Enhanced permittivity and energy density in neat poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) terpolymer films through control of morphology.

Polymer materials with large dielectric constants are desirable for the development of high energy density capacitors. We show that the dielectric properties of poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE)] can be improved by the use of processing conditions that favor formation of a highly crystalline morphology of the nonpolar α-phase. Through the use of spin coating, thermal treatment above the melting temperature, and quenching, we were able to attain a highly crystalline, α-phase rich morphology that has a quite large dielectric constant of 77 ± 10 at 1 kHz. The final morphology and phase composition of the terpolymer films depend strongly on the postprocessing thermal treatment and the quality of the solvent. Evaluation of the polarization behavior of the terpolymer films as a function of electric field reveal that the polymer exhibits a relaxor-ferroelectric behavior and has a substantial energy density of 9.7 J/cm(3) at fields of up to approximately 470 V/μm. Under millisecond pulsed charge-discharge measurements a 3-fold increase in energy density (27 J/cm(3)) is obtained at high fields (∼600 V/μm). Our study demonstrates that the processing conditions and morphology of fluorinated terpolymer films are controlling factors for achievement of high dielectric permittivity and energy density that are critical for high performance capacitors.