Origin of lithium whisker formation and growth under stress

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Abstract

Lithium metal has the lowest standard electrochemical redox potential and very high theoretical specific capacity, making it the ultimate anode material for rechargeable batteries. However, its application in batteries has been impeded by the formation of Li whiskers, which consume the electrolyte, deplete active Li and may lead to short-circuit of the battery. Tackling these issues successfully is dependent on acquiring sufficient understanding of the formation mechanisms and growth of Li whiskers under the mechanical constraints of a separator. Here, by coupling an atomic force microscopy cantilever into a solid open-cell set-up in environmental transmission electron microscopy, we directly capture the nucleation and growth behaviour of Li whiskers under elastic constraint. We show that Li deposition is initiated by a sluggish nucleation of a single crystalline Li particle, with no preferential growth directions. Remarkably, we find that retarded surface transport of Li plays a decisive role in the subsequent deposition morphology. We then explore the validity of these findings in practical cells using a series of carbonate-poisoned ether-based electrolytes. Finally, we show that Li whiskers can yield, buckle, kink or stop growing under certain elastic constraints.

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Fig. 1: The AFM–ETEM solid open-cell set-up for the in-situ study.
Fig. 2: Li whisker formation during electrochemical deposition of Li in a CO2 environment.
Fig. 3: Intentional poisoning of the baseline electrolyte to identify the role of EC in Li whisker formation in coin cells.
Fig. 4: Diverse growth behaviours of Li whisker under AFM constraints.

Data availability

All data that support the findings of this study have been included in the main text, supplementary information and supplementary videos. Original data are kept at the Environmental Molecular Sciences Laboratory at Pacific Northwest National Laboratory and are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy (DOE) under contract no. DE-AC02-05CH11231, subcontract no. 6951379 under the Advanced Battery Materials Research (BMR) Program and the US–Germany Cooperation on Energy Storage. The work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the Department of Energy under contract DE-AC05-76RLO1830. The authors acknowledge D. Lv, S. Hu, B. Liu and R. Yi from PNNL for helpful discussions.

Author information

C.W. and W.X. conceived the project. Y.H. conducted the in-situ ETEM, cryo-TEM and SEM characterizations and drafted the manuscript under the direction of C.W. and W.X. Y.X. assisted on the cryo-TEM experiments. X.R. performed the coin-cell tests. M.E. carried out the XPS measurements. X.L., J.X., J.L. and J.-G.Z. contributed to the discussion and revision of the manuscript.

Correspondence to Wu Xu or Chongmin Wang.

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Competing interests

The authors declare no competing interests.

Additional information

Peer review statement Nature Nanotechnology thanks Xiao-Qing Yang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–10 and discussion.

Supplementary Video 1

In-situ TEM observation of the Li whisker formation in CO2 environment.

Supplementary Video 2

In-situ TEM observation of the Li deposition in N2 environment.

Supplementary Video 3

In-situ TEM observation of the Li whisker ‘failure’ by buckling.

Supplementary Video 4

In-situ TEM observation of the Li whisker ‘failure’ by buckling.

Supplementary Video 5

In-situ TEM observation of the Li whisker ‘failure’ by cessation of Li deposition on the solid electrolyte–whisker interface.

Supplementary Video 6

In-situ TEM observation of the Li whisker ‘failure’ by cessation of Li deposition on the solid electrolyte–whisker interface.

Supplementary Video 7

In-situ TEM observation of the Li whisker ‘failure’ by kink formation.

Supplementary Video 8

In-situ TEM observation of the Li whisker ‘failure’ by a combined effect of yielding and buckling.

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He, Y., Ren, X., Xu, Y. et al. Origin of lithium whisker formation and growth under stress. Nat. Nanotechnol. 14, 1042–1047 (2019) doi:10.1038/s41565-019-0558-z

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