Navigating thermal stability intricacies of high-nickel cathodes for high-energy lithium batteries

Cui, Zehao; Liu, Chen; Wang, Feng; Manthiram, Arumugam

doi:10.1038/s41560-025-01731-x

Title: Navigating thermal stability intricacies of high-nickel cathodes for high-energy lithium batteries

Journal Article · Fri Mar 07 00:00:00 UTC 2025 · Nature Energy

DOI: https://doi.org/10.1038/s41560-025-01731-x · OSTI ID:2998692

^[1];

^[2];

^[1]

Univ. of Texas, Austin, TX (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

High-nickel oxide cathodes, LiNi_xM_1−xO₂ (x ≥ 0.8), are preferred in automotive lithium batteries, but they face thermal instability challenges. Inconsistent literature reports and unstandardized testing protocols further complicate quantitative assessments of the thermal stability of these cathodes. Here, we present here a statistical thermal analysis based on the differential scanning calorimetry measurements of 15 representative cathode materials with different compositions, morphologies and states of charge. The findings reveal that each cathode has a critical state of charge that defines its safe operating limit, which is affected by the metal–oxygen bond strength and surface reactivity. The thermal runaway temperature is dictated by the layered Li_1−xNiO₂ to LiNi₂O₄ spinel-like phase transition, which is thermodynamically determined by the metal–oxygen bond covalency and kinetically influenced by the cation mixing and particle size. Raman spectroscopy is used to predict the thermal runaway temperature on the basis of the linear relationship between them. Finally, we propose a thermal stability index to quantify cathode thermal stability as a guide for developing safer high-nickel cathodes.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)

Grant/Contract Number:: AC02-06CH11357; AC05-76RL01830

OSTI ID:: 2998692

Journal Information:: Nature Energy, Journal Name: Nature Energy Journal Issue: 4 Vol. 10; ISSN 2058-7546

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

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 Nam, Kyung-Wan; Bak, Seong-Min; Hu, Enyuan Advanced Functional Materials, Vol. 23, Issue 8 https://doi.org/10.1002/adfm.201200693	journal	June 2012
Tracking the Influence of Thermal Expansion and Oxygen Vacancies on the Thermal Stability of Ni‐Rich Layered Cathode Materials Lee, Eunkang; Muhammad, Shoaib; Kim, Taewhan Advanced Science, Vol. 7, Issue 12 https://doi.org/10.1002/advs.201902413	journal	April 2020
Magnesium Substitution in Ni‐Rich NMC Layered Cathodes for High‐Energy Lithium Ion Batteries Gomez‐Martin, Aurora; Reissig, Friederike; Frankenstein, Lars Advanced Energy Materials, Vol. 12, Issue 8 https://doi.org/10.1002/aenm.202103045	journal	January 2022
Challenges and Opportunities to Mitigate the Catastrophic Thermal Runaway of High‐Energy Batteries Wang, Yu; Feng, Xuning; Huang, Wensheng Advanced Energy Materials, Vol. 13, Issue 15 https://doi.org/10.1002/aenm.202203841	journal	February 2023
Assessing the Intrinsic Roles of Key Dopant Elements in High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries Cui, Zehao; Guo, Zezhou; Manthiram, Arumugam Advanced Energy Materials, Vol. 13, Issue 12 https://doi.org/10.1002/aenm.202203853	journal	February 2023
There and Back Again-The Journey of LiNiO ₂ as a Cathode Active Material Bianchini, Matteo; Roca-Ayats, Maria; Hartmann, Pascal Angewandte Chemie International Edition, Vol. 58, Issue 31 https://doi.org/10.1002/anie.201812472	journal	May 2019
Kinetic Limitations in Single‐Crystal High‐Nickel Cathodes Wang, Feng; Ge, Mingyuan; Wi, Sungun Angewandte Chemie International Edition https://doi.org/10.1002/anie.202012773	journal	November 2020
Comparative study of LiCoO2, LiNi12Co12O2 and LiNiO2 for 4 volt secondary lithium cells Ohzuku, Tsutomu; Ueda, Atsushi; Nagayama, Masatoshi Electrochimica Acta, Vol. 38, Issue 9 https://doi.org/10.1016/0013-4686(93)80046-3	journal	June 1993
Temperature-programmed reduction and oxidation of metals supported on $gamma;-alumina Kadkhodayan, A. Journal of Catalysis, Vol. 117, Issue 2 https://doi.org/10.1016/0021-9517(89)90342-4	journal	June 1989
ARC studies of the thermal stability of three different cathode materials: LiCoO2; Li[Ni0.1Co0.8Mn0.1]O2; and LiFePO4, in LiPF6 and LiBoB EC/DEC electrolytes Jiang, J.; Dahn, J. R. Electrochemistry Communications, Vol. 6, Issue 1 https://doi.org/10.1016/j.elecom.2003.10.011	journal	January 2004
A 3D thermal runaway propagation model for a large format lithium ion battery module Feng, Xuning; Lu, Languang; Ouyang, Minggao Energy, Vol. 115 https://doi.org/10.1016/j.energy.2016.08.094	journal	November 2016
Thermal runaway mechanism of lithium ion battery for electric vehicles: A review Feng, Xuning; Ouyang, Minggao; Liu, Xiang Energy Storage Materials, Vol. 10 https://doi.org/10.1016/j.ensm.2017.05.013	journal	January 2018
Unlocking the self-supported thermal runaway of high-energy lithium-ion batteries Hou, Junxian; Feng, Xuning; Wang, Li Energy Storage Materials, Vol. 39 https://doi.org/10.1016/j.ensm.2021.04.035	journal	August 2021
Boron doped Ni-rich LiNi0.85Co0.10Mn0.05O2 cathode materials studied by structural analysis, solid state NMR, computational modeling, and electrochemical performance Amalraj, Susai Francis; Raman, Ravikumar; Chakraborty, Arup Energy Storage Materials, Vol. 42 https://doi.org/10.1016/j.ensm.2021.08.005	journal	November 2021
Probing the thermal degradation mechanism of polycrystalline and single-crystal Li(Ni0.8Co0.1Mn0.1)O2 cathodes from the perspective of oxygen vacancy diffusion Wei, Zesen; Liang, Chen; Jiang, Lihua Energy Storage Materials, Vol. 56 https://doi.org/10.1016/j.ensm.2023.01.029	journal	February 2023
Investigating the critical characteristics of thermal runaway process for LiFePO4/graphite batteries by a ceased segmented method Tang, Xuan; Zhang, Guangxu; Wang, Xueyuan iScience, Vol. 24, Issue 10 https://doi.org/10.1016/j.isci.2021.103088	journal	October 2021
Thermal Runaway of Lithium-Ion Batteries without Internal Short Circuit Liu, Xiang; Ren, Dongsheng; Hsu, Hungjen Joule, Vol. 2, Issue 10 https://doi.org/10.1016/j.joule.2018.06.015	journal	October 2018
Mitigating Thermal Runaway of Lithium-Ion Batteries Feng, Xuning; Ren, Dongsheng; He, Xiangming Joule, Vol. 4, Issue 4 https://doi.org/10.1016/j.joule.2020.02.010	journal	April 2020
Time-resolved XRD study on the thermal decomposition of nickel-based layered cathode materials for Li-ion batteries Yoon, Won-Sub; Chung, Kyung Yoon; Balasubramanian, Mahalingam Journal of Power Sources, Vol. 163, Issue 1 https://doi.org/10.1016/j.jpowsour.2006.01.043	journal	December 2006
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 Noh, Hyung-Joo; Youn, Sungjune; Yoon, Chong Seung Journal of Power Sources, Vol. 233 https://doi.org/10.1016/j.jpowsour.2013.01.063	journal	July 2013
A highly safe battery with a non-flammable triethyl-phosphate-based electrolyte Matsumoto, Kazuaki; Inoue, Kazuhiko; Utsugi, Koji Journal of Power Sources, Vol. 273 https://doi.org/10.1016/j.jpowsour.2014.09.086	journal	January 2015
Comprehensive calorimetry of the thermally-induced failure of a lithium ion battery Liu, Xuan; Stoliarov, Stanislav I.; Denlinger, Matthew Journal of Power Sources, Vol. 280 https://doi.org/10.1016/j.jpowsour.2015.01.125	journal	April 2015
Effects of vibrations and shocks on lithium-ion cells Brand, Martin J.; Schuster, Simon F.; Bach, Tobias Journal of Power Sources, Vol. 288 https://doi.org/10.1016/j.jpowsour.2015.04.107	journal	August 2015
A systematic study on the reactivity of different grades of charged Li[NixMnyCoz]O2 with electrolyte at elevated temperatures using accelerating rate calorimetry Ma, Lin; Nie, Mengyun; Xia, Jian Journal of Power Sources, Vol. 327 https://doi.org/10.1016/j.jpowsour.2016.07.039	journal	September 2016
A solvent-anchored non-flammable electrolyte Huang, Zhuojun; Lai, Jian-Cheng; Kong, Xian Matter, Vol. 6, Issue 2 https://doi.org/10.1016/j.matt.2022.11.003	journal	February 2023
Different thermal degradation mechanisms: Role of aluminum in Ni-rich layered cathode materials Jo, Eunmi; Park, Jae-Ho; Park, Junbeom Nano Energy, Vol. 78 https://doi.org/10.1016/j.nanoen.2020.105367	journal	December 2020
Thermal runaway mechanism of lithium-ion battery with LiNi0.8Mn0.1Co0.1O2 cathode materials Li, Yan; Liu, Xiang; Wang, Li Nano Energy, Vol. 85 https://doi.org/10.1016/j.nanoen.2021.105878	journal	July 2021
A Mg-Doped High-Nickel Layered Oxide Cathode Enabling Safer, High-Energy-Density Li-Ion Batteries Xie, Qiang; Li, Wangda; Manthiram, Arumugam Chemistry of Materials, Vol. 31, Issue 3 https://doi.org/10.1021/acs.chemmater.8b03900	journal	January 2019
Insights into Boron-Based Polyanion-Tuned High-Nickel Cathodes for High-Energy-Density Lithium-Ion Batteries Xie, Qiang; Li, Wangda; Dolocan, Andrei Chemistry of Materials, Vol. 31, Issue 21 https://doi.org/10.1021/acs.chemmater.9b02916	journal	October 2019
Probing Thermal Stability of Li-Ion Battery Ni-Rich Layered Oxide Cathodes by means of Operando Gas Analysis and Neutron Diffraction Geng, Linxiao; Liu, Jue; Wood, David L. ACS Applied Energy Materials, Vol. 3, Issue 7 https://doi.org/10.1021/acsaem.0c01105	journal	June 2020
Gradient Boracic Polyanion Doping-Derived Surface Lattice Modulation of High-Voltage Ni-Rich Layered Cathodes for High-Energy-Density Li-Ion Batteries Li, Fangkun; Liu, Zhengbo; Liao, Caijian ACS Energy Letters, Vol. 8, Issue 11 https://doi.org/10.1021/acsenergylett.3c02072	journal	October 2023
Structural and Electrochemical Aspects of LiNi _0.8 Co _0.1 Mn _0.1 O ₂ Cathode Materials Doped by Various Cations Weigel, Tina; Schipper, Florian; Erickson, Evan M. ACS Energy Letters, Vol. 4, Issue 2 https://doi.org/10.1021/acsenergylett.8b02302	journal	January 2019
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 Bak, Seong-Min; Hu, Enyuan; Zhou, Yongning ACS Applied Materials & Interfaces, Vol. 6, Issue 24 https://doi.org/10.1021/am506712c	journal	December 2014
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 Bak, Seong-Min; Nam, Kyung-Wan; Chang, Wonyoung Chemistry of Materials, Vol. 25, Issue 3 https://doi.org/10.1021/cm303096e	journal	January 2013
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
Raman Microspectrometry Applied to the Study of Electrode Materials for Lithium Batteries Baddour-Hadjean, Rita; Pereira-Ramos, Jean-Pierre Chemical Reviews, Vol. 110, Issue 3 https://doi.org/10.1021/cr800344k	journal	March 2010
Tuning of Thermal Stability in Layered Li(Ni _x Mn _y Co _z )O ₂ Zheng, Jiaxin; Liu, Tongchao; Hu, Zongxiang Journal of the American Chemical Society, Vol. 138, Issue 40 https://doi.org/10.1021/jacs.6b07771	journal	September 2016
A solid future for battery development Janek, Jürgen; Zeier, Wolfgang G. Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.141	journal	September 2016
A reflection on lithium-ion battery cathode chemistry Manthiram, Arumugam Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15355-0	journal	March 2020
Non-flammable solvent-free liquid polymer electrolyte for lithium metal batteries Zhu, Guo-Rui; Zhang, Qin; Liu, Qing-Song Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-40394-8	journal	August 2023
Current status and challenges for automotive battery production technologies Kwade, Arno; Haselrieder, Wolfgang; Leithoff, Ruben Nature Energy, Vol. 3, Issue 4 https://doi.org/10.1038/s41560-018-0130-3	journal	April 2018
Non-flammable electrolytes with high salt-to-solvent ratios for Li-ion and Li-metal batteries Zeng, Ziqi; Murugesan, Vijayakumar; Han, Kee Sung Nature Energy, Vol. 3, Issue 8 https://doi.org/10.1038/s41560-018-0196-y	journal	July 2018
Characterising thermal runaway within lithium-ion cells by inducing and monitoring internal short circuits Finegan, Donal P.; Darcy, Eric; Keyser, Matthew Energy & Environmental Science, Vol. 10, Issue 6 https://doi.org/10.1039/C7EE00385D	journal	January 2017
Measuring Oxygen Release from Delithiated LiNi _x Mn _y Co _1-x-y O ₂ and Its Effects on the Performance of High Voltage Li-Ion Cells Xiong, D. J.; Ellis, L. D.; Li, J. Journal of The Electrochemical Society, Vol. 164, Issue 13 https://doi.org/10.1149/2.0291713jes	journal	January 2017
Determination of the Voltage Dependence of Parasitic Heat Flow in Lithium Ion Cells Using Isothermal Microcalorimetry Downie, L. E.; Dahn, J. R. Journal of The Electrochemical Society, Vol. 161, Issue 12 https://doi.org/10.1149/2.0301412jes	journal	January 2014
Is Cobalt Needed in Ni-Rich Positive Electrode Materials for Lithium Ion Batteries? Li, Hongyang; Cormier, Marc; Zhang, Ning Journal of The Electrochemical Society, Vol. 166, Issue 4 https://doi.org/10.1149/2.1381902jes	journal	January 2019
Towards Understanding Heat Generation Characteristics of Li-Ion Batteries by Calorimetry, Impedance, and Potentiometry Studies Manikandan, Balasundaram; Yap, Christopher; Balaya, Palani Journal of The Electrochemical Society, Vol. 164, Issue 12 https://doi.org/10.1149/2.1811712jes	journal	January 2017
In situ and Operando Raman Spectroscopy of Layered Transition Metal Oxides for Li-ion Battery Cathodes Flores, Eibar; Novák, Petr; Berg, Erik J. Frontiers in Energy Research, Vol. 6 https://doi.org/10.3389/fenrg.2018.00082	journal	August 2018
Electrical safety of commercial Li-ion cells based on NMC and NCA technology compared to LFP technology Brand, Martin; Gläser, Simon; Geder, Jan World Electric Vehicle Journal, Vol. 6, Issue 3 https://doi.org/10.3390/wevj6030572	journal	September 2013