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Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries

Abstract

Electrolyte engineering is critical for developing Li metal batteries. While recent works improved Li metal cyclability, a methodology for rational electrolyte design remains lacking. Herein, we propose a design strategy for electrolytes that enable anode-free Li metal batteries with single-solvent single-salt formations at standard concentrations. Rational incorporation of –CF2– units yields fluorinated 1,4-dimethoxylbutane as the electrolyte solvent. Paired with 1 M lithium bis(fluorosulfonyl)imide, this electrolyte possesses unique Li–F binding and high anion/solvent ratio in the solvation sheath, leading to excellent compatibility with both Li metal anodes (Coulombic efficiency ~ 99.52% and fast activation within five cycles) and high-voltage cathodes (~6 V stability). Fifty-μm-thick Li|NMC batteries retain 90% capacity after 420 cycles with an average Coulombic efficiency of 99.98%. Industrial anode-free pouch cells achieve ~325 Wh kg−1 single-cell energy density and 80% capacity retention after 100 cycles. Our design concept for electrolytes provides a promising path to high-energy, long-cycling Li metal batteries.

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Fig. 1: Design concepts and electrochemical stability of electrolytes studied in this work.
Fig. 2: Li metal full battery performance.
Fig. 3: Li metal morphology and SEI.
Fig. 4: Unique solvation structure in 1 M LiFSI/FDMB.

Data availability

All relevant data are included in the paper and its Supplementary Information.

Code availability

The Python script for analysing the Li+ solvation structure is available at https://github.com/xianshine/LiSolvationStructure.git.

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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, Battery Materials Research (BMR) Program, and by the Battery 500 Consortium. Part of this work was performed at the Stanford Nano Shared Facilities, supported by the National Science Foundation under award ECCS-1542152. Z.Y. thanks X. Xu from Hunan Li-Fun Technology for fabricating pouch cells, Beijing Golden Feather New Energy Technology for providing LiFSI and Z. Yao for discussion on the DFT calculations. All authors thank K. Zaghib from Hydro-Québec for preparing and providing the thin Li metal foils. D.G.M. acknowledges support by the National Science Foundation Graduate Research Fellowship Program under grant no. (DGE‐114747). C.V.A. acknowledges the TomKat Center Postdoctoral Fellowship in Sustainable Energy for funding support.

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Authors

Contributions

Z.Y., H.W., Y.C. and Z.B. conceived the idea. Z.Y. and H.W. designed the experiments. Y.C. and Z.B. directed the project. Z.Y. performed the syntheses, material characterizations, DFT calculations, electrochemical measurements and coin-cell tests. H.W. performed the XPS measurements, pouch-cell fabrication and tests, and coin-cell tests. X.K. and J.Q. conducted the MD simulations and rationales. William Huang performed the cryo-TEM and cryogenic energy-dispersive X-ray spectroscopy measurements. Y.T., William Huang and E.G.L. performed the SEM experiments. K.W. and X.W. helped with the single-crystal measurement and structure refinement. D.G.M. and C.V.A. collected the 7Li-NMR spectra. Wenxiao Huang helped with the pouch-cell fabrication and tests. S.C. measured the viscosities. Y.Z. collected the ultraviolet–visible spectra. S.T.H. measured the water contents. Y.M. helped with the syntheses. All authors discussed and analysed the data. Z.Y., H.W., Y.C. and Z.B. wrote and revised the manuscript.

Corresponding authors

Correspondence to Yi Cui or Zhenan Bao.

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Competing interests

This work has been filed as US Provisional Patent Application No. 62/928,638.

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Supplementary information

Supplementary Information

Supplementary Tables 1–3, Figs. 1–53 and refs. 1–16.

Crystallographic Data 1

LiTf-FDMB single crystal.

Crystallographic Data 2

LiTf-DMB single crystal.

Supplementary Video

Flammability test of conventional carbonate electrolyte (left, 1 M LiPF6 in EC/EMC) and FDMB (right). It can be observed that conventional carbonate electrolyte was flammable immediately after touching the fire of the lighter; however, FDMB can tolerate the direct touch of fire for at least three seconds.

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Yu, Z., Wang, H., Kong, X. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat Energy 5, 526–533 (2020). https://doi.org/10.1038/s41560-020-0634-5

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