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Rational solvent molecule tuning for high-performance lithium metal battery electrolytes

Nature Energy volume 7, pages 94–106 (2022)Cite this article

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Abstract

Electrolyte engineering improved cycling of Li metal batteries and anode-free cells at low current densities; however, high-rate capability and tuning of ionic conduction in electrolytes are desirable yet less-studied. Here, we design and synthesize a family of fluorinated-1,2-diethoxyethanes as electrolyte solvents. The position and amount of F atoms functionalized on 1,2-diethoxyethane were found to greatly affect electrolyte performance. Partially fluorinated, locally polar –CHF2 is identified as the optimal group rather than fully fluorinated –CF3 in common designs. Paired with 1.2 M lithium bis(fluorosulfonyl)imide, these developed single-salt-single-solvent electrolytes simultaneously enable high conductivity, low and stable overpotential, >99.5% Li||Cu half-cell efficiency (up to 99.9%, ±0.1% fluctuation) and fast activation (Li efficiency >99.3% within two cycles). Combined with high-voltage stability, these electrolytes achieve roughly 270 cycles in 50-μm-thin Li||high-loading-NMC811 full batteries and >140 cycles in fast-cycling Cu||microparticle-LiFePO4 industrial pouch cells under realistic testing conditions. The correlation of Li+–solvent coordination, solvation environments and battery performance is investigated to understand structure–property relationships.

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Fig. 1: Step-by-step design principles of the fluorinated-DEE solvent family.
Fig. 2: Ionic conductivity and cycling overpotential of FDMB and fluorinated-DEE electrolytes.
Fig. 3: Theoretical and experimental study on the Li+ solvation structures and the structure–property correlations.
Fig. 4: Li metal efficiency and high-voltage stability.
Fig. 5: Full-cell performance of FDMB and fluorinated-DEE electrolytes.
Fig. 6: Li metal morphology in fluorinated-DEE electrolytes.
Fig. 7: SEI examination in fluorinated-DEE electrolytes.
Fig. 8: Summary and overall evaluation of fluorinated-DEE electrolytes.

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Data availability

All relevant data are included in the paper and its Supplementary Information. Source data are provided with this paper.

Code availability

The Python script and rationale for analysing the Li+ solvation structures are available at https://github.com/xianshine/LiSolvationStructure.

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Acknowledgements

This work is supported by the US Department of Energy, under the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, the Battery Materials Research Program and Battery500 Consortium. Part of this work was performed at the Stanford Nano Shared Facilities, supported by the National Science Foundation under award no. ECCS-2026822. Z.Y. thanks B. Siegl at Arkema for providing LiFSI. Z.Y. also thanks J. Yang at Stanford University for measuring mass spectrometry and X. Chen at Tsinghua University for discussing the definition of Li+ solvates. Z.Z. acknowledges support from Stanford Interdisciplinary Graduate Fellowship. S.T.O. acknowledges support from the Knight Hennessy Scholarship for graduate studies at Stanford University. G.A.K. gratefully acknowledges support from the National Science Foundation Graduate Research Fellowship under grant no. 1650114.

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Authors and Affiliations

  1. Department of Chemical Engineering, Stanford University, Stanford, CA, USA

    Zhiao Yu, Paul E. Rudnicki, Solomon T. Oyakhire, Yuelang Chen, Xian Kong, Yu Zheng, Gaurav A. Kamat, Mun Sek Kim, Stacey F. Bent, Jian Qin & Zhenan Bao

  2. Department of Chemistry, Stanford University, Stanford, CA, USA

    Zhiao Yu, Yuelang Chen & Yu Zheng

  3. Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA

    Zewen Zhang, Zhuojun Huang, Sang Cheol Kim, Xin Xiao, Hansen Wang, Mun Sek Kim & Yi Cui

  4. College of Chemistry Nuclear Magnetic Resonance Facility (CoC-NMR), University of California, Berkeley, CA, USA

    Hasan Celik

  5. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Yi Cui

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Contributions

Z.Y., Y.Cui and Z.B. conceived the idea. J.Q., Y.Cui and Z.B. directed the project. Z.Y. designed the logical flow and experiments. Z.Y. performed syntheses, material characterizations, DFT calculations, electrochemical measurements and battery tests. P.E.R., X.K. and J.Q. conducted molecular dynamics simulations and rationales. Z.Z. performed cryo-TEM and cryo-TEM EDS experiments. Z.H. took SEM images and collected viscosity data. H.C. performed DOSY–NMR experiments. S.T.O. collected XPS data. Y.Chen collected 7Li- and 19F-NMR and contributed to key discussion. S.C.K. measured solvation free energies. X.X. carried out ion milling and took part of SEM images. H.W. helped with electrochemical measurements and battery testing. Y.Z. and G.A.K. helped with syntheses. M.S.K. helped with discussion. All authors discussed and analysed the data. Z.Y., S.F.B., J.Q., Y.Cui and Z.B. cowrote and revised the manuscript.

Corresponding authors

Correspondence to Jian Qin, Yi Cui or Zhenan Bao.

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Z.B., Y.Cui. and Z.Y. declare that this work has been filed as US Provisional Patent Application No. 63/283,828. The remaining authors declare no competing interests.

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Nature Energy thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary Tables 1–5, Figs. 1–66 and Refs. 1–31.

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Yu, Z., Rudnicki, P.E., Zhang, Z. et al. Rational solvent molecule tuning for high-performance lithium metal battery electrolytes. Nat Energy 7, 94–106 (2022). https://doi.org/10.1038/s41560-021-00962-y

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