Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Mechanical regulation of lithium intrusion probability in garnet solid electrolytes

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

This article has been updated


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.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Get just this article for as long as you need it


Prices may be subject to local taxes which are calculated during checkout

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

Change history


  1. Zhao, Q., Stalin, S., Zhao, C.-Z. & Archer, L. A. Designing solid-state electrolytes for safe, energy-dense batteries. Nat. Rev. Mater. 5, 229–252 (2020).

    Article  Google Scholar 

  2. Yu, Z. et al. Dendrites in solid-state batteries: ion transport behavior, advanced characterization, and interface regulation. Adv. Energy Mater. 11, 2003250 (2021).

    Article  Google Scholar 

  3. Chen, Y. et al. Understanding the lithium dendrites growth in garnet-based solid-state lithium metal batteries. J. Power Sources 521, 230921 (2022).

    Article  Google Scholar 

  4. Frenck, L., Sethi, G. K., Maslyn, J. A. & Balsara, N. P. Factors that control the formation of dendrites and other morphologies on lithium metal anodes. Front. Energy Res. 7, 115 (2019).

    Article  Google Scholar 

  5. Kazyak, E. et al. Li penetration in ceramic solid electrolytes: operando microscopy analysis of morphology, propagation, and reversibility. Matter 2, 1025–1048 (2020).

    Article  Google Scholar 

  6. Monroe, C. & Newman, J. Dendrite growth in lithium/polymer systems: a propagation model for liquid electrolytes under galvanostatic conditions. J. Electrochem. Soc. 150, A1377 (2003).

    Article  Google Scholar 

  7. Monroe, C. & Newman, J. The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces. J. Electrochem. Soc. 152, A396 (2005).

    Article  Google Scholar 

  8. Ni, J. E., Case, E. D., Sakamoto, J. S., Rangasamy, E. & Wolfenstine, J. B. Room temperature elastic moduli and Vickers hardness of hot-pressed LLZO cubic garnet. J. Mater. Sci. 47, 7978–7985 (2012).

    Article  Google Scholar 

  9. Yu, S. et al. Elastic properties of the solid electrolyte Li7La3Zr2O12 (LLZO). Chem. Mater. 28, 197–206 (2016).

    Article  Google Scholar 

  10. Lu, Y. et al. Critical current density in solid‐state lithium metal batteries: mechanism, influences, and strategies. Adv. Funct. Mater. 31, 2009925 (2021).

    Article  Google Scholar 

  11. Fu, C. et al. Universal chemomechanical design rules for solid-ion conductors to prevent dendrite formation in lithium metal batteries. Nat. Mater. 19, 758–766 (2020).

    Article  Google Scholar 

  12. Porz, L. et al. Mechanism of lithium metal penetration through inorganic solid electrolytes. Adv. Energy Mater. 7, 1701003 (2017).

    Article  Google Scholar 

  13. Park, R. J.-Y. et al. Semi-solid alkali metal electrodes enabling high critical current densities in solid electrolyte batteries. Nat. Energy 6, 314–322 (2021).

    Article  Google Scholar 

  14. Schmidt, R. D. & Sakamoto, J. In-situ, non-destructive acoustic characterization of solid state electrolyte cells. J. Power Sources 324, 126–133 (2016).

    Article  Google Scholar 

  15. Krauskopf, T. et al. Lithium-metal growth kinetics on LLZO garnet-type solid electrolytes. Joule 3, 2030–2049 (2019).

    Article  Google Scholar 

  16. Krauskopf, T. et al. The fast charge transfer kinetics of the lithium metal anode on the garnet‐type solid electrolyte Li6.25Al0.25La3Zr2O12. Adv. Energy Mater. 10, 2000945 (2020).

    Article  Google Scholar 

  17. Golozar, M. et al. Direct observation of lithium metal dendrites with ceramic solid electrolyte. Sci. Rep. 10, 18410 (2020).

    Article  Google Scholar 

  18. Zhao, J. et al. In situ observation of Li deposition‐induced cracking in garnet solid electrolytes. Energy Environ. Mater. (2021).

  19. Kinzer, B. et al. Operando analysis of the molten Li|LLZO interface: understanding how the physical properties of Li affect the critical current density. Matter (2021).

  20. Barroso-Luque, L., Tu, Q. & Ceder, G. An analysis of solid-state electrodeposition-induced metal plastic flow and predictions of stress states in solid ionic conductor defects. J. Electrochem. Soc. 167, 020534 (2020).

    Article  Google Scholar 

  21. Klinsmann, M., Hildebrand, F. E., Ganser, M. & McMeeking, R. M. Dendritic cracking in solid electrolytes driven by lithium insertion. J. Power Sources 442, 227226 (2019).

    Article  Google Scholar 

  22. Bucci, G. & Christensen, J. Modeling of lithium electrodeposition at the lithium/ceramic electrolyte interface: the role of interfacial resistance and surface defects. J. Power Sources 441, 227186 (2019).

    Article  Google Scholar 

  23. De Jonghe, L. C., Feldman, L. & Beuchele, A. Slow degradation and electron conduction in sodium/beta-aluminas. J. Mater. Sci. 16, 780–786 (1981).

    Article  Google Scholar 

  24. Feldman, L. A. & De Jonghe, L. C. Initiation of mode I degradation in sodium-beta alumina electrolytes. J. Mater. Sci. 17, 517–524 (1982).

    Article  Google Scholar 

  25. Han, F. et al. High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes. Nat. Energy 4, 187–196 (2019).

    Article  Google Scholar 

  26. Liu, X. et al. Local electronic structure variation resulting in Li ‘filament’ formation within solid electrolytes. Nat. Mater. 20, 1485–1490 (2021).

    Article  Google Scholar 

  27. Dong, Y., Zhang, Z., Alvarez, A. & Chen, I.-W. Potential jumps at transport bottlenecks cause instability of nominally ionic solid electrolytes in electrochemical cells. Acta Mater. 199, 264–277 (2020).

    Article  Google Scholar 

  28. Tu, Q., Shi, T., Chakravarthy, S. & Ceder, G. Understanding metal propagation in solid electrolytes due to mixed ionic-electronic conduction. Matter 4, 3248–3268 (2021).

    Article  Google Scholar 

  29. Zheng, H. et al. Intrinsic lithiophilicity of Li-garnet electrolytes enabling high-rate lithium cycling. Adv. Funct. Mater. 30, 1906189 (2020).

    Article  Google Scholar 

  30. Hitz, G. T. et al. High-rate lithium cycling in a scalable trilayer Li-garnet-electrolyte architecture. Mater. Today 22, 50–57 (2019).

    Article  Google Scholar 

  31. Cao, D. et al. Lithium dendrite in all-solid-state batteries: growth mechanisms, suppression strategies, and characterizations. Matter 3, 57–94 (2020).

    Article  Google Scholar 

  32. Lv, Q. et al. Suppressing lithium dendrites within inorganic solid-state electrolytes. Cell Rep. Phys. Sci. 3, 100706 (2022).

    Article  Google Scholar 

  33. Tian, H.-K., Liu, Z., Ji, Y., Chen, L.-Q. & Qi, Y. Interfacial electronic properties dictate Li dendrite growth in solid electrolytes. Chem. Mater. 31, 7351–7359 (2019).

    Article  Google Scholar 

  34. Ji, X. et al. Solid-state electrolyte design for lithium dendrite suppression. Adv. Mater. 32, 2002741 (2020).

    Article  Google Scholar 

  35. Efron, B. & Tibshirani, R. An Introduction to the Bootstrap (Chapman & Hall, 1993).

  36. Zok, F. W. On weakest link theory and Weibull statistics. J. Am. Ceram. Soc. 100, 1265–1268 (2017).

    Article  Google Scholar 

  37. Wu, E. Y. & Vollertsen, R.-P. On the Weibull shape factor of intrinsic breakdown of dielectric films and its accurate experimental determination—part I: theory, methodology, experimental techniques. IEEE Trans. Electron Devices 49, 2131–2140 (2002).

    Article  Google Scholar 

  38. Cheng, E. J., Sharafi, A. & Sakamoto, J. Intergranular Li metal propagation through polycrystalline Li6.25Al0.25La3Zr2O12 ceramic electrolyte. Electrochim. Acta 223, 85–91 (2017).

    Article  Google Scholar 

  39. Swamy, T. et al. Lithium metal penetration induced by electrodeposition through solid electrolytes: example in single-crystal Li6La3ZrTaO12 garnet. J. Electrochem. Soc. 165, A3648–A3655 (2018).

    Article  Google Scholar 

  40. Mukhopadhyay, A. K., Chakraborty, D., Swain, M. V. & Mai, Y.-W. Scratch deformation behaviour of alumina under a sharp indenter. J. Eur. Ceram. Soc. 17, 91–100 (1997).

    Article  Google Scholar 

  41. Swain, M. V. Microfracture about scratches in brittle solids. Proc. R. Soc. Lond. Math. Phys. Sci. 366, 575–597 (1979).

    Google Scholar 

  42. Yan, G. et al. An investigation on strength distribution, subcritical crack growth and lifetime of the lithium-ion conductor Li7La3Zr2O12. J. Mater. Sci. 54, 5671–5681 (2019).

    Article  Google Scholar 

  43. Swab, J. J. et al. Knoop hardness-apparent yield stress relationship in ceramics. Int. J. Appl. Ceram. Technol. 9, 650–655 (2012).

    Article  Google Scholar 

  44. Kondo, S., Ishihara, A., Tochigi, E., Shibata, N. & Ikuhara, Y. Direct observation of atomic-scale fracture path within ceramic grain boundary core. Nat. Commun. 10, 2112 (2019).

    Article  Google Scholar 

  45. Fincher, C. D. et al. Controlling dendrite propagation in solid-state batteries with engineered stress. Joule. 6, 2794–2809 (2022).

    Article  Google Scholar 

  46. Adepalli, K. K., Yang, J., Maier, J., Tuller, H. L. & Yildiz, B. Tunable oxygen diffusion and electronic conduction in SrTiO3 by dislocation‐induced space charge fields. Adv. Funct. Mater. 27, 1700243 (2017).

    Article  Google Scholar 

  47. Qi, Y., Ban, C. & Harris, S. J. A new general paradigm for understanding and preventing Li metal penetration through solid electrolytes. Joule (2020).

  48. Tippens, J. et al. Visualizing chemomechanical degradation of a solid-state battery electrolyte. ACS Energy Lett. 4, 1475–1483 (2019).

    Article  Google Scholar 

  49. Quinn, J. B. & Quinn, G. D. A practical and systematic review of Weibull statistics for reporting strengths of dental materials. Dent. Mater. 26, 135–147 (2010).

    Article  Google Scholar 

  50. Reiser, J. et al. Ductilisation of tungsten (W): on the increase of strength AND room-temperature tensile ductility through cold-rolling. Int. J. Refract. Met. Hard Mater. 64, 261–278 (2017).

    Article  Google Scholar 

Download references


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.

Author information

Authors and Affiliations



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.

Corresponding authors

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

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Energy thanks Josefine McBrayer and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

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

Supplementary information

Supplementary Information

Supplementary Figs. 1–18 and Discussion.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

McConohy, G., Xu, X., Cui, T. et al. Mechanical regulation of lithium intrusion probability in garnet solid electrolytes. Nat Energy 8, 241–250 (2023).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing