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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All relevant data are included in the paper and its Supplementary Information.
The Python script for analysing the Li+ solvation structure is available at https://github.com/xianshine/LiSolvationStructure.git.
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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.
This work has been filed as US Provisional Patent Application No. 62/928,638.
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Supplementary Tables 1–3, Figs. 1–53 and refs. 1–16.
LiTf-FDMB single crystal.
LiTf-DMB single crystal.
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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