Improved Thermal Stability of Oxysulfide Glassy Solid-State Electrolytes

Gonzalez Malabet, Hernando J.; Zhang, Yubin; Salvador, James R.; Schmidt, Robert D.; Yersak, Thomas A.

doi:10.1149/1945-7111/ad07ff

Title: Improved Thermal Stability of Oxysulfide Glassy Solid-State Electrolytes

Journal Article · 07 November 2023 · Journal of the Electrochemical Society

DOI: https://doi.org/10.1149/1945-7111/ad07ff · OSTI ID:2205243

Gonzalez Malabet, Hernando J.; Zhang, Yubin; Salvador, James R.; Schmidt, Robert D.;

In this study, the crystallization kinetics of (oxy)sulfide 70Li ₂ S·(30-x)P ₂ S ₅ ·xP ₂ O ₅ (x = 0, 2, 5) solid-state electrolytes are reported. It was found that 5 mol% P ₂ O ₅ glass co-former slowed the crystallization rate of the Li ₇ P ₃ S _11−x/4 O _x/4 ceramic phase by a factor of 10. After 10 min at 230 °C, a 70Li ₂ S·30P ₂ S ₅ sulfide glass was 92% devitrified whereas a 70Li ₂ S·25P ₂ S ₅ ·5P ₂ O ₅ oxysulfide glass was only 8% devitrified. The improved thermal stability of oxysulfide glasses was then utilized to demonstrate the fabrication of a standalone, reinforced SSE separator by hot pressing. More importantly, it was recognized that the microstructure of 70Li ₂ S·25P ₂ S ₅ ·5P ₂ O ₅ oxysulfide SSE separators could be modified by hot pressing without changing ionic conductivity. This result was achieved because the precipitation of a superionically conductive Li ₇ P ₃ S _11−x/4 O _x/4 ceramic phase was limited. A study was then conducted to determine what effect microstructure has on the susceptibility of SSE separators to shorting by lithium metal penetration. Hot-pressed separators were found to be more susceptible to shorting than cold-pressed separators. X-ray Computer Tomography (XCT) of post-mortem samples showed that hot-pressed samples failed by transverse microcrack pathways, which underscores the importance of low defect density in dense SSE separators.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; EE0008857

OSTI ID:: 2205243

Alternate ID(s):: OSTI ID: 2326213; OSTI ID: 2204064

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 11 Vol. 170; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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