Fabrication of polymer electrolyte via lithium salt-induced surface-initiated radical polymerization for lithium metal batteries

Abstract The fabrication of flexible polymer electrolytes (PEs) which possess simultaneously high thermal stability, robust mechanical strength, and high ionic conductivity is very challenging for lithium (Li) batteries. Herein, cellulose-based PE is fabricated via a Li salt-induced surface-initiated radical polymerization of polyethylene glycol methyl ether acrylate (PEGA). The polymerization of PEGA is catalyzed by various Li salts, such as Li perchlorate (LiClO4), bis(trifluoromethane)sulfonimide Li (LiTFSI), Li difluoro(oxalato)borate (LiDFOB), and LiClO4/LiDFOB, which also serve as charge transfer carriers in PEs. The Li salt can be used as the catalyst to promote the cleavage of C–Br bond on the surface of Br-modified cellulose, and then initiate the polymerization of PEGA. The PE obtained from the dual salt (LiClO4/LiDFOB)-induced radical polymerization system exhibits high ionic conductivity of 3.5 × 10−5 S cm−1 at 30 °C, good thermal stability (up to 240 °C), and wide electrochemical stability window (5.0 V vs. Li/Li+). Moreover, Li/PE/Li symmetric cells show good interfacial stability between PE and Li foil and the assembled Li/PE/LiFePO4 cells possess 150 mA h g−1 at 0.1C. Li salt-induced surface-initiated polymerization provides a simple and efficient method for fabricating PE for high-performance Li metal batteries (LMBs).