硅酸盐学报

反铁电材料铪酸铅研究进展

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李东亮 ¹ , 唐新桂 ¹ , 姜登辉 ² , 蒋艳平 ¹ , 刘秋香 ¹

硅酸盐学报 | 电介质储能材料专刊—综合评述 2024,52(4): 1451-1459

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硅酸盐学报 |电介质储能材料专刊—综合评述 2024 , 52 (4) : 1451 -1459

反铁电材料铪酸铅研究进展

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李东亮¹, 唐新桂¹, 姜登辉², 蒋艳平¹, 刘秋香¹

作者信息

^1．广东工业大学物理与光电工程学院，广州 510000

^2．西安电子科技大学先进材料与纳米技术学院，西安 710126

通讯作者:

唐新桂（1963—），男，博士，研究员。

作者简介:

李东亮（1995—），男，博士研究生。

Recent Development on Antiferroelectric Lead Hafnate

Dongliang LI¹, Xingui TANG¹, Denghui JIANG², Yanpiang JIANG¹, Qiuxiang LIU¹

Affiliations

^1.School of Physics & Optoelectric Engineering, Guangdong University of Technology, Guangzhou 510006, China

^2.School of Advanced Materials and Nanotechnology, Xidian University, Xi'an 710126, China

Corresponding Author:

TANG Xingui (1963-), male, Ph.D., Professor. E-mail: xgtang@gdut.edu.cn

LI Dongliang (1995-), male, Doctoral candidate. E-mail: dongl_lee1122@163.com

出版时间: 2024-04-20 doi: 10.14062/j.issn.0454-5648.20230834

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摘要

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反铁电材料因具有独特的双电滞回线特征而受到了学术界广泛关注。目前反铁电材料相关研究的深入性和全面性不足，仍阻碍了其在更多领域的应用。因此，进一步研究和开发反铁电材料，对于推动科技的发展和社会的进步具有重要意义。本文综述了反铁电材料铪酸铅的研究现状，发展趋势及应用前景。详细介绍了铪酸铅基材料的基本储能性能参数、晶体结构、相变机制、离子掺杂改性以及制备工艺等。研究表明：铪酸铅反铁电材料具有快速充放电，极高的功率密度和能量密度以及杰出的电卡效应，这在储能和固态制冷等领域具有广泛的应用前景。

关键词

铪酸铅 / 反铁电 / 相变机制 / 储能 / 电卡效应

Abstract

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Antiferroelectric materials are considered as the most promising candidate materials for pulsed power capacitors due to their high breakdown electric field, high saturation polarization, low remanent polarization, and electrical hysteresis. The absence of deep and comprehensive research on antiferroelectric materials still hinders its application. Hence, a further research on antiferroelectric materials is of great importance to promote the development of science and technology and the progress of society.

PbHfO₃ (PHO) is a special antiferroelectric material with a perovskite structure. Its unique double hysteresis loop becomes a research hotspot. PHO has a high recoverable energy density and a great energy efficiency, which can be used to develop high-performance energy storage devices such as supercapacitors and pulse power capacitors. In addition, PHO antiferroelectric materials also have superior electrocaloric effects, which can achieve energy recovery and utilization at different temperatures, thus providing a novel approach for thermal energy utilization and energy conversion. The research of PHO antiferroelectric materials mainly focuses on the crystal structure, phase transition mechanism, energy storage performance (i.e., recoverable energy density, energy efficiency, charge/discharge energy density, etc.), and electrocaloric effect.

There are still many controversies on the crystal structure and phase transition mechanism of PHO. The multiple-phase transition process is rather complex. At present, it is generally believed that PHO has two temperature-induced phase transitions, i.e., the orthogonal symmetry antiferroelectric phase (AFE1) transitions to the intermediate antiferroelectric phase (AFE2) at 433 K, and the AFE2 transitions to the cubic symmetry paraelectric phase at 476 K. However, little work on the intermediate antiferroelectric phase has been reported yet. Some research work was carried out in the energy storage performance of PHO. Ion displacement, lattice distortion, and grain size are the major factors affecting the energy storage performance. As a result, ion doping becomes an effective way to adjust the electrical properties of PHO, thereby improving the energy storage characteristics such as recoverable energy density and energy efficiency, as well as charge and discharge energy density. The performance can be tuned by A-site, B-site, or A/B-site doping since PHO has a perovskite structure. For instance, A-site doping with elements such as Sr, Ba, La, etc. can change the lattice structure and improve the breakdown strength of the system, thus increasing the energy storage performance. B-site doping with Sn, Zr, and Ti can also be used to enhance the antiferroelectricity of the system to achieve a high recoverable energy density. A/B co-doping is also an effective way to improve the energy storage performance of PHO. In addition, the preparation process has a great influence on the crystal structure and energy storage performance of PHO. The rolling process and cold isostatic pressing can reduce the grain size of PHO to achieve the effect of fine crystal reinforcement, which increases its breakdown strength and achieves the excellent recoverable energy density and efficiency. In addition, the electrocaloric effect of PHO-based antiferroelectric materials gives it broad application prospects in electrocaloric refrigeration. At an external electric field, PHO exhibits a polarization reversal to produce a significant thermal effect, thereby achieving efficient refrigeration. The electrocaloric refrigeration method has a higher energy utilization efficiency and a lower power consumption, compared with the conventional mechanical refrigeration method.

Summary and prospects

This review represented recent development and application on the antiferroelectric lead hafnate. The basic energy storage parameters, crystal structure, phase transition mechanism, ion doping modification and preparation of PbHfO₃-based materials were introduced. In contrast to energy storage and refrigeration applications, PHO also has a wide range of potential applications in other fields. The unique crystal structure and phase transition mechanism of PHO enable the development of sensors and logic devices. Its antiferroelectric properties can be used to create electronic devices with a ultra-low power consumption, such as antiferroelectric transistors and memory devices. Although several important advances are made in the investigation of PHO, it still has some challenges. For instance, the multi-phase transition mechanism is still controversial, the intermediate phase is unclear, the breakdown field strength is not high enough, and the saturation polarization value needs to be further improved. It is impossible to achieve a high energy density and a high recoverable energy density simultaneously. However, the existing research shows that PHO has broad application prospects in the fields of energy storage and solid-state refrigeration due to its fast charging and discharging capacity, extremely high recoverable energy density and power density, and superior electrocaloric effect.

Key words

lead hafnate / antiferroelectric / phase transformation mechanism / energy storage / electrocaloric effects

引用本文

李东亮, 唐新桂, 姜登辉, 蒋艳平, 刘秋香. 反铁电材料铪酸铅研究进展. 硅酸盐学报, 2024 , 52 (4) : 1451 -1459 . DOI: 10.14062/j.issn.0454-5648.20230834

Dongliang LI, Xingui TANG, Denghui JIANG, Yanpiang JIANG, Qiuxiang LIU. Recent Development on Antiferroelectric Lead Hafnate[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (4) : 1451 -1459 . DOI: 10.14062/j.issn.0454-5648.20230834

基金

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国家自然科学基金(12172093)
广东省自然科学基金(2021A1515012607)

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2024年第52卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230834

接收时间：2023-10-29
首发时间：2026-10-22
出版时间：2024-04-20

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出版历史

收稿日期：2023-10-29
修回日期：2023-12-28

基金

国家自然科学基金(12172093)

广东省自然科学基金(2021A1515012607)

作者信息

^1．广东工业大学物理与光电工程学院，广州 510000

^2．西安电子科技大学先进材料与纳米技术学院，西安 710126

通讯作者:

唐新桂（1963—），男，博士，研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230834

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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