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Suspension electrolyte with modified Li+ solvation environment for lithium metal batteries

Abstract

Designing a stable solid–electrolyte interphase on a Li anode is imperative to developing reliable Li metal batteries. Herein, we report a suspension electrolyte design that modifies the Li+ solvation environment in liquid electrolytes and creates inorganic-rich solid–electrolyte interphases on Li. Li2O nanoparticles suspended in liquid electrolytes were investigated as a proof of concept. Through theoretical and empirical analyses of Li2O suspension electrolytes, the roles played by Li2O in the liquid electrolyte and solid–electrolyte interphases of the Li anode are elucidated. Also, the suspension electrolyte design is applied in conventional and state-of-the-art high-performance electrolytes to demonstrate its applicability. Based on electrochemical analyses, improved Coulombic efficiency (up to ~99.7%), reduced Li nucleation overpotential, stabilized Li interphases and prolonged cycle life of anode-free cells (~70 cycles at 80% of initial capacity) were achieved with the suspension electrolytes. We expect this design principle and our findings to be expanded into developing electrolytes and solid–electrolyte interphases for Li metal batteries.

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Fig. 1: Liquid and suspension electrolytes for the Li0 anode.
Fig. 2: Compact SEI analysis via cryo-STEM.
Fig. 3: Simulations for the Li+ solvation environment of RCE and SCE.
Fig. 4: Further analysis of the suspension electrolyte.
Fig. 5: High-performance electrolytes with the suspension electrolyte design.
Fig. 6: Full cell electrochemical performances of the suspension electrolytes.

Data availability

The authors declare that all the data and relevant information are available within the article and Supplementary Information. Additional data are available from the corresponding author upon reasonable request.

Code availability

The MD and DFT simulation codes are available at https://github.com/prudnick94/LiSolvation_Li2OSuspension and https://github.com/exenGT/Li2O, respectively.

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Acknowledgements

We acknowledge support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under the Battery Materials Research Program and Battery 500 Consortium. Z.Z. acknowledges the support from the Stanford Interdisciplinary Graduate Fellowship. S.T.O. acknowledges support from the Knight Hennessy scholarship for graduate studies at Stanford University.

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Contributions

M.S.K. and Y. Cui conceived the idea and conceptualized the work. M.S.K. performed the experiments and analysed the data with guidance from Y. Cui. M.S.K., Z.Z. and Y. Cui wrote the manuscript. Z.Z. performed cryo-STEM and SEM experiments and analyses. P.E.R. performed MD simulations and analysed the data. J.W. conducted DFT calculations. Z.Y. synthesized FDMB electrolyte and helped to take impedance measurements. S.T.O. performed XPS analysis. Y. Chen performed 7Li NMR analysis. S.C.K. measured the cell potential and relative Li+ solvation energy of the electrolytes. W.Z. helped take SEM images. Z.Y., H.W., S.C.K., D.T.B., X.K., Z.H. and W.H. provided technical help and helpful discussions. S.F.B. and L.-W.W. reviewed the manuscript. Y. Cui, Z.B. and J.Q. supervised the overall study. All the authors discussed the manuscript and provided comments.

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Correspondence to Yi Cui.

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

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Supplementary Figs. 1–37, Figure Captions 1 and 2, Tables 1–5, Notes 1–21 and references.

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Kim, M.S., Zhang, Z., Rudnicki, P.E. et al. Suspension electrolyte with modified Li+ solvation environment for lithium metal batteries. Nat. Mater. 21, 445–454 (2022). https://doi.org/10.1038/s41563-021-01172-3

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