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:
-
[1];
[2];
[4];
[4];
[5];
[3];
[4]
- Robert Bosch LLC, Sunnyvale, CA (United States); Karlsruhe Inst. of Technology (KIT) (Germany)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Robert Bosch LLC, Sunnyvale, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
- Karlsruhe Inst. of Technology (KIT) (Germany); Aalen Univ. (Germany)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (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. https://doi.org/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. https://doi.org/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 = {Wed Apr 24 00:00:00 EDT 2019},
month = {Wed Apr 24 00:00:00 EDT 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 39 works
Citation information provided by
Web of Science
Web of Science
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:
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
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
Singlet oxygen evolution from layered transition metal oxide cathode materials and its implications for lithium-ion batteries
journal, October 2018
- Wandt, Johannes; Freiberg, Anna T. S.; Ogrodnik, Alexander
- Materials Today, Vol. 21, Issue 8
The application of synchrotron X-ray techniques to the study of rechargeable batteries
journal, November 2018
- Gong, Zhengliang; Yang, Yong
- Journal of Energy Chemistry, Vol. 27, Issue 6
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
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
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
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
Thermal behavior of delithiated Li(Ni0.8Co0.15Al0.05)O2 and Li1.1(Ni1/3Co1/3Mn1/3)0.9O2 powders
journal, December 2007
- Belharouak, Ilias; Lu, Wenquan; Liu, Jun
- Journal of Power Sources, Vol. 174, Issue 2
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
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
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
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
Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials
journal, April 2018
- Mu, Linqin; Lin, Ruoqian; Xu, Rong
- Nano Letters, Vol. 18, Issue 5
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
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
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
Explore the Effects of Microstructural Defects on Voltage Fade of Li- and Mn-Rich Cathodes
journal, September 2016
- Hu, Enyuan; Lyu, Yingchun; Xin, Huolin L.
- Nano Letters, Vol. 16, Issue 10
SIXPack a Graphical User Interface for XAS Analysis Using IFEFFIT
journal, January 2005
- Webb, S. M.
- Physica Scripta
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
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
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
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
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
- Konishi, Hiroaki; Yoshikawa, Masanori; Hirano, Tatsumi
- Journal of Power Sources, Vol. 244
Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries
journal, July 2013
- Noh, Hyung-Joo; Youn, Sungjune; Yoon, Chong Seung
- Journal of Power Sources, Vol. 233
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
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
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
Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials
journal, March 2018
- Tian, Chixia; Xu, Yahong; Nordlund, Dennis
- Joule, Vol. 2, Issue 3
Changes in electronic structure of the electrochemically Li-ion deintercalated LiNiO2 system investigated by soft X-ray absorption spectroscopy
journal, December 2006
- Yoon, Won-Sub; Chung, Kyung Yoon; McBreen, James
- Journal of Power Sources, Vol. 163, Issue 1
A New High Power LiNi 0.81 Co 0.1 Al 0.09 O 2 Cathode Material for Lithium-Ion Batteries
journal, April 2014
- Jo, Minki; Noh, Mijung; Oh, Pilgun
- Advanced Energy Materials, Vol. 4, Issue 13
Mesoscale Battery Science: The Behavior of Electrode Particles Caught on a Multispectral X-ray Camera
journal, June 2018
- Wei, Chenxi; Xia, Sihao; Huang, Hai
- Accounts of Chemical Research, Vol. 51, Issue 10
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
Formation of an Anti-Core–Shell Structure in Layered Oxide Cathodes for Li-Ion Batteries
journal, October 2017
- Zhang, Hanlei; Omenya, Fredrick; Whittingham, M. Stanley
- ACS Energy Letters, Vol. 2, Issue 11
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
Trainable Weka Segmentation: a machine learning tool for microscopy pixel classification
journal, March 2017
- Arganda-Carreras, Ignacio; Kaynig, Verena; Rueden, Curtis
- Bioinformatics, Vol. 33, Issue 15
Safety characteristics of Li(Ni0.8Co0.15Al0.05)O2 and Li(Ni1/3Co1/3Mn1/3)O2
journal, February 2006
- Belharouak, Ilias; Lu, Wenquan; Vissers, Donald
- Electrochemistry Communications, Vol. 8, Issue 2
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
- Nam, Kyung-Wan; Yoon, Won-Sub; Yang, Xiao-Qing
- Journal of Power Sources, Vol. 189, Issue 1
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
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
Atomic-Resolution Visualization of Distinctive Chemical Mixing Behavior of Ni, Co, and Mn with Li in Layered Lithium Transition-Metal Oxide Cathode Materials
journal, July 2015
- Yan, Pengfei; Zheng, Jianming; Lv, Dongping
- Chemistry of Materials, Vol. 27, Issue 15
Factors that affect Li mobility in layered lithium transition metal oxides
journal, September 2006
- Kang, Kisuk; Ceder, Gerbrand
- Physical Review B, Vol. 74, Issue 9
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
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
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
Combining In Situ Synchrotron X-Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium-Ion Batteries
journal, June 2012
- Nam, Kyung-Wan; Bak, Seong-Min; Hu, Enyuan
- Advanced Functional Materials, Vol. 23, Issue 8
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
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
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
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
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
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
- Mukherjee, Pinaki; Faenza, Nicholas V.; Pereira, Nathalie
- Chemistry of Materials, Vol. 30, Issue 23
Nickel-Rich Layered Cathode Materials for Automotive Lithium-Ion Batteries: Achievements and Perspectives
journal, December 2016
- Myung, Seung-Taek; Maglia, Filippo; Park, Kang-Joon
- ACS Energy Letters, Vol. 2, Issue 1
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
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
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
A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries
journal, January 2017
- Manthiram, Arumugam; Song, Bohang; Li, Wangda
- Energy Storage Materials, Vol. 6
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
MAGIs regulate aPKC to enable balanced distribution of intercellular tension for epithelial sheet homeostasis
journal, March 2021
- Matsuzawa, Kenji; Ohga, Hayato; Shigetomi, Kenta
- Communications Biology, Vol. 4, Issue 1
Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li1-xCo1/3Ni1/3Mn1/3O2 Electrode System by Combination of Soft and Hard X-Ray Absorption Spectroscopy.
journal, March 2006
- Yoon, Won-Sub; Balasubramanian, Mahalingam; Chung, Kyung Yoon
- ChemInform, Vol. 37, Issue 13
Works referencing / citing this record:
Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies
journal, December 2019
- Liang, Longwei; Zhang, Wenheng; Zhao, Fei
- Advanced Materials Interfaces, Vol. 7, Issue 3
Long-term chemothermal stability of delithiated NCA in polymer solid-state batteries
journal, January 2019
- Besli, Münir M.; Usubelli, Camille; Metzger, Michael
- Journal of Materials Chemistry A, Vol. 7, Issue 47
Using in situ and operando methods to characterize phase changes in charged lithium nickel cobalt aluminum oxide cathode materials
journal, January 2020
- Hwang, Sooyeon; Stach, Eric A.
- Journal of Physics D: Applied Physics, Vol. 53, Issue 11
Long-Term Chemothermal Stability of Delithiated NCA in Polymer Solid-State Batteries
text, January 2019
- Besli, Münir M.; Usubelli, Camille; Metzger, Michael
- Karlsruhe