硅酸盐学报

反铁电储能陶瓷及电容器的极化特性

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李缨萱 ¹ , 乔峰 ² , 张玲 ² , 王岗 ¹ , 王晓智 ¹ , 朱青山 ³ , 徐然 ¹ , 徐卓 ¹ , 冯玉军 ¹

硅酸盐学报 | 电介质储能材料专刊—研究论文 2024,52(4): 1277-1287

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硅酸盐学报 |电介质储能材料专刊—研究论文 2024 , 52 (4) : 1277 -1287

反铁电储能陶瓷及电容器的极化特性

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李缨萱¹, 乔峰², 张玲², 王岗¹, 王晓智¹, 朱青山³, 徐然¹, 徐卓¹, 冯玉军¹

作者信息

^1．西安交通大学，电子陶瓷与器件教育部重点实验室，西安 710049

^2．成都宏科电子科技有限公司，成都 610199

^3．工业和信息化部电子第五研究所，广州 510642

通讯作者:

徐然（1988—），男，博士，副教授。

作者简介:

李缨萱（1999—），女，硕士研究生。

Polarization Effect of Antiferroelectric Energy Storage Ceramic and Capacitor

Yingxuan LI¹, Feng QIAO², Ling ZHANG², Gang WANG¹, Xiaozhi WANG¹, Qingshan ZHU³, Ran XU¹, Zhuo XU¹, Yujun FENG¹

Affiliations

^1.Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education, Xi'an Jiaotong University, Xi'an 710049, China

^2.Chengdu Hongke Electronic Technology Co, Chengdu 610199, China

^3.The Fifth Electronics Research Institute of the Ministry of Industry and Information, Guangzhou 510642, China

Corresponding Author:

XU Ran (1988-), male, Ph.D., Associate Professor. E-mail: xuran99@xjtu.edu.cn

LI Yingxuan (1999-), female, Master candidate. E-mail: liyingxuan@stu.xjtu.edu.cn

出版时间: 2024-04-20 doi: 10.14062/j.issn.0454-5648.20230746

文章导航

摘要

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反铁电多层陶瓷电容器（MLCC）作为储能器件在脉冲功率技术、电力电子技术等领域具有重要的应用。与常规的Ⅰ类或Ⅱ类陶瓷电容器不同，反铁电电容器在出厂前会进行极化处理并标记极性。该极化过程可能对反铁电MLCC的应用带来影响，因此有必要研究反铁电陶瓷材料及电容器的极化特性。本工作采用固相反应法制备了电滞回线形状为“方直”和“细斜”的两类典型的反铁电陶瓷样品，通过对比未经极化与经过极化处理样品的电滞回线，分析预极化对反铁电陶瓷性能及储能密度的影响。通过不同温度退极化后反铁电陶瓷材料与MLCC电容值的差异，分析得出退极化现象对其性能的影响。结果表明：反铁电陶瓷材料及电容器未经过预极化或退极化后，极化强度、电容值与脉冲放电电流峰值均有所下降，且退极化程度均会随着温度升高而升高。对于“方直”型反铁电陶瓷材料，极性现象对其影响较为显著，而对于“细斜”型反铁电陶瓷材料，极性现象影响较为微弱。该研究对反铁电MLCC在实际应用中如何正确发挥出其优异的性能具有重要的意义。

关键词

反铁电陶瓷 / 多层陶瓷电容器 / 极化 / 储能密度

Abstract

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Introduction

Antiferroelectric ceramic and multilayer ceramic capacitors have the advantages of high energy storage density, fast discharge speed, high discharge current, etc., which can improve the energy storage density of pulse power device and effectively suppress ripple in power electronic system, etc. Unlike ferroelectrics, antiferroelectric materials adjacent to the lattice of dipoles reverse parallel, and therefore do not show a macroscopic spontaneous polarization phenomenon. In a certain external electric field, the dipoles redirect, the antiferroelectric phase converts to a ferroelectric phase, the polarization intensity increases abruptly after the withdrawal of the external electric field, and it returns to an antiferroelectric phase. This polarization/phase transition behavior can be characterized by the hysteresis loop. In the hysteresis loop, antiferroelectric material shows a double loop, and it is divided into two kinds, i.e., "Square" and "Slant" according to the different shapes of the antiferroelectric hysteresis loop. The polarization effect of the antiferroelectric capacitor gives it the better energy storage characteristics and discharge performance, thus having an advantage in practical applications. General capacitors are polarized under a certain period of time and voltage in the factory. However, changes of external conditions (i.e., temperature, voltage, time, etc.) can depolarize the antiferroelectric capacitor. Also, some antiferroelectric capacitors need to consider the effect of polarity. As a result, the practical application of antiferroelectric MLCCs is different from that of conventional Class I or Class II MLCCs. Therefore, in this paper, antiferroelectric ceramics with hysteresis loop shapes of "square" and "slant" were prepared by a conventional solid-phase reaction method to investigate the polarization effect of antiferroelectric ceramics and capacitors, and provide a guidance for the application of antiferroelectric MLCCs.

Methods

For the preparation of the antiferroelectric ceramic, the raw materials were weighed according to the chemical formula. The excess Pb₃O₄ was used to compensate for lead loss in sintering. The weighed raw materials were mixed in a mass ratio of 1.0∶1.0∶1.5 and ground in anhydrous alcohol by grinding in a ball mill with zirconium balls at 300 rpm for 20 h. After ball-milling, the slurry was pre-fired at 850 ℃ for 3 h. The film was formed, and heated at 1 280 ℃ for 2 h. The samples were prepared after polished with sandpaper to a certain thickness (less than or equal to 0.1 mm) and sputtered with gold electrodes. The micro-morphology of the samples was measured by a model JSM-6390A scanning electron microscope (SEM, JOEL Co., Japan). The crystalline phase composition was determined by a model D/Max-2400 X-ray diffractometer (XRD, Rigaku Co., Japan), using Cu K_α rays, with a scanning range of 20°-70°. The hysteresis loops and polarization current curves of the samples were examined by a model TF Analyzer 2000 ferroelectric test system (aix-ACCT Co., Germany). The basic principle of the test was based on the Sawyer-Tower circuit. The test frequency was 1 Hz, and the voltage waveform was a triangular wave. The pulse discharge test used a self-built platform.

Results and discussion

From the SEM images of the samples, the grains are uniform and have a good densification. From the XRD patterns of the samples, the prepared samples have a quadrilateral phase structure. The prepared samples have a typical double hysteresis loop, and the shapes of hysteresis loops for sample S1 and S2 are "square" and "slant". The hysteresis loops of the samples after and before polarization indicate that for the unpolarized ceramic sample, the transition field is higher, the stored energy density and energy conversion efficiency are lower. This phenomenon is also related to the shape of the hysteresis loops, so the polarization has a certain impact on the practical application of antiferroelectric ceramics. The electric hysteresis loop nearby transition field shows that for capacitors with antiferroelectric ceramic dielectrics, the antiferroelectric capacitor is unpolarized (or is depolarized) if the operating voltage is set nearby the transition field, thus leading to a weakening of its performance. To analyze whether high temperature should have an effect on the degree of polarization of antiferroelectric ceramics, the capacitances of the antiferroelectric ceramics are tested after depolarization at different temperatures, and the pulse discharge currents of the antiferroelectric MLCCs after depolarization at different temperatures are tested. The results show that if the antiferroelectric capacitor is overheated and warmed up, and although the temperature is recovered after using, the temperature still has a certain effect on the performance of antiferroelectric capacitor, especially at a lower applied voltage. To study the effect of polarity on the antiferroelectric material, the hysteresis loops of antiferroelectric ceramics in positive and negative electric fields were tested, and the pulse discharge of antiferroelectric MLCCs in different polarity electric fields was tested. The results show that the antiferroelectric domains are preferentially oriented, and the antiferroelectric domains have a memory effect after a certain direction of the electric field polarization, preventing its entry into the opposite direction of the ferroelectric domains. And this effect is more serious on the antiferroelectric ceramics with a "square" hysteresis loop.

Conclusions

The antiferroelectric polarization and polarity characteristics had dominant effects on their applications. Those effects above were lower although antiferroelectric capacitors were generally made of materials with "slant" hysteresis loops. However, since antiferroelectric materials were in an electric field that was slightly higher than the E_AFE-FE phase transition field, their depolarization and polarity characteristics still affected their performance. In addition, a slight attenuation of the antiferroelectric MLCCs performance still adversely affected the reliability of the whole system since some applications required an extremely high reliability. In practice, antiferroelectric MLCCs were bound to depolarize after soldering, and their performance could be greatly degraded if the applied electric filed was lower than the transition field.

Key words

antiferroelectric ceramics / multilayer ceramic capacitor / polarization / energy storage density

引用本文

李缨萱, 乔峰, 张玲, 王岗, 王晓智, 朱青山, 徐然, 徐卓, 冯玉军. 反铁电储能陶瓷及电容器的极化特性. 硅酸盐学报, 2024 , 52 (4) : 1277 -1287 . DOI: 10.14062/j.issn.0454-5648.20230746

Yingxuan LI, Feng QIAO, Ling ZHANG, Gang WANG, Xiaozhi WANG, Qingshan ZHU, Ran XU, Zhuo XU, Yujun FENG. Polarization Effect of Antiferroelectric Energy Storage Ceramic and Capacitor[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (4) : 1277 -1287 . DOI: 10.14062/j.issn.0454-5648.20230746

基金

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国家自然科学基金青年基金项目(52002311)
国家自然科学基金重点项目(52032010)

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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.0454-5648.20230746

接收时间：2023-09-27
首发时间：2026-10-22
出版时间：2024-04-20

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收稿日期：2023-09-27
修回日期：2023-10-23

基金

国家自然科学基金青年基金项目(52002311)

国家自然科学基金重点项目(52032010)

作者信息

^1．西安交通大学，电子陶瓷与器件教育部重点实验室，西安 710049

^2．成都宏科电子科技有限公司，成都 610199

^3．工业和信息化部电子第五研究所，广州 510642

通讯作者:

徐然（1988—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230746

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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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