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Corrosion of lithium metal anodes during calendar ageing and its microscopic origins

Abstract

Rechargeable lithium (Li) metal batteries must have long cycle life and calendar life (retention of capacity during storage at open circuit). Particular emphasis has been placed on prolonging the cycle life of Li metal anodes, but calendar ageing is less understood. Here, we show that Li metal loses at least 2–3% of its capacity after only 24 hours of ageing, regardless of the electrolyte chemistry. These losses of capacity during calendar ageing also shorten the cycle life of Li metal batteries. Cryogenic transmission electron microscopy shows that chemical corrosion of Li and the continuous growth of the solid electrolyte interphase—a passivation film on Li—cause the loss of capacity. Electrolytes with long cycle life do not necessarily form a solid electrolyte interphase with more resistance to chemical corrosion, so functional electrolytes must simultaneously minimize the rate of solid electrolyte interphase growth and the surface area of electrodeposited Li metal.

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Fig. 1: Effect of resting intervals on the CE of lithium metal anodes.
Fig. 2: Cryo-(S)TEM mapping of SEI growth on Li metal during calendar ageing in both low- and high-performance electrolytes.
Fig. 3: Time-dependent interfacial resistance and microstructure of electrodeposited Li metal in select electrolytes.
Fig. 4: Effect of calendar ageing on the cycle life of anode-free full-cells. The full-cells use the LiBF4/LiDFOB (FEC:DEC) electrolyte and a LFP cathode (2 mA h cm–2 loading, cycling at C/2, 1 mA cm–2).
Fig. 5: Schematic of the relationship between the rate of SEI growth, surface area (SA) of Li and capacity loss of Li metal anodes in liquid electrolytes.

Data availability

The datasets analysed and generated during the current study are included in the paper and its Supplementary Information file.

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Acknowledgements

We acknowledge support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under the Battery Materials Research (BMR) Program and Battery 500 Consortium. The cryo-TEM research is supported by the Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering under contract DE-AC02-76SF00515. D.T.B. acknowledges support from the National Science Foundation Graduate Research Fellowship Program. Scanning electron microscopy and TEM were performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-1542152. The K3 IS camera and support are courtesy of Gatan. We also acknowledge H. Wang for help designing the schematic in Fig. 5.

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D.T.B. and Y.C. conceived the idea. D.T.B. designed the research with guidance from Y.C., carried out the electrochemical measurements and analysed the data. W.H. and Y.L. helped design the cryo-(S)TEM experiments, and W.H. carried out the cryo-(S)TEM experiments and analysed the data. W.Z. carried out the cryo-TEM selected area electron diffraction (SAED) and additional EELS measurements. H.W. and H.C. helped carry out and interpret the XPS experiments and synthesized host materials. H.C. helped with scanning electron microscopy. Z.Y. synthesized electrolyte materials. D.T.B., W.H. and Y.C. wrote the manuscript.

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Correspondence to Yi Cui.

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Peer review information Nature Energy thanks Marian Stan, Yifei Yuan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–21, Tables 1–2 and references.

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Boyle, D.T., Huang, W., Wang, H. et al. Corrosion of lithium metal anodes during calendar ageing and its microscopic origins. Nat Energy 6, 487–494 (2021). https://doi.org/10.1038/s41560-021-00787-9

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