Abstract
Lithium metal batteries represent a promising technology for next-generation energy storage, but they still suffer from poor cycle life due to lithium dendrite formation and cathode cracking. Fluorinated solvents can improve battery longevity by improving LiF content in the solid–electrolyte interphase; however, the high cost and environmental concerns of fluorinated solvents limit battery viability. Here we designed a series of fluorine-free solvents through the methylation of 1,2-dimethoxyethane, which promotes inorganic LiF-rich interphase formation through anion reduction and achieves high oxidation stability. The anion-derived LiF interphases suppress lithium dendrite growth on the lithium anode and minimize cathode cracking under high-voltage operation. The Li+-solvent structure is investigated through in situ techniques and simulations to draw correlations between the interphase compositions and electrochemical performances. The methylation strategy provides an alternative pathway for electrolyte engineering towards high-voltage electrolytes while reducing dependence on expensive fluorinated solvents.
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Data availability
We declare that the data supporting the findings of this study are available within the article and its Supplementary Information. An archive containing a final configuration from molecular dynamics simulations, force field, simulation parameters and molecular dynamics code is provided. Source data are provided with this paper.
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Acknowledgements
This work was supported by the US Department of Energy (DOE) under award no. DE-EE0008202 (C.W.) & DE-SC0023408 (C.W.) at the University of Maryland (UMD). The work at Brookhaven National Laboratory is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the US Department of Energy (DOE) through the Advanced Battery Materials Research (BMR) Program under contract no. DE-SC0012704 (E.H. and X.-Q.Y.). This research used 28-ID-2 beamline of the National Synchrotron Light Source II, US DOE Office of Science User Facilities, operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704 (E.H. and X.-Q.Y.). Modelling work was supported by DEVCOM ARL and the Center for Research on Extreme Batteries (O.B.).
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A.-M.L. and C.W. conceived the idea for the project and wrote the paper. O.B. and T.P.P. conducted and analysed the DFT calculations and molecular dynamics simulations and also assisted with paper revision and mechanism identification. W.Z and N.Z. assisted with electrochemical cell tests. F.C. helped with the NMR set-up. C.J. and B.L.L. helped with the XPS data collection. S.T., E.H. and X.-Q.Y. helped with the synchrotron data collection and analysis. All of the authors discussed the results and analysed the data.
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Li, AM., Borodin, O., Pollard, T.P. et al. Methylation enables the use of fluorine-free ether electrolytes in high-voltage lithium metal batteries. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01497-x
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DOI: https://doi.org/10.1038/s41557-024-01497-x