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Li metal deposition and stripping in a solid-state battery via Coble creep

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Abstract

Solid-state lithium metal batteries require accommodation of electrochemically generated mechanical stress inside the lithium: this stress can be1,2 up to 1 gigapascal for an overpotential of 135 millivolts. Maintaining the mechanical and electrochemical stability of the solid structure despite physical contact with moving corrosive lithium metal is a demanding requirement. Using in situ transmission electron microscopy, we investigated the deposition and stripping of metallic lithium or sodium held within a large number of parallel hollow tubules made of a mixed ionic-electronic conductor (MIEC). Here we show that these alkali metals—as single crystals—can grow out of and retract inside the tubules via mainly diffusional Coble creep along the MIEC/metal phase boundary. Unlike solid electrolytes, many MIECs are electrochemically stable in contact with lithium (that is, there is a direct tie-line to metallic lithium on the equilibrium phase diagram), so this Coble creep mechanism can effectively relieve stress, maintain electronic and ionic contacts, eliminate solid-electrolyte interphase debris, and allow the reversible deposition/stripping of lithium across a distance of 10 micrometres for 100 cycles. A centimetre-wide full cell—consisting of approximately 1010 MIEC cylinders/solid electrolyte/LiFePO4—shows a high capacity of about 164 milliampere hours per gram of LiFePO4, and almost no degradation for over 50 cycles, starting with a 1× excess of Li. Modelling shows that the design is insensitive to MIEC material choice with channels about 100 nanometres wide and 10–100 micrometres deep. The behaviour of lithium metal within the MIEC channels suggests that the chemical and mechanical stability issues with the metal–electrolyte interface in solid-state lithium metal batteries can be overcome using this architecture.

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Fig. 1: Mixed ionic-electronic conductor (MIEC) tubules as 3D Li hosts.
Fig. 2: Lithium plating/stripping inside carbon tubules.
Fig. 3: Lithiophilicity from ZnOx.
Fig. 4: Electrochemical performance of scaled-up Li metal cell with about 1010 MIEC cylinders.

Data availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

We acknowledge support by the Department of Energy, Basic Energy Sciences under award number DE-SC0002633 (‘Chemomechanics of far-from-equilibrium interfaces’), and by NSF ECCS-1610806. We thank KISCO Ltd for providing the PEO-based/LiTFSI solid electrolyte film.

Author information

Affiliations

Authors

Contributions

The experiments were conceived and designed by Y.C., Z.W. and J.L.; Y.C. and Z.W. performed the in situ TEM experiments, TEM imaging analysis, materials characterization, and the electrochemical performance assessments; Y.C., Z.W., X.L. and X.Y. synthesized the materials; Y. L., N.W. and J.B.G. helped with the electrochemical characterization; S.Y.K. and Y.-W.M. performed the nanoindentations; Y.C., Z.W. and J.L. wrote the paper; Y.-W.M., Z.W., X.L., X.Y., C.W., W.X., D.Y., F.Y., A.K., G.Z., H.H., J.B.G. and J. L. analysed the data, discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Ju Li.

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Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature thanks Werner Sitte and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

This file contains Supplementary Figures 1–29, a list of the Supplementary Videos and Supplementary References.

Video 1

An in situ TEM video showing Li plating inside the carbon hollow tubule with ZnOx (Fig. 2b–d).

Video 2

An in situ SAED video showing the changes of SAED on tubule region for the carbon tubule with ZnOx when Li plating occurs (Fig. 2e, f).

Video 3

An in situ TEM video showing the HRTEM imaging of Li plating inside the carbon tubule when the fresh Li crystal first forms inside the field of camera (Fig. 2g–i).

Video 4

A speeded-up in situ TEM video showing the Li stripping process inside the carbon tubule when there is a void plug between Li metal and the solid electrolyte (Fig. 2j–l and Supplementary Fig. 17).

Video 5

A speeded-up in situ TEM video showing some typical plating/stripping cycles including the 1st and 30th in the double aligned carbon tubules (Supplementary Fig. 8).

Video 6

A speeded-up in situ TEM video showing Li plating/stripping for 100 cycles in the single carbon tubules (Supplementary Fig. 10).

Video 7

A speeded-up in situ TEM video showing Na plating inside the carbon tubules (Supplementary Fig. 15).

Video 8

A speeded-up in situ TEM video showing Na stripping inside the carbon tubules (Supplementary Fig. 15).

Video 9

An in situ TEM video showing the dark-field imaging of the complete wetting of Li, spreading along the tubule outer surface with zero contact angle (Fig. 3b–f).

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Chen, Y., Wang, Z., Li, X. et al. Li metal deposition and stripping in a solid-state battery via Coble creep. Nature 578, 251–255 (2020). https://doi.org/10.1038/s41586-020-1972-y

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