Self‐Extinguishing and Low‐Cost Quasi‐Solid Polymer Electrolyte for Room Temperature Lithium Metal Batteries

Abstract Most modification strategies of polyethylene oxide (PEO)‐based solid polymer electrolyte focus on improving the room temperature ionic conductivity, while disregarding its inherent flammability that poses substantial safety hazard. Herein, a self‐extinguishing quasi‐solid‐state polymer electrolyte (PTTF‐SPE), which combines excellent room temperature electrochemical properties and high safety, has been developed by introducing triethyl phosphate (TEP) as a low‐cost and highly effective flame retardant. The cross‐linking structure derived from −CH 2 −CH 2 −O− segments of tetramethylene glycol dimethyl ether (TEGDME) and PEO makes a contribution to a high amorphous state of polymer. A robust solid electrolyte interphase (SEI) formed by preferential decomposition of fluoroethylene carbonate (FEC) that acts as a film‐forming additive, which can prevent TEP from degradation at lithium metal anode. The optimized PTTF‐SPE exhibits high ionic conductivity (0.54×10 −3 S/cm) and lithium transference number (0.71) at room temperature. The LiFePO 4 ||Li battery demonstrates excellent cycle life over 500 cycles at 0.5 C with a high average discharge capacity of 131 mAh/g. A symmetric Li||Li battery that operating for 850 hours indicates a good compatibility of PTTF‐SPE towards lithium metal. This work provides a new idea for developing high‐energy‐density and high‐safety lithium‐metal batteries (LMBs) for room temperature.