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Suppressing strain propagation in ultrahigh-Ni cathodes during fast charging via epitaxial entropy-assisted coating

Nature Energy volume 9, pages 345–356 (2024)Cite this article

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Abstract

Surface reconstruction and the associated severe strain propagation have long been reported as the major cause of cathode failure during fast charging and long-term cycling. Despite tremendous attempts, no known strategies can simultaneously address the electro-chemomechanical instability without sacrificing energy and power density. Here we report an epitaxial entropy-assisted coating strategy for ultrahigh-Ni LiNixCoyMn1−x−yO2 (x ≥ 0.9) cathodes via an oriented attachment-driven reaction between Wadsley–Roth phase-based oxides and the layered-oxide cathodes. The high anti-cracking and anti-corrosion tolerances as well as the fast ionic transport of the entropy-assisted surface effectively improved the fast charging/discharging capability, wide temperature tolerance and thermal stability of the ultrahigh-Ni cathodes. Comprehensive analysis from the primary and secondary particle level to the electrode level using multi-scale in situ synchrotron X-ray probes reveals greatly reduced lattice dislocations, anisotropic lattice strain and oxygen release as well as improved bulk/local structural stability, even when charging beyond the threshold state of charge (75%) of layered cathodes.

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Fig. 1: The design principle and structures of epitaxial entropy-assisted coating.
Fig. 2: Electrochemical and post mortem evaluations.
Fig. 3: Bulk and local phase structure stability characterizations.
Fig. 4: Strain evaluation within the cathode particle through BCDI characterizations.
Fig. 5: Local structure/environment analysis during operation.
Fig. 6: Comparison between entropy-assisted cathodes.

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Data availability

The data supporting the findings of this study are included within the article and its Supplementary Information files. Source data are provided with this paper.

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Acknowledgements

Research at the Argonne National Laboratory was funded by the US Department of Energy, Vehicle Technologies Office. Use of the APS and the Center for Nanoscale Materials, both Office of Science user facilities, was supported by the US Department of Energy, Office of Science and Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. G.-L.X. and K.A. thank the Clean Vehicle Consortium, US–China Clean Energy Research Center (CERC-CVC2), for support.

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Author notes

  1. These authors contributed equally: Chen Zhao, Chuanwei Wang.

Authors and Affiliations

  1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA

    Chen Zhao, Xiang Liu, Yan Qin, Zhenzhen Yang, Wenquan Lu, Gui-Liang Xu & Khalil Amine

  2. College of Energy, Xiamen University, Xiamen, China

    Chuanwei Wang & Jun-Tao Li

  3. X-ray Science Division, Argonne National Laboratory, Lemont, IL, USA

    Inhui Hwang, Tianyi Li, Junjing Deng, Wenqian Xu, Chengjun Sun, Wonsuk Cha, Ross Harder, Yi Jiang, Tekin Bicer & Luxi Li

  4. Center for Nanoscale Materials, Argonne National Laboratory, Lemont, IL, USA

    Xinwei Zhou, Guanyi Wang & Yuzi Liu

  5. London Centre for Nanotechnology, University College London, London, UK

    Jiecheng Diao & Ian Robinson

  6. Center for Transformative Science, ShanghaiTech University, Shanghai, China

    Jiecheng Diao

  7. Condensed Matter Physics and Materials Science Department, Brookhaven National Laboratory, Upton, NY, USA

    Longlong Wu & Ian Robinson

  8. Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry of Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen, China

    Shi-Gang Sun

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Contributions

G.-L.X., C.Z. and K.A. conceived the ideas. G.-L.X. and K.A. supervised the project. C.W., C.Z., J.-T. L. and S.-G.S. developed and synthesized cathode materials. C.Z. conducted electrochemical tests for various cells. Y.L., C.Z., G.W. and X.Z. conducted the TEM and SEM characterizations. Z.Y. conducted the cross-section SEM characterizations. C.Z., X.L., T.L. and W.X. carried out synchrotron HEXRD studies of various materials. L.L. and C.Z. conducted the in situ CMCD and BCDI characterization and analysis with the help of J. Diao, L.W., W.C., R.H. and I.R. I.H., C.S. and C.Z. conducted the XAS studies of various materials. J. Deng conducted the X-ray ptychography and data processing with the help of Y.J. and T.B. Y.Q. and W.L. conducted DSC tests. G.-L.X. and C.Z. drafted the paper with the help of all the other authors.

Corresponding authors

Correspondence to Luxi Li, Yuzi Liu, Gui-Liang Xu or Khalil Amine.

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Competing interests

For G.-L.X., C.Z., Y.L. and K.A., a US non-provisional patent application, patent application no. 17/955,092, has been filed for this work. The patent is related to the coating strategy reported in this work and submitted by Argonne National Laboratory. All other authors declare no competing interests.

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Nature Energy thanks Ben Breitung and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–32, Tables 1–6 and discussion.

Supplementary Video 1

Complete evolution patterns of in situ coherent multi-crystal diffraction characterization.

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Statistical source data.

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Zhao, C., Wang, C., Liu, X. et al. Suppressing strain propagation in ultrahigh-Ni cathodes during fast charging via epitaxial entropy-assisted coating. Nat Energy 9, 345–356 (2024). https://doi.org/10.1038/s41560-024-01465-2

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