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Exceptional layered cathode stability at 4.8 V via supersaturated high-valence cation design

Nature Energy volume 10, pages 1107–1115 (2025)Cite this article

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Abstract

High-energy-density lithium-ion batteries for extreme conditions require cathodes that remain stable under harsh operation, including ultrahigh cutoff voltage and extreme temperatures. For Ni-rich layered cathodes, raising the charge voltage from 4.3 V to 4.8 V (versus Li+/Li) increases the energy density, yet this sacrifices cycling stability and remains challenging. Here we report a dopant-pairing method that achieves highly enriched Ti4+ (~9-nm surface layer) in LiNi0.8Co0.1Mn0.1O2 facilitated by Na+, enabling significantly enhanced high-voltage cyclability. Such high surface Ti4+ concentrations are unattainable without pairing Na+, representing a form of supersaturation within the layered cathode matrix. The enhanced stability is linked to improved structural integrity and reduced cathode–electrolyte side reactions (for example, O2 and CO2 evolution). In addition, ion transport is better preserved even after prolonged cycling at 4.8 V. This work highlights the power of supersaturated high-valence d0 cation Mz+ (z ≥ 4) in modifying the cathode–electrolyte interactions and degradation pathway.

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Fig. 1: Ti4+ surface doping induced partially ordered structure on NT-NCM.
Fig. 2: Superior electrochemical performance of NT-NCM over P-NCM at extremely high voltage and high temperature.
Fig. 3: Stability mechanism analysis for NT-NCM.
Fig. 4: Characterizations of stability mechanisms in long-term cycling against high voltage.

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Data supporting the findings in the present work are included in the Article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

F.H. acknowledges the support by Science and Technology Commission of Shanghai Municipality (23DZ1200800).

Author information

Authors and Affiliations

  1. College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Hengyi Liao

  2. State Key Lab of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai, China

    Hengyi Liao & Fuqiang Huang

  3. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China

    Yufeng Tang & Wenqin Ma

  4. Shanghai Institute of Space Power-Sources, Shanghai, China

    Yong Liu

  5. State Key Lab of New Ceramic Materials, School of Materials Science and Engineering, Tsinghua University, Beijing, China

    Yanhao Dong

  6. Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, China

    Fuqiang Huang

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  1. Hengyi Liao
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  2. Yufeng Tang
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  4. Yong Liu
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  5. Yanhao Dong
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Contributions

F.H. supervised the project. H.L. synthesized the materials and conducted the electrochemical testing and the characterizations. H.L., Y.D., Y.L. and F.H. analysed the data. H.L., Y.D. and F.H. wrote the paper. Y.T., Y.L. and W.M. contributed to pouch-type full cell assembly. All authors discussed and contributed to the writing.

Corresponding authors

Correspondence to Yanhao Dong or Fuqiang Huang.

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Nature Energy thanks Noriyoshi Matsumi and the other, anonymous, reviewers for their contribution to the peer review of this work.

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Supplementary Figs. 1–60, Notes 1 and 2 and Table 1.

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Liao, H., Tang, Y., Ma, W. et al. Exceptional layered cathode stability at 4.8 V via supersaturated high-valence cation design. Nat Energy 10, 1107–1115 (2025). https://doi.org/10.1038/s41560-025-01831-8

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