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Hybrid electrolyte enables solid-state sodium batteries sustaining 50,000 cycles

Nature Sustainability volume 8, pages 661–671 (2025)Cite this article

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Abstract

Solid-state sodium (Na) batteries open the opportunity for more sustainable energy storage due to their safety, low cost and high energy density. Inorganic solid electrolytes show notable advantages for such technologies but suffer from poor interfacial compatibility, rendering hybrid solid–liquid electrolytes an alternative. Here we show that the interfacial failure in the hybrid electrolyte system (Na3Zr2Si2PO12 (NZSP) and 1 M NaClO4 in propylene carbonate/ethylene carbonate/fluoroethylene carbonate) is closely associated with Na vacancies on the surface of NZSP. Asymmetric kinetics of solid and liquid electrolytes lead to the formation of Na vacancies and an unstable environment in the Helmholtz layer, while the organic molecules (propylene carbonate) are energetically favourable towards undesirable dehydrogenation. To eliminate the Na vacancies layer, we designed an ion-anchoring interlayer that serves to minimize the interfacial polarization. The unique O–Na coordination between the interfacial layer and NSZP confers stability to the solid–liquid interface. As demonstrated, the sodium battery with the modified hybrid electrolyte sustains 50,000 cycles with capacity retention of 86.3%. Our work provides a new path for the design of solid-state Na batteries, highlighting their potential for widespread practical applications.

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Fig. 1: Internal failure induced by dynamic mismatch in the hybrid electrolyte.
Fig. 2: Na vacancies drive the decomposition of polar molecules.
Fig. 3: Design principles for the ion-anchoring interphase to eliminate Na vacancies.
Fig. 4: Architecture of the Na-anchoring interlayer.
Fig. 5: Long-term cycling stability and high rate performance of batteries.

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Data availability

The data that support the findings of this study are available on request from the corresponding author. Source data are provided with this paper (Figshare https://doi.org/10.6084/m9.figshare.28473926).

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (no. 92372110 and no. 22075063), the Chinesisch-Deutsches Mobilitätspropgamm (M-0281), the Opening Project of State Key Laboratory of Space Power-Sources, the Fundamental Research Funds for the Central Universities (grant no. HIT.OCEF.2023039), the Heilongjiang Touyan Team (no. HITTY-20190033), the ‘Young Scientist Studio’ of Harbin Institute of Technology (HIT) and funds from Chongqing Research Institute of HIT. We thank the Shanghai Synchrotron Radiation Facility (SSRF) for providing the beamlines of BL13HB, BL18B and BL08U1A for completing STXM and SR-CT measurements. Finally, we extend gratitude to E. J. Hansen from the Advanced Materials for Energy Storage Lab at the University of British Columbia (UBCO) for proofreading the manuscript.

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Authors and Affiliations

  1. MOE Engineering Research Center for Electrochemical Energy Storage and Carbon Neutrality in Cold Regions, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, China

    Hanwen An, Menglu Li, Qingsong Liu, Yajie Song & Jiajun Wang

  2. National Key Laboratory of Science and Technology on Power Sources, Tianjin Institute of Power Sources, Tianjin, China

    Hanwen An, Xingjiang Liu & Jiajun Wang

  3. Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, China

    Biao Deng

  4. Chongqing Research, Institute of HIT, Chongqing, P. R. China

    Jiajun Wang

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  1. Hanwen An
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Contributions

All authors have approved the final version of the manuscript. J.W. proposed the research direction and conceived and led the project. H.A. designed and performed experiments with other co-authors. M.L., Q.L. and Y.S. performed STXM and CT measurements, analysed and discussed experimental results and drafted the manuscript. B.D. aided with the synchrotron radiation data collection at the SSRF. X.L. offered access to the experimental platform and equipment for pouch cells fabrication and testing. All authors participated in discussions and contributed valuable comments.

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Correspondence to Jiajun Wang.

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Nature Sustainability thanks Cheng Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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An, H., Li, M., Liu, Q. et al. Hybrid electrolyte enables solid-state sodium batteries sustaining 50,000 cycles. Nat Sustain 8, 661–671 (2025). https://doi.org/10.1038/s41893-025-01544-6

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