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Mechanistic understanding of interphase-driven ageing in silicon anodes

Nature Energy (2026)Cite this article

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Abstract

Conventional solid electrolyte interphases (SEIs) strongly adhere to micro-silicon (µ-Si) and crack under volume changes, causing poor cycling performance. Nano-silicon improves cycling performance but remains costly with limited calendar life. Here potentiostatic ageing tests demonstrate that both calendar and cycle ageing are governed by SEI cracking and dissolution with different relative contributions. When the system is not dominated by SEI dissolution, the relative calendar life of Si anodes could correlates positively with their cycle life. LiF-rich SEI that enables long cycle life in µ-Si is therefore expected to enhance calendar life as well. Using this framework, we screened electrolytes, SEIs and electrodes and validated them with full-cell storage. LiF-rich SEI minimizes cracking and dissolution, enabling μ-Si to achieve excellent calendar life, whereas nano-silicon suffers from SEI dissolution and needs reduced electrolyte–electrode contact for better calendar life. This work clarifies calendar-ageing behaviour and accelerates electrolytes and SEI development for long-life Si anodes.

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Fig. 1: Schematic of calendar life in Silicon anode.
Fig. 2: Calendar life of Si anodes with different electrolytes.
Fig. 3: The SEI compositions in a variety of electrolytes and the passivation ability of these compositions.
Fig. 4: The calendar life of µ-Si vs n-Si.
Fig. 5: SEI growth in different SEI with different repair abilities.
Fig. 6: Full-cell calendar ageing.
Fig. 7: Summary of the relationship between the calendar life and surface area and SEI instability.

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The authors declare that all data supporting the findings of this study are available within the paper and Supplementary Information files. Source data are provided with this paper.

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Acknowledgements

This research was supported by US Department of Energy, Vehicle Technologies Office (DOE-VTO) under the Silicon Consortium Project, directed by N. Eidson, C. Steinway, T. Do and B. Cunningham, and managed by A. Burrell. The was supported by DOE Office of Energy Efficiency and Renewable Energy (EERE) grant DE-EE0009183 (W.Z. and C.W.) We acknowledge the technical support from the Maryland NanoCenter.

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Author notes

  1. These authors contributed equally: Weiran Zhang, Nan Zhang, Zeyi Wang, Ai-Min Li.

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA

    Weiran Zhang & Chunsheng Wang

  2. Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA

    Weiran Zhang, Nan Zhang, Zeyi Wang, Ai-Min Li, Sufu Liu, Taeyong Lee, Yawei Chen, Yijie Liu, Zheng Li, Hongli Wan, Joseph Roschella, Lei Zheng & Chunsheng Wang

  3. Institute for Research in Electronics and Applied Physics, University of Maryland, College Park, MD, USA

    Sz-Chian Liou & Jiancun Rao

  4. Department of Chemistry, Rutgers, the State University of New Jersey, Newark, NJ, USA

    Zhiyuan Zhang & Huixin He

  5. Department of Chemistry, University of Rhode Island, Kingston, RI, USA

    Brett L. Lucht

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

    Christopher S. Johnson

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Contributions

W.Z. conceived the idea, performed experiments and wrote the manuscript. N.Z. performed EQCM measurements and assisted with electrochemical tests. Z.W. performed calculations. A.-M.L. provided ionic liquids and assisted with related full-cell ageing. S.L., Y.L. and Z.L. helped with the testing. T.L., Y.C. and L.Z. helped on electrode engineering. H.W., S.-C.L. and J. Rao helped on transmission electron microscopy. J. Roschella edited and improved the manuscript. Z.Z. and H.H. conduced the AFM at Rutgers University. B.L.L. helped with the XPS test. C.S.J. guided the analysis and manuscript writing. C.W. supervised the study and the manuscript writing. All authors discussed the results.

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Correspondence to Chunsheng Wang.

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Zhang, W., Zhang, N., Wang, Z. et al. Mechanistic understanding of interphase-driven ageing in silicon anodes. Nat Energy (2026). https://doi.org/10.1038/s41560-026-01967-1

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