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

Title: Quantifying redox heterogeneity in single-crystalline LiCoO2 cathode particles

Abstract

Active cathode particles are fundamental architectural units for the composite electrode of Li-ion batteries. The microstructure of the particles has a profound impact on their behavior and, consequently, on the cell-level electrochemical performance. LiCoO2(LCO, a dominant cathode material) is often in the form of well-shaped particles, a few micrometres in size, with good crystallinity. In contrast to secondary particles (an agglomeration of many fine primary grains), which are the other common form of battery particles populated with structural and chemical defects, it is often anticipated that good particle crystallinity leads to superior mechanical robustness and suppressed charge heterogeneity. Yet, sub-particle level charge inhomogeneity in LCO particles has been widely reported in the literature, posing a frontier challenge in this field. Herein, this topic is revisited and it is demonstrated that X-ray absorption spectra on single-crystalline particles with highly anisotropic lattice structures are sensitive to the polarization configuration of the incident X-rays, causing some degree of ambiguity in analyzing the local spectroscopic fingerprint. To tackle this issue, a methodology is developed that extracts the white-line peak energy in the X-ray absorption near-edge structure spectra as a key data attribute for representing the local state of charge in the LCO crystal. This method demonstrates significantlymore » improved accuracy and reveals the mesoscale chemical complexity in LCO particles with better fidelity. In addition to the implications on the importance of particle engineering for LCO cathodes, the method developed herein also has significant impact on spectro-microscopic studies of single-crystalline materials at synchrotron facilities, which is broadly applicable to a wide range of scientific disciplines well beyond battery research.« less

Authors:
ORCiD logo [1];  [2];  [3];  [2]; ORCiD logo [2];  [4]
  1. Univ. of Science and Technology of China, Hefei (China) ; SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Chinese Academy of Sciences (CAS), Beijing (China)
  3. Univ. of Science and Technology of China, Hefei (China)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1633187
Grant/Contract Number:  
2017YFA0402904; 2016YFB0100100; AC02-76SF00515; 51822211; 11574281; 51421002
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Synchrotron Radiation (Online)
Additional Journal Information:
Journal Name: Journal of Synchrotron Radiation (Online); Journal Volume: 27; Journal Issue: 3; Journal ID: ISSN 1600-5775
Publisher:
International Union of Crystallography
Country of Publication:
United States
Language:
English
Subject:
73 NUCLEAR PHYSICS AND RADIATION PHYSICS; spectro-microscopy; X-ray polarization; single-crystalline LiCoO2

Citation Formats

Wei, Chenxi, Hong, Yanshuai, Tian, Yangchao, Yu, Xiqian, Liu, Yijin, and Pianetta, Piero. Quantifying redox heterogeneity in single-crystalline LiCoO2 cathode particles. United States: N. p., 2020. Web. https://doi.org/10.1107/s1600577520002076.
Wei, Chenxi, Hong, Yanshuai, Tian, Yangchao, Yu, Xiqian, Liu, Yijin, & Pianetta, Piero. Quantifying redox heterogeneity in single-crystalline LiCoO2 cathode particles. United States. https://doi.org/10.1107/s1600577520002076
Wei, Chenxi, Hong, Yanshuai, Tian, Yangchao, Yu, Xiqian, Liu, Yijin, and Pianetta, Piero. Fri . "Quantifying redox heterogeneity in single-crystalline LiCoO2 cathode particles". United States. https://doi.org/10.1107/s1600577520002076. https://www.osti.gov/servlets/purl/1633187.
@article{osti_1633187,
title = {Quantifying redox heterogeneity in single-crystalline LiCoO2 cathode particles},
author = {Wei, Chenxi and Hong, Yanshuai and Tian, Yangchao and Yu, Xiqian and Liu, Yijin and Pianetta, Piero},
abstractNote = {Active cathode particles are fundamental architectural units for the composite electrode of Li-ion batteries. The microstructure of the particles has a profound impact on their behavior and, consequently, on the cell-level electrochemical performance. LiCoO2(LCO, a dominant cathode material) is often in the form of well-shaped particles, a few micrometres in size, with good crystallinity. In contrast to secondary particles (an agglomeration of many fine primary grains), which are the other common form of battery particles populated with structural and chemical defects, it is often anticipated that good particle crystallinity leads to superior mechanical robustness and suppressed charge heterogeneity. Yet, sub-particle level charge inhomogeneity in LCO particles has been widely reported in the literature, posing a frontier challenge in this field. Herein, this topic is revisited and it is demonstrated that X-ray absorption spectra on single-crystalline particles with highly anisotropic lattice structures are sensitive to the polarization configuration of the incident X-rays, causing some degree of ambiguity in analyzing the local spectroscopic fingerprint. To tackle this issue, a methodology is developed that extracts the white-line peak energy in the X-ray absorption near-edge structure spectra as a key data attribute for representing the local state of charge in the LCO crystal. This method demonstrates significantly improved accuracy and reveals the mesoscale chemical complexity in LCO particles with better fidelity. In addition to the implications on the importance of particle engineering for LCO cathodes, the method developed herein also has significant impact on spectro-microscopic studies of single-crystalline materials at synchrotron facilities, which is broadly applicable to a wide range of scientific disciplines well beyond battery research.},
doi = {10.1107/s1600577520002076},
journal = {Journal of Synchrotron Radiation (Online)},
number = 3,
volume = 27,
place = {United States},
year = {2020},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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


Local structure adaptability through multi cations for oxygen redox accommodation in Li-Rich layered oxides
journal, January 2020


Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries
journal, September 2017


Coupling of electrochemically triggered thermal and mechanical effects to aggravate failure in a layered cathode
journal, June 2018


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

Emerging In Situ and Operando Nanoscale X-Ray Imaging Techniques for Energy Storage Materials
journal, February 2015

  • Nelson Weker, Johanna; Toney, Michael F.
  • Advanced Functional Materials, Vol. 25, Issue 11
  • DOI: 10.1002/adfm.201403409

In Situ Study of Silicon Electrode Lithiation with X-ray Reflectivity
journal, November 2016


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


Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate
journal, October 2017


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

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
  • DOI: 10.1038/ncomms4529

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


Mesoscale Phase Distribution in Single Particles of LiFePO 4 following Lithium Deintercalation
journal, April 2013

  • Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin
  • Chemistry of Materials, Vol. 25, Issue 9
  • DOI: 10.1021/cm400106k

Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles
journal, January 2019

  • Besli, Münir M.; Shukla, Alpesh Khushalchand; Wei, Chenxi
  • Journal of Materials Chemistry A, Vol. 7, Issue 20
  • DOI: 10.1039/C9TA01720H

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


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


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

Emerging X-ray imaging technologies for energy materials
journal, April 2020


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


Solid Electrolyte Interphase on Native Oxide-Terminated Silicon Anodes for Li-Ion Batteries
journal, March 2019


Phase retrieval using polychromatic illumination for transmission X-ray microscopy
journal, January 2011

  • Liu, Yijin; Andrews, Joy C.; Wang, Junyue
  • Optics Express, Vol. 19, Issue 2
  • DOI: 10.1364/OE.19.000540

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

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
  • DOI: 10.1039/C8TA06875E

Unveiling the Role and Mechanism of Mechanochemical Activation on Lithium Cobalt Oxide Powders from Spent Lithium-Ion Batteries
journal, September 2018

  • Wang, Mengmeng; Tan, Quanyin; Li, Jinhui
  • Environmental Science & Technology, Vol. 52, Issue 22
  • DOI: 10.1021/acs.est.8b03469

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

Elucidating anionic oxygen activity in lithium-rich layered oxides
journal, March 2018


Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries
journal, January 2017

  • Yan, Pengfei; Zheng, Jianming; Gu, Meng
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14101

Finding a Needle in the Haystack: Identification of Functionally Important Minority Phases in an Operating Battery
journal, November 2017


Application of Operando X-ray Diffraction and Raman Spectroscopies in Elucidating the Behavior of Cathode in Lithium-Ion Batteries
journal, July 2018


In situ/operando synchrotron-based X-ray techniques for lithium-ion battery research
journal, July 2018


Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V
journal, June 2019


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


The nanoscale structure of the electrolyte–metal oxide interface
journal, January 2018

  • Steinrück, Hans-Georg; Cao, Chuntian; Tsao, Yuchi
  • Energy & Environmental Science, Vol. 11, Issue 3
  • DOI: 10.1039/C7EE02724A

Developments in X-ray tomography characterization for electrochemical devices
journal, December 2019


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


New Insights Related to Rechargeable Lithium Batteries: Li Metal Anodes, Ni Rich LiNi x Co y Mn z O 2 Cathodes and Beyond Them
journal, January 2019

  • Markevich, Elena; Salitra, Gregory; Hartmann, Pascal
  • Journal of The Electrochemical Society, Vol. 166, Issue 3
  • DOI: 10.1149/2.0261903jes

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

Operando Spectroscopic Microscopy of LiCoO2 Cathodes Outside Standard Operating Potentials
journal, September 2017


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

Structural Distortion-Induced Charge Gradient Distribution of Co Ions in Delithiated LiCoO 2 Cathode
journal, November 2019


Operando characterization of batteries using x-ray absorption spectroscopy: advances at the beamline XAFS at synchrotron Elettra
journal, January 2017

  • Aquilanti, Giuliana; Giorgetti, Marco; Dominko, Robert
  • Journal of Physics D: Applied Physics, Vol. 50, Issue 7
  • DOI: 10.1088/1361-6463/aa519a