铌镁酸铅-钛酸铅(PMN-PT)陶瓷的电卡效应

doi:10.15541/jim20250077

无机材料学报 ›› 2026, Vol. 41 ›› Issue (1): 96-104.DOI: 10.15541/jim20250077 CSTR: 32189.14.10.15541/jim20250077

铌镁酸铅-钛酸铅(PMN-PT)陶瓷的电卡效应

蒋妮玉¹(), 孙浩宸¹, 林明梅¹, 王定远², 刘来君¹()

1.桂林理工大学材料科学与工程学院, 桂林 541004
2.数字化家电国家重点实验室, 青岛 266103

收稿日期:2025-02-22 修回日期:2025-04-04 出版日期:2026-01-20 网络出版日期:2025-05-09
通讯作者: 刘来君, 教授. E-mail: ljliu2@163.com
作者简介:蒋妮玉(2004-), 女, 硕士研究生. E-mail: nyjiang6271@163.com
基金资助:
国家自然科学基金(12264012);山东省重点研发计划(2022CXGC020203)

Electrocaloric Effect of Lead Magnesium Niobate-lead Titanate (PMN-PT) Ceramics

JIANG Niyu¹(), SUN Haochen¹, LIN Mingmei¹, WANG Dingyuan², LIU Laijun¹()

1. College of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, China
2. State Key Laboratory of Digital Home Appliances, Qingdao 266103, China

Received:2025-02-22 Revised:2025-04-04 Published:2026-01-20 Online:2025-05-09
Contact: LIU Laijun, professor. E-mail: ljliu2@163.com
About author:JIANG Niyu (2004-), female, Master candidate. E-mail: nyjiang6271@163.com
Supported by:
National Natural Science Foundation of China(12264012);Key Technology Research and Development Program of Shandong Province(2022CXGC020203)

摘要/Abstract

摘要： 电卡效应制冷技术因其高效节能、易小型化及环境友好等优势成为固态制冷领域的研究热点, 然而在低电场下实现大绝热温变(ΔT)和宽工作温区(T_span)仍面临挑战。本研究通过传统固相反应法制备了不同钛酸铅(PT)含量的(1-x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃(x=0.08, 0.10, 0.12, 0.14)铁电弛豫体陶瓷, 探究了PT含量对材料电卡性能的影响机制。结果表明, 随着PT含量增加, 材料的弛豫体特性逐渐减弱, 介电频率色散程度降低, 铁电行为趋于典型铁电体。其中, 0.88PMN-0.12PT样品在50 kV/cm低电场下表现出优异的电卡性能, ΔT最大值达1.60 K, 且在30~180 ℃宽温区内ΔT均高于0.5 K。压电力显微镜(Piezoresponse force microscopy, PFM)显示该样品具有均匀分布的长程铁电畴结构, 其温度变化源于电场卸载过程中铁电畴从有序态向无序态转变引起的熵变。结合介电、铁电及畴结构分析, 揭示了弛豫铁电体的弥散相变特性与宽温区电卡性能的关联性。本研究为低场驱动、宽温区适用的铅基电卡材料设计提供了理论依据, 并展示了其在固态制冷器件中的潜在应用价值。

关键词: 铌镁酸铅-钛酸铅, 电卡效应, 弛豫铁电体, 宽温度区间

Abstract:

Electrocaloric refrigeration technology has emerged as a research hotspot in solid-state cooling due to its advantages of high energy efficiency, miniaturization potential and environmental friendliness. However, achieving a large adiabatic temperature change (ΔT) and a wide operation temperature (T_span) under low electric fields remains challenging. In this study, a new type of ceramics, (1-x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMN-PT, x=0.08, 0.10, 0.12, 0.14) ferroelectric relaxor with different PT contents, was synthesized via a conventional solid-state reaction method. The influence of PT concentration on their electrocaloric performance was investigated. Results indicate that increasing PT content weakens their relaxor characteristics, reduces their dielectric frequency dispersion, and drives their relaxor ferroelectric behavior toward normal ferroelectric. Notably, the 0.88PMN-0.12PT ceramic exhibits outstanding electrocaloric properties under a low electric field of 50 kV/cm, achieving a maximum ΔT of 1.60 K, with ΔT exceeding 0.5 K across a broad temperature range of 30-180 ℃. Piezoresponse force microscopy (PFM) reveals its uniformly distributed long-range ferroelectric domain structure. The electrocaloric effect originates from entropy changes induced by transition of ferroelectric domains from an ordered to a disordered state during electric field unloading. By integrating dielectric, ferroelectric and domain structure analyses, the diffuse phase transition of relaxor ferroelectrics is correlated to their wide-temperature-range electrocaloric performance. This study provides theoretical guidance for designing lead-based electrocaloric materials compatible with low-field driving and wide temperature ranges, which has potential for applications in solid-state refrigeration devices.

Key words: lead magnesium niobate-lead titanate, electrocaloric effect, relaxor ferroelectric, wide operating temperature

中图分类号:

TB321

蒋妮玉, 孙浩宸, 林明梅, 王定远, 刘来君. 铌镁酸铅-钛酸铅(PMN-PT)陶瓷的电卡效应[J]. 无机材料学报, 2026, 41(1): 96-104.

JIANG Niyu, SUN Haochen, LIN Mingmei, WANG Dingyuan, LIU Laijun. Electrocaloric Effect of Lead Magnesium Niobate-lead Titanate (PMN-PT) Ceramics[J]. Journal of Inorganic Materials, 2026, 41(1): 96-104.

图/表 11

图1 (1-x)PMN-xPT陶瓷的XRD图谱

Fig. 1 XRD patterns of (1-x)PMN-xPT ceramics

图2 0.88PMN-0.12PT陶瓷的(a) SEM照片和(b)晶粒尺寸分布

Fig. 2 (a) SEM image and (b) grain size distribution of 0.88PMN-0.12PT ceramic

图3 (1-x)PMN-xPT陶瓷的介电温谱和介电损耗随温度的变化曲线

Fig. 3 Temperature dependence of dielectric spectra and dielectric loss of (1-x)PMN-xPT ceramics (a) x=0.08; (b) x=0.10; (c) x=0.12; (d) x=0.14

图4 10 kHz下(1-x)PMN-xPT陶瓷的Lorentz拟合关系

Fig. 4 Lorentz fitting relationships of (1-x)PMN-xPT ceramics at 10 kHz (a) x=0.08; (b) x=0.10; (c) x=0.12; (d) x=0.14

图5 室温下(1-x)PMN-xPT陶瓷介电常数随频率对数的变化关系

Fig. 5 Variations of dielectric constants of (1-x)PMN-xPT ceramics with logarithm of frequency at room temperature

图6 30 kV/cm外加电场下(1-x)PMN-xPT陶瓷在30~180 ℃范围内电滞回线的演变

Fig. 6 Evolution of P-E loops in the range of 30-180 ℃ in an applied electric field of 30 kV/cm for (1-x)PMN-xPT ceramics (a) x=0.08; (b) x=0.10; (c) x=0.12; (d) x=0.14

图7 (1-x)PMN-xPT陶瓷在选定的外加电场下热释电系数(∂P/∂T)E与温度的关系

Fig. 7 Temperature dependence of pyroelectric coefficient (∂P/∂T)E in selected electric fields for (1-x)PMN-xPT ceramics (a) x=0.08; (b) x=0.10; (c) x=0.12; (d) x=0.14

图8 (1-x)PMN-xPT陶瓷在10~30 kV/cm电场下ΔT的温度依赖性

Fig. 8 Temperature dependence of ΔT in the electric field range of 10-30 kV/cm for (1-x)PMN-xPT ceramics (a) x=0.08; (b) x=0.10; (c) x=0.12; (d) x=0.14

图9 50 kV/cm外加电场下0.88PMN-0.12PT陶瓷的电卡性能

Fig. 9 Electrocaloric properties of 0.88PMN-0.12PT ceramics in an applied electric field of 50 kV/cm (a) Evolution of P-E loops from 30 ℃ to 180 ℃; (b) Temperature dependence of pyroelectric coefficient (∂P⁄∂T)E; (c) Temperature dependence of ΔT

图10 0.88PMN-0.12PT陶瓷的PFM振幅图和PFM相位图

Fig. 10 PFM amplitude images and PFM phase images for 0.88PMN-0.12PT ceramic (a) 20 μm×20 μm; (b) 5 μm×5 μm

图11 不同铅基陶瓷的ΔT和Tspan比较[22,34 -41]

Fig. 11 Comparison of ΔT and Tspan for different lead- based ceramics[22,34 -41]

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铌镁酸铅-钛酸铅(PMN-PT)陶瓷的电卡效应

Electrocaloric Effect of Lead Magnesium Niobate-lead Titanate (PMN-PT) Ceramics

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