Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide
Abstract
Lithium-rich nickel-manganese-cobalt (LirNMC) layered material is a promising cathode for lithium-ion batteries thanks to its large energy density enabled by coexisting cation and anion redox activities. It however suffers from a voltage decay upon cycling, urging for an in-depth understanding of the particle-level structure and chemical complexity. In this work, we investigate the Li1.2Ni0.13Mn0.54Co0.13O2 particles morphologically, compositionally, and chemically in three-dimensions. While the composition is generally uniform throughout the particle, the charging induces a strong depth dependency in transition metal valence. Such a valence stratification phenomenon is attributed to the nature of oxygen redox which is very likely mostly associated with Mn. The depth-dependent chemistry could be modulated by the particles’ core-multi-shell morphology, suggesting a structural-chemical interplay. These findings highlight the possibility of introducing a chemical gradient to address the oxygen-loss-induced voltage fade in LirNMC layered materials.
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES); National Key Research and Development Program of China; National Science Foundation (NSF)
- OSTI Identifier:
- 1735389
- Alternate Identifier(s):
- OSTI ID: 1737442; OSTI ID: 1779170
- Report Number(s):
- BNL-220716-2020-JAAM
Journal ID: ISSN 2041-1723; 6342; PII: 20198
- Grant/Contract Number:
- SC0012704; AC02-76SF00515; 2016YFA0400900; ECCS-1542152
- Resource Type:
- Published Article
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Name: Nature Communications Journal Volume: 11 Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; batteries; lithium-rich layered; spectro-imaging
Citation Formats
Zhang, Jin, Wang, Qinchao, Li, Shaofeng, Jiang, Zhisen, Tan, Sha, Wang, Xuelong, Zhang, Kai, Yuan, Qingxi, Lee, Sang-Jun, Titus, Charles J., Irwin, Kent D., Nordlund, Dennis, Lee, Jun-Sik, Pianetta, Piero, Yu, Xiqian, Xiao, Xianghui, Yang, Xiao-Qing, Hu, Enyuan, and Liu, Yijin. Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide. United Kingdom: N. p., 2020.
Web. doi:10.1038/s41467-020-20198-w.
Zhang, Jin, Wang, Qinchao, Li, Shaofeng, Jiang, Zhisen, Tan, Sha, Wang, Xuelong, Zhang, Kai, Yuan, Qingxi, Lee, Sang-Jun, Titus, Charles J., Irwin, Kent D., Nordlund, Dennis, Lee, Jun-Sik, Pianetta, Piero, Yu, Xiqian, Xiao, Xianghui, Yang, Xiao-Qing, Hu, Enyuan, & Liu, Yijin. Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide. United Kingdom. https://doi.org/10.1038/s41467-020-20198-w
Zhang, Jin, Wang, Qinchao, Li, Shaofeng, Jiang, Zhisen, Tan, Sha, Wang, Xuelong, Zhang, Kai, Yuan, Qingxi, Lee, Sang-Jun, Titus, Charles J., Irwin, Kent D., Nordlund, Dennis, Lee, Jun-Sik, Pianetta, Piero, Yu, Xiqian, Xiao, Xianghui, Yang, Xiao-Qing, Hu, Enyuan, and Liu, Yijin. Fri .
"Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide". United Kingdom. https://doi.org/10.1038/s41467-020-20198-w.
@article{osti_1735389,
title = {Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide},
author = {Zhang, Jin and Wang, Qinchao and Li, Shaofeng and Jiang, Zhisen and Tan, Sha and Wang, Xuelong and Zhang, Kai and Yuan, Qingxi and Lee, Sang-Jun and Titus, Charles J. and Irwin, Kent D. and Nordlund, Dennis and Lee, Jun-Sik and Pianetta, Piero and Yu, Xiqian and Xiao, Xianghui and Yang, Xiao-Qing and Hu, Enyuan and Liu, Yijin},
abstractNote = {Lithium-rich nickel-manganese-cobalt (LirNMC) layered material is a promising cathode for lithium-ion batteries thanks to its large energy density enabled by coexisting cation and anion redox activities. It however suffers from a voltage decay upon cycling, urging for an in-depth understanding of the particle-level structure and chemical complexity. In this work, we investigate the Li1.2Ni0.13Mn0.54Co0.13O2 particles morphologically, compositionally, and chemically in three-dimensions. While the composition is generally uniform throughout the particle, the charging induces a strong depth dependency in transition metal valence. Such a valence stratification phenomenon is attributed to the nature of oxygen redox which is very likely mostly associated with Mn. The depth-dependent chemistry could be modulated by the particles’ core-multi-shell morphology, suggesting a structural-chemical interplay. These findings highlight the possibility of introducing a chemical gradient to address the oxygen-loss-induced voltage fade in LirNMC layered materials.},
doi = {10.1038/s41467-020-20198-w},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United Kingdom},
year = {Fri Dec 11 00:00:00 EST 2020},
month = {Fri Dec 11 00:00:00 EST 2020}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1038/s41467-020-20198-w
https://doi.org/10.1038/s41467-020-20198-w
Other availability
Search WorldCat to find libraries that may hold this journal
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:
Chemomechanical interplay of layered cathode materials undergoing fast charging in lithium batteries
journal, November 2018
- Xia, Sihao; Mu, Linqin; Xu, Zhengrui
- Nano Energy, Vol. 53
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
The Origin of Capacity Fade in the Li 2 MnO 3 ·Li M O 2 ( M = Li, Ni, Co, Mn) Microsphere Positive Electrode: An Operando Neutron Diffraction and Transmission X-ray Microscopy Study
journal, July 2016
- Chen, Chih-Jung; Pang, Wei Kong; Mori, Tatsuhiro
- Journal of the American Chemical Society, Vol. 138, Issue 28
Short- and Long-Range Order in the Positive Electrode Material, Li(NiMn) 0.5 O 2 : A Joint X-ray and Neutron Diffraction, Pair Distribution Function Analysis and NMR Study
journal, May 2005
- Bréger, Julien; Dupré, Nicolas; Chupas, Peter J.
- Journal of the American Chemical Society, Vol. 127, Issue 20
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
Soft X-ray spectroscopy with transition-edge sensors at Stanford Synchrotron Radiation Lightsource beamline 10-1
journal, November 2019
- Lee, Sang-Jun; Titus, Charles J.; Alonso Mori, Roberto
- Review of Scientific Instruments, Vol. 90, Issue 11
Charging Up Lithium-Ion Battery Cathodes
journal, March 2018
- Johnson, Christopher S.
- Joule, Vol. 2, Issue 3
Quantification of Heterogeneous Degradation in Li‐Ion Batteries
journal, May 2019
- Yang, Yang; Xu, Rong; Zhang, Kai
- Advanced Energy Materials, Vol. 9, Issue 25
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
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
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
Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials
journal, July 2018
- Mu, Linqin; Yuan, Qingxi; Tian, Chixia
- Nature Communications, Vol. 9, Issue 1
Insitu nanotomography and operando transmission X-ray microscopy of micron-sized Ge particles
journal, January 2014
- Weker, J. Nelson; Liu, N.; Misra, S.
- Energy Environ. Sci., Vol. 7, Issue 8
Thermally driven mesoscale chemomechanical interplay in Li 0.5 Ni 0.6 Mn 0.2 Co 0.2 O 2 cathode materials
journal, January 2018
- Wei, Chenxi; Zhang, Yan; Lee, Sang-Jun
- Journal of Materials Chemistry A, Vol. 6, Issue 45
Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries
journal, January 2018
- Tsai, Ping-Chun; Wen, Bohua; Wolfman, Mark
- Energy & Environmental Science, Vol. 11, Issue 4
Structural absorption by barbule microstructures of super black bird of paradise feathers
journal, January 2018
- McCoy, Dakota E.; Feo, Teresa; Harvey, Todd Alan
- Nature Communications, Vol. 9, Issue 1
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
Li-Rich Layered Oxides and Their Practical Challenges: Recent Progress and Perspectives
journal, March 2019
- Hu, Sijiang; Pillai, Anoop. S.; Liang, Gemeng
- Electrochemical Energy Reviews, Vol. 2, Issue 2
Origin of voltage decay in high-capacity layered oxide electrodes
journal, December 2014
- Sathiya, M.; Abakumov, A. M.; Foix, D.
- Nature Materials, Vol. 14, Issue 2
Thermal stress-induced charge and structure heterogeneity in emerging cathode materials
journal, May 2020
- Alvarado, Judith; Wei, Chenxi; Nordlund, Dennis
- Materials Today, Vol. 35
Persistent State-of-Charge Heterogeneity in Relaxed, Partially Charged Li 1− x Ni 1/3 Co 1/3 Mn 1/3 O 2 Secondary Particles
journal, May 2016
- Gent, William E.; Li, Yiyang; Ahn, Sungjin
- Advanced Materials, Vol. 28, Issue 31
Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling
journal, July 2014
- Yang, Feifei; Liu, Yijin; Martha, Surendra K.
- Nano Letters, Vol. 14, Issue 8
Mesoscale Chemomechanical Interplay of the LiNi 0.8 Co 0.15 Al 0.05 O 2 Cathode in Solid-State Polymer Batteries
journal, December 2018
- Besli, Münir M.; Xia, Sihao; Kuppan, Saravanan
- Chemistry of Materials, Vol. 31, Issue 2
Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2
journal, January 2018
- Tian, Chixia; Nordlund, Dennis; Xin, Huolin L.
- Journal of The Electrochemical Society, Vol. 165, Issue 3
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
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
Direct Atomic-Resolution Observation of Two Phases in the Li 1.2 Mn 0.567 Ni 0.166 Co 0.067 O 2 Cathode Material for Lithium-Ion Batteries
journal, April 2013
- Yu, Haijun; Ishikawa, Ryo; So, Yeong-Gi
- Angewandte Chemie International Edition, Vol. 52, Issue 23
Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes
journal, January 2020
- Finegan, Donal P.; Vamvakeros, Antonis; Tan, Chun
- Nature Communications, Vol. 11, Issue 1
Three-dimensional imaging of chemical phase transformations at the nanoscale with full-field transmission X-ray microscopy
journal, July 2011
- Meirer, Florian; Cabana, Jordi; Liu, Yijin
- Journal of Synchrotron Radiation, Vol. 18, Issue 5
Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release
journal, July 2018
- Hu, Enyuan; Yu, Xiqian; Lin, Ruoqian
- Nature Energy, Vol. 3, Issue 8
Visualization of anisotropic-isotropic phase transformation dynamics in battery electrode particles
journal, August 2016
- Wang, Jiajun; Karen Chen-Wiegart, Yu-chen; Eng, Christopher
- Nature Communications, Vol. 7, Issue 1
Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides
journal, February 2019
- Hong, Jihyun; Gent, William E.; Xiao, Penghao
- Nature Materials, Vol. 18, Issue 3
Heterogeneous damage in Li-ion batteries: Experimental analysis and theoretical modeling
journal, August 2019
- Xu, Rong; Yang, Yang; Yin, Fei
- Journal of the Mechanics and Physics of Solids, Vol. 129
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
Quantifying the heterogeneity of shale through statistical combination of imaging across scales
journal, August 2017
- Semnani, Shabnam J.; Borja, Ronaldo I.
- Acta Geotechnica, Vol. 12, Issue 6
Mesoscale Battery Science: The Behavior of Electrode Particles Caught on a Multispectral X-ray Camera
journal, June 2018
- Wei, Chenxi; Xia, Sihao; Huang, Hai
- Accounts of Chemical Research, Vol. 51, Issue 10
TXM-Wizard : a program for advanced data collection and evaluation in full-field transmission X-ray microscopy
journal, January 2012
- Liu, Yijin; Meirer, Florian; Williams, Phillip A.
- Journal of Synchrotron Radiation, Vol. 19, Issue 2
Nanoscale elemental sensitivity study of Nd 2 Fe 14 B using absorption correlation tomography : Nanoscale Elemental Sensitivity Study of N
journal, August 2013
- Kao, Thomas L.; Shi, Crystal Y.; Wang, Junyue
- Microscopy Research and Technique, Vol. 76, Issue 11
TOPAS and TOPAS-Academic : an optimization program integrating computer algebra and crystallographic objects written in C++
journal, February 2018
- Coelho, Alan A.
- Journal of Applied Crystallography, Vol. 51, Issue 1
Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes
journal, December 2019
- House, Robert A.; Maitra, Urmimala; Pérez-Osorio, Miguel A.
- Nature, Vol. 577, Issue 7791
Structural integrity—Searching the key factor to suppress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques
journal, October 2016
- Xu, Yahong; Hu, Enyuan; Yang, Feifei
- Nano Energy, Vol. 28
Atomic-Resolution Visualization of Distinctive Chemical Mixing Behavior of Ni, Co, and Mn with Li in Layered Lithium Transition-Metal Oxide Cathode Materials
journal, July 2015
- Yan, Pengfei; Zheng, Jianming; Lv, Dongping
- Chemistry of Materials, Vol. 27, Issue 15
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
Li2MnO3-stabilized LiMO2 (M = Mn, Ni, Co) electrodes for lithium-ion batteries
journal, January 2007
- Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S.
- Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125
In situ Visualization of State-of-Charge Heterogeneity within a LiCoO 2 Particle that Evolves upon Cycling at Different Rates
journal, April 2017
- Xu, Yahong; Hu, Enyuan; Zhang, Kai
- ACS Energy Letters, Vol. 2, Issue 5
Three-dimensional mapping of nickel oxidation states using full field x-ray absorption near edge structure nanotomography
journal, April 2011
- Nelson, George J.; Harris, William M.; Izzo, John R.
- Applied Physics Letters, Vol. 98, Issue 17
New Insights into Improving Rate Performance of Lithium-Rich Cathode Material
journal, May 2015
- Wang, Yongqing; Yang, Zhenzhong; Qian, Yumin
- Advanced Materials, Vol. 27, Issue 26
Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging
journal, July 2018
- Singer, A.; Zhang, M.; Hy, S.
- Nature Energy, Vol. 3, Issue 8
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
Layered Li[Ni[sub x]Co[sub 1−2x]Mn[sub x]]O[sub 2] Cathode Materials for Lithium-Ion Batteries
journal, January 2001
- Lu, Zhonghua; MacNeil, D. D.; Dahn, J. R.
- Electrochemical and Solid-State Letters, Vol. 4, Issue 12
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