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

Marm B. Dixit; Bairav S. Vishugopi; Wahid Zaman; Peter Kenesei; Jun Sang Park; Jonathan Almer; Partha P. Mukherjee; Kelsey B. Hatzell

doi:10.1038/s41563-022-01333-y

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

Marm B. Dixit, Bairav S. Vishugopi, Wahid Zaman, Peter Kenesei, Jun Sang Park, Jonathan Almer, Partha P. Mukherjee, Kelsey B. Hatzell

Emerging and Solid-State Batteries

Research output: Contribution to journal › Article › peer-review

48 Scopus citations

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.

Original language	English
Pages (from-to)	1298-1305
Number of pages	8
Journal	Nature Materials
Volume	21
Issue number	11
DOIs	https://doi.org/10.1038/s41563-022-01333-y
State	Published - Nov 2022

Funding

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). 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 ).

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title = "Polymorphism of garnet solid electrolytes and its implications for grain-level chemo-mechanics",

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.",

author = "Dixit, {Marm B.} and Vishugopi, {Bairav S.} and Wahid Zaman and Peter Kenesei and Park, {Jun Sang} and Jonathan Almer and Mukherjee, {Partha P.} and Hatzell, {Kelsey B.}",

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AU - Dixit, Marm B.

AU - Vishugopi, Bairav S.

AU - Zaman, Wahid

AU - Kenesei, Peter

AU - Park, Jun Sang

AU - Almer, Jonathan

AU - Mukherjee, Partha P.

AU - Hatzell, Kelsey B.

PY - 2022/11

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N2 - 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.

AB - 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.

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

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