Cooling is essential for human lives. Refrigeration that relies on the traditional vapor-compressor system has been developed for more than a century, but it still has unavoidable disadvantages such as low efficiency, noise, leakage of ozone-depleting agents and failure to meet the cooling demands of modern technologies. Electrocaloric cooling, which can be accomplished with the reversible electric field-driven polarization change and the associated adiabatic temperature change of electrocaloric materials, is one of the emerging solid-state cooling technologies that has the potential to replace the traditional one. Therefore, this dissertation aims to develop efficient electrocaloric cooling from both the material and the device aspects.
Poly(vinylidene fluoride-ter-trifluoroethylene-ter-chlorofluoroethylene) [P(VDF-TrFE-CFE)] terpolymer is a relaxor ferroelectric material exhibiting giant electrocaloric effect at room temperature. The excellent electrocaloric performances, high breakdown strength and flexible character of the terpolymer material render it promising potential to be used for constructing practical solid-state refrigerators. This dissertation starts from a detailed introduction of fabricating high-quality P(VDF-TrFE-CFE) thin films with various phase compositions. To understand the connections between films’ electrocaloric performances and the fabrication processes, and to determine the molecular origin of the electrocaloric activity of this terpolymer, multiple characterizations have been conducted on a pool of terpolymer films processed from different conditions. The core characterization couples the Fourier transform infrared with a high-voltage source to operandoly observe the dipole switching mechanism of P(VDF-TrFE-CFE) under an electrical field. It is found that the polar short trans sequences (T3Gs) along the molecular chains can be reversibly switched by the electric field, which is responsible for the giant electrocaloric effect.
A solid-state electrocaloric cooler named self-regenerative heat pump (SRHP) is constructed using the P(VDF-TrFE-CFE) film stacks with enhanced adiabatic temperature change. The SRHP exploits the concurrent electrocaloric and electrostrictive effects of P(VDF-TrFE-CFE), automatically synchronizing the material’s thermodynamic cycle with a mechanical heat transfer mechanism for refrigeration purposes. Therefore, the need for any external driving facilities for actuations is eliminated. The SRHP is composed of a cascade of six film stacks. A polyimide backing layer stuck on top of each film stack transforms the irregular in-plane electrostrictive expansion of the films under the field into a large out-of-plane actuation to make good thermal contact with the bottom film stacks. The SRHP with consecutive stages working in antiphase of their electrocaloric cycles achieves unidirectional heat transfer and refrigeration of the heat source. Finally, the SRHP achieves a cooling of 8.8 K below the ambient temperature in 30 s, a temperature lift of 14.2 K, and a maximum specific cooling power of 1.52W/g, corresponding to a 0.78 W cooling power over an active cooling area of 4.52 cm². The performances rank the SRHP the best electrocaloric solid-state cooler made of polymer materials.