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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All analysis was performed using open-source computational packages in Python 3.8. Code is available at https://doi.org/10.5281/zenodo.7332149.
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).
Yu, Z. et al. Dendrites in solid-state batteries: ion transport behavior, advanced characterization, and interface regulation. Adv. Energy Mater. 11, 2003250 (2021).
Chen, Y. et al. Understanding the lithium dendrites growth in garnet-based solid-state lithium metal batteries. J. Power Sources 521, 230921 (2022).
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).
Kazyak, E. et al. Li penetration in ceramic solid electrolytes: operando microscopy analysis of morphology, propagation, and reversibility. Matter 2, 1025–1048 (2020).
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).
Monroe, C. & Newman, J. The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces. J. Electrochem. Soc. 152, A396 (2005).
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).
Yu, S. et al. Elastic properties of the solid electrolyte Li7La3Zr2O12 (LLZO). Chem. Mater. 28, 197–206 (2016).
Lu, Y. et al. Critical current density in solid‐state lithium metal batteries: mechanism, influences, and strategies. Adv. Funct. Mater. 31, 2009925 (2021).
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).
Porz, L. et al. Mechanism of lithium metal penetration through inorganic solid electrolytes. Adv. Energy Mater. 7, 1701003 (2017).
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).
Schmidt, R. D. & Sakamoto, J. In-situ, non-destructive acoustic characterization of solid state electrolyte cells. J. Power Sources 324, 126–133 (2016).
Krauskopf, T. et al. Lithium-metal growth kinetics on LLZO garnet-type solid electrolytes. Joule 3, 2030–2049 (2019).
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).
Golozar, M. et al. Direct observation of lithium metal dendrites with ceramic solid electrolyte. Sci. Rep. 10, 18410 (2020).
Zhao, J. et al. In situ observation of Li deposition‐induced cracking in garnet solid electrolytes. Energy Environ. Mater. https://doi.org/10.1002/eem2.12261 (2021).
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 https://doi.org/10.1016/j.matt.2021.04.016 (2021).
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).
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).
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).
De Jonghe, L. C., Feldman, L. & Beuchele, A. Slow degradation and electron conduction in sodium/beta-aluminas. J. Mater. Sci. 16, 780–786 (1981).
Feldman, L. A. & De Jonghe, L. C. Initiation of mode I degradation in sodium-beta alumina electrolytes. J. Mater. Sci. 17, 517–524 (1982).
Han, F. et al. High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes. Nat. Energy 4, 187–196 (2019).
Liu, X. et al. Local electronic structure variation resulting in Li ‘filament’ formation within solid electrolytes. Nat. Mater. 20, 1485–1490 (2021).
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).
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).
Zheng, H. et al. Intrinsic lithiophilicity of Li-garnet electrolytes enabling high-rate lithium cycling. Adv. Funct. Mater. 30, 1906189 (2020).
Hitz, G. T. et al. High-rate lithium cycling in a scalable trilayer Li-garnet-electrolyte architecture. Mater. Today 22, 50–57 (2019).
Cao, D. et al. Lithium dendrite in all-solid-state batteries: growth mechanisms, suppression strategies, and characterizations. Matter 3, 57–94 (2020).
Lv, Q. et al. Suppressing lithium dendrites within inorganic solid-state electrolytes. Cell Rep. Phys. Sci. 3, 100706 (2022).
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).
Ji, X. et al. Solid-state electrolyte design for lithium dendrite suppression. Adv. Mater. 32, 2002741 (2020).
Efron, B. & Tibshirani, R. An Introduction to the Bootstrap (Chapman & Hall, 1993).
Zok, F. W. On weakest link theory and Weibull statistics. J. Am. Ceram. Soc. 100, 1265–1268 (2017).
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).
Cheng, E. J., Sharafi, A. & Sakamoto, J. Intergranular Li metal propagation through polycrystalline Li6.25Al0.25La3Zr2O12 ceramic electrolyte. Electrochim. Acta 223, 85–91 (2017).
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).
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).
Swain, M. V. Microfracture about scratches in brittle solids. Proc. R. Soc. Lond. Math. Phys. Sci. 366, 575–597 (1979).
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).
Swab, J. J. et al. Knoop hardness-apparent yield stress relationship in ceramics. Int. J. Appl. Ceram. Technol. 9, 650–655 (2012).
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).
Fincher, C. D. et al. Controlling dendrite propagation in solid-state batteries with engineered stress. Joule. 6, 2794–2809 (2022).
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).
Qi, Y., Ban, C. & Harris, S. J. A new general paradigm for understanding and preventing Li metal penetration through solid electrolytes. Joule https://doi.org/10.1016/j.joule.2020.10.009 (2020).
Tippens, J. et al. Visualizing chemomechanical degradation of a solid-state battery electrolyte. ACS Energy Lett. 4, 1475–1483 (2019).
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).
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).
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.
The authors declare no competing interests.
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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