High‐Performance Solid Lithium Metal Batteries Enabled by LiF/LiCl/LiIn Hybrid SEI via InCl3‐Driven In Situ Polymerization of 1,3‐Dioxolane

The use of poly(1,3-dioxolane) (PDOL) electrolyte for lithium batteries has gained attention due to its high ionic conductivity, low cost, and potential for large-scale applications. However, its compatibility with Li metal needs improvement to build a stable solid electrolyte interface (SEI) toward metallic Li anode for practical lithium batteries. To address this concern, this study utilized a simple InCl3 -driven strategy for polymerizing DOL and building a stable LiF/LiCl/LiIn hybrid SEI, confirmed through X-ray photoelectron spectroscopy (XPS) and cryogenic-transmission electron microscopy (Cryo-TEM). Furthermore, density functional theory (DFT) calculations and finite element simulation (FES) verify that the hybrid SEI exhibits not only excellent electron insulating properties but also fast transport properties of Li+ . Moreover, the interfacial electric field shows an even potential distribution and larger Li+ flux, resulting in uniform dendrite-free Li deposition. The use of the LiF/LiCl/LiIn hybrid SEI in Li/Li symmetric batteries shows steady cycling for 2000 h, without experiencing a short circuit. The hybrid SEI also provided excellent rate performance and outstanding cycling stability in LiFePO4 /Li batteries, with a high specific capacity of 123.5 mAh g-1 at 10 C rate. This study contributes to the design of high-performance solid lithium metal batteries utilizing PDOL electrolytes.