High cyclic stability of electrocaloric effect in relaxor poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) terpolymers in the absence of ferroelectric phase transition

The incorporation of bulky defects into ferroelectric poly(vinylidene fluoride-trifluoroethylene) copolymers can result in a relaxor behavior, accompanied by outstanding electrocaloric properties near room temperature. However, it remains elusive whether ferroelectric transition occurs in relaxor terpolymers, which is critical for the design of electrocaloric cooling devices. In this work, we study the electrocaloric fatigue in poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (61.8/30.4/7.8 mol. %) terpolymer, in which we revisit its controversial issue of the phase transition. We observe that the electrocaloric response of the terpolymers remains nearly constant (ΔS = 25.5 J K^-1kg^-1, ΔT = 5.1 K at 100 MV m^-1) within 50 cycles at different temperatures around room temperature. Moreover, we conduct temperature-dependent X-ray diffraction and Fourier-transform infrared spectroscopy measurements on the terpolymer to provide insights into the evolution in intermolecular lattice spacing and intramolecular conformation. We find no clear evidence of the ferroelectric-to-paraelectric phase transition near the temperature range, where differential scanning calorimeter measurement displays an endothermic peak.