A Mechanically Robust In-Situ Solidified Polymer Electrolyte for SiOx-Based Anodes Toward High-Energy Lithium Batteries

Abstract Silicon suboxide (SiO x , 0 < x < 2) is an appealing anode material to replace traditional graphite owing to its much higher theoretical specific capacity enabling higher-energy-density lithium batteries. Nevertheless, the huge volume change and rapid capacity decay of SiO x electrodes during cycling pose huge challenges to their large-scale practical applications. To eliminate this bottleneck, a dragonfly wing microstructure-inspired polymer electrolyte (denoted as PPM-PE) is developed based on in-situ polymerization of bicyclic phosphate ester- and urethane motif-containing monomer and methyl methacrylate in traditional liquid electrolyte. PPM-PE delivers excellent mechanical properties, highly correlated with the formation of a micro-phase separation structure similar with dragonfly wings. By virtue of superior mechanical properties and the in-situ solidified preparation method, PPM-PE can form a 3D polymer network buffer against stress within the electrode particles gap, enabling much suppressed electrode volume expansion and more stabilized solid electrolyte interface along with evidently decreased electrolyte decomposition. Resultantly, PPM-PE shows significant improvements in both cycling and rate performance in button and soft package batteries with SiO x -based electrodes, compared with the liquid electrolyte counterpart. Such a dragonfly wing microstructure-inspired design philosophy of in-situ solidified polymer electrolytes helps facilitate the practical implementation of high-energy lithium batteries with SiO x -based anodes.