Tailoring poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) membrane microstructure for lithium-ion battery separator applications

Novel battery separators based on poly(vinylidene fluoride-co-trifluoroethylene-chlorofluoroethylene)– P(VDF-TrFE-CFE)- were produced by different processing techniques (non-solvent and thermally induced phase separation, salt leaching and electrospinning), in order to evaluate their effect on separator morphology, degree of porosity and pore size, electrochemical parameters and battery cycling behavior. It has been demonstrated that the different processing techniques have a significant influence on the morphology and mechanical properties of membranes. The degree of porosity varies between 23 % and 66 %, for membranes obtained by salt leaching and thermally induced phase separation, respectively.

The membranes present a high ionic conductivity value ranging between 1.8 mS.cm⁻¹ for the electrospun membrane and 0.20 mS.cm⁻¹ for the membrane processed by thermally induced phase separator. The lithium transference number value for all membranes is above 0.20, the highest value of 0.55 being obtained for samples prepared by salt leaching and thermally induced phase separation.

For all membranes, battery capacity values have been obtained at different C-rates with excellent reversibility. P(VDF-TrFE-CFE) samples present an excellent battery performance at 1C-rate after 100 cycles with 74 mAh.g⁻¹ and excellent coulombic efficiency, for membrane processed by the salt leaching technique. This work demonstrates that P(VDF-TrFE-CFE) terpolymer can be used as a porous membrane in lithium-ion battery separator application, the membrane processing technique allowing to tailor its morphology and, consequently, battery performance.