Skip to main content

Thank you for visiting nature.com. 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.

  • Article
  • Published:

Polymorphism of garnet solid electrolytes and its implications for grain-level chemo-mechanics

Nature Materials volume 21, pages 1298–1305 (2022)Cite this article

Subjects

Abstract

Understanding and mitigating filament formation, short-circuit and solid electrolyte fracture is necessary for advanced all-solid-state batteries. Here, we employ a coupled far-field high-energy diffraction microscopy and tomography approach for assessing the chemo-mechanical behaviour for dense, polycrystalline garnet (Li7La3Zr2O12) solid electrolytes with grain-level resolution. In situ monitoring of grain-level stress responses reveals that the failure mechanism is stochastic and affected by local microstructural heterogeneity. Coupling high-energy X-ray diffraction and far-field high-energy diffraction microscopy measurements reveals the presence of phase heterogeneity that can alter local chemo-mechanics within the bulk solid electrolyte. These local regions are proposed to be regions with the presence of a cubic polymorph of LLZO, potentially arising from local dopant concentration variation. The coupled tomography and FF-HEDM experiments are combined with transport and mechanics modelling to illustrate the degradation of polycrystalline garnet solid electrolytes. The results showcase the pathways for processing high-performing solid-state batteries.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Fig. 1: Mechanical response of a polycrystalline LLZO material.
Fig. 2: Stress response of polycrystalline LLZO material.
Fig. 3: Local phase anisotropy in garnet solid electrolytes.
Fig. 4: Hydrostatic stress evolution during cycling.
Fig. 5: Correlating FF-HEDM and tomography datasets.
Fig. 6: Evaluating stress flow directions in bulk solid electrolytes.

Similar content being viewed by others

Data availability

Data presented in this study are available from the corresponding authors upon request.

References

  1. Krauskopf, T., Richter, F. H., Zeier, W. G. & Janek, J. Physicochemical concepts of the lithium metal anode in solid-state batteries. Chem. Rev. 120, 7745–7794 (2020).

    CAS  Google Scholar 

  2. Randau, S. et al. Benchmarking the performance of all-solid-state lithium batteries. Nat. Energy 5, 259–270 (2020).

    CAS  Google Scholar 

  3. Hatzell, K. B. et al. Challenges in lithium metal anodes for solid-state batteries. ACS Energy Lett. 5, 922–934 (2020).

    CAS  Google Scholar 

  4. Mistry, A. & Mukherjee, P. P. Molar volume mismatch: a malefactor for irregular metallic electrodeposition with solid electrolytes. J. Electrochem. Soc. 167, 082510 (2020).

    CAS  Google Scholar 

  5. Dixit, M. B., Park, J. S., Kenesei, P., Almer, J. & Hatzell, K. B. Status and prospect of in situ and operando characterization of solid-state batteries. Energy Environ. Sci. 14, 4672–4711 (2021).

    CAS  Google Scholar 

  6. Lewis, J. A. et al. Linking void and interphase evolution to electrochemistry in solid-state batteries using operando X-ray tomography. Nat. Mater. 20, 503–510 (2021).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  8. Shen, F., Dixit, M. B., Xiao, X. & Hatzell, K. B. Effect of pore connectivity on Li dendrite propagation within LLZO electrolytes observed with synchrotron X-ray tomography. ACS Energy Lett. 3, 1056–1061 (2018).

    CAS  Google Scholar 

  9. Kasemchainan, J. et al. Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells. Nat. Mater. 18, 1105–1111 (2019).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

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

    Google Scholar 

  12. Wenzel, S., Sedlmaier, S. J., Dietrich, C., Zeier, W. G. & Janek, J. Interfacial reactivity and interphase growth of argyrodite solid electrolytes at lithium metal electrodes. Solid State Ion. 318, 102–112 (2018).

    CAS  Google Scholar 

  13. Dixit, M. B. et al. In situ investigation of chemomechanical effects in thiophosphate solid electrolytes. Matter 3, 2138–2159 (2020).

    Google Scholar 

  14. Wang, M. J., Choudhury, R. & Sakamoto, J. Characterizing the Li-solid-electrolyte interface dynamics as a function of stack pressure and current density. Joule 3, 2165–2178 (2019).

    CAS  Google Scholar 

  15. Asano, T. et al. Solid halide electrolytes with high lithium-ion conductivity for application in 4 V class bulk-type all-solid-state batteries. Adv. Mater. 30, 1803075 (2018).

    Google Scholar 

  16. Dawson, J., Famprikis, T. & Johnston, K. E. Anti-perovskites for solid-state batteries: recent developments, current challenges and future prospects. J. Mater. Chem. A 9, 18746–18772 (2021).

    CAS  Google Scholar 

  17. Wang, A. N. et al. Mechanical properties of the solid electrolyte Al-substituted Li7La3Zr2O12 (LLZO) by utilizing micro-pillar indentation splitting test. J. Eur. Ceram. Soc. 38, 3201–3209 (2018).

    CAS  Google Scholar 

  18. Fu, Z. et al. Probing the mechanical properties of a doped Li7La3Zr2O12 garnet thin electrolyte for solid-state batteries. ACS Appl. Mater. Interfaces 12, 24693–24700 (2020).

    CAS  Google Scholar 

  19. Sharafi, A., Haslam, C. G., Kerns, R. D., Wolfenstine, J. & Sakamoto, J. Controlling and correlating the effect of grain size with the mechanical and electrochemical properties of Li7La3Zr2O12 solid-state electrolyte. J. Mater. Chem. A 5, 21491–21504 (2017).

    CAS  Google Scholar 

  20. Kim, Y. et al. The effect of relative density on the mechanical properties of hot-pressed cubic Li7La3Zr2O12. J. Am. Ceram. Soc. 99, 1367–1374 (2016).

    CAS  Google Scholar 

  21. El-Shinawi, H., Paterson, G. W., MacLaren, D. A., Cussen, E. J. & Corr, S. A. Low-temperature densification of Al-doped LLZO: a reliable and controllable synthesis of fast-ion conducting garnets. J. Mater. Chem. A 5, 319–329 (2016).

    Google Scholar 

  22. Van Den Broek, J., Afyon, S. & Rupp, J. L. Interface-engineered all-solid-state Li-ion batteries based on garnet-type fast Li+ conductors. Adv. Energy Mater. 6, 1600736 (2016).

    Google Scholar 

  23. Afyon, S., Krumeich, F. & Rupp, J. L. A shortcut to garnet-type fast Li-ion conductors for all-solid state batteries. J. Mater. Chem. A 3, 18636–18648 (2015).

    CAS  Google Scholar 

  24. Rettenwander, D. et al. Structural and electrochemical consequences of Al and Ga cosubstitution in Li7La3Zr2O12 solid electrolytes. Chem. Mater. 28, 2384–2392 (2016).

    CAS  Google Scholar 

  25. 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).

    CAS  Google Scholar 

  26. Sharafi, A., Meyer, H. M., Nanda, J., Wolfenstine, J. & Sakamoto, J. Characterizing the Li–Li7La3Zr2O12 interface stability and kinetics as a function of temperature and current density. J. Power Sources 302, 135–139 (2016).

    CAS  Google Scholar 

  27. Cheng, L. et al. Effect of surface microstructure on electrochemical performance of garnet solid electrolytes. ACS Appl. Mater. interfaces 7, 2073–2081 (2015).

    CAS  Google Scholar 

  28. Qi, Y., Ban, C. & Harris, S. J. A new general paradigm for understanding and preventing Li metal penetration through solid electrolytes. Joule 4, 2599–2608 (2020).

    CAS  Google Scholar 

  29. Ma, C. et al. Interfacial stability of Li metal–solid electrolyte elucidated via in situ electron microscopy. Nano Lett. 16, 7030–7036 (2016).

    CAS  Google Scholar 

  30. Park, K. et al. Electrochemical nature of the cathode interface for a solid-state lithium-ion battery: interface between LiCoO2 and garnet-Li7La3Zr2O12. Chem. Mater. 28, 8051–8059 (2016).

    CAS  Google Scholar 

  31. Brugge, R. H. et al. The origin of chemical inhomogeneity in garnet electrolytes and its impact on the electrochemical performance. J. Mater. Chem. A 8, 14265–14276 (2020).

    CAS  Google Scholar 

  32. Yang, Y. et al. In situ electron holography for characterizing Li ion accumulation in the interface between electrode and solid-state-electrolyte. J. Mater. Chem. A 9, 15038–15044 (2021).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  34. Schuren, J. C. et al. New opportunities for quantitative tracking of polycrystal responses in three dimensions. Curr. Opin. Solid State Mater. Sci. 19, 235–244 (2015).

    CAS  Google Scholar 

  35. Dixit, M. B. et al. Synchrotron imaging of pore formation in Li metal solid-state batteries aided by machine learning. ACS Appl. Energy Mater. 3, 9534–9542 (2020).

    CAS  Google Scholar 

  36. Wang, M. & Sakamoto, J. Correlating the interface resistance and surface adhesion of the Li metal-solid electrolyte interface. J. Power Sources 377, 7–11 (2018).

    CAS  Google Scholar 

  37. Park, J. S., Lienert, U., Dawson, P. R. & Miller, M. P. Quantifying three-dimensional residual stress distributions using spatially-resolved diffraction measurements and finite element based data reduction. Exp. Mech. 53, 1491–1507 (2013).

    Google Scholar 

  38. Haeffner, D. R., Almer, J. D. & Lienert, U. The use of high energy X-rays from the Advanced Photon Source to study stresses in materials. Mater. Sci. Eng. A 399, 120–127 (2005).

    Google Scholar 

  39. Birkbak, M. E. et al. Concurrent determination of nanocrystal shape and amorphous phases in complex materials by diffraction scattering computed tomography. J. Appl. Cryst. 50, 192–197 (2017).

    CAS  Google Scholar 

  40. Martins, R. V., Ohms, C. & Decroos, K. Full 3D spatially resolved mapping of residual strain in a 316L austenitic stainless steel weld specimen. Mater. Sci. Eng. A 527, 4779–4787 (2010).

    Google Scholar 

  41. Bernier, J. V., Barton, N. R., Lienert, U. & Miller, M. P. Far-field high-energy diffraction microscopy: a tool for intergranular orientation and strain analysis. J. Strain Anal. Eng. Des. 46, 527–547 (2011).

    Google Scholar 

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

    CAS  Google Scholar 

  43. Vishnugopi, B. S. et al. Mesoscale interrogation reveals mechanistic origins of lithium filaments along grain boundaries in inorganic solid electrolytes. Adv. Energy Mater. 12, 2102825 (2022).

    CAS  Google Scholar 

  44. Vishnugopi, B. S., Hao, F., Verma, A. & Mukherjee, P. P. Double-edged effect of temperature on lithium dendrites. ACS Appl. Mater. Interfaces 12, 23931–23938 (2020).

    CAS  Google Scholar 

  45. Ma, C. et al. Excellent stability of a lithium-ion-conducting solid electrolyte upon reversible Li+/H+ exchange in aqueous solutions. Angew. Chem. 127, 131–135 (2015).

    Google Scholar 

  46. Cussen, E. J. Structure and ionic conductivity in lithium garnets. J. Mater. Chem. 20, 5167–5173 (2010).

    CAS  Google Scholar 

  47. Yu, S. & Siegel, D. J. Grain boundary softening: a potential mechanism for lithium metal penetration through stiff solid electrolytes. ACS Appl. Mater. Interfaces 10, 38151–38158 (2018).

    CAS  Google Scholar 

  48. Larson, J. M. et al. Pascalammetry with operando microbattery probes: sensing high stress in solid-state batteries. Sci. Adv. 4, eaas8927 (2018).

    Google Scholar 

  49. Cannarella, J. et al. Mechanical properties of a battery separator under compression and tension. J. Electrochem. Soc. 161, F3117 (2014).

    CAS  Google Scholar 

  50. Gor, G. Y., Cannarella, J., Prévost, J. H. & Arnold, C. B. A model for the behavior of battery separators in compression at different strain/charge rates. J. Electrochem. Soc. 161, F3065 (2014).

    CAS  Google Scholar 

  51. Bernuy-Lopez, C. et al. Atmosphere controlled processing of Ga-substituted garnets for high Li-ion conductivity ceramics. Chem. Mater. 26, 3610–3617 (2014).

    CAS  Google Scholar 

  52. Tan, J. & Tiwari, A. Synthesis of cubic phase Li7La3Zr2O12 electrolyte for solid-state lithium-ion batteries. Electrochem. Solid-State Lett. 15, A37 (2011).

    Google Scholar 

  53. Hatzell, K. B. & Zheng, Y. Prospects on large-scale manufacturing of solid state batteries. MRS Energy Sustain. 8, 33–39 (2021).

    Google Scholar 

  54. Fritsch, C. et al. Garnet to hydrogarnet: effect of post synthesis treatment on cation substituted LLZO solid electrolyte and its effect on Li ion conductivity. RSC Adv. 11, 30283–30294 (2021).

    CAS  Google Scholar 

  55. Wagner, R. et al. Crystal structure of garnet-related Li-ion conductor Li7–3xGaxLa3Zr2O12: fast Li-ion conduction caused by a different cubic modification? Chem. Mater. 28, 1861–1871 (2016).

    CAS  Google Scholar 

  56. Zhao, L. et al. Laplace-Fourier transform solution to the electrochemical kinetics of a symmetric lithium cell affected by interface conformity. J. Power Sources 531, 231305 (2022).

    CAS  Google Scholar 

  57. Li, R. et al. Unveiling the origins of work-hardening enhancement and mechanical instability in laser shock peened titanium. Acta Mater. 229, 117810 (2022).

    CAS  Google Scholar 

  58. Nielsen, S. F. et al. A conical slit for three-dimensional XRD mapping. J. Synchrotron Rad. 7, 103–109 (2000).

    CAS  Google Scholar 

  59. Suter, R. M., Hennessy, D., Xiao, C. & Lienert, U. Forward modeling method for microstructure reconstruction using X-ray diffraction microscopy: single-crystal verification. Rev. Sci. Instrum. 77, 123905 (2006).

    Google Scholar 

Download references

Acknowledgements

This work was supported by the National Science Foundation under grant nos. 2140376, 2140472, and 1847029. We acknowledge the Vanderbilt Institute of Nanoscience and Engineering (VINSE) for access to their shared characterization facilities. P.P.M. acknowledges support in part from the National Science Foundation (award no. 2041499). This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory, under contract no. DE-AC02-06CH11357. This research was carried out in part at the Oak Ridge National Laboratory, managed by UT–Battelle, for the US DOE under contract DE-AC05-00OR22725. M.B.D. was also supported in part by Alvin M. Weinberg Fellowship at the Oak Ridge National Laboratory. Notice: This manuscript has been authored by UT–Battelle under contract no. DE-AC0500OR22725 with the US DOE. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for the United States Government purposes. The US DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (https://www.energy.gov/downloads/doe-public-access-plan).

Author information

Author notes

  1. Kelsey B. Hatzell

    Present address: Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ, USA

Authors and Affiliations

  1. Department of Mechanical Engineering, Vanderbilt University, Nashville, TN, USA

    Marm B. Dixit, Wahid Zaman & Kelsey B. Hatzell

  2. Electrification and Energy Infrastructures Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Marm B. Dixit

  3. School of Mechanical Engineering, Purdue University, West Lafayette, IN, USA

    Bairav S. Vishugopi & Partha P. Mukherjee

  4. Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ, USA

    Wahid Zaman

  5. Advanced Photon Source, Argonne National Laboratory, Lemont, IL, USA

    Peter Kenesei, Jun-Sang Park & Jonathan Almer

  6. Andlinger Center for Energy and the Environment, Princeton University, Princeton, NJ, USA

    Kelsey B. Hatzell

Authors
  1. Marm B. Dixit
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Bairav S. Vishugopi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Wahid Zaman
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Peter Kenesei
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jun-Sang Park
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jonathan Almer
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Partha P. Mukherjee
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Kelsey B. Hatzell
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

M.B.D. and K.B.H. conceived the concept and idea. M.B.D. and W.Z. performed the synchrotron imaging and diffraction experiments. J-S.P., J.A. and P.K. performed the synchrotron measurements and helped with the analysis. M.B.D. completed the image processing and analysis from the synchrotron experiments. B.S.V. and P.P.M. carried out the modelling efforts. M.D. and K.B.H. wrote the manuscript. The manuscript was edited by all the authors.

Corresponding authors

Correspondence to Marm B. Dixit or Kelsey B. Hatzell.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Materials thanks Marca Doeff, Ainara Aguadero 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.

Extended data

Extended Data Fig. 1 Evaluating the presence of trace phases in sintered LLZO pellets.

(a) High resolution, X-Ray diffraction patterns from specified locations of an LLZO pellet. (b) Spatially resolved high resolution XRD map of the LLZO pellet. (c) Spatially resolved XRD map zoomed to the anticipated location of the low-structure factor peak corresponding to < 141 > plane in the 230 space group LLZO.

Extended Data Fig. 2 Correlating grain-level mechanics to the bulk microstructure.

(a) Difference in the pore structure of a hot-spot neighbourhood between the pristine and the failed sample. The structure represents the modification of pore network between pristine and the failed sample. The scale bar in the figure is 100 μm (b) Depth averaged Δporosity values for identical sub-volume sizes taken at a hot spot region (right) and other (unstrained) regions of the bulk pellet. The porosity difference is calculated between the pristine and the failed sample. The scale bar in the figure is 10 μm. (c) Difference in porosity values tracked over the hot-spot and cold-spots for each step plotted as a box plot. Additionally, the average porosity difference over the entire pellet between each step is overlayed and connected by a solid line. As the sample undergoes degradation with cycling, the hot-/cold- neighbourhoods clearly show very high variance in the porosity change compared to the bulk sample value.

Supplementary information

Supplementary Information

Supplementary Figs. 1–28 and details on data analysis.

Rights and permissions

Springer Nature or its licensor 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

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Dixit, M.B., Vishugopi, B.S., Zaman, W. et al. Polymorphism of garnet solid electrolytes and its implications for grain-level chemo-mechanics. Nat. Mater. 21, 1298–1305 (2022). https://doi.org/10.1038/s41563-022-01333-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-022-01333-y

This article is cited by

Search

Advanced search

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