant inelastic X-ray scattering, and operando differential electrochemical mass spectrometry, we are able to clarify the redox reactions of transition metals in the bulk and at the surface, reversible lattice oxygen redox, and irreversible oxygen release associated with surface reactions. Many results introduced here bring attention to different types of oxygen activities and metal-oxygen interactions in layered oxides, which are of crucial importance to the advancement of a Ni-rich layered oxide cathode for high capacity and long cycling performance.
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States)
- Shell International Exploration & Production, Houston, TX (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1594940
- Grant/Contract Number:
- AC02-05CH11231; AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Energy Letters
- Additional Journal Information:
- Journal Volume: 4; Journal Issue: 12; Journal ID: ISSN 2380-8195
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Redox reactions; Oxides; Lattices; Oxygen Oxidation
Citation Formats
Li, Ning, Sallis, Shawn, Papp, Joseph K., Wei, James, McCloskey, Bryan D., Yang, Wanli, and Tong, Wei. Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode. United States: N. p., 2019.
Web. doi:10.1021/acsenergylett.9b02147.
Li, Ning, Sallis, Shawn, Papp, Joseph K., Wei, James, McCloskey, Bryan D., Yang, Wanli, & Tong, Wei. Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode. United States. https://doi.org/10.1021/acsenergylett.9b02147
Li, Ning, Sallis, Shawn, Papp, Joseph K., Wei, James, McCloskey, Bryan D., Yang, Wanli, and Tong, Wei. Thu .
"Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode". United States. https://doi.org/10.1021/acsenergylett.9b02147. https://www.osti.gov/servlets/purl/1594940.
@article{osti_1594940,
title = {Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode},
author = {Li, Ning and Sallis, Shawn and Papp, Joseph K. and Wei, James and McCloskey, Bryan D. and Yang, Wanli and Tong, Wei},
abstractNote = {Increasing interest in high-energy lithium-ion batteries has triggered the demand to clarify the reaction mechanism in battery cathodes during high-potential operation. Yet, the reaction mechanism often involves both transition-metal and oxygen activities that remain elusive. Here we report a comprehensive study of both cationic and anionic redox mechanisms of LiNiO2 nearly full delithiation. Selection of pure LiNiO2 removes the complication of multiple transition metals. Using combined X-ray absorption spectroscopy, resonant inelastic X-ray scattering, and operando differential electrochemical mass spectrometry, we are able to clarify the redox reactions of transition metals in the bulk and at the surface, reversible lattice oxygen redox, and irreversible oxygen release associated with surface reactions. Many results introduced here bring attention to different types of oxygen activities and metal-oxygen interactions in layered oxides, which are of crucial importance to the advancement of a Ni-rich layered oxide cathode for high capacity and long cycling performance.},
doi = {10.1021/acsenergylett.9b02147},
journal = {ACS Energy Letters},
number = 12,
volume = 4,
place = {United States},
year = {2019},
month = {10}
}
Web of Science
Works referenced in this record:
Building better batteries
journal, February 2008
- Armand, M.; Tarascon, J.-M.
- Nature, Vol. 451, Issue 7179, p. 652-657
Structure and electrochemistry of Li1±yNiO2 and a new Li2NiO2 phase with the Ni (OH)2 structure
journal, December 1990
- Dahn, J.
- Solid State Ionics, Vol. 44, Issue 1-2
Electrochemistry and Structural Chemistry of LiNiO[sub 2] (R3m) for 4 Volt Secondary Lithium Cells
journal, January 1993
- Ohzuku, Tsutomu
- Journal of The Electrochemical Society, Vol. 140, Issue 7
Various aspects of LiNiO 2 chemistry: A review
journal, January 2005
- Kalyani, P.; Kalaiselvi, N.
- Science and Technology of Advanced Materials, Vol. 6, Issue 6
Understanding Surface Densified Phases in Ni-Rich Layered Compounds
journal, February 2019
- Xiao, Penghao; Shi, Tan; Huang, Wenxuan
- ACS Energy Letters, Vol. 4, Issue 4
Optimization of the Composition of the Li[sub 1−z]Ni[sub 1+z]O[sub 2] Electrode Materials: Structural, Magnetic, and Electrochemical Studies
journal, January 1996
- Rougier, A.
- Journal of The Electrochemical Society, Vol. 143, Issue 4
A review of Ni-based layered oxides for rechargeable Li-ion batteries
journal, January 2017
- Xu, Jing; Lin, Feng; Doeff, Marca M.
- Journal of Materials Chemistry A, Vol. 5, Issue 3
First-Principles Simulation of the (Li–Ni–Vacancy)O Phase Diagram and Its Relevance for the Surface Phases in Ni-Rich Li-Ion Cathode Materials
journal, September 2017
- Das, Hena; Urban, Alexander; Huang, Wenxuan
- Chemistry of Materials, Vol. 29, Issue 18
There and Back Again-The Journey of LiNiO 2 as a Cathode Active Material
journal, May 2019
- Bianchini, Matteo; Roca-Ayats, Maria; Hartmann, Pascal
- Angewandte Chemie International Edition, Vol. 58, Issue 31
Updating the Structure and Electrochemistry of Li x NiO 2 for 0 ≤ x ≤ 1
journal, January 2018
- Li, Hongyang; Zhang, Ning; Li, Jing
- Journal of The Electrochemical Society, Vol. 165, Issue 13
Structural Stability of LiNiO 2 Cycled above 4.2 V
journal, April 2017
- Yoon, Chong S.; Jun, Do-Wook; Myung, Seung-Taek
- ACS Energy Letters, Vol. 2, Issue 5
Synthesis of LiNiO 2 powders by a sol–gel method
journal, January 1997
- Sun, Yang-Kook; Sun, Yang-Kook
- Journal of Materials Science Letters, Vol. 16, Issue 1
Preparation and characterization of LiNiO2 synthesized from Ni(OH)2 and LiOH·H2O
journal, June 1999
- Yang, H. X.; Dong, Q. F.; Hu, X. H.
- Journal of Power Sources, Vol. 79, Issue 2
Understanding the Degradation Mechanism of Lithium Nickel Oxide Cathodes for Li-Ion Batteries
journal, November 2016
- Xu, Jing; Hu, Enyuan; Nordlund, Dennis
- ACS Applied Materials & Interfaces, Vol. 8, Issue 46
Phase Transformation Behavior and Stability of LiNiO 2 Cathode Material for Li‐Ion Batteries Obtained from In Situ Gas Analysis and Operando X‐Ray Diffraction
journal, April 2019
- de Biasi, Lea; Schiele, Alexander; Roca‐Ayats, Maria
- ChemSusChem, Vol. 12, Issue 10
Kinetic Stability of Bulk LiNiO 2 and Surface Degradation by Oxygen Evolution in LiNiO 2 -Based Cathode Materials
journal, November 2018
- Kong, Fantai; Liang, Chaoping; Wang, Luhua
- Advanced Energy Materials, Vol. 9, Issue 2
First-principles calculations of lithium ordering and phase stability on
journal, August 2002
- Arroyo y. de Dompablo, M. E.; Van der Ven, A.; Ceder, G.
- Physical Review B, Vol. 66, Issue 6
Compositionally and structurally redesigned high-energy Ni-rich layered cathode for next-generation lithium batteries
journal, March 2019
- Kim, Un-Hyuck; Kim, Jae-Hyung; Hwang, Jang-Yeon
- Materials Today, Vol. 23
Extracting maximum capacity from Ni-rich Li[Ni 0.95 Co 0.025 Mn 0.025 ]O 2 cathodes for high-energy-density lithium-ion batteries
journal, January 2018
- Yoon, Chong S.; Ryu, Hoon-Hee; Park, Geon-Tae
- Journal of Materials Chemistry A, Vol. 6, Issue 9
Is Cobalt Needed in Ni-Rich Positive Electrode Materials for Lithium Ion Batteries?
journal, January 2019
- Li, Hongyang; Cormier, Marc; Zhang, Ning
- Journal of The Electrochemical Society, Vol. 166, Issue 4
Structural, Electrochemical, and Thermal Properties of Nickel-Rich LiNi x Mn y Co z O 2 Materials
journal, November 2018
- Zhang, Ning; Li, Jing; Li, Hongyang
- Chemistry of Materials, Vol. 30, Issue 24
Nickel-Rich and Lithium-Rich Layered Oxide Cathodes: Progress and Perspectives
journal, October 2015
- Manthiram, Arumugam; Knight, James C.; Myung, Seung-Taek
- Advanced Energy Materials, Vol. 6, Issue 1
Changes in electronic structure of the electrochemically Li-ion deintercalated LiNiO2 system investigated by soft X-ray absorption spectroscopy
journal, December 2006
- Yoon, Won-Sub; Chung, Kyung Yoon; McBreen, James
- Journal of Power Sources, Vol. 163, Issue 1
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
In Situ Structural and Electrochemical Study of Ni1−xCoxO2 Metastable Oxides Prepared by Soft Chemistry
journal, October 1999
- Tarascon, J. M.; Vaughan, G.; Chabre, Y.
- Journal of Solid State Chemistry, Vol. 147, Issue 1
Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides
journal, July 1997
- Aydinol, M. K.; Kohan, A. F.; Ceder, G.
- Physical Review B, Vol. 56, Issue 3
Identification of cathode materials for lithium batteries guided by first-principles calculations
journal, April 1998
- Ceder, G.; Chiang, Y. -M.; Sadoway, D. R.
- Nature, Vol. 392, Issue 6677
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
Different oxygen redox participation for bulk and surface: A possible global explanation for the cycling mechanism of Li1.20Mn0.54Co0.13Ni0.13O2
journal, August 2013
- Koga, Hideyuki; Croguennec, Laurence; Ménétrier, Michel
- Journal of Power Sources, Vol. 236
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
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
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
Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries
journal, April 2018
- Assat, Gaurav; Tarascon, Jean-Marie
- Nature Energy, Vol. 3, Issue 5
Elucidating anionic oxygen activity in lithium-rich layered oxides
journal, March 2018
- Xu, Jing; Sun, Meiling; Qiao, Ruimin
- Nature Communications, Vol. 9, Issue 1
Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides
journal, December 2017
- Gent, William E.; Lim, Kipil; Liang, Yufeng
- Nature Communications, Vol. 8, Issue 1
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
Anionic Redox in Rechargeable Lithium Batteries
journal, June 2017
- Li, Biao; Xia, Dingguo
- Advanced Materials, Vol. 29, Issue 48
Unexpectedly high energy density of a Li-Ion battery by oxygen redox in LiNiO2 cathode: First-principles study
journal, January 2019
- Choi, Daehyeon; Kang, Joonhee; Han, Byungchan
- Electrochimica Acta, Vol. 294
Elucidation of the surface characteristics and electrochemistry of high-performance LiNiO 2
journal, January 2016
- Xu, Jing; Lin, Feng; Nordlund, Dennis
- Chemical Communications, Vol. 52, Issue 22
Self-Passivation of a LiNiO 2 Cathode for a Lithium-Ion Battery through Zr Doping
journal, June 2018
- Yoon, Chong S.; Kim, Un-Hyuck; Park, Geon-Tae
- ACS Energy Letters, Vol. 3, Issue 7
X-ray absorption spectroscopy to analyze nuclear geometry and electronic structure of biological metal centers?potential and questions examined with special focus on the tetra-nuclear manganese complex of oxygenic photosynthesis
journal, July 2003
- Dau, Holger; Liebisch, Peter; Haumann, Michael
- Analytical and Bioanalytical Chemistry, Vol. 376, Issue 5
Understanding the Rate Capability of High-Energy-Density Li-Rich Layered Li 1.2 Ni 0.15 Co 0.1 Mn 0.55 O 2 Cathode Materials
journal, December 2013
- Yu, Xiqian; Lyu, Yingchun; Gu, Lin
- Advanced Energy Materials, Vol. 4, Issue 5
Tuning P2-Structured Cathode Material by Na-Site Mg Substitution for Na-Ion Batteries
journal, December 2018
- Wang, Qin-Chao; Meng, Jing-Ke; Yue, Xin-Yang
- Journal of the American Chemical Society, Vol. 141, Issue 2
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
Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials
journal, March 2018
- Tian, Chixia; Xu, Yahong; Nordlund, Dennis
- Joule, Vol. 2, Issue 3
Electrochemical Characteristics of Layered Transition Metal Oxide Cathode Materials for Lithium Ion Batteries: Surface, Bulk Behavior, and Thermal Properties
journal, December 2017
- Tian, Chixia; Lin, Feng; Doeff, Marca M.
- Accounts of Chemical Research, Vol. 51, 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
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
Direct evidence of gradient Mn(II) evolution at charged states in LiNi0.5Mn1.5O4 electrodes with capacity fading
journal, January 2015
- Qiao, Ruimin; Wang, Yuesheng; Olalde-Velasco, Paul
- Journal of Power Sources, Vol. 273
Spectroscopic Signature of Oxidized Oxygen States in Peroxides
journal, October 2018
- Zhuo, Zengqing; Pemmaraju, Chaitanya Das; Vinson, John
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 21
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
Fingerprint Oxygen Redox Reactions in Batteries through High-Efficiency Mapping of Resonant Inelastic X-ray Scattering
journal, January 2019
- Wu, Jinpeng; Li, Qinghao; Sallis, Shawn
- Condensed Matter, Vol. 4, Issue 1
Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen
journal, April 2018
- Mahne, Nika; Renfrew, Sara E.; McCloskey, Bryan D.
- Angewandte Chemie International Edition, Vol. 57, Issue 19
Anionic redox processes for electrochemical devices
journal, January 2016
- Grimaud, A.; Hong, W. T.; Shao-Horn, Y.
- Nature Materials, Vol. 15, Issue 2
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
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
Nickel-Rich Layered Cathode Materials for Automotive Lithium-Ion Batteries: Achievements and Perspectives
journal, December 2016
- Myung, Seung-Taek; Maglia, Filippo; Park, Kang-Joon
- ACS Energy Letters, Vol. 2, Issue 1
Works referencing / citing this record:
In situ X-ray Raman spectroscopy and magnetic susceptibility study on the Li[Li 0.15 Mn 1.85 ]O 4 oxygen anion redox reaction
journal, January 2020
- Mukai, Kazuhiko; Nonaka, Takamasa; Uyama, Takeshi
- Chemical Communications, Vol. 56, Issue 11