Fast Li+ Transport Polyurethane-Based Single-Ion Conducting Polymer Electrolyte with Sulfonamide Side chains in the Hard Segment for Lithium Metal Batteries

Single-ion conducting polymer electrolytes (SICPEs) are considered as one of the most promising candidates for achieving lithium metal batteries (LMBs). However, the application of traditional SICPEs is hindered by their low ionic conductivity and poor mechanical stability. Herein, a self-standing and flexible polyurethane-based single-ion conductor membrane was prepared via covalent tethering of the trifluoromethanesulfonamide anion to polyurethane, which was synthesized using a facile reaction of diisocyanates with poly(ethylene oxide) and 3,5-diaminobenzoic acid (or 3,5-dihydroxybenzoic acid). The polymer electrolyte exhibited excellent ionic conductivity, mechanical properties, lithium-ion transference number, thermal stability, and a broad electrochemical window because of the bulky anions and unique two-phase structures with lithium-ion nanochannels in the hard domains. Consequently, the plasticized electrolyte membrane showed exceptional stability and reliability in a Li||Li symmetric battery. The assembled LiFePO₄||Li battery exhibited an outstanding capacity (∼180 mA h g^-1), Coulombic efficiency (>96%), and capacity retention. This research provides a promising polymer electrolyte for high-performance LMBs.