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Designing an isotropic epilayer for stable 4.2 V solid-state Na batteries

Nature Energy volume 10, pages 1305–1314 (2025)Cite this article

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Abstract

Side reactions between high-voltage cathodes and electrolytes remain a critical obstacle to the advancement of solid-state batteries—particularly for Na-ion systems—due to the higher Na+/Na redox potential. Despite recent extensive efforts, achieving a long cycle life is still challenging at the 4.2 V cut-off (versus Na+/Na). Here we design a room-temperature isotropic epitaxial growth to achieve a relatively uniform and dense metal–organic framework epilayer on Na3V2O2(PO4)2F surfaces. Despite using polyethylene oxide, a typical ether-based solid polymer electrolyte, the cathode with isotropic epilayer exhibits enhanced cycling performance at the 4.2 V cut-off (retaining up to 77.9% of its initial capacity after 1,500 cycles). Combining experimental measurements and theoretical analyses, the key factor governing isotropic epitaxial growth behaviour is explicitly elucidated. Furthermore, we develop a self-designed high-sensitivity characterization method, in situ linear sweep voltammetry coupled with gas chromatography–mass spectrometry, to elucidate the failure mechanism of polyethylene oxide on Na3V2O2(PO4)2F surfaces and and to reveal the excellent electrochemical stability of the isotropic epilayer. Interestingly, the universality of this approach has also been validated, highlighting its strong potential as an effective strategy for enabling high-energy-density batteries.

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Fig. 1: Schematics of the surface engineering and Na+ transport mechanism.
Fig. 2: Characterization of the isotropic MOF epilayer.
Fig. 3: Electrochemical performances of ASSBs with as-prepared materials.
Fig. 4: The degradation mechanism of the PEO electrolyte.

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

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Acknowledgements

This work was supported by National Natural Science Foundation (NSFC) of China (grant nos. 52394170 and 52394174, Y.-S.H.; 22422906 and 92372116; X.R.; 52072370 and 92472201; J.Z.), Strategic Priority Research Program of the Chinese Academy of Sciences (grant no. XDA0400000; Y.-S.H.) and Beijing Natural Science Foundation (grant nos. JQ24006; X.R.; 2222078; J.Z.). We acknowledge N. Wu at the Center for Physicochemical Analysis and Measurements in lCCAS for solid-state NMR measurements.

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Author notes

  1. These authors contributed equally: Yuan Liu, Huican Mao.

Authors and Affiliations

  1. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Yuan Liu, Rui Bai, Suting Weng, Qiangqiang Zhang, Chu Zhang, Shuai Han, Feixiang Ding, Xuefeng Wang, Yaxiang Lu, Liquan Chen & Yong-Sheng Hu

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

    Yuan Liu & Yong-Sheng Hu

  3. Department of Materials Science and Key Laboratory of Automobile Materials, MOE, Jilin University, Changchun, China

    Huican Mao

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

    Xiaohui Rong

  5. Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, China

    Xiao Chen & Fei Wei

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

    Yaxiang Lu & Yong-Sheng Hu

  7. CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China

    Junmei Zhao

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Contributions

Y.-S.H., X.R., Y. Lu and J.Z. designed and supervised the project. Y. Liu synthesized, characterized (XRD, IR, BET, SEM, EIS and LSV–GCMS) and electrochemically tested the samples and analysed the data with Q.Z., R.B. S.H., F.D., L.C. and X.R. X.C., S.W., C.Z., X.W. and F.W. performed the STEM measurements and analysis. H.M., C.Z. and Y. Liu designed and performed DFT calculations and analysis. C.Z. performed the TEM and electron energy loss spectroscopy measurements and analysis. Y. Liu, Y.X.L., X.R. and Y.-S.H. wrote the manuscript. All the authors participated in the discussion to improve the paper and made revisions of the whole manuscript.

Corresponding authors

Correspondence to Xiaohui Rong, Yaxiang Lu, Junmei Zhao or Yong-Sheng Hu.

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Liu, Y., Mao, H., Bai, R. et al. Designing an isotropic epilayer for stable 4.2 V solid-state Na batteries. Nat Energy 10, 1305–1314 (2025). https://doi.org/10.1038/s41560-025-01857-y

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