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All-solid-state batteries (ASSBs) are viewed as promising next-generation energy storage devices, due to their enhanced safety by replacing organic liquid electrolytes with non-flammable solid-state electrolytes (SSEs). The high ionic conductivity and low Young's modulus of sulfide SSEs make them suitable candidates for commercial ASSBs. Nevertheless, sulfide SSEs are generally reported to be unstable in ambient air. Moreover, instead of gloveboxes used for laboratory scale studies, large scale production of batteries is usually conducted in dry rooms. Thus, this study aims to elucidate the chemical evolution of a sulfide electrolyte, Li 6 PS 5 Cl (LPSCl), during air exposure and to evaluate its dry room compatibility. When LPSCl is exposed to ambient air, hydrolysis, hydration, and carbonate formation can occur. Moreover, hydrolysis can lead to irreversible sulfur loss and therefore LPSCl cannot be fully recovered in the subsequent heat treatment. During heat treatment, exposed LPSCl undergoes dehydration, decomposition of carbonate species, and reformation of the LPSCl phase. Finally, LPSCl was found to exhibit good stability in a dry room environment and was subject to only minor conductivity loss due to carbonate formation. The dry room exposed LPSCl sample was tested in a LiNi 0.8 Co 0.1 Mn 0.1 O 2 |LiIn half-cell, exhibiting no significant loss of electrochemical performance compared with the pristine LPSCl, proving it to be compatible with dry room manufacturing processes.
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This content will become publicly available on December 1, 2026
Surface molecular engineering to enable processing of sulfide solid electrolytes in humid ambient air
Abstract Sulfide solid-state electrolytes (SSEs) are promising candidates to realize all solid-state batteries (ASSBs) due to their superior ionic conductivity and excellent ductility. However, their hypersensitivity to moisture requires processing environments that are not compatible with today’s lithium-ion battery manufacturing infrastructure. Herein, we present a reversible surface modification strategy that enables the processability of sulfide SSEs (e. g., Li6PS5Cl) under humid ambient air. We demonstrate that a long chain alkyl thiol, 1-undecanethiol, is chemically compatible with the electrolyte with negligible impact on its ion conductivity. Importantly, the thiol modification extends the amount of time that the sulfide SSE can be exposed to air with 33% relative humidity (33% RH) with limited degradation of its structure while retaining a conductivity of above 1 mS cm-1for up to 2 days, a more than 100-fold improvement in protection time over competing approaches. Experimental and computational results reveal that the thiol group anchors to the SSE surface, while the hydrophobic hydrocarbon tail provides protection by repelling water. The modified Li6PS5Cl SSE maintains its function after exposure to ambient humidity when implemented in a Li0.5In | |LiNi0.8Co0.1Mn0.1O2ASSB. The proposed protection strategy based on surface molecular interactions represents a major step forward towards cost-competitive and energy-efficient sulfide SSE manufacturing for ASSB applications.
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- PAR ID:
- 10589405
- Publisher / Repository:
- Springer Nature Publishing
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 16
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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