Correlating the Interfacial Chemistries With Ion Conduction and Lithium Deactivation in Hybrid Solid Electrolytes

Abstract

Inactive lithium (dead Li) is the key factor leading to the performance degradation of solid-state Li metal batteries. Such a deactivated material comprises a useless solid–electrolyte interphase and electrically or ionically isolated Li⁰ debris. Dead Li exists at both the “extrinsic” Li/electrolyte and intrinsic electrolyte/electrolyte interfaces and is associated with the ion transport behavior at such interfaces. Herein, we evaluate the different interfacial structures and compositions in a prototype poly(ethylene oxide)–Li₄SnS₄ hybrid electrolyte and clarify its influence on Li deactivation suppression. Cryotransmission electron microscopy reveals that the intrinsic interface between poly(ethylene oxide) and Li₄SnS₄ is mainly composed of Li₂S and Li₂CO₃. Notably, the extrinsic interface at Li and poly(ethylene oxide)–Li₄SnS₄ contains extra Li₂S and reduced Li₂O compared with poly(ethylene oxide) electrolyte. The increase of low energy barrier Li₂S (0.13 eV) components significantly accelerates the interfacial ion migration and reduces the content of dead Li (10.6%). The optimized interface enables the Li || Li cell to operate stably for over 3000 h. This work by interface regulation reduces the formation of electron- and ion-isolated dead Li in solid-state Li metal batteries, which is of reference significance for the design of dead Li suppression or activation strategies in solid-state Li metal battery systems.

Keywords

dead lithium / hybrid solid electrolyte / interface / lithium metal battery

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RIGHTS & PERMISSIONS

2026 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.