Abstract
Lithium (Li) metal batteries (LMBs) are promising for high-energy-density rechargeable batteries1,2,3. However, Li dendrites formed by the reaction between highly active Li and non-aqueous electrolytes lead to safety concerns and rapid capacity decay4,5,6,7. Developing a reliable solid–electrolyte interphase is critical for realizing high-rate and long-life LMBs, but remains technically challenging4,8. Here we demonstrate that adding excess m-Li2ZrF6 (monoclinic) nanoparticles to a commercial LiPF6-containing carbonate electrolyte of LMBs facilitates the release of abundant ZrF62– ions into the electrolyte driven by the applied voltage, converting to t-Li2ZrF6 (trigonal) and creating a stable solid–electrolyte interphase in situ with high Li-ion conductivity. Computational and cryogenic transmission electron microscopy studies revealed that the in situ formation of the t-Li2ZrF6-rich solid–electrolyte interphase markedly enhanced Li-ion transfer and suppressed the growth of Li dendrites. As a result, LMBs assembled with LiFePO4 cathodes (areal loading, 1.8/2.2 mAh cm−2), three-dimensional Li–carbon anodes (50-µm-thick Li) and Li2ZrF6-based electrolyte displayed greatly improved cycling stability with high capacity retention (>80.0%) after 3,000 cycles (1C/2C rate). This achievement represents leading performance and, thus, delivers a reliable Li2ZrF6-based electrolyte for durable LMBs under practical high-rate conditions.
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Data availability
The data that support the findings of this study are available from the corresponding authors upon request. Source data are provided with this paper.
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Acknowledgements
This work was supported by the Department of Science and Technology of Guangdong Province (grant nos. 2019ZT08L075 and 2019QN01L054), National Natural Science Foundation of China (grant nos. 52225208, 22176063, 22393904, U21A20174, U1910208 and 22393900), National Key Research and Development Program of China (grant nos. 2022YFB2502000 and 2018YFA0209600), Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang (grant no. 2020R01002) and Beijing Engineering Research Center of Advanced Solid Batteries. G.I.N.W. is supported by a James Cook Research Fellowship from New Zealand Government funding, administered by the Royal Society Te Apārangi.
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Y.Q. and K.Y. led the project. Q.X., Y.Q., H.L., K.Y. and L.G. conceived the idea and drafted the manuscript. T.L. performed the DFT calculations. Q.X., L.G., H.L., K.Y. and Y.Q. designed and performed the experiments and analysed the data. X.T., K.Y., G.C., X.L., Q.X., G.I.N.W., Y.L. and G.Z. helped to develop the action mechanism. Z.J., Q.X. and X.T. performed the cryo-TEM characterizations. All authors discussed the results and revised the manuscript. All the authors express sincere condolences for the passing of author Y.Q. (who was originally a corresponding author) and acknowledge his invaluable contribution.
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Xu, Q., Li, T., Ju, Z. et al. Li2ZrF6-based electrolytes for durable lithium metal batteries. Nature 637, 339–346 (2025). https://doi.org/10.1038/s41586-024-08294-z
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DOI: https://doi.org/10.1038/s41586-024-08294-z
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