TY - JOUR
T1 - Mesoscale Interrogation Reveals Mechanistic Origins of Lithium Filaments along Grain Boundaries in Inorganic Solid Electrolytes
AU - Vishnugopi, Bairav S.
AU - Dixit, Marm B.
AU - Hao, Feng
AU - Shyam, Badri
AU - Cook, John B.
AU - Hatzell, Kelsey B.
AU - Mukherjee, Partha P.
N1 - Funding Information:
P.P.M. acknowledges support in part from the National Science Foundation (award no.: 2041499) and the Alfred P. Sloan Foundation through a Scialog: Advanced Energy Storage award. K.B.H. and M.B.D. were supported by the National Science Foundation under grant No. 1727863 and 1847029. K.B.H. and M.B.D. acknowledge the Vanderbilt Institute of Nanoscience and Engineering (VINSE) for access to their shared characterization facilities. This research used resources of the Advanced Photon Source, a U.S. 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.
Funding Information:
P.P.M. acknowledges support in part from the National Science Foundation (award no.: 2041499) and the Alfred P. Sloan Foundation through a Scialog: Advanced Energy Storage award. K.B.H. and M.B.D. were supported by the National Science Foundation under grant No. 1727863 and 1847029. K.B.H. and M.B.D. acknowledge the Vanderbilt Institute of Nanoscience and Engineering (VINSE) for access to their shared characterization facilities. This research used resources of the Advanced Photon Source, a U.S. 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.
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2022/1/20
Y1 - 2022/1/20
N2 - Solid-state batteries (SSBs), utilizing a lithium metal anode, promise to deliver enhanced energy and power densities compared to conventional lithium-ion batteries. Penetration of lithium filaments through the solid-state electrolytes (SSEs) during electrodeposition poses major constraints on the safety and rate performance of SSBs. While microstructural attributes, especially grain boundaries (GBs) within the SSEs are considered preferential metal propagation pathways, the underlying mechanisms are not fully understood yet. Here, a comprehensive insight is presented into the mechanistic interactions at the mesoscale including the electrochemical-mechanical response of the GB-electrode junction and competing ion transport dynamics in the SSE. Depending on the GB transport characteristics, a highly non-uniform electrodeposition morphology consisting of either cavities or protrusions at the GB-electrode interface is identified. Mechanical stability analysis reveals localized strain ramps in the GB regions that can lead to brittle fracture of the SSE. For ionically less conductive GBs compared to the grains, a crack formation and void filling mechanism, triggered by the heterogeneous nature of electrochemical-mechanical interactions is delineated at the GB-electrode junction. Concurrently, in situ X-ray tomography of pristine and failed Li7La3Zr2O12 (LLZO) SSE samples confirm the presence of filamentous lithium penetration and validity of the proposed mesoscale failure mechanisms.
AB - Solid-state batteries (SSBs), utilizing a lithium metal anode, promise to deliver enhanced energy and power densities compared to conventional lithium-ion batteries. Penetration of lithium filaments through the solid-state electrolytes (SSEs) during electrodeposition poses major constraints on the safety and rate performance of SSBs. While microstructural attributes, especially grain boundaries (GBs) within the SSEs are considered preferential metal propagation pathways, the underlying mechanisms are not fully understood yet. Here, a comprehensive insight is presented into the mechanistic interactions at the mesoscale including the electrochemical-mechanical response of the GB-electrode junction and competing ion transport dynamics in the SSE. Depending on the GB transport characteristics, a highly non-uniform electrodeposition morphology consisting of either cavities or protrusions at the GB-electrode interface is identified. Mechanical stability analysis reveals localized strain ramps in the GB regions that can lead to brittle fracture of the SSE. For ionically less conductive GBs compared to the grains, a crack formation and void filling mechanism, triggered by the heterogeneous nature of electrochemical-mechanical interactions is delineated at the GB-electrode junction. Concurrently, in situ X-ray tomography of pristine and failed Li7La3Zr2O12 (LLZO) SSE samples confirm the presence of filamentous lithium penetration and validity of the proposed mesoscale failure mechanisms.
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U2 - 10.1002/aenm.202102825
DO - 10.1002/aenm.202102825
M3 - Article
AN - SCOPUS:85121372788
VL - 12
JO - Advanced Energy Materials
JF - Advanced Energy Materials
SN - 1614-6832
IS - 3
M1 - 2102825
ER -