Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2
Abstract
Nickel-rich layered materials are emerging as cathodes of choice for next-generation high energy density lithium ion batteries intended for electric vehicles. This is because of their higher practical capacities compared to compositions with lower Ni content, as well as the potential for lower raw materials cost. The higher practical capacity of these materials comes at the expense of shorter cycle life, however, due to undesirable structure and chemical transformations, especially at particle surfaces. To understand these changes more fully, the charge compensation mechanism and bulk and surface structural changes of LiNi0.6Mn0.2Co0.2O2 were probed using synchrotron techniques and electron energy loss spectroscopy in this study. In the bulk, both the crystal and electronic structure changes are reversible upon cycling to high voltages, whereas particle surfaces undergo significant reduction and structural reconstruction. While Ni is the major contributor to charge compensation, Co and O (through transition metal-oxygen hybridization) are also redox active. An important finding from depth-dependent transition metal L-edge and O K-edge X-ray spectroscopy is that oxygen redox activity exhibits depth-dependent characteristics. This likely drives the structural and chemical transformations observed at particle surfaces in Ni-rich materials.
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (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:
- 1425689
- Alternate Identifier(s):
- OSTI ID: 1458538; OSTI ID: 1466615; OSTI ID: 1466712
- Report Number(s):
- BNL-207961-2018-JAAM
Journal ID: ISSN 0013-4651; /jes/165/3/A696.atom
- Grant/Contract Number:
- AC02-05CH11231; SC0012704; AC02-76SF00515
- Resource Type:
- Published Article
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society Journal Volume: 165 Journal Issue: 3; Journal ID: ISSN 0013-4651
- Publisher:
- IOP Publishing - The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; cathode; Li-ion battery; NMC; 36 MATERIALS SCIENCE; Redox Behavior
Citation Formats
Tian, Chixia, Nordlund, Dennis, Xin, Huolin L., Xu, Yahong, Liu, Yijin, Sokaras, Dimosthenis, Lin, Feng, and Doeff, Marca M.. Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2. United States: N. p., 2018.
Web. doi:10.1149/2.1021803jes.
Tian, Chixia, Nordlund, Dennis, Xin, Huolin L., Xu, Yahong, Liu, Yijin, Sokaras, Dimosthenis, Lin, Feng, & Doeff, Marca M.. Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2. United States. https://doi.org/10.1149/2.1021803jes
Tian, Chixia, Nordlund, Dennis, Xin, Huolin L., Xu, Yahong, Liu, Yijin, Sokaras, Dimosthenis, Lin, Feng, and Doeff, Marca M.. Thu .
"Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2". United States. https://doi.org/10.1149/2.1021803jes.
@article{osti_1425689,
title = {Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2},
author = {Tian, Chixia and Nordlund, Dennis and Xin, Huolin L. and Xu, Yahong and Liu, Yijin and Sokaras, Dimosthenis and Lin, Feng and Doeff, Marca M.},
abstractNote = {Nickel-rich layered materials are emerging as cathodes of choice for next-generation high energy density lithium ion batteries intended for electric vehicles. This is because of their higher practical capacities compared to compositions with lower Ni content, as well as the potential for lower raw materials cost. The higher practical capacity of these materials comes at the expense of shorter cycle life, however, due to undesirable structure and chemical transformations, especially at particle surfaces. To understand these changes more fully, the charge compensation mechanism and bulk and surface structural changes of LiNi0.6Mn0.2Co0.2O2 were probed using synchrotron techniques and electron energy loss spectroscopy in this study. In the bulk, both the crystal and electronic structure changes are reversible upon cycling to high voltages, whereas particle surfaces undergo significant reduction and structural reconstruction. While Ni is the major contributor to charge compensation, Co and O (through transition metal-oxygen hybridization) are also redox active. An important finding from depth-dependent transition metal L-edge and O K-edge X-ray spectroscopy is that oxygen redox activity exhibits depth-dependent characteristics. This likely drives the structural and chemical transformations observed at particle surfaces in Ni-rich materials.},
doi = {10.1149/2.1021803jes},
journal = {Journal of the Electrochemical Society},
number = 3,
volume = 165,
place = {United States},
year = {2018},
month = {2}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1149/2.1021803jes
https://doi.org/10.1149/2.1021803jes
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 97 works
Citation information provided by
Web of Science
Web of Science
Figures / Tables:
Figure 1: (a) SEM images of secondary particles and (inset) primary particles of NMC-622 prepared by spray pyrolysis. (b) XRD pattern with Rietveld refinement. (c) High-resolution Z-contrast ADF-STEM image of NMC-622 primary particle. (d) EELS survey image and (e) EELS spectra integrated from surface to bulk (red arrow direction) ofmore »
All figures and tables
(7 total)
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Microscopy and Spectroscopy of Lithium Nickel Oxide-Based Particles Used in High Power Lithium-Ion Cells
journal, January 2003
- Abraham, D. P.; Twesten, R. D.; Balasubramanian, M.
- Journal of The Electrochemical Society, Vol. 150, Issue 11
Possibility for an intermediate-spin ground state in the charge-transfer material
journal, May 1995
- Potze, R.; Sawatzky, G.; Abbate, M.
- Physical Review B, Vol. 51, Issue 17, p. 11501-11506
Estimating Hybridization of Transition Metal and Oxygen States in Perovskites from O K -edge X-ray Absorption Spectroscopy
journal, January 2014
- Suntivich, Jin; Hong, Wesley T.; Lee, Yueh-Lin
- The Journal of Physical Chemistry C, Vol. 118, 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
Investigation of the Local Structure of the LiNi[sub 0.5]Mn[sub 0.5]O[sub 2] Cathode Material during Electrochemical Cycling by X-Ray Absorption and NMR Spectroscopy
journal, January 2002
- Yoon, Won-Sub; Paik, Younkee; Yang, Xiao-Qing
- Electrochemical and Solid-State Letters, Vol. 5, Issue 11
Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries
journal, January 2016
- Lin, Feng; Nordlund, Dennis; Li, Yuyi
- Nature Energy, Vol. 1, Issue 1
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
Aliovalent titanium substitution in layered mixed Li Ni–Mn–Co oxides for lithium battery applications
journal, January 2011
- Kam, Kinson C.; Doeff, Marca M.
- Journal of Materials Chemistry, Vol. 21, Issue 27
Atomic Insights into the Enhanced Surface Stability in High Voltage Cathode Materials by Ultrathin Coating
journal, January 2017
- Fang, Xin; Lin, Feng; Nordlund, Dennis
- Advanced Functional Materials, Vol. 27, Issue 7
Local orbital occupation and energy levels of Co in : A soft x-ray absorption study
journal, March 2010
- Lin, H. -J.; Chin, Y. Y.; Hu, Z.
- Physical Review B, Vol. 81, Issue 11
Soft X-Ray Absorption Spectroscopic Study of a LiNi[sub 0.5]Mn[sub 0.5]O[sub 2] Cathode during Charge
journal, January 2004
- Yoon, Won-Sub; Balasubramanian, Mahalingam; Yang, Xiao-Qing
- Journal of The Electrochemical Society, Vol. 151, Issue 2
2 p x-ray absorption of 3 d transition-metal compounds: An atomic multiplet description including the crystal field
journal, September 1990
- de Groot, F. M. F.; Fuggle, J. C.; Thole, B. T.
- Physical Review B, Vol. 42, Issue 9
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
Changes in electronic structure by Li ion deintercalation in LiNiO2 from nickel L-edge and O K-edge XANES
journal, July 2001
- Uchimoto, Yoshiharu; Sawada, Hiroshi; Yao, Takeshi
- Journal of Power Sources, Vol. 97-98
Recent progress in cathode materials research for advanced lithium ion batteries
journal, May 2012
- Xu, Bo; Qian, Danna; Wang, Ziying
- Materials Science and Engineering: R: Reports, Vol. 73, Issue 5-6
Li-ion battery materials: present and future
journal, June 2015
- Nitta, Naoki; Wu, Feixiang; Lee, Jung Tae
- Materials Today, Vol. 18, Issue 5
Impedance Studies on the Capacity Fading Mechanism of Li(Ni 0.5 Co 0.2 Mn 0.3 )O 2 Cathode with High-Voltage and High-Temperature
journal, January 2015
- Zhao, Xing; Zhuang, Quan-Chao; Wu, Chao
- Journal of The Electrochemical Society, Vol. 162, Issue 14
Nanoporous spherical LiFePO4 for high performance cathodes
journal, January 2011
- Liu, Jun; Conry, Thomas E.; Song, Xiangyun
- Energy & Environmental Science, Vol. 4, Issue 3
Charge Compensation Mechanism during Cycles in Fe-Containing Li 2 MnO 3 Cathode for High Energy Density and Low-Cost Lithium-Ion Batteries
journal, January 2016
- Yuge, Ryota; Toda, Akio; Kuroshima, Sadanori
- Electrochimica Acta, Vol. 189
Influence of synthesis conditions on the surface passivation and electrochemical behavior of layered cathode materials
journal, January 2014
- Lin, Feng; Nordlund, Dennis; Pan, Taijun
- J. Mater. Chem. A, Vol. 2, Issue 46
Electrochemical and Physical Properties of Ti-Substituted Layered Nickel Manganese Cobalt Oxide (NMC) Cathode Materials
journal, January 2012
- Kam, Kinson C.; Mehta, Apurva; Heron, John T.
- Journal of The Electrochemical Society, Vol. 159, Issue 8
Electronic structural changes of the electrochemically Li-ion deintercalated LiNi0.8Co0.15Al0.05O2 cathode material investigated by X-ray absorption spectroscopy
journal, December 2007
- Yoon, Won-Sub; Chung, Kyung Yoon; McBreen, James
- Journal of Power Sources, Vol. 174, Issue 2
The Impact of Electrolyte Additives and Upper Cut-off Voltage on the Formation of a Rocksalt Surface Layer in LiNi 0.8 Mn 0.1 Co 0.1 O 2 Electrodes
journal, January 2017
- Li, Jing; Liu, Hanshuo; Xia, Jian
- Journal of The Electrochemical Society, Vol. 164, Issue 4
Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches
journal, February 2015
- Hausbrand, R.; Cherkashinin, G.; Ehrenberg, H.
- Materials Science and Engineering: B, Vol. 192
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
Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries
journal, July 2013
- Noh, Hyung-Joo; Youn, Sungjune; Yoon, Chong Seung
- Journal of Power Sources, Vol. 233
Computational and Experimental Investigation of Ti Substitution in Li 1 (Ni x Mn x Co 1–2 x – y Ti y )O 2 for Lithium Ion Batteries
journal, October 2014
- Markus, Isaac M.; Lin, Feng; Kam, Kinson C.
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 21
Nickel-Rich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries
journal, March 2015
- Liu, Wen; Oh, Pilgun; Liu, Xien
- Angewandte Chemie International Edition, Vol. 54, Issue 15
XAS Investigation of Inhomogeneous Metal-Oxygen Bond Covalency in Bulk and Surface for Charge Compensation in Li-Ion Battery Cathode Li[Ni[sub 1∕3]Co[sub 1∕3]Mn[sub 1∕3]]O[sub 2] Material
journal, January 2005
- Kim, Min Gyu; Shin, Hyun Joon; Kim, Jung-Hyun
- Journal of The Electrochemical Society, Vol. 152, 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
Development of Microstrain in Aged Lithium Transition Metal Oxides
journal, June 2014
- Lee, Eung-Ju; Chen, Zonghai; Noh, Hyung-Ju
- Nano Letters, Vol. 14, Issue 8
Tailoring the surface properties of LiNi 0.4 Mn 0.4 Co 0.2 O 2 by titanium substitution for improved high voltage cycling performance
journal, January 2015
- Wolff-Goodrich, Silas; Lin, Feng; Markus, Isaac M.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 34
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
Stabilizing nickel-rich layered cathode materials by a high-charge cation doping strategy: zirconium-doped LiNi 0.6 Co 0.2 Mn 0.2 O 2
journal, January 2016
- Schipper, Florian; Dixit, Mudit; Kovacheva, Daniela
- Journal of Materials Chemistry A, Vol. 4, Issue 41
Review—High-Capacity Li[Ni 1- x Co x /2 Mn x /2 ]O 2 ( x = 0.1, 0.05, 0) Cathodes for Next-Generation Li-Ion Battery
journal, January 2015
- Yoon, Chong S.; Choi, Moon Ho; Lim, Byung-Beom
- Journal of The Electrochemical Society, Vol. 162, Issue 14
A Consideration of Electrolyte Additives for LiNi 0.5 Mn 1.5 O 4 /Li 4 Ti 5 O 12 Li-Ion Cells
journal, January 2013
- Li, S. R.; Sinha, N. N.; Chen, C. H.
- Journal of The Electrochemical Society, Vol. 160, Issue 11
Self-Terminated Artificial SEI Layer for Nickel-Rich Layered Cathode Material via Mixed Gas Chemical Vapor Deposition
journal, October 2015
- Son, In Hyuk; Park, Jong Hwan; Kwon, Soonchul
- Chemistry of Materials, Vol. 27, Issue 21
Material/element-dependent fluorescence-yield modes on soft X-ray absorption spectroscopy of cathode materials for Li-ion batteries
journal, March 2016
- Asakura, Daisuke; Hosono, Eiji; Nanba, Yusuke
- AIP Advances, Vol. 6, Issue 3
Through the eyes of a chemist
journal, December 2015
- Francl, Michelle
- Nature Chemistry, Vol. 8, 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
Spherical nanoporous LiCoPO4/C composites as high performance cathode materials for rechargeable lithium-ion batteries
journal, January 2011
- Liu, Jun; Conry, Thomas E.; Song, Xiangyun
- Journal of Materials Chemistry, Vol. 21, Issue 27
Surface changes on LiNi0.8Co0.2O2 particles during testing of high-power lithium-ion cells
journal, August 2002
- Abraham, D. P.; Twesten, R. D.; Balasubramanian, M.
- Electrochemistry Communications, Vol. 4, Issue 8
A New Type of Protective Surface Layer for High-Capacity Ni-Based Cathode Materials: Nanoscaled Surface Pillaring Layer
journal, February 2013
- Cho, Yonghyun; Oh, Pilgun; Cho, Jaephil
- Nano Letters, Vol. 13, Issue 3
Understanding the Degradation Mechanisms of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Material in Lithium Ion Batteries
journal, August 2013
- Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun
- Advanced Energy Materials, Vol. 4, Issue 1
Synthesis, structural, magnetic and electrochemical properties of LiNi1/3Mn1/3Co1/3O2 prepared by a sol–gel method using table sugar as chelating agent
journal, December 2013
- Kızıltaş-Yavuz, Nilüfer; Herklotz, Markus; Hashem, Ahmed M.
- Electrochimica Acta, Vol. 113
High-energy cathode material for long-life and safe lithium batteries
journal, March 2009
- Sun, Yang-Kook; Myung, Seung-Taek; Park, Byung-Chun
- Nature Materials, Vol. 8, Issue 4
Diagnosis of power fade mechanisms in high-power lithium-ion cells
journal, June 2003
- Abraham, D. P.; Liu, J.; Chen, C. H.
- Journal of Power Sources, Vol. 119-121
A comparative study on structural changes of LiCo1/3Ni1/3Mn1/3O2 and LiNi0.8Co0.15Al0.05O2 during first charge using in situ XRD
journal, August 2006
- Yoon, Won-Sub; Chung, Kyung Yoon; McBreen, James
- Electrochemistry Communications, Vol. 8, Issue 8
Direct observation of reversible oxygen anion redox reaction in Li-rich manganese oxide, Li 2 MnO 3 , studied by soft X-ray absorption spectroscopy
journal, January 2016
- Oishi, Masatsugu; Yamanaka, Keisuke; Watanabe, Iwao
- Journal of Materials Chemistry A, Vol. 4, Issue 23
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
A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries
journal, January 2017
- Manthiram, Arumugam; Song, Bohang; Li, Wangda
- Energy Storage Materials, Vol. 6
Study of the Failure Mechanisms of LiNi 0.8 Mn 0.1 Co 0.1 O 2 Cathode Material for Lithium Ion Batteries
journal, January 2015
- Li, Jing; Downie, Laura E.; Ma, Lin
- Journal of The Electrochemical Society, Vol. 162, Issue 7
New findings on the phase transitions in Li1−xNiO2: in situ synchrotron X-ray diffraction studies
journal, June 1999
- Yang, X. Q.; Sun, X.; McBreen, J.
- Electrochemistry Communications, Vol. 1, Issue 6
Electronic structure variation of the surface and bulk of a LiNi 0.5 Mn 1.5 O 4 cathode as a function of state of charge: X-ray absorption spectroscopic study
journal, January 2014
- Zhou, Jigang; Hong, Da; Wang, Jian
- Phys. Chem. Chem. Phys., Vol. 16, Issue 27
Works referencing / citing this record:
High‐Voltage Charging‐Induced Strain, Heterogeneity, and Micro‐Cracks in Secondary Particles of a Nickel‐Rich Layered Cathode Material
journal, March 2019
- Mao, Yuwei; Wang, Xuelong; Xia, Sihao
- Advanced Functional Materials, Vol. 29, Issue 18
Surface Degradation and Chemical Electrolyte Oxidation Induced by the Oxygen Released from Layered Oxide Cathodes in Li−Ion Batteries
journal, March 2019
- Leanza, Daniela; Mirolo, Marta; Vaz, Carlos A. F.
- Batteries & Supercaps, Vol. 2, Issue 5
Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials
journal, January 2020
- Xu, Zhengrui; Jiang, Zhisen; Kuai, Chunguang
- Nature Communications, Vol. 11, Issue 1
Chemomechanical behaviors of layered cathode materials in alkali metal ion batteries
journal, January 2018
- Xu, Zhengrui; Rahman, Muhammad Mominur; Mu, Linqin
- Journal of Materials Chemistry A, Vol. 6, Issue 44
Single-crystal based studies for correlating the properties and high-voltage performance of Li[Ni x Mn y Co 1−x−y ]O 2 cathodes
journal, January 2019
- Zhu, Jian; Chen, Guoying
- Journal of Materials Chemistry A, Vol. 7, Issue 10
Oriented porous LLZO 3D structures obtained by freeze casting for battery applications
journal, January 2019
- Shen, Hao; Yi, Eongyu; Amores, Marco
- Journal of Materials Chemistry A, Vol. 7, Issue 36
Structural Degradation of Layered Cathode Materials in Lithium-Ion Batteries Induced by Ball Milling
journal, January 2019
- Pan, Taijun; Alvarado, Judith; Zhu, Jian
- Journal of The Electrochemical Society, Vol. 166, Issue 10
The Role of Electrolyte in the First-Cycle Transformations of LiNi 0.6 Mn 0.2 Co 0.2 O 2
journal, January 2019
- Renfrew, Sara E.; McCloskey, Bryan D.
- Journal of The Electrochemical Society, Vol. 166, Issue 13
Degradation and Aging Routes of Ni-Rich Cathode Based Li-Ion Batteries
journal, January 2020
- Teichert, Philipp; Eshetu, Gebrekidan Gebresilassie; Jahnke, Hannes
- Batteries, Vol. 6, Issue 1
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.