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The passivity of lithium electrodes in liquid electrolytes for secondary batteries

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Abstract

Rechargeable Li metal batteries are currently limited by safety concerns, continuous electrolyte decomposition and rapid consumption of Li. These issues are mainly related to reactions occurring at the Li metal–liquid electrolyte interface. The formation of a passivation film (that is, a solid electrolyte interphase) determines ionic diffusion and the structural and morphological evolution of the Li metal electrode upon cycling. In this Review, we discuss spontaneous and operation-induced reactions at the Li metal–electrolyte interface from a corrosion science perspective. We highlight that the instantaneous formation of a thin protective film of corrosion products at the Li surface, which acts as a barrier to further chemical reactions with the electrolyte, precedes film reformation, which occurs during subsequent electrochemical stripping and plating of Li during battery operation. Finally, we discuss solutions to overcoming remaining challenges of Li metal batteries related to Li surface science, electrolyte chemistry, cell engineering and the intrinsic instability of the Li metal–electrolyte interface.

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Fig. 1: Energy density of various battery chemistries with metal electrodes and corresponding corrosion reactions.
Fig. 2: Li corrosion in non-aqueous electrolyte.
Fig. 3: Parameters determining the Li metal–liquid electrolyte interface and interphase.
Fig. 4: Naturally formed and artificial solid interphases.
Fig. 5: Factors impacting the evolution of the interface and interphase.
Fig. 6: Relevant parameters for the commercial application of Li metal batteries.

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Acknowledgements

This Review article is the result of a concerted approach within the LILLINT research project, jointly funded by the US Department of Energy (DOE) and the German Federal Ministry of Education and Research (BMBF). X.H. and R.K. kindly acknowledge the financial support of Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office (VTO), under the Advanced Battery Materials Research (BMR) Program, of the US DOE under contract no. DE-AC02-05CH11231. R.A., C.-C.S., J.S. and K.A. acknowledge US DOE, VTO. Argonne National Laboratory is operated by DOE Office of Science by UChicago Argonne, LLC, under contract no. DE-AC02-06CH11357. P.B.B., F.A.S., V.P. and J.M.S. acknowledge the financial support from the US DOE DE-AC02-06CH11357 through a subcontract to Argonne National Lab. W.X., H.J., C.W. and Y.X. at Pacific Northwest National Laboratory (PNNL) acknowledge the support of the Assistant Secretary for Energy Efficiency and Renewable Energy, VTO of the US DOE under contract no. DE-AC05-76RL01830 under the BMR Program and the US–Germany Cooperation on Energy Storage. PNNL is operated by Battelle for the DOE under contract DE-AC05-76RL01830. 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 inter-agency agreement between the US DOE and the Office of the Director of National Intelligence. Y.S.-H. and C.T.M. acknowledge the financial support of the Assistant Secretary for Energy Efficiency and Renewable Energy, VTO, under the BMR Program, of the US DOE under contract no. DE-AC02-06CH11357, subcontract no. 9F-60231. F.B. and U.K. acknowledge the BMBF in the framework of LILLINT (project number 03XP0225F). D.B. and S.P. thank the BMBF for financial support within the LILLINT project (03XP0225D). I.C.-L., S.W.-M. and M.W. acknowledge the financial support within the LILLINT project (13XP0225B).

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X.H., D.B., S.P., A.L. and R.K. drafted the outline for this Review article. X.H. performed the literature research. X.H. and D.B. prepared the first draft of the manuscript. F.B., U.K. and W.X. wrote the first draft of Box 1. J.L. revised and optimized Fig. 2. All authors contributed to the discussion of the manuscript, commented on its development at all stages, added significant thoughts and paragraphs to all chapters and carefully revised the continuously evolving versions of the manuscript in a highly collaborative manner.

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Correspondence to Stefano Passerini, Arnulf Latz or Robert Kostecki.

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He, X., Bresser, D., Passerini, S. et al. The passivity of lithium electrodes in liquid electrolytes for secondary batteries. Nat Rev Mater 6, 1036–1052 (2021). https://doi.org/10.1038/s41578-021-00345-5

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