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Title: Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles

Abstract

The structural integrity of layered Ni-rich oxide cathode materials is one of the most significant factors that critically affect the performance and reliability of lithium-ion batteries. Prolonged battery operation many times involves repeated phase transitions, buildup of mechanical stresses, and could provoke thermal spikes. Such sophisticated chemo-thermo-mechanical interplay can cause performance degradation through structural disintegration of the cathode active materials (CAMs). In this work, we systematically investigate the thermal decomposition, fracture, and oxygen evolution of chemically delithiated Li0.3Ni0.8Co0.15Al0.05O2 (NCA) particles upon heating from 25 °C to 450 °C using a number of advanced X-ray and electron probes. We observed a continuous reduction of the Ni oxidation state upon heating, as well as the release of oxygen from the NCA lattice that undergoes the thermally induced phase transformations. The release of oxygen also created numerous mesopores throughout the analyzed particles, which could significantly affect the chemical and mechanical properties of the electrode. In addition, intergranular and intragranular fracturing at elevated temperatures also contribute to the degradation of the NCA cathode under these conditions. Our investigation of the mechanical integrity at elevated temperatures provides a fundamental understanding of the thermally driven chemomechanical breakdown of the NCA cathode active materials.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [5];  [4];  [3];  [6];  [4];  [4]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [3]; ORCiD logo [4]
  1. Robert Bosch LLC, Sunnyvale, CA (United States); Karlsruhe Inst. of Technology (KIT) (Germany)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Robert Bosch LLC, Sunnyvale, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  6. Karlsruhe Inst. of Technology (KIT) (Germany); Aalen Univ. (Germany)
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 Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1547284
Alternate Identifier(s):
OSTI ID: 1511062; OSTI ID: 1581069
Grant/Contract Number:  
AC02-05CH11231; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 7; Journal Issue: 20; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Besli, Münir M., Shukla, Alpesh Khushalchand, Wei, Chenxi, Metzger, Michael, Alvarado, Judith, Boell, Julian, Nordlund, Dennis, Schneider, Gerhard, Hellstrom, Sondra, Johnston, Christina, Christensen, Jake, Doeff, Marca M., Liu, Yijin, and Kuppan, Saravanan. Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles. United States: N. p., 2019. Web. doi:10.1039/c9ta01720h.
Besli, Münir M., Shukla, Alpesh Khushalchand, Wei, Chenxi, Metzger, Michael, Alvarado, Judith, Boell, Julian, Nordlund, Dennis, Schneider, Gerhard, Hellstrom, Sondra, Johnston, Christina, Christensen, Jake, Doeff, Marca M., Liu, Yijin, & Kuppan, Saravanan. Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles. United States. doi:10.1039/c9ta01720h.
Besli, Münir M., Shukla, Alpesh Khushalchand, Wei, Chenxi, Metzger, Michael, Alvarado, Judith, Boell, Julian, Nordlund, Dennis, Schneider, Gerhard, Hellstrom, Sondra, Johnston, Christina, Christensen, Jake, Doeff, Marca M., Liu, Yijin, and Kuppan, Saravanan. Wed . "Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles". United States. doi:10.1039/c9ta01720h. https://www.osti.gov/servlets/purl/1547284.
@article{osti_1547284,
title = {Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles},
author = {Besli, Münir M. and Shukla, Alpesh Khushalchand and Wei, Chenxi and Metzger, Michael and Alvarado, Judith and Boell, Julian and Nordlund, Dennis and Schneider, Gerhard and Hellstrom, Sondra and Johnston, Christina and Christensen, Jake and Doeff, Marca M. and Liu, Yijin and Kuppan, Saravanan},
abstractNote = {The structural integrity of layered Ni-rich oxide cathode materials is one of the most significant factors that critically affect the performance and reliability of lithium-ion batteries. Prolonged battery operation many times involves repeated phase transitions, buildup of mechanical stresses, and could provoke thermal spikes. Such sophisticated chemo-thermo-mechanical interplay can cause performance degradation through structural disintegration of the cathode active materials (CAMs). In this work, we systematically investigate the thermal decomposition, fracture, and oxygen evolution of chemically delithiated Li0.3Ni0.8Co0.15Al0.05O2 (NCA) particles upon heating from 25 °C to 450 °C using a number of advanced X-ray and electron probes. We observed a continuous reduction of the Ni oxidation state upon heating, as well as the release of oxygen from the NCA lattice that undergoes the thermally induced phase transformations. The release of oxygen also created numerous mesopores throughout the analyzed particles, which could significantly affect the chemical and mechanical properties of the electrode. In addition, intergranular and intragranular fracturing at elevated temperatures also contribute to the degradation of the NCA cathode under these conditions. Our investigation of the mechanical integrity at elevated temperatures provides a fundamental understanding of the thermally driven chemomechanical breakdown of the NCA cathode active materials.},
doi = {10.1039/c9ta01720h},
journal = {Journal of Materials Chemistry. A},
number = 20,
volume = 7,
place = {United States},
year = {2019},
month = {4}
}

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Works referenced in this record:

Tuning the Activity of Oxygen in LiNi 0.8 Co 0.15 Al 0.05 O 2 Battery Electrodes
journal, October 2016

  • Karki, Khim; Huang, Yiqing; Hwang, Sooyeon
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 41
  • DOI: 10.1021/acsami.6b09585

The Role of Oxygen Release from Li- and Mn-Rich Layered Oxides during the First Cycles Investigated by On-Line Electrochemical Mass Spectrometry
journal, December 2016

  • Strehle, Benjamin; Kleiner, Karin; Jung, Roland
  • Journal of The Electrochemical Society, Vol. 164, Issue 2
  • DOI: 10.1149/2.1001702jes

Singlet oxygen evolution from layered transition metal oxide cathode materials and its implications for lithium-ion batteries
journal, October 2018


The application of synchrotron X-ray techniques to the study of rechargeable batteries
journal, November 2018


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

In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes
journal, October 2016

  • Zhao, Jianqing; Zhang, Wei; Huq, Ashfia
  • Advanced Energy Materials, Vol. 7, Issue 3
  • DOI: 10.1002/aenm.201601266

A study of room-temperature LixMn1.5Ni0.5O4 solid solutions
journal, January 2015

  • Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep08027

In Situ X-Ray Absorption Studies of a High-Rate LiNi[sub 0.85]Co[sub 0.15]O[sub 2] Cathode Material
journal, January 2000

  • Balasubramanian, M.; Sun, X.; Yang, X. Q.
  • Journal of The Electrochemical Society, Vol. 147, Issue 8
  • DOI: 10.1149/1.1393624

Thermal behavior of delithiated Li(Ni0.8Co0.15Al0.05)O2 and Li1.1(Ni1/3Co1/3Mn1/3)0.9O2 powders
journal, December 2007


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

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

Thermal and electrochemical decomposition of lithium peroxide in non-catalyzed carbon cathodes for Li–air batteries
journal, January 2013

  • Beyer, H.; Meini, S.; Tsiouvaras, N.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 26
  • DOI: 10.1039/c3cp51056e

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


In Situ XAFS Analysis of Li(Mn, M)2O4 (M=Cr, Co, Ni) 5V Cathode Materials for Lithium-Ion Secondary Batteries
journal, February 2001

  • Terada, Yasuko; Yasaka, Kenji; Nishikawa, Fumishige
  • Journal of Solid State Chemistry, Vol. 156, Issue 2
  • DOI: 10.1006/jssc.2000.8990

Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study
journal, January 2011

  • Xu, Bo; Fell, Christopher R.; Chi, Miaofang
  • Energy & Environmental Science, Vol. 4, Issue 6
  • DOI: 10.1039/c1ee01131f

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

Explore the Effects of Microstructural Defects on Voltage Fade of Li- and Mn-Rich Cathodes
journal, September 2016


Electrochemistry and Structural Chemistry of LiNiO[sub 2] (R3m) for 4 Volt Secondary Lithium Cells
journal, January 1993

  • Ohzuku, Tsutomu
  • Journal of The Electrochemical Society, Vol. 140, Issue 7
  • DOI: 10.1149/1.2220730

Investigation of Changes in the Surface Structure of Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode Materials Induced by the Initial Charge
journal, December 2013

  • Hwang, Sooyeon; Chang, Wonyoung; Kim, Seung Min
  • Chemistry of Materials, Vol. 26, Issue 2
  • DOI: 10.1021/cm403332s

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

Investigating Local Degradation and Thermal Stability of Charged Nickel-Based Cathode Materials through Real-Time Electron Microscopy
journal, August 2014

  • Hwang, Sooyeon; Kim, Seung Min; Bak, Seong-Min
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 17
  • DOI: 10.1021/am503278f

The effect of thermal stability for high-Ni-content layer-structured cathode materials, LiNi0.8Mn0.1−xCo0.1MoxO2 (x = 0, 0.02, 0.04)
journal, December 2013


Nickel-Rich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries
journal, March 2015

  • Liu, Wen; Oh, Pilgun; Liu, Xien
  • Angewandte Chemie International Edition, Vol. 54, Issue 15
  • DOI: 10.1002/anie.201409262

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

Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes: II. Lithium-Rich, xLi
journal, January 2017

  • Erickson, Evan M.; Schipper, Florian; Penki, Tirupathi Rao
  • Journal of The Electrochemical Society, Vol. 164, Issue 1
  • DOI: 10.1149/2.0461701jes

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


Changes in electronic structure of the electrochemically Li-ion deintercalated LiNiO2 system investigated by soft X-ray absorption spectroscopy
journal, December 2006


A New High Power LiNi 0.81 Co 0.1 Al 0.09 O 2 Cathode Material for Lithium-Ion Batteries
journal, April 2014


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


A perspective on the high-voltage LiMn1.5Ni0.5O4 spinel cathode for lithium-ion batteries
journal, January 2014

  • Manthiram, Arumugam; Chemelewski, Katharine; Lee, Eun-Sung
  • Energy & Environmental Science, Vol. 7, Issue 4
  • DOI: 10.1039/c3ee42981d

Formation of an Anti-Core–Shell Structure in Layered Oxide Cathodes for Li-Ion Batteries
journal, October 2017


Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries
journal, March 2016

  • Huang, Yiqing; Lin, Yuh-Chieh; Jenkins, David M.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 11
  • DOI: 10.1021/acsami.5b12081

Trainable Weka Segmentation: a machine learning tool for microscopy pixel classification
journal, March 2017


Safety characteristics of Li(Ni0.8Co0.15Al0.05)O2 and Li(Ni1/3Co1/3Mn1/3)O2
journal, February 2006


Structural changes and thermal stability of charged LiNi1/3Co1/3Mn1/3O2 cathode material for Li-ion batteries studied by time-resolved XRD
journal, April 2009


Atomic Insight into the Layered/Spinel Phase Transformation in Charged LiNi 0.80 Co 0.15 Al 0.05 O 2 Cathode Particles
journal, January 2017

  • Zhang, Hanlei; Karki, Khim; Huang, Yiqing
  • The Journal of Physical Chemistry C, Vol. 121, Issue 3
  • DOI: 10.1021/acs.jpcc.6b10220

Structural and Electrochemical Investigation of Li(Ni[sub 0.4]Co[sub 0.15]Al[sub 0.05]Mn[sub 0.4])O[sub 2] Cathode Material
journal, January 2010

  • Rumble, C.; Conry, T. E.; Doeff, Marca
  • Journal of The Electrochemical Society, Vol. 157, Issue 12
  • DOI: 10.1149/1.3494211

Factors that affect Li mobility in layered lithium transition metal oxides
journal, September 2006


A New Type of Protective Surface Layer for High-Capacity Ni-Based Cathode Materials: Nanoscaled Surface Pillaring Layer
journal, February 2013

  • Cho, Yonghyun; Oh, Pilgun; Cho, Jaephil
  • Nano Letters, Vol. 13, Issue 3
  • DOI: 10.1021/nl304558t

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

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

Chemical versus Electrochemical Electrolyte Oxidation on NMC111, NMC622, NMC811, LNMO, and Conductive Carbon
journal, September 2017

  • Jung, Roland; Metzger, Michael; Maglia, Filippo
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 19
  • DOI: 10.1021/acs.jpclett.7b01927

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

In situ soft XAS study on nickel-based layered cathode material at elevated temperatures: A novel approach to study thermal stability
journal, October 2014

  • Yoon, Won-Sub; Haas, Otto; Muhammad, Shoaib
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep06827

Microstructural Changes in LiNi0.8Co0.15Al0.05O2 Positive Electrode Material during the First Cycle
journal, January 2011

  • Zheng, Shijian; Huang, Rong; Makimura, Yoshinari
  • Journal of The Electrochemical Society, Vol. 158, Issue 4
  • DOI: 10.1149/1.3544843

Effect of Ambient Storage on the Degradation of Ni-Rich Positive Electrode Materials (NMC811) for Li-Ion Batteries
journal, January 2018

  • Jung, Roland; Morasch, Robert; Karayaylali, Pinar
  • Journal of The Electrochemical Society, Vol. 165, Issue 2
  • DOI: 10.1149/2.0401802jes

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

Surface Structural and Chemical Evolution of Layered LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) under High Voltage and Elevated Temperature Conditions
journal, November 2018


Nickel-Rich Layered Cathode Materials for Automotive Lithium-Ion Batteries: Achievements and Perspectives
journal, December 2016


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

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

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 perspective on nickel-rich layered oxide cathodes for lithium-ion batteries
journal, January 2017


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