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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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.
The authors declare no competing interests.
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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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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