Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Distinct Surface and Bulk Thermal Behaviors of LiNi0.6Mn0.2Co0.2O2 Cathode Materials as a Function of State of Charge

Abstract

Understanding how structural and chemical transformations take place in particles under thermal conditions can inform designing thermally robust electrode materials. Such a study necessitates the use of diagnostic techniques that are capable of probing the transformations at multiple length scales and at different states of charge (SOC). In this study, the thermal behavior ofLiNi0.6Mn0.2Co0.2O2 (NMC-622) was examined as a function of SOC, using an array of bulk and surface-sensitive techniques. In general, thermal stability decreases as lithium content is lowered and conversion in the bulk to progressively reduced metal oxides (spinels, rock salt) occurs as the temperature is raised. Hard X-ray absorption spectroscopy (XAS) and X-ray Raman spectroscopy (XRS) experiments, which probe the bulk, reveal that Ni and Co are eventually reduced when partially delithiated samples (regardless of the SOC) are heated, although Mn is not. Surface-sensitive synchrotron techniques, such as soft XAS and transmission X-ray microscopy (TXM), however, reveal that for 50% delithiated samples, apparent oxidation of nickel occurs at particle surfaces under some circumstances. This is partially compensated by reduction of cobalt but may also be a consequence of redistribution of lithium ions upon heating. TXM results indicate the movement of reduced nickel ions into particle interiors ormore » oxidized nickel ions to the surface or both. These experiments illustrate the complexity of the thermal behavior of NMC cathode materials. The study also informs the importance of investigating the surface and bulk difference as a function of SOC when studying the thermal behaviors of battery materials.« less

Authors:
 [1];  [2]; ORCiD logo [3];  [2];  [2]; ORCiD logo [4];  [5]; ORCiD logo [2]; ORCiD logo [6]
+ Show Author Affiliations
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Dongguan Neutron Science Center, Guangdong (China)
  4. Xi'an Jiaotong Univ., Shaanxi (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Xi'an Jiaotong Univ., Shaanxi (China)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1633948
Alternate Identifier(s):
OSTI ID: 1783096
Grant/Contract Number:  
AC02-76SF00515; AC02-05CH11231; 11805034; 21704105; 2017A030313021
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 12; Journal Issue: 10; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; lithium-ion battery; NMC-662 cathode; thermal behavior; x-ray absorption spectroscopy; x-ray Raman spactroscopy

Citation Formats

Tian, Chixia, Xu, Yahong, Kan, Wang Hay, Sokaras, Dimosthenis, Nordlund, Dennis, Shen, Hao, Chen, Kai, Liu, Yijin, and Doeff, Marca. Distinct Surface and Bulk Thermal Behaviors of LiNi0.6Mn0.2Co0.2O2 Cathode Materials as a Function of State of Charge. United States: N. p., 2020. Web. doi:10.1021/acsami.9b21288.
Copy to clipboard
Tian, Chixia, Xu, Yahong, Kan, Wang Hay, Sokaras, Dimosthenis, Nordlund, Dennis, Shen, Hao, Chen, Kai, Liu, Yijin, & Doeff, Marca. Distinct Surface and Bulk Thermal Behaviors of LiNi0.6Mn0.2Co0.2O2 Cathode Materials as a Function of State of Charge. United States. https://doi.org/10.1021/acsami.9b21288
Copy to clipboard
Tian, Chixia, Xu, Yahong, Kan, Wang Hay, Sokaras, Dimosthenis, Nordlund, Dennis, Shen, Hao, Chen, Kai, Liu, Yijin, and Doeff, Marca. Fri . "Distinct Surface and Bulk Thermal Behaviors of LiNi0.6Mn0.2Co0.2O2 Cathode Materials as a Function of State of Charge". United States. https://doi.org/10.1021/acsami.9b21288. https://www.osti.gov/servlets/purl/1633948.
Copy to clipboard
@article{osti_1633948,
title = {Distinct Surface and Bulk Thermal Behaviors of LiNi0.6Mn0.2Co0.2O2 Cathode Materials as a Function of State of Charge},
author = {Tian, Chixia and Xu, Yahong and Kan, Wang Hay and Sokaras, Dimosthenis and Nordlund, Dennis and Shen, Hao and Chen, Kai and Liu, Yijin and Doeff, Marca},
abstractNote = {Understanding how structural and chemical transformations take place in particles under thermal conditions can inform designing thermally robust electrode materials. Such a study necessitates the use of diagnostic techniques that are capable of probing the transformations at multiple length scales and at different states of charge (SOC). In this study, the thermal behavior ofLiNi0.6Mn0.2Co0.2O2 (NMC-622) was examined as a function of SOC, using an array of bulk and surface-sensitive techniques. In general, thermal stability decreases as lithium content is lowered and conversion in the bulk to progressively reduced metal oxides (spinels, rock salt) occurs as the temperature is raised. Hard X-ray absorption spectroscopy (XAS) and X-ray Raman spectroscopy (XRS) experiments, which probe the bulk, reveal that Ni and Co are eventually reduced when partially delithiated samples (regardless of the SOC) are heated, although Mn is not. Surface-sensitive synchrotron techniques, such as soft XAS and transmission X-ray microscopy (TXM), however, reveal that for 50% delithiated samples, apparent oxidation of nickel occurs at particle surfaces under some circumstances. This is partially compensated by reduction of cobalt but may also be a consequence of redistribution of lithium ions upon heating. TXM results indicate the movement of reduced nickel ions into particle interiors or oxidized nickel ions to the surface or both. These experiments illustrate the complexity of the thermal behavior of NMC cathode materials. The study also informs the importance of investigating the surface and bulk difference as a function of SOC when studying the thermal behaviors of battery materials.},
doi = {10.1021/acsami.9b21288},
journal = {ACS Applied Materials and Interfaces},
number = 10,
volume = 12,
place = {United States},
year = {Fri Feb 14 00:00:00 EST 2020},
month = {Fri Feb 14 00:00:00 EST 2020}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsami.9b21288
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
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:

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

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

Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds
journal, January 2019

Direct synthesis of LiNi1/3Co1/3Mn1/3O2 from nitrate precursors
journal, August 2004

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

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
  • DOI: 10.1149/1.1513001

X-ray Absorption Near-Edge Structure (XANES) Spectroscopy
journal, January 2014

  • Henderson, G. S.; de Groot, F. M. F.; Moulton, B. J. A.
  • Reviews in Mineralogy and Geochemistry, Vol. 78, Issue 1
  • DOI: 10.2138/rmg.2014.78.3

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

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

Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery
journal, April 2019

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials
journal, April 2018

Electronic structural studies on the improved thermal stability of Li(Ni0.8Co0.15Al0.05)O2 by ZrO2 coating for lithium ion batteries
journal, March 2017

  • Kim, Ji-Young; Kim, Sang Hoon; Kim, Dong Hyun
  • Journal of Applied Electrochemistry, Vol. 47, Issue 5
  • DOI: 10.1007/s10800-017-1062-5

Applications of Hard X‐ray Full‐Field Transmission X‐ray Microscopy at SSRL
conference, January 2011

  • Liu, Y.; Andrews, J. C.; Meirer, F.
  • THE 10TH INTERNATIONAL CONFERENCE ON X‐RAY MICROSCOPY, AIP Conference Proceedings
  • DOI: 10.1063/1.3625377

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
  • DOI: 10.1021/acsami.6b11111

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

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

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
  • DOI: 10.1016/j.mser.2012.05.003

Proton Insertion into Oxide Cathodes during Chemical Delithiation
journal, January 2006

  • Choi, J.; Alvarez, E.; Arunkumar, T. A.
  • Electrochemical and Solid-State Letters, Vol. 9, Issue 5
  • DOI: 10.1149/1.2184495

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

The 1s x-ray absorption pre-edge structures in transition metal oxides
journal, February 2009

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

The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013

  • Goodenough, John B.; Park, Kyu-Sung
  • Journal of the American Chemical Society, Vol. 135, Issue 4
  • DOI: 10.1021/ja3091438

Thermal runaway caused fire and explosion of lithium ion battery
journal, June 2012

A method for normalization of X-ray absorption spectra
journal, June 2005

  • Weng, Tsu-Chien; Waldo, Geoffrey S.; Penner-Hahn, James E.
  • Journal of Synchrotron Radiation, Vol. 12, Issue 4
  • DOI: 10.1107/S0909049504034193

Profiling the nanoscale gradient in stoichiometric layered cathode particles for lithium-ion batteries
journal, January 2014

  • Lin, Feng; Nordlund, Dennis; Markus, Isaac M.
  • Energy & Environmental Science, Vol. 7, Issue 9
  • DOI: 10.1039/C4EE01400F

Structural Origin of Overcharge-Induced Thermal Instability of Ni-Containing Layered-Cathodes for High-Energy-Density Lithium Batteries
journal, September 2011

  • Wu, Lijun; Nam, Kyung-Wan; Wang, Xiaojian
  • Chemistry of Materials, Vol. 23, Issue 17
  • DOI: 10.1021/cm201452q

Nanostructured high-energy cathode materials for advanced lithium batteries
journal, October 2012

  • Sun, Yang-Kook; Chen, Zonghai; Noh, Hyung-Joo
  • Nature Materials, Vol. 11, Issue 11
  • DOI: 10.1038/nmat3435

In Situ X-Ray Absorption Study of a Layered Manganese-Chromium Oxide-Based Cathode Material
journal, January 2002

  • Balasubramanian, M.; McBreen, J.; Davidson, I. J.
  • Journal of The Electrochemical Society, Vol. 149, Issue 2
  • DOI: 10.1149/1.1431962

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

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
  • DOI: 10.1021/ja0530568

Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials
journal, March 2018

A review of recent research on nonequilibrium solid solution behavior in LiXFePO4
journal, October 2018

Accelerated Evolution of Surface Chemistry Determined by Temperature and Cycling History in Nickel-Rich Layered Cathode Materials
journal, June 2018

  • Steiner, James D.; Mu, Linqin; Walsh, Julia
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 28
  • DOI: 10.1021/acsami.8b06399

EXPGUI , a graphical user interface for GSAS
journal, April 2001

Recent developments in cathode materials for lithium ion batteries
journal, February 2010

Soft X-ray absorption spectroscopic studies with different probing depths: Effect of an electrolyte additive on electrode surfaces
journal, February 2014

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
  • DOI: 10.1039/C5CC09434H

A high resolution and large solid angle x-ray Raman spectroscopy end-station at the Stanford Synchrotron Radiation Lightsource
journal, April 2012

  • Sokaras, D.; Nordlund, D.; Weng, T. -C.
  • Review of Scientific Instruments, Vol. 83, Issue 4
  • DOI: 10.1063/1.4704458

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
  • DOI: 10.1021/jp013735e

In Situ X-ray Diffraction Study of Layered Li–Ni–Mn–Co Oxides: Effect of Particle Size and Structural Stability of Core–Shell Materials
journal, December 2015

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
  • DOI: 10.1002/aenm.201300787

Lithium batteries: To the limits of lithium
journal, October 2015

In situ x-ray absorption spectroscopic study of the Li[Ni1∕3Co1∕3Mn1∕3]O2 cathode material
journal, June 2005

  • Deb, Aniruddha; Bergmann, Uwe; Cramer, Stephen P.
  • Journal of Applied Physics, Vol. 97, Issue 11
  • DOI: 10.1063/1.1921328

In Situ Transmission X-Ray Absorption Fine Structure Analysis of the Li Deintercalation Process in Li(Ni[sub 0.5]Co[sub 0.5])O[sub 2]
journal, January 1999

  • Nakai, Izumi
  • Electrochemical and Solid-State Letters, Vol. 1, Issue 6
  • DOI: 10.1149/1.1390705

Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy
journal, February 2017

  • Kuppan, Saravanan; Xu, Yahong; Liu, Yijin
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14309

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

Soft X-ray absorption spectroscopy studies on the chemically delithiated commercial LiCoO2 cathode material
journal, December 2007

Correlating Structural Changes and Gas Evolution during the Thermal Decomposition of Charged Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode Materials
journal, January 2013

  • Bak, Seong-Min; Nam, Kyung-Wan; Chang, Wonyoung
  • Chemistry of Materials, Vol. 25, Issue 3
  • DOI: 10.1021/cm303096e

Electronic Structure of Chemically-Prepared Li x Mn 2 O 4 Determined by Mn X-ray Absorption and Emission Spectroscopies
journal, October 2000

  • Horne, Craig R.; Bergmann, Uwe; Grush, Melissa M.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 41
  • DOI: 10.1021/jp994475s

Oxygen Release and Its Effect on the Cycling Stability of LiNi x Mn y Co z O 2 (NMC) Cathode Materials for Li-Ion Batteries
journal, January 2017

  • Jung, Roland; Metzger, Michael; Maglia, Filippo
  • Journal of The Electrochemical Society, Vol. 164, Issue 7
  • DOI: 10.1149/2.0021707jes

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
  • DOI: 10.1149/2.1011507jes

Bulk-sensitive XAS characterization of light elements: from X-ray Raman scattering to X-ray Raman spectroscopy
journal, April 2002

Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes
journal, September 2014

  • Li, Yiyang; El Gabaly, Farid; Ferguson, Todd R.
  • Nature Materials, Vol. 13, Issue 12
  • DOI: 10.1038/nmat4084

New findings on the phase transitions in Li1−xNiO2: in situ synchrotron X-ray diffraction studies
journal, June 1999

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 Changes and Thermal Stability of Charged LiNi x Mn y Co z O 2 Cathode Materials Studied by Combined In Situ Time-Resolved XRD and Mass Spectroscopy
journal, December 2014

  • Bak, Seong-Min; Hu, Enyuan; Zhou, Yongning
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 24
  • DOI: 10.1021/am506712c
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: