UV-cured Polymer Solid Electrolyte Reinforced using a Ceramic-Polymer Composite Layer for Stable Solid-State Li Metal Batteries

Abstract

In recent years, solid-state Li metal batteries (SSLBs) have attracted significant attention as the next-generation batteries with high energy and power densities. However, uncontrolled dendrite growth and the resulting pulverization of Li during repeated plating/stripping processes must be addressed for practical applications. Herein, we report a plastic-crystal-based polymer/ceramic composite solid electrolyte (PCCE) to resolve these issues. To fabricate the one-side ceramic-incorporated PCCE (CI-PCCE) film, a mixed precursor solution comprising plastic-crystal-based polymer (succinonitrile, SN) with garnet-structured ceramic (Li₇La₃Zr₂O₁₂, LLZO) particles was infused into a thin cellulose membrane, which was used as a mechanical framework, and subsequently solidified by using UV-irradiation. The CI-PCCE exhibited good flexibility and a high room-temperature ionic conductivity of over 10⁻³ S cm⁻¹. The Li symmetric cell assembled with CI-PCCE provided enhanced durability against Li dendrite penetration through the solid electrolyte (SE) layer than those with LLZO-free PCCEs and exhibited long-term cycling stability (over 200 h) for Li plating/stripping. The enhanced Li⁺ transference number and lower interfacial resistance of CI-PCCE indicate that the ceramic-polymer composite layer in contact with the Li anode enabled the uniform distribution of Li⁺ flux at the interface between the Li metal and CI-PCCE, thereby promoting uniform Li plating/stripping. Consequently, the Li//LiFePO₄ (LFP) full cell constructed with CI-PCCE demonstrated superior rate capability (~120 mAh g⁻¹ at 2 C) and stable cycle performance (80% after 100 cycles) than those with ceramic-free PCCE.