Abstract: | Highly porous poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVdF–HFP)‐based polymer membranes filled with fumed silica (SiO2) were prepared by a phase‐inversion technique, and films were also cast by a conventional casting method for comparison. N‐Methyl‐2‐pyrrolidone as a solvent was used to dissolve the polymer and to make the slurry with SiO2. Phase inversion occurred just after the impregnation of the applied slurry on a glass plate into flowing water as a nonsolvent, and then a highly porous structure developed by mutual diffusion between the solvent and nonsolvent components. The PVdF–HFP/SiO2 cast films and phase‐inversion membranes were then characterized by an examination of the morphology, thermal and crystalline properties, absorption ability of an electrolyte solution, ionic conductivity, electrochemical stability, and interfacial resistance with a lithium electrode. LiPF6 (1M) dissolved in a liquid mixture of ethylene carbonate and dimethyl carbonate (1:1 w/w) was used as the electrolyte solution. Through these characterizations, the phase‐inversion polymer electrolytes were proved to be superior to the cast‐film electrolytes for application to rechargeable lithium batteries. In particular, phase‐inversion PVdF–HFP/SiO2 (30–40 wt %) electrolytes could be recommended to have optimum properties for the application. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 140–148, 2006 |