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Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes

Abstract

As Li-ion battery costs decrease, energy density and thus driving range remains a roadblock for mass-market vehicle electrification. While Li-metal anodes help achieve Department of Energy targets of 500 Wh kg−1 (750 Wh l−1), Li Coulombic efficiencies fall below the 99.95+% required for 1,000+ cycles. Here we examine historical electrolyte developments underlying increased Coulombic efficiency and discuss emerging frameworks that support rational strategies to move beyond 99.9%. While multiple electrolytes reach 98–99% Coulombic efficiency over subsets of cycles, achieving >99.9% Coulombic efficiency consistently throughout cycling is an as yet unmet challenge. We analyse important interplays between electrolyte, solid electrolyte interphase composition, plating–stripping kinetics and Li morphology, many of which are only recently being quantified experimentally at the Li interface, and which collectively determine Coulombic efficiency. We also discuss forward-looking strategies that, if mastered, represent new opportunities to refine understanding and support new record values of Coulombic efficiency in the coming years.

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Fig. 1: Historical electrolyte strategies towards Li-metal reversibility.
Fig. 2: CE of select electrolyte systems.
Fig. 3: Quantifying morphology and composition of electrochemically inactive Li.
Fig. 4: Interplay between Li+ transport and redox kinetics.

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Acknowledgements

G.M.H., R.G. and B.M.G. acknowledge support from the National Science Foundation under award number 1804247. J.L. acknowledges support by an appointment to the Intelligence Community Postdoctoral Research Fellowship Program at the Massachusetts Institute of Technology, administered by Oak Ridge Institute for Science and Education through an interagency agreement between the US Department of Energy and the Office of the Director of National Intelligence. Y.S.-H. and N.M. acknowledge the financial support of the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Advanced Battery Materials Research (BMR) Program, of the US Department of Energy under contract no. DE-AC02-06CH11357, subcontract no. 9F-60231. A.B. and Y.S.M. acknowledge the Zable Endowed Chair fund for energy technologies for efforts related to this work.

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Correspondence to Y. Shirley Meng, Yang Shao-Horn or Betar M. Gallant.

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Supplementary Data 1

Complete electrolyte and cycle conditions underlying referenced data points in Figs. 1, 2, and 4 in the main text.

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Hobold, G.M., Lopez, J., Guo, R. et al. Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes. Nat Energy 6, 951–960 (2021). https://doi.org/10.1038/s41560-021-00910-w

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