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

Nature Energy volume 10, pages 490–501 (2025)Cite this article

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A Publisher Correction to this article was published on 28 March 2025

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Abstract

High-nickel oxide cathodes, LiNixM1−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. 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 Li1−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.

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Fig. 1: Design of materials for statistical analysis of the thermal stability of high-Ni cathodes.
Fig. 2: Thermal stability evaluation of LNO and single-element-doped cathodes.
Fig. 3: Thermally driven phase evolution using synchrotron-based in situ-heating XRD.
Fig. 4: Impact of particle morphology on the thermal stability of NMC cathodes.
Fig. 5: Raman spectroscopy for characterizing the thermal stability of the cathode.
Fig. 6: Delineating the factors that influence the thermal stability metrics.

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The data that support the findings of this study are available within the Article and its Supplementary Information.

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy (EERE), Office of Vehicle Technologies of the US Department of Energy through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) award number DE-AC05-76RLO1830 (Z.C. and A.M.) and the Welch Foundation grant F-1254 (C.L. and A.M.). The synchrotron characterization work was supported by the US Department of Energy EERE, Vehicle Technologies Office, under Contract No. DE-AC02-06CH11357 (F.W.). We would like to thank S. Lee, S. Kmiec, A. Tayal and D. Wu for their assistance in the single-crystal cathode synthesis, Raman spectroscopy data collection, in situ-heating XRD data processing and ARC data collection, respectively. We thank R. Sim for insightful discussions.

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Authors and Affiliations

  1. Walker Department of Mechanical Engineering and Texas Materials Institute, The University of Texas at Austin, Austin, TX, USA

    Zehao Cui, Chen Liu & Arumugam Manthiram

  2. Argonne National Laboratory, Lemont, IL, USA

    Feng Wang

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Contributions

Z.C., C.L. and A.M. conceived the idea and designed the experiments. Z.C. and C.L. performed the synthesis of the materials, DSC and TGA measurements and characterized the physico-chemical properties of the other materials. F.W. performed the in situ heating XRD experiments. All authors wrote the paper. A.M. supervised the work.

Corresponding author

Correspondence to Arumugam Manthiram.

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Competing interests

A.M. is a co-founder of TexPower EV Technologies, a company focusing on cobalt-free cathode materials for lithium-based batteries. The other authors declare no competing interests.

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Nature Energy thanks Yaxiang Lu, Jinbao Zhao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–50, Tables 1–4, Notes 1–9 and Refs. 1–60.

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Cui, Z., Liu, C., Wang, F. et al. Navigating thermal stability intricacies of high-nickel cathodes for high-energy lithium batteries. Nat Energy 10, 490–501 (2025). https://doi.org/10.1038/s41560-025-01731-x

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