Dual-Component Interlayer Enables Uniform Lithium Deposition and Dendrite Suppression for Solid-State Batteries

β-Lithium thiophosphate (LPS) exhibits high Li + conductivity and has been identified as a promising ceramic electrolyte for safe and high-energy-density all-solid-state batteries. Integrating LPS into solid-state lithium (Li) batteries would enable the use of a Li electrode with the highest deliverable capacity. However, LPS-based batteries operate at a limited current density before short-circuiting, posing a major challenge for the development of application-relevant batteries. In this work, we designed a dual-component interfacial protective layer called LiSn–LiN that forms in situ between the Li electrode and LPS electrolyte. The LiSn component, Li 22 Sn 5, exhibits enhanced Li diffusivity compared with the metallic lithium and facilitates a more uniform lithium deposition across the electrode surface, thus eliminating Li dendrite formation. Meanwhile, the LiN component, Li 3 N, shows enhanced mechanical stiffness compared with LPS and functions to suppress dendrite penetration. This chemically robust LiSn–LiN interlayer provides a more than doubled deliverable critical current density compared to systems without interfacial protection. Through combined XPS and XAFS analyses, we determined the local structure and the formation kinetics of the key functional Li 22 Sn 5 phase formed via the electrochemical reduction of a Sn 3 N 4 precursor. This work demonstrates an example of the structural-specific design of a protective interlayer with a desired function – dendrite suppression. The structure of a functional protective layer for a given solid-state battery should be tailored based on the given battery configuration and its unique interfacial chemistry.