Developing a viable metallic lithium anode is a prerequisite for next-generation batteries. However, the low redox potential of lithium metal renders it prone to corrosion, which must be thoroughly understood for it to be used in practical energy-storage devices. Here we report a previously overlooked mechanism by which lithium deposits can corrode on a copper surface. Voids are observed in the corroded deposits and a Kirkendall-type mechanism is validated through electrochemical analysis. Although it is a long-held view that lithium corrosion in electrolytes involves direct charge-transfer through the lithium–electrolyte interphase, the corrosion observed here is found to be governed by a galvanic process between lithium and the copper substrate—a pathway largely neglected by previous battery corrosion studies. The observations are further rationalized by detailed analyses of the solid–electrolyte interphase formed on copper and lithium, where the disparities in electrolyte reduction kinetics on the two surfaces can account for the fast galvanic process.
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Y.C. acknowledges 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 Battery500 consortium.
The authors declare no competing interests.
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Supplementary Fig. 1–40, Supplementary Methods, and Supplementary Movie Captions
Movie of FIB millings of 10 representative Li deposits without rest in the electrolyte
Movie of FIB millings of 10 representative Li deposits after rest in the electrolyte for 100 hours
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