skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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.

Authors:
; ; ; ; ORCiD logo; ; ; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo
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 & 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. 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, & 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 = {2020},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1038/s41467-020-20198-w

Save / Share:

Works referenced in this record:

Chemomechanical interplay of layered cathode materials undergoing fast charging in lithium batteries
journal, November 2018


ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


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
  • DOI: 10.1021/jacs.6b03932

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
  • DOI: 10.1021/ja050697u

Fingerprint Oxygen Redox Reactions in Batteries through High-Efficiency Mapping of Resonant Inelastic X-ray Scattering
journal, January 2019


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
  • DOI: 10.1063/1.5119155

Charging Up Lithium-Ion Battery Cathodes
journal, March 2018


Quantification of Heterogeneous Degradation in Li‐Ion Batteries
journal, May 2019


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
  • DOI: 10.1038/nchem.2524

Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries
journal, January 2016


Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials
journal, July 2018


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
  • DOI: 10.1039/C4EE01384K

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
  • DOI: 10.1039/C8TA08973F

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
  • DOI: 10.1039/C8EE00001H

Structural absorption by barbule microstructures of super black bird of paradise feathers
journal, January 2018


Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes
journal, December 2017


Li-Rich Layered Oxides and Their Practical Challenges: Recent Progress and Perspectives
journal, March 2019


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
  • DOI: 10.1038/nmat4137

Thermal stress-induced charge and structure heterogeneity in emerging cathode materials
journal, May 2020


Computational investigation of chalcogenide spinel conductors for all-solid-state Mg batteries
journal, January 2020

  • Koettgen, Julius; Bartel, Christopher J.; Ceder, Gerbrand
  • Chemical Communications, Vol. 56, Issue 13
  • DOI: 10.1039/C9CC09510A

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
  • DOI: 10.1002/adma.201601273

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
  • DOI: 10.1021/nl502090z

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


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
  • DOI: 10.1149/2.1021803jes

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
  • DOI: 10.1063/1.4977592

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
  • DOI: 10.1002/adfm.201900247

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
  • DOI: 10.1002/anie.201301236

Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes
journal, January 2020


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
  • DOI: 10.1107/S0909049511019364

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
  • DOI: 10.1038/ncomms12372

Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides
journal, February 2019


Heterogeneous damage in Li-ion batteries: Experimental analysis and theoretical modeling
journal, August 2019


Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials
journal, January 2020


Quantifying the heterogeneity of shale through statistical combination of imaging across scales
journal, August 2017


Mesoscale Battery Science: The Behavior of Electrode Particles Caught on a Multispectral X-ray Camera
journal, June 2018


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
  • DOI: 10.1107/S0909049511049144

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
  • DOI: 10.1002/jemt.22273

TOPAS and TOPAS-Academic : an optimization program integrating computer algebra and crystallographic objects written in C++
journal, February 2018


Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes
journal, December 2019


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
  • DOI: 10.1039/b702425h

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
  • DOI: 10.1063/1.3574774

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
  • DOI: 10.1002/adma.201500956

Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging
journal, July 2018


Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides
journal, December 2017


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
  • DOI: 10.1149/1.1413182

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
  • DOI: 10.1021/jacs.9b05349