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Study on the Electrocaloric Effect in Ferroelectric Thin Films for Heat Pump Applications

松下 裕司 大阪府立大学 DOI:info:doi/10.24729/00016970

2020.07.07

概要

Thanks to the decades of studies about the EC effect, the directly measured EC temperature change has reached 5.5 °C in Pb(Sco.5Tao.5)03 MLCs so far. Furthermore, the heat pumps using the EC effect generally consist of the EC materials and refrigerants. Thus it is required the mechanical part to move the refrigerant of fluids or solids, which makes the driving frequency lower than 10 Hz. Therefore, to enhance the output power, the bulk materials are employed as the EC components in the heat pumps to realize the sufficient heat capacity of the active elements in the devices. Additionally, since the A7fc has a proportional relationship against Δ£ as shown in Fig. 1-4, the high voltage in a range of kV is employed in the most EC devices. This thesis focuses on the EC effect in fenoelectric thin films, which is attributed not only to downsizing the device but also lowering the driving voltage. Although the small heat capacity makes it difficult to obtain the adiabatic EC temperature change and the large heat flow, the high-frequency driving can solve these issues even in thin-film structures. Finally, an all-solid-state heat pump was proposed based on the high- frequency induced EC effect in ferroelectric polymer thin films.

In Chapter 2, the direct measurement method was developed for the EC effect in ferroelectric thin films. A thin-film thermocouple was employed for the thermometer as well as the top electrode, which allows that the electric field is applied to the EC materials using bottom and top (thermocouple) electrode subsequently measuring temperature change to detect the thermoelectromotive force. BaTiCh ceramics were used for the EC materials, and approximately the same EC effect was obtained under a rectangular pulse and AC electric field, respectively. The direct measurement of EC eflfeet in thin films was also discussed.

In Chapter 3, the EC effect in ferroelectric polymer thin films was investigated. P(VDF-TrFE) was employed for EC film; Using the finite element method analysis, it was revealed that the ΔΤ could be obtained above 1 kHz at μm-thick films. Furthermore, the extractive heat density, which is in and out heat density from the films, was enhanced with increasing the frequency. Then, the gm-thick PfVDF-TrFE) were fabricated. It was found that the e31f coefficient strongly depended on the annealing temperature. Eventually, the direct measurement of the EC effect was carried out using the gm-thick P(VDF-TrFE) films. After eliminating the thermal dissipation effect, the temperature change of the films, of 0.29 °C was obtained, which corresponds to extractive heat, Qex, of 0.69 W/cm2 at 10 kHz.

In Chapter 4, the all-solid-state heat pump was proposed using a concept of a bucket-brigade operation and the ΔΤ/y/m experimentally detected in relaxor polymer films. The gm- thick PfVDF-TrFE-CFE) films were fabricated, which showed the non- ergodic relaxor properties. Under the uni-polar AC electric field, the frequency­ dependent LTfiim was obtained as 0.80 and 0.65 °C at 1.5 and 10 kHz, respectively. In spite of the decreasing of ΔT film against frequency, the enhancement of Qex was observed. The largest extractive heat of 1.54 W/cm2 at 10 kHz was higher than that in P(VDF-TrFE). Then, the all-solid-state heat pump with stacking layered structure was
investigated, and a pumping heat density of 0.30 mW/cm2 was obtained.

Chapter 5 summarizes the results and presents the conclusions of this thesis.

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