Scalable Interfacial Engineering with Lithiophilic-Lithiophobic Layers for High-Performance All-Solid-State Li-Metal Batteries

Abstract

The stability of the lithium-metal/solid electrolyte interface remains a critical challenge in the development of all-solid-state lithium-metal batteries (ASSLMBs), as it directly influences their cycling performance, rate capability, and safety. Here, a thin, flexible, and lithium-stable sulfide electrolyte membrane is presented with high ionic conductivity (3.25 × 10⁻³ S cm⁻¹) and low electronic conductivity (1.45 × 10⁻⁹ S cm⁻¹) at room temperature, prepared with an AlCl₃ coating in a low-cost wet process. The in situ formation of a lithiophilic Li-Al alloy and a lithiophobic LiCl layer at the interface creates a stable dual-layer structure, effectively suppressing Li-dendrite growth and enhancing Li-transport across the interface. Symmetric Li/Li cells with this coated membrane exhibit exceptional cycling stability, operating for over 10000 h at 0.5 mA cm⁻². ASSLMBs assembled with a LiNi_0.8Co_0.1Mn_0.1O₂ cathode and a metallic lithium anode exhibit excellent cycling performance, highlighting the potential of this coating strategy to stabilize the Li/solid electrolyte interface and expedite the commercialization of ASSLBs.