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Mechanical regulation of lithium intrusion probability in garnet solid electrolytes

Nature Energy volume 8, pages 241–250 (2023)Cite this article

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An Author Correction to this article was published on 07 March 2023

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Abstract

Solid electrolytes in rechargeable lithium-metal batteries are susceptible to lithium-metal short circuiting during plating, and the root cause is under debate. In this work, we investigated statistically the effect of locally and globally applied stress on lithium penetration initiation in Li6.6La3Ta0.4Zr1.6O12 (LLZO) via operando microprobe scanning electron microscopy. Statistical analysis revealed that the cumulative probability of intrusion as a function of lithium-metal diameter follows a Weibull distribution. Upon increasing the microprobe–LLZO contact force, the characteristic failure diameter of lithium metal decreases significantly. In addition, we control the direction of intrusion propagation by applying a 0.070% compressive strain via operando cantilever beam-bending experiments. Overall, we find that the root cause of lithium intrusion into the electrolyte is a combination of current focusing and the presence of nanoscale cracks, rather than electronic leakage or electrochemical reduction. These insights highlight the mechanical tunability of electrochemical plating reactions in brittle solid electrolytes.

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Fig. 1: Electroplating lithium metal onto LLZO via operando microprobe experiments inside SEM.
Fig. 2: Electrochemical analysis of three nominally identical SEM microprobe experiments as a function of applied potential at a contact load of 0.1 mN and histograms of lithium-whisker diameter and current density at failure at different contact loads.
Fig. 3: Statistical analysis of intrusion initiation suggesting a defect-driven intrusion-initiation mechanism.
Fig. 4: SEM images of lithium intrusions after electrochemical measurements and ex situ nanoindentation and FEM simulations analysing the contact damage modes in LLZO from the tungsten microprobe.
Fig. 5: Operando LLZO cantilever-bending experiments revealing a strong mechanical strain effect on regulating the intrusion propagation behaviour.

Data availability

All relevant data are contained in the manuscript and supplementary information.

Code availability

All analysis was performed using open-source computational packages in Python 3.8. Code is available at https://doi.org/10.5281/zenodo.7332149.

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Acknowledgements

This work was supported by the Samsung Advanced Institute of Technology. Some characterization aspects of the work were supported by the Assistant Secretary for Energy Efficiency, Vehicle Technologies Office of the US Department of Energy under the Advanced Battery Materials Research Program. T.C. and X.W.G. acknowledge financial support from StorageX Initiative at Stanford University. We thank R. Chin, J. Jamtgaard and L. Lechner for assistance with installing and operating the microprobe system. We also thank M. Wang, O. Tertuliano, N. Rolston, W. Nix, L. Miara, S. Chakravarthy and S. J. Harris for helpful discussions. Finally, we thank X. Cui, H. Thaman and S. Narasimhan for helpful discussions and comments on the manuscript. Part of this work was performed at the Stanford Nano Shared Facilities, supported by the National Science Foundation under award ECCS-2026822. This material is based on work supported by the National Science Foundation Graduate Research Fellowship under grant number 1656518.

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Author notes

  1. These authors contributed equally: Geoff McConohy, Xin Xu, Teng Cui.

Authors and Affiliations

  1. Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA

    Geoff McConohy, Xin Xu, Edward Barks, Emma Kaeli, Celeste Melamed & William C. Chueh

  2. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Geoff McConohy, Xin Xu, Edward Barks, Sunny Wang & William C. Chueh

  3. Department of Mechanical Engineering, Stanford University, Stanford, CA, USA

    Teng Cui & X. Wendy Gu

  4. Department of Chemistry, Stanford University, Stanford, CA, USA

    Sunny Wang

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Contributions

G.M., X.X. and T.C. performed most of the experiments and their analysis. E.B. and S.W. assisted with LLZO sample preparation and EIS measurement. E.K. assisted with electrical measurement and data analysis. C.M. performed X-ray diffraction measurements and analysis. X.W.G. supervised and assisted with the design of cantilever-bending experiments and FEM simulations. G.M., X.X. and W.C.C. designed the research plan. G.M., X.X., T.C. and W.C.C. wrote the manuscript with input from all authors.

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Correspondence to Geoff McConohy, Xin Xu or William C. Chueh.

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McConohy, G., Xu, X., Cui, T. et al. Mechanical regulation of lithium intrusion probability in garnet solid electrolytes. Nat Energy 8, 241–250 (2023). https://doi.org/10.1038/s41560-022-01186-4

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