Visualizing surface-reaction-driven chloride migration and cascading failure in sulfide solid electrolytes
Abstract
Moisture instability of sulfide solid electrolytes limits practical use in all-solid-state batteries. Spatially resolving gas--solid reactions during moisture exposure remains challenging. Here, cryogenic four-dimensional scanning transmission electron microscopy (cryo-4D-STEM) maps nanoscale degradation in low- and high-Cl argyrodite electrolytes, Li6PS5Cl and Li5.5PS4.5Cl1.5. Li6PS5Cl undergoes predominantly surface-localized degradation that progressively extends inward, whereas Li5.5PS4.5Cl1.5 exhibits rapid interior amorphization accompanied by outward chloride redistribution. Density functional theory calculations indicate a lower chloride-migration barrier along the modeled pathway in the higher-Cl composition, while chloride removal and vacancy formation distort the PS43− framework and may destabilize the lattice. Surface treatment suppresses detectable large-scale chloride segregation and improves moisture tolerance, retaining 99.9% of the capacity measured at the start of 0.33 C cycling after 150 cycles. These results identify chloride redistribution as a key process in degradation propagation and suggest a route toward moisture-tolerant solid-state batteries.
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BibTeX
@misc{he2026visualizing,
title = {{Visualizing surface-reaction-driven chloride migration and cascading failure in sulfide solid electrolytes}},
author = {Xiaoya He and Haoran Zhang and Xinyang Yue and Hang Liu and Zian Mao and Jialong Wang and Min Liu and Shufen Chu and Liwei Chen and Zhaoxin Yu and Xi Liu and Chuying Ouyang and Ziyang Ning and Yujun Xie},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.22394},
eprint = {2610.22394},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.22394},
note = {CC BY-NC-SA 4.0},
}
RIS
TY - UNPB
TI - Visualizing surface-reaction-driven chloride migration and cascading failure in sulfide solid electrolytes
AU - Xiaoya He
AU - Haoran Zhang
AU - Xinyang Yue
AU - Hang Liu
AU - Zian Mao
AU - Jialong Wang
AU - Min Liu
AU - Shufen Chu
AU - Liwei Chen
AU - Zhaoxin Yu
AU - Xi Liu
AU - Chuying Ouyang
AU - Ziyang Ning
AU - Yujun Xie
PY - 2026
DA - 2026/10/14
PB - arXiv
DO - 10.48550/arxiv.2610.22394
UR - https://arxiv.org/abs/2610.22394
AB - Moisture instability of sulfide solid electrolytes limits practical use in all-solid-state batteries. Spatially resolving gas--solid reactions during moisture exposure remains challenging. Here, cryogenic four-dimensional scanning transmission electron microscopy (cryo-4D-STEM) maps nanoscale degradation in low- and high-Cl argyrodite electrolytes, Li_6PS_5Cl and Li_5.5PS_4.5Cl_1.5. Li_6PS_5Cl undergoes predominantly surface-localized degradation that progressively extends inward, whereas Li_5.5PS_4.5Cl_1.5 exhibits rapid interior amorphization accompanied by outward chloride redistribution. Density functional theory calculations indicate a lower chloride-migration barrier along the modeled pathway in the higher-Cl composition, while chloride removal and vacancy formation distort the PS_4^3− framework and may destabilize the lattice. Surface treatment suppresses detectable large-scale chloride segregation and improves moisture tolerance, retaining 99.9% of the capacity measured at the start of 0.33 C cycling after 150 cycles. These results identify chloride redistribution as a key process in degradation propagation and suggest a route toward moisture-tolerant solid-state batteries.
ER -