BST-BZT叠层弛豫铁电陶瓷的制备及其电卡效应研究

doi:10.16553/j.cnki.issn1000-985x.2025.0112

摘要/Abstract

摘要： 无铅弛豫铁电基叠层陶瓷是环境友好型电卡固态制冷器件的重要选择之一。本研究采用流延工艺制备了x（Ba_0.65Sr_0.35）TiO₃-（1-x）Ba（Zr_0.2Ti_0.8）O₃（0.8BST-0.2BZT，x=0.8；0.2BST-0.8BZT，x=0.2）陶瓷厚膜生坯，然后采用逐层堆叠工艺构筑了0.8BST-0.2BZT/0.2BST-0.8BZT/0.8BST-0.2BZT叠层陶瓷体系。同时通过传统固相法合成了纯相的0.8BST-0.2BZT和0.2BST-0.8BZT陶瓷作为对比，研究了其微观形貌、介温特性、铁电性与电卡效应。结果表明，叠层陶瓷具有更显著的介电弛豫特性和更大的极化强度差值（P_m-P_r）。采用间接法测得叠层陶瓷在50 kV/cm电场下具有显著的电卡效应（ΔT=0.9 K）和宽工作温区（T_span=50 ℃），并通过直接法在25 kV/cm电场下进一步验证了这一结果，同样观测到较大的电卡效应（ΔT=0.25 K）和大的T_span（>45 ℃）。本文的研究工作表明，所制备的叠层陶瓷具有优异的电卡效应和宽温域适应性，展现了其在电卡应用中的巨大潜力。

关键词: 弛豫铁电体; 叠层陶瓷; 电卡效应; 工作温区; 直接法测量; 间接法测量

Abstract: Lead-free relaxor ferroelectric based laminated ceramics are one of the important choices for environmentally friendly electrocaloric solid-state refrigeration devices. In this study， the x（Ba_0.65Sr_0.35）TiO₃-（1-x）Ba（Zr_0.2Ti_0.8）O₃（0.8BST-0.2BZT， x=0.8； 0.2BST-0.8BZT， x=0.2） thick films were prepared via tape-casting process， and the laminated ceramics of 0.8BST-0.2BZT/0.2BST-0.8BZT/0.8BST-0.2BZT were constructed using a stacking process. Meanwhile， 0.8BST-0.2BST and 0.2BST-0.8BZT ceramics were prepared by solid-state reaction for comparison， and their microstructure， dielectric temperature characteristics， ferroelectricity， and electrocaloric effects were studied. The research results indicate that laminated ceramics have more pronounced dielectric relaxation characteristics and larger polarization difference （P_s-P_r）. The significant electrocaloric effect （ΔT=0.9 K） and wide broad working temperature span （T_span=50 ℃） of laminated ceramics were measured using indirect measurements under an electric field of 50 kV/cm. This result is further verified by direct measurements under 25 kV/cm， and significant electrocaloric temperature change （ΔT=0.25 K） and T_span （>45 ℃） were observed. This work demonstrates that the developed laminated ceramics possess excellent temperature stability and wide temperature range adaptability， showing great potential for electrocaloric cooling applications.

Key words: relaxor ferroelectric; laminated ceramics; electrocaloric effect; working temperature span; direct measurement; indirect measurement

中图分类号:

O738

薛飞, 田娅晖, 金玲. BST-BZT叠层弛豫铁电陶瓷的制备及其电卡效应研究[J]. 人工晶体学报, 2026, 55(1): 93-102.

XUE Fei, TIAN Yahui, JIN Ling. Preparation of BST-BZT Laminated Relaxor Ferroelectric Ceramics and Their Electrocaloric Effect[J]. Journal of Synthetic Crystals, 2026, 55(1): 93-102.

图/表 9

图1 研究设计的思路图

Fig.1 Schematic diagram of research design

图2 叠层陶瓷的加工工艺流程图（a）、烧结曲线（b）与成品图（c）

Fig.2 Fabrication process flow chart （a）， sintering curve （b） and finished product image （c） of laminated ceramics

图3 BST-BZT陶瓷的XRD图谱（a），以及0.8BST-0.2BZT（b）和0.2BST-0.8BZT（c）陶瓷的Rietveld结构精修

Fig.3 XRD patterns of BST-BZT ceramics （a）， Rietveld refinement plots of 0.8BST-0.2BZT （b） and 0.2BST-0.8BZT （c） ceramics

图4 叠层陶瓷断面的显微结构与成分分析。（a）×5 000倍；（b）×500倍；（c）0.8BST-0.2BZT截面热腐蚀SEM照片；（d）0.2BST-0.8BZT截面热腐蚀SEM照片；（e）~（h）EDS点分析谱图（对应A~D点）；（i）叠层陶瓷厚度方向的EDS线扫描谱

Fig.4 Microstructure and composition analysis of laminated ceramic cross-section. （a） ×5 000 times；（b） ×500 times；（c） SEM images of 0.8BST-0.2BZT cross-section for thermal corrosion；（d） SEM images of 0.2BST-0.8BZT cross-section for thermal corrosion；（e）~（h） EDS point analysis spectra （corresponding to points A~D）；（i） EDS line scan spectra in the thickness direction of the laminated ceramics

图5 样品的介温和弥散特性。（a）介温谱；（b）居里-外斯公式拟合；（c）H-W2/3-m的峰宽对比；（d）弥散温度的高斯拟合；（e）弥散温度的对比

Fig.5 Dielectric permittivity-temperature and diffusive properties of samples. （a） Dielectric permittivity-temperature spectra；（b） Curie-Weiss law fitting；（c） comparison of H-W2/3-m peak width；（d） Gaussian fitting of diffuse phase transition temperature；（e） comparison of diffuse phase transition temperatures

图6 样品的铁电性能。（a）P-E曲线；（b）极化特性比较；（c）矫顽场；（d）I-V特性曲线

Fig.6 Ferroelectric properties of samples. （a） P-E hysteresis loops；（b） comparison of polarization properties；（c） coercive field；（d） I-V characteristic curves

图7 0.8BST-0.2BZT（a）、0.2BST-0.8BZT（b）、叠层陶瓷（c）在50 kV/cm电场作用下变温P-E曲线；（d）间接法测得ΔT随温度变化曲线

Fig.7 Temperature-dependent P-E hysteresis loops of 0.8BST-0.2BZT （a）， 0.2BST-0.8BZT （b）， laminated ceramics （c） under an electric field of 50 kV/cm；（d） ΔT versus temperature curves obtained by indirect measurement method

图8 采用直接法测得的BZT-BST陶瓷的电卡温变

Fig.8 Electrocaloric temperature change of BZT-BST ceramics measured by directly method

图9 不同体系铁电陶瓷的直接法电卡效应比较

Fig.9 Comparative study of directly measured electrocaloric effects in different ferroelectric ceramic systems

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