Negative Electrocaloric Effects in Antiferroelectric Materials: a Review

doi:10.15541/jim20210420

Abstract

Abstract:

The electrocaloric effect refers to the phenomenon of the temperature change of a material caused by the application or removal of an electric field, and includes two types, positive electrocaloric effect and negative electrocaloric effect. As a high-efficiency, noise-free and environment-friendly refrigeration effect, the electrocaloric effect shows promising application in the field of solid-state refrigeration, especially in integrated circuit refrigeration, and has attracted extensive research interests over the past decades. It is reported that the cooling capacity of the electrocaloric effect can be significantly improved by combining the positive and negative electrocaloric effects. However, different from the widely studied positive electrocaloric effect, the research on negative electrocaloric effect is relatively rare due to its complex physical origin. This article focuses on the latest research progress of the negative electrocaloric effect in antiferroelectric materials. The specific content includes the following four parts. Firstly, starting from the research history of the electrocaloric effect, the principle of refrigeration of the electrocaloric effect is introduced, as well as a typical dual refrigeration cycle that can combine positive and negative electrocaloric effect. Secondly, the indirect measurement method of negative electrocaloric effect based on Maxwell relationship, and several direct measurement methods of negative electrocaloric effect, and the suitable applying conditions as well as the advantages and disadvantages of different methods are discussed. Thirdly, taking antiferroelectric which is a typical negative electrocaloric effect materials as an example, the physical origin of negative electrocaloric effect is narrated. Then the recent progress of negative electrocaloric effect in the antiferroelectric film and antiferroelectric bulk materials is reviewed. In addition, the negative electrocaloric effect in some other ferroelectric materials is also briefly introduced. Finally, a summary and prospect of the research on the negative electrocaloric effect are put forward.

Key words: negative electrocaloric effect, antiferroelectric, PbZrO₃, review

CLC Number:

TB64

WU Ming, XIAO Yanan, LI Huaqiang, LIU Yongbin, GAO Jinghui, ZHONG Lisheng, LOU Xiaojie. Negative Electrocaloric Effects in Antiferroelectric Materials: a Review[J]. Journal of Inorganic Materials, 2022, 37(4): 376-386.

Figures/Tables 9

Fig. 1 Schematic of polarization switching, temperature change and entropy change during cooling cycle of electrocaloric effect (a) In virgin state, the ferroelectric polarization randomly distributs; (b) With the application of electric field, the ferroelectric polarization is aligned, and the temperature of the ferroelectric materials is increased; (c) After an isothermal process, the temperature of the ferroelectric materials decreases to the environment temperature; (d) After removal of the electric field, the ferroelectric polarization recovers randomly distribution, the temperature of the ferroelectric materials decreases

Fig. 2 Feasible combination of positive and negative electrocaloric effect[10] (a) Schematic of the cooling cycle; (b) Heat flow of the dual cooling cycle measured by DSC

Fig. 3 Direct measurements of electrocaloric effect (a) Thermocouple or thermometer[15]; (b) Scanning thermal microscopy[16]; (c) Infra-red camera[17]; (d) Modified differential scanning calorimetry[18]

Fig. 4 Electric domain and representative hysteresis loop of antiferroelectrics, schematic of a possible mechanism of negative electrocaloric effect in antiferroelectrics[27] Electric domain of antiferroelectrics (a) before and (b) after being polarized; (c) Representative hysteresis loop of antiferroelectrics; Schematic of a possible mechanism of negative ECE in antiferroelectrics (d1) without any electric field and (d2) under a modest electric field

Fig. 5 Negative electrocaloric effect in PbZrO3-based antiferroelectric thin films (a) P-T curves and (b) temperature change of (Pb0.97, La0.02)(Zr0.95,Ti0.05)O3 thin film[21]; (c) P-T curves and (d) temperature change of 4% (molar ratio) Eu doped PbZrO3 thin film[32]; (e) P-T curves and (f) temperature change of 1% Yb (molar ratio) doped PbZrO3 thin film[33]

Fig. 6 Interface-defect-enhanced negative electrocaloric effect in PbZrO3 thin films[29] (a) Mechanism of the defect-dipole-suppressed antiferroelectric-ferroelectric phase transition during electric cycling; (b) Antiferroelctric-ferroelectric phase transition field of the PbZrO3 thin films with interface defect (p-PZO) and without interface defect (f-PZO); (c) Comparison of negative ECE in different materials Colorful figures are available on website

Fig. 7 Negative electrocaloric effects of PbZrO3, (Pb0.97,La0.02)(Zr0.95,Ti0.05)O3 and B-site nonstoichiometric (Pb0.97,La0.02)(Zr0.95,Ti0.05)1+yO3 (y=-0.03, -0.01, 0.01, 0.03) ceramics under different electric fields (a) PbZrO3[34]; (b) (Pb0.97,La0.02)(Zr0.95,Ti0.05)O3[35]; (c) B-site nonstoichiometric (Pb0.97,La0.02)(Zr0.95,Ti0.05)1+yO3 (y=-0.03, -0.01, 0.01, 0.03)[36] Colorful figures are available on website

Fig. 8 Hysteresis loops of PNZST13/2/2 and PNZST43/8/2 under different temperatures, P-T curves, temperature change ΔT and entropy change ΔS of PNZST13/2/2 and PNZST43/8/2[37] (a) Hysteresis loops of PNZST13/2/2; (b) Hysteresis loops of PNZST43/8/2; (c-e) P-T curves, temperature change ΔT and entropy change ΔS of PNZST13/2/2; (f-h) P-T curves, temperature change ΔT and entropy change ΔS of PNZST43/8/2 Colorful figures are available on website

Fig. 9 Electrocaloric effect of (Pb0.97La0.02)(Zr0.66Sn0.23Ti0.11)O3 single crystal, (Pb0.97La0.02)(Zr0.66Sn0.27Ti0.07)O3 single crystal, (Pb0.97La0.02)(Zr0.80Sn0.14Ti0.06)O3 ceramics, and (Pb0.97La0.02)(ZrxSn0.94-xTi0.06)O3 ceramics (a, b) Hysteresis loops and temperature change ΔT of the (Pb0.97La0.02)(Zr0.66Sn0.23Ti0.11)O3 single crystal[9]; (c, d) Hysteresis loops and temperature change ΔT of the (Pb0.97La0.02)(Zr0.66Sn0.27Ti0.07)O3 single crystal[40]; (e) Temperature change ΔT of the (Pb0.97La0.02)(Zr0.80Sn0.14Ti0.06)O3 ceramics[39]; (f) Comparison of the temperature change in (Pb0.97La0.02)(ZrxSn0.94-xTi0.06)O3 ceramics with other dielectric materials[39] Colorful figures are available on website

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