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Tailoring planar strain for robust structural stability in high-entropy layered sodium oxide cathode materials

Nature Energy (2024)Cite this article

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Abstract

High-entropy oxides have expanded the potential for high-performance Na-ion battery cathodes due to their vast compositional space and entropy-driven stabilization. However, a rational design approach for optimizing their composition is still lacking. Here, we develop an O3-type oxide cathode composed of all-3d transition metals, NaNi0.3Cu0.1Fe0.2Mn0.3Ti0.1O2 (NCFMT), which exhibits improved reversible specific capacity and exceptional cycling stability. Replacing Ti4+ with Sn4+ ions (NaNi0.3Cu0.1Fe0.2Mn0.3Sn0.1O2; NCFMS) results in poor structural reversibility and diminished cycling stability. Our investigations suggest that the structural integrity of the layered cathode is affected by the compatibility of constituent elements within the transition metal layers (TMO2). In NCFMS, planar strain induced by metal-ion displacement triggers elemental segregation and crack formation during repeated cycling. In contrast, NCFMT demonstrates a robust structural framework for stable Na+ storage due to its high mechanochemical compatibility among constituent elements. This understanding provides insights for designing outstanding layered high-entropy cathode materials.

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Fig. 1: Atomic structure difference between NCFMT and NCFMS.
Fig. 2: Superior electrochemical performance of NCFMT over NCFMS.
Fig. 3: Structural characterizations of the NCFMS and NCFMT cathodes.
Fig. 4: Structural characterizations of the cycled NCFMS and NCFMT cathodes.
Fig. 5: Sn segregation in the interior of NCFMS single-crystal particles.
Fig. 6: Full-cell performance of NCFMT//HC in different voltage ranges.

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The data supporting the findings of this study are available within the article and its Supplementary Information files.

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Acknowledgements

Y. Lu acknowledges the support of the National Key R&D Program of China (2022YFB3807800), Y. Lu, Y.-S.H. and F.D. acknowledge the support of the National Natural Science Foundation (NSFC) of China (52122214, 52394174 and 52202332) and Y. Lu acknowledges the support of the Youth Innovation Promotion Association of the Chinese Academy of Sciences (2020006). Y.-S.H. acknowledges the support of the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA0400000) and the Jiangsu Provincial Carbon Peak and Neutrality Innovation Program (Industry Tackling on Prospect and Key Technology), China (BE2022002-5). We thank the 1W1B beamline of Beijing Synchrotron Radiation Facility for support.

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Authors and Affiliations

  1. Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Feixiang Ding, Pengxiang Ji, Zhen Han, Xueyan Hou, Yang Yang, Zilin Hu, Yaoshen Niu, Yuan Liu, Jiao Zhang, Xiaohui Rong, Yaxiang Lu, Dong Su, Liquan Chen & Yong-Sheng Hu

  2. Huairou Division, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Feixiang Ding, Yaxiang Lu, Dong Su, Liquan Chen & Yong-Sheng Hu

  3. College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing, China

    Pengxiang Ji, Yang Yang, Zilin Hu, Yuan Liu, Xiaohui Rong, Yaxiang Lu, Dong Su, Liquan Chen & Yong-Sheng Hu

  4. Yangtze River Delta Physics Research Center Co. Ltd, Liyang, China

    Xiaohui Rong, Yaxiang Lu, Liquan Chen & Yong-Sheng Hu

  5. Department of Energy Storage Science and Engineering, School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing, China

    Huican Mao

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Contributions

F.D., Y. Lu and Y.-S.H. conceived the idea and directed the project. F.D. synthesized the high-entropy oxide materials and carried out the electrochemical experiments and materials characterization with X.H., Y.Y., Z. Hu, Y.N., Y. Liu and J.Z. P.J., Z. Han, X.R. and D.S. contributed to the FIB and STEM analyses. H.M. contributed to DFT/BV simulations. F.D. wrote the original draft; Y. Lu, H.M., D.S., L.C. and Y.-S.H. reviewed and edited the manuscript. All the authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Yaxiang Lu, Huican Mao, Dong Su or Yong-Sheng Hu.

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Nature Energy thanks Shaohua Guo, Weifeng Wei and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–22, Discussions 1 and 2, Tables 1–8 and References.

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Ding, F., Ji, P., Han, Z. et al. Tailoring planar strain for robust structural stability in high-entropy layered sodium oxide cathode materials. Nat Energy (2024). https://doi.org/10.1038/s41560-024-01616-5

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