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Title: Thermal stress-induced charge and structure heterogeneity in emerging cathode materials

Abstract

Nickel-rich layered oxide cathode materials are attractive near-term candidates for boosting the energy density of next generation lithium-ion batteries. The practical implementation of these materials is, however, hindered by unsatisfactory capacity retention, poor thermal stability, and oxygen release as a consequence of structural decomposition, which may have serious safety consequences. The undesired side reactions are often exothermic, causing complicated electro-chemo-mechanical interplay at elevated temperatures. In this work, we explore the effects of thermal exposure on chemically delithiated LiNi0.8Mn0.1Co0.1O2 (NMC-811) at a practical state-of-charge (50% Li content) and an over-charged state (25% Li content). A systematic study using a suite of advanced synchrotron radiation characterization tools reveals the dynamics of thermal behavior of the charged NMC-811, which involves sophisticated structural and chemical evolution; e.g. lattice phase transformation, transition metal (TM) cation migration and valence change, and lithium redistribution. These intertwined processes exhibit a complex 3D spatial heterogeneity and, collectively, form a valence state gradient throughout the particles. Our study sheds light on the response of NMC-811 to elevated temperature and highlights the importance of the cathode's thermal robustness for battery performance and safety.

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1580280
Alternate Identifier(s):
OSTI ID: 1601214; OSTI ID: 1638171
Grant/Contract Number:  
AC02-05CH11231; AC02-76SF00515
Resource Type:
Published Article
Journal Name:
Materials Today
Additional Journal Information:
Journal Name: Materials Today; Journal ID: ISSN 1369-7021
Publisher:
Elsevier
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Alvarado, Judith, Wei, Chenxi, Nordlund, Dennis, Kroll, Thomas, Sokaras, Dimosthenis, Tian, Yangchao, Liu, Yijin, and Doeff, Marca M. Thermal stress-induced charge and structure heterogeneity in emerging cathode materials. United Kingdom: N. p., 2019. Web. doi:10.1016/j.mattod.2019.11.009.
Alvarado, Judith, Wei, Chenxi, Nordlund, Dennis, Kroll, Thomas, Sokaras, Dimosthenis, Tian, Yangchao, Liu, Yijin, & Doeff, Marca M. Thermal stress-induced charge and structure heterogeneity in emerging cathode materials. United Kingdom. https://doi.org/10.1016/j.mattod.2019.11.009
Alvarado, Judith, Wei, Chenxi, Nordlund, Dennis, Kroll, Thomas, Sokaras, Dimosthenis, Tian, Yangchao, Liu, Yijin, and Doeff, Marca M. Sun . "Thermal stress-induced charge and structure heterogeneity in emerging cathode materials". United Kingdom. https://doi.org/10.1016/j.mattod.2019.11.009.
@article{osti_1580280,
title = {Thermal stress-induced charge and structure heterogeneity in emerging cathode materials},
author = {Alvarado, Judith and Wei, Chenxi and Nordlund, Dennis and Kroll, Thomas and Sokaras, Dimosthenis and Tian, Yangchao and Liu, Yijin and Doeff, Marca M.},
abstractNote = {Nickel-rich layered oxide cathode materials are attractive near-term candidates for boosting the energy density of next generation lithium-ion batteries. The practical implementation of these materials is, however, hindered by unsatisfactory capacity retention, poor thermal stability, and oxygen release as a consequence of structural decomposition, which may have serious safety consequences. The undesired side reactions are often exothermic, causing complicated electro-chemo-mechanical interplay at elevated temperatures. In this work, we explore the effects of thermal exposure on chemically delithiated LiNi0.8Mn0.1Co0.1O2 (NMC-811) at a practical state-of-charge (50% Li content) and an over-charged state (25% Li content). A systematic study using a suite of advanced synchrotron radiation characterization tools reveals the dynamics of thermal behavior of the charged NMC-811, which involves sophisticated structural and chemical evolution; e.g. lattice phase transformation, transition metal (TM) cation migration and valence change, and lithium redistribution. These intertwined processes exhibit a complex 3D spatial heterogeneity and, collectively, form a valence state gradient throughout the particles. Our study sheds light on the response of NMC-811 to elevated temperature and highlights the importance of the cathode's thermal robustness for battery performance and safety.},
doi = {10.1016/j.mattod.2019.11.009},
journal = {Materials Today},
number = ,
volume = ,
place = {United Kingdom},
year = {2019},
month = {12}
}

Works referenced in this record:

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
  • DOI: 10.1039/C8TA10329A

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


Soft X-ray Absorption Spectroscopic and Raman Studies on Li 1.2 Ni 0.2 Mn 0.6 O 2 for Lithium-Ion Batteries
journal, November 2012

  • Hy, Sunny; Su, Wei-Nien; Chen, Jing-Ming
  • The Journal of Physical Chemistry C, Vol. 116, Issue 48
  • DOI: 10.1021/jp309313m

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


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

Structural evolution and capacity degradation mechanism of LiNi0.6Mn0.2Co0.2O2 cathode materials
journal, October 2018


Thermal stability of LixCoO2, LixNiO2 and λ-MnO2 and consequences for the safety of Li-ion cells
journal, August 1994


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

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

Comparative Performance Evaluation of Flame Retardant Additives for Lithium Ion Batteries - I. Safety, Chemical and Electrochemical Stabilities
journal, August 2018

  • Dagger, Tim; Rad, Babak R.; Schappacher, Falko M.
  • Energy Technology, Vol. 6, Issue 10
  • DOI: 10.1002/ente.201800132

Cathode materials review
conference, January 2014

  • Daniel, Claus; Mohanty, Debasish; Li, Jianlin
  • REVIEW ON ELECTROCHEMICAL STORAGE MATERIALS AND TECHNOLOGY: Proceedings of the 1st International Freiberg Conference on Electrochemical Storage Materials, AIP Conference Proceedings
  • DOI: 10.1063/1.4878478

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

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

Electron Enrichment in 3d Transition Metal Oxide Hetero-Nanostructures
journal, September 2011

  • Kronawitter, Coleman X.; Bakke, Jonathan R.; Wheeler, Damon A.
  • Nano Letters, Vol. 11, Issue 9
  • DOI: 10.1021/nl201944h

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


Exploring Oxygen Activity in the High Energy P2-Type Na 0.78 Ni 0.23 Mn 0.69 O 2 Cathode Material for Na-Ion Batteries
journal, March 2017

  • Ma, Chuze; Alvarado, Judith; Xu, Jing
  • Journal of the American Chemical Society, Vol. 139, Issue 13
  • DOI: 10.1021/jacs.7b00164

X-ray absorption spectroscopy and X-ray Raman scattering of water and ice; an experimental view
journal, March 2010

  • Nilsson, A.; Nordlund, D.; Waluyo, I.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 177, Issue 2-3
  • DOI: 10.1016/j.elspec.2010.02.005

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

Li-ion battery materials: present and future
journal, June 2015


Novel lithium insertion material of LiCo1/3Ni1/3Mn1/3O2 for advanced lithium-ion batteries
journal, June 2003


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

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


Oxygen 1 s x-ray-absorption edges of transition-metal oxides
journal, September 1989


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

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
  • DOI: 10.1039/C6TA07991A

A consideration of lithium cell safety
journal, September 1999


Direct tomography with chemical-bond contrast
journal, May 2011

  • Huotari, Simo; Pylkkänen, Tuomas; Verbeni, Roberto
  • Nature Materials, Vol. 10, Issue 7
  • DOI: 10.1038/nmat3031

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


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

In situ x-ray diffraction and electrochemical studies of Li1−xNiO2
journal, December 1993