Electron Insulative Interface Based on Schottky Contact Enabling Dendrite‐free Solid‐state Lithium Metal Batteries

Abstract A novel approach is proposed to address the lithium dendrite penetration issue in solid‐state lithium metal batteries based on the garnet‐type electrolyte Li _6.4 La ₃ Zr _1.4 Ta _0.6 O ₁₂ (LLZTO). Se and Te nanofilms are deposited on LLZTO using a chemical vapor deposition process and subsequently reacted with molten lithium in situ to form a tightly‐bonded Li‐LLZTO interface, facilitating the interfacial lithium‐ion conduction. Most importantly, the constructed Li ₂ Se/Li ₂ Te semiconductor interlayers form a p ‐type Schottky contact with lithium metal, impeding the electron injection from Li to LLZTO electrolyte, resulting in a dramatical decrease in leakage electronic current. Benefiting from the effective blocking of electrons and the facilitated interfacial lithium conduction, the constructed Li|Se‐LLZTO‐Se|Li symmetric cell achieves a high critical current density of 2.3 mA cm ⁻² and can be stably cycled for over 2000 h at 0.2 mA cm ⁻² .