Integrating high ionic conductive PDOL solid/gel composite electrolyte for enhancement of interface combination and lithium dentrite inhibition of solid-state lithium battery

High interface impedance, slow ion transmission, and easy growth of lithium dendrites in solid-state lithium battery are main obstacles to its development and application. Good interface combination and compatibility between electrolyte and electrodes is an important way to solve these problems. In this work, we successfully combined a high ionic conductive polymerized 1,3-dioxolane (PDOL) solid-state electrolyte and a PDOL gel-state electrolyte to form a rigid-flexible composite structural electrolyte and realized the gelation modification of solid electrolyte/electrode interface. This "PDOL SE + PDOL Gel" composite structure not only improves the electrode/electrolyte interfacial contact, reduces the interfacial impedance, but also inhibits the growth of lithium dendrites in the interface between lithium anode and electrolyte by forming an uniform Li-Zr-O and LiF composite protection layer. This composite electrolyte has high ionic conductivity of 5.96 × 10^-4 S/cm and wide electrochemical stability window of 5.0 V. The Li/PDOL SE + PDOL Gel/Li cells can be cycled stably for nearly 400 h at a current density of 1.0 mA/cm². The assembled LiCoO₂/PDOL SE + PDOL Gel/Li cells can be cycled for 250 cycles at 0.5 C with a capacity retention of 80%. This PDOL solid/gel composite electrolyte shows high promising commercial application prospect due to its high security performance, excellent interfacial properties and dendrite inhibition ability.