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Fast galvanic lithium corrosion involving a Kirkendall-type mechanism

Abstract

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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All the data supporting the findings of this study are available within the article and its Supplementary Information, and from the corresponding authors upon reasonable request.

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Acknowledgements

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.

Author information

D.L., Y.Liu and Y.C. conceived the project and designed the experiments. D.L. and Y.Liu performed the electrochemical studies. D.L. and Y.Liu conducted the FIB characterizations. Ya.Li and Yu.Li performed the cryo-EM characterizations. A.P. and D.L. performed the 3D modelling and finite element analysis. J.X. carried out the ALD coating of LiF on the Cu substrates. D.L. analysed the results. D.L. and Y.C. co-wrote the manuscript. All the authors discussed the results and commented on the manuscript.

Correspondence to Yi Cui.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

Supplementary Fig. 1–40, Supplementary Methods, and Supplementary Movie Captions

Supplementary Movie 1

Movie of FIB millings of 10 representative Li deposits without rest in the electrolyte

Supplementary Movie 2

Movie of FIB millings of 10 representative Li deposits after rest in the electrolyte for 100 hours

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Further reading

Fig. 1: Kirkendall voids formed in Li deposits.
Fig. 2: Dendritic Li growth on Li deposits with interval rests.
Fig. 3: Coulombic loss of Li at various rest times.
Fig. 4: Quantifying the galvanic corrosion and proposed mechanisms.
Fig. 5: SEI analyses on Cu and Li surfaces with cryo-EM and XPS.