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Critical interphase overpotential as a lithium dendrite-suppression criterion for all-solid-state lithium battery design

Nature Energy volume 8, pages 473–481 (2023)Cite this article

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Abstract

Critical current density (CCD) is currently used to evaluate Li dendrite-suppression capability of solid-state electrolytes (SSEs). However, CCD values vary with engineering parameters, resulting in a large deviation of CCD values for the same SSE. Herein we evaluate lithium dendrite-suppression capability of SSEs using critical interphase overpotential (CIOP). The CIOP is the intrinsic property of the interphase, which depends on electronic/ionic conductivity, lithiophobicity and mechanical strength. When the applied interphase overpotential (AIOP) is larger than CIOP, Li will grow into interphase as dendrites. To reduce AIOP but increase CIOP, we design a mix-conductive Li2NH-Mg interlayer between Li6PS5Cl SSE and Li-1.0 wt% La anode, which transfers into Li6PS5Cl/LiMgSx/LiH-Li3N/LiMgLa after Mg migration during annealing and activation cycles. The LiMgSx interphase increases the CIOP from ~10 mV (for Li6PS5Cl) to ~220 mV. The Li plates on the LiMgLa surface, and reversible penetration into formed porous LiH-Li3N reduces AIOP. The CIOP provides a design guideline for high-energy and room temperature all-solid-state lithium-metal batteries.

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Fig. 1: CIOP definition, designing principle and the realization of lithium dendrite-free interlayer.
Fig. 2: Ion and element distribution, morphology of interlayer with Li anode and Li6PS5Cl electrolyte.
Fig. 3: CIOP and CCD of Li6PS5Cl electrolyte with Li2NH-Mg interlayer inserted between Li-1.0 wt% La and Li6PS5Cl.
Fig. 4: Electrochemical performance of NMC622/Li3YCl6/Li6PS5Cl/Li2NH-Mg/Li-1.0 wt% La cell.

Data availability

The data supporting the findings of this study are available within the article and its Supplementary Information files.

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Acknowledgements

This work was supported by the US Department of Energy under award number DEEE0008856 (received by C.W.) and the Advanced Research Projects Agency-Energy under award DE-AR0000781 (received by C.W). We thank T. Deng for providing LiNiO2 cathode material.

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Author notes

  1. These authors contributed equally: Hongli Wan, Zeyi Wang.

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA

    Hongli Wan, Zeyi Wang, Sufu Liu, Xinzi He & Chunsheng Wang

  2. School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore

    Bao Zhang

  3. Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA

    Weiran Zhang

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  1. Hongli Wan
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Contributions

H.W. and C.W. conceived the idea for this project. H.W. prepared the materials and performed the characterization and electrochemical measurements. Z.W. and B.Z. conducted the simulations. Z.W. assisted on contact angle test and materials preparation. S.L. assisted on three-electrode cell tests. X.H. and W.Z. assisted on battery testing.

Corresponding author

Correspondence to Chunsheng Wang.

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Nature Energy thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–39, Table 1 and Note 1.

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Wan, H., Wang, Z., Liu, S. et al. Critical interphase overpotential as a lithium dendrite-suppression criterion for all-solid-state lithium battery design. Nat Energy 8, 473–481 (2023). https://doi.org/10.1038/s41560-023-01231-w

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