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The spherical-like and honeycomb LiCe0.1Ca0.8TiO3 particles are successfully synthesized by sol-gel and spray-drying combined with following pyrolysis processes.The P(VDF-HFP)-based composite polymer electrolyte (CPE) membrane doped with the particle was prepared by phase inversion method and the desirable CPE was obtained after being activated in liquid electrolyte.The physicochemical properties of the CPE were characterized by SEM,XRD,TG,and electrochemical measurements..