A scalable Li-Al-Cl stratified structure for stable all-solid-state lithium metal batteries

Abstract Sulfides are promising electrolyte materials for all-solid-state Li metal batteries due to their high ionic conductivity and machinability. However, compatibility issues at the negative electrode/sulfide electrolyte interface hinder their practical implementation. Despite previous studies have proposed considerable strategies to improve the negative electrode/sulfide electrolyte interfacial stability, industrial-scale engineering solutions remain elusive. Here, we introduce a scalable Li-Al-Cl stratified structure, formed through the strain-activated separating behavior of thermodynamically unfavorable Li/Li 9 Al 4 and Li/LiCl interfaces, to stabilize the negative electrode/sulfide electrolyte interface. In the Li-Al-Cl stratified structure, Li 9 Al 4 and LiCl are enriched at the surface to serve as a robust solid electrolyte interphase and are diluted in bulk by Li metal to construct a skeleton. Enabled by its unique structural characteristic, the Li-Al-Cl stratified structure significantly enhances the stability of negative electrode/sulfide electrolyte interface. This work reports a strain-activated phase separation phenomenon and proposes a practical pathway for negative electrode/sulfide electrolyte interface engineering.