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Electrochemomechanical failure in layered oxide cathodes caused by rotational stacking faults

Nature Materials (2024)Cite this article

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Abstract

Electrochemomechanical degradation is one of the most common causes of capacity deterioration in high-energy-density cathodes, particularly intercalation-based layered oxides. Here we reveal the presence of rotational stacking faults (RSFs) in layered lithium transition-metal oxides, arising from specific stacking sequences at different angles, and demonstrate their critical role in determining structural/electrochemical stability. Our combined experiments and calculations show that RSFs facilitate oxygen dimerization and transition-metal migration in layered oxides, fostering microcrack nucleation/propagation concurrently with cumulative electrochemomechanical degradation on cycling. We further show that thermal defect annihilation as a potential solution can suppress RSFs, reducing microcracks and enhancing cyclability in lithium-rich layered cathodes. The common but previously overlooked occurrence of RSFs suggests a new synthesis guideline of high-energy-density layered oxide cathodes.

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Fig. 1: RSFs in layered structures.
Fig. 2: Correlation between RSFs and planar cracking in layered structures.
Fig. 3: Thermal effects to annihilate RSFs.
Fig. 4: Suppression of electrochemomechanical degradation through thermal annihilation.

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All relevant experimental and computational data within the article are available from the corresponding author upon reasonable request.

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Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2021R1A6A3A13039400, 2022R1A6A3A01086197 and 2021R1C1C2004527) as well as by the Korean government (MSIT) (no. RS-2023-00261543). This work was also supported by the Center for Nanoparticle Research at the Institute for Basic Science (IBS) (IBS-R006-A2) and LG Energy Solution.

Author information

Author notes

  1. Donggun Eum

    Present address: Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA

  2. These authors contributed equally: Donggun Eum, Sung-O Park, Ho-Young Jang.

Authors and Affiliations

  1. Department of Materials Science and Engineering, Institute for Rechargeable Battery Innovations, Research Institute of Advanced Materials, Seoul National University, Seoul, Republic of Korea

    Donggun Eum, Sung-O Park, Ho-Young Jang, Youngjun Jeon, Jun-Hyuk Song, Sangwook Han, Kyoungoh Kim & Kisuk Kang

  2. Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul National University, Seoul, Republic of Korea

    Donggun Eum & Kisuk Kang

  3. Institute of Engineering Research, College of Engineering, Seoul National University, Seoul, Republic of Korea

    Kisuk Kang

  4. School of Chemical and Biological Engineering, College of Engineering, Seoul National University, Seoul, Republic of Korea

    Kisuk Kang

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Contributions

D.E. and K. Kang conceived the original idea of this study, and D.E., S.-O.P., H.-Y.J. and K. Kang designed this research project. D.E. and H.-Y.J. conducted and analysed all the experiments, with constructive advice from Y.J., S.H. and K. Kim. S.-O.P. mainly performed all the computational calculations, and J.-H.S. contributed with the preliminary results for the DFT calculations. D.E., S.-O.P., H.-Y.J. and K. Kang wrote the paper together, and K. Kang supervised all aspects of the project.

Corresponding author

Correspondence to Kisuk Kang.

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Nature Materials thanks Hui Xia and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Notes 1–8 and Figs. 1–24.

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Eum, D., Park, SO., Jang, HY. et al. Electrochemomechanical failure in layered oxide cathodes caused by rotational stacking faults. Nat. Mater. (2024). https://doi.org/10.1038/s41563-024-01899-9

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