硅酸盐学报

锆锡钛酸镧铅反铁电体陶瓷的低温烧结和储能特性

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余宇梁 ¹ , 王世斌 ¹ , 李伟湫 ¹ , 何厚铸 ¹ , 赵小波 ¹ , 姚英邦 ¹ , 陶涛 ¹ , 梁波 ¹ , 鲁圣国 ¹^,²

硅酸盐学报 | 电介质储能材料专刊—研究论文 2024,52(4): 1403-1412

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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) : 1403 -1412

锆锡钛酸镧铅反铁电体陶瓷的低温烧结和储能特性

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余宇梁¹, 王世斌¹, 李伟湫¹, 何厚铸¹, 赵小波¹, 姚英邦¹, 陶涛¹, 梁波¹, 鲁圣国¹^,²

作者信息

^1．广东工业大学材料与能源学院，广东省智能材料和能量转化器件工程技术研究中心，广州 510006

^2．东莞华南设计创新院，广东东莞 523830

通讯作者:

鲁圣国（1963—），男，博士，教授。

作者简介:

余宇梁（1998—），男，硕士研究生。

Low-Temperature Sintering and Energy Storage Properties of Lead Lanthanum Zirconate Stannate-Titanate Antiferroelectric Ceramics

Yuliang YU¹, Shibin WANG¹, Weiqiu LI¹, Houzhu HE¹, Xiaobo ZHAO¹, Yingbang YAO¹, Tao TAO¹, Bo LIANG¹, Sheng Guo LU¹^,²

Affiliations

^1.School of Materials and Energy, Guangdong University of Technology, Guangdong Provincial Research Center on Smart Materials and Energy Conversion Devices, Guangzhou 510006, China

^2.Dongguan South China Design and Innovation Institute, Dongguan 523830, Guangdong, China

Corresponding Author:

LU Sheng Guo (1963-), male, Ph.D., Professor. E-mail: sglu@gdut.edu.cn

YU Yuliang (1998-), male, Master candidate. E-mail: 920538572@qq.com

出版时间: 2024-04-20 doi: 10.14062/j.issn.0454-5648.20230938

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摘要

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随着风电、光电等绿色能源的利用和对大功率电力电子装备需求的增加，大功率储能器件受到了广泛的关注，而具有高储能密度和高储能效率的（Pb, La）（Zr, Sn, Ti）O₃（PLZST）反铁电体陶瓷用于超级介电储能电容器具有明显的优势。但是，受到陶瓷本身高烧结温度（1 200~1 300 ℃）的限制，难以适应贱金属内电极多层陶瓷电容器的应用。为了适应贱金属铜（Cu）内电极的烧结，将玻璃粉MgO-Al₂O₃-ZnO-B₂O₃-SiO₂（MAZBS）添加到（Pb_0.97La_0.02）（Zr_0.55Sn_0.41Ti_0.04）O₃（PLZST）反铁电体陶瓷中，使烧结温度低于铜内电极的熔点。研究结果表明：当添加了玻璃粉MAZBS的质量分数为0.75%时，PLZST陶瓷在较低的温度（930 ℃）下可以实现致密烧结，且陶瓷在室温和外加电场300 kV/cm下具有较高的放电储能密度（6.08 J/cm³），和储能效率（77%）。

关键词

锆锡钛酸镧铅 / 反铁电陶瓷 / 低温烧结 / 储能密度 / 储能效率

Abstract

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Introduction

There exist severe problems in the society, i.e., environmental pollution, energy shortage, and climate change. These problems directly affect the living environment and have significant threats to globally sustainable development. In the past decades, some low-carbon new energy solutions are developed to address the continuously growing energy demand and mitigate the adverse impacts of climate change. Despite of the continuous emergence of new energy devices, it is still important to face the challenges, i.e., relatively low power density, safety, large volume, etc..

In this paper, the dielectric materials for multilayer energy storage capacitors (MLCC) were prepared by a solid-state reaction method at a lower sintering temperature with low-cost base metal electrodes (e.g., Cu). In addition, the energy storage properties of the MLCC were also characterized.

Methods

(Pb_0.97La_0.02)(Zr_0.55Sn_0.41Ti_0.04)O₃ (PLZST)-x% MgO-Al₂O₃-ZnO-B₂O₃-SiO₂ (MAZBS, x=0.00, 0.25, 0.50, 0.75, 1.00, 1.25) ceramics were synthesized by a conventional solid-state reaction method. The fabricated ceramics were characterized by Fourie transformation infrared spectroscopy (FTIR), thermal analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The dielectric, ferroelectric, and energy storage properties were examined by a LCR impedance analyzer and a polarization-electric field (P-E) hysteresis loop analyzer.

PbO (purity: 99.0% in mass fraction, the same below), La₂O₃ (99.5%), ZrO₂ (99.5%), SnO₂ (99.8%), and TiO₂ (99.8%) were used as raw materials to synthesize PLZST. MAZBS glass powders were prepared by a water quench method. Afterwards, they were mixed with the oxides powders in a designed mass ratio, ground by high-energy ball milling for 24 h, dried at 80 ℃ for 10 h, and then sintered to form PLZST-x% MAZBS (x=0.00, 0.25, 0.50, 0.75, 1.00, 1.25) antiferroelectric ceramics. The calcined powders with 5% polyvinyl butyral (PVB) as a binder were pressed into discs with 12 mm in diameter and 1 mm in thickness at 20 MPa. Finally, the green bodies with added MAZBS glass phase were sintered at 930-1 000 ℃ for 4 h, while the sample without x was sintered at 1 200-1 300 ℃ for 2 h. For the properties test, the ceramics were firstly polished, and gold electrodes were then deposited on the both surfaces. The electrode diameter and thickness for each sample were (3.00±0.11) mm and (0.055±0.007) mm as x=0.00, (0.82±0.19) mm and (0.072±0.07) mm as x=0.25, (1.68±0.04) mm and (0.076±0.007) mm as x=0.50, (2.28±0.33) mm and (0.055±0.004) mm as x=0.75, (0.87±0.30) mm and (0.066±0.003) mm as x=1.00, (1.90±0.44) mm and (0.062±0.005) mm as x=1.25.

Results and discussion

The XRD patterns of PLZST-x% MAZBS (x=0.00, 0.25, 0.50, 0.75, 1.00, 1.25) antiferroelectric ceramics reveal a shift towards low angles for a peak (200) at 43°-45° when the glass content increases. This shift indicates a possible substitution of Ti⁴⁺ (with the radium of 0.60 Å) by Mg²⁺ (with the radium of 0.69 Å). Concurrently, the dielectric constant decreases with increasing the glass content due to the lower dielectric constant of glass. The P-E hysteresis loop results demonstrate that PLZST-x% MAZBS ceramics exhibit an optimum energy storage performance when x=0.75, and a good performance at different frequencies. However, a further increase in glass content leads to the entrance of metallic ions from the glass phase into the ceramic lattice, causing the defects and reduction of the dielectric breakdown strength of the ceramics.

Conclusions

The impact of MAZBS glass content on the energy storage properties of PLZST ceramics was investigated. It was indicated that an appropriate content of MAZBS glass phase could reduce the sintering temperature of PLZST ceramics from 1 200 ℃ to 930 ℃. The XRD patterns confirmed a perovskite structure of PLZST-x% MAZBS ceramics. The FTIR spectroscopy revealed the formation of non-bridging oxygen bonds due to the doping of Al³⁺, Zn²⁺, and Mg²⁺. The glass transition temperature and softening temperature of MAZBS glass were examined via the TG/DSC analysis. The dielectric analysis indicated a tetragonal antiferroelectric-ferroelectric phase transition with increasing the temperature, and the dielectric constant peak gradually decreased with the increase of glass content. The results of P-E hysteresis loop illustrated the electric field-induced antiferroelectric-ferroelectric phase transition characteristics of ceramics, with the maximum polarization achieved at the glass phase content of 0.75%. The PLZST-0.75% MAZBS ceramics had a maximum energy storage density of 6.08 J/cm³ and an efficiency of 77% at 300 kV/cm. This result indicated that PLZST-MAZBS ceramics could be developed into high-energy density ceramic capacitors with cost-effective copper inner electrodes.

Key words

lead lanthanum zirconate stannate-titanate / antiferroelectrics ceramics / low-temperature sintering / energy storage density / energy storage efficiency

引用本文

余宇梁, 王世斌, 李伟湫, 何厚铸, 赵小波, 姚英邦, 陶涛, 梁波, 鲁圣国. 锆锡钛酸镧铅反铁电体陶瓷的低温烧结和储能特性. 硅酸盐学报, 2024 , 52 (4) : 1403 -1412 . DOI: 10.14062/j.issn.0454-5648.20230938

Yuliang YU, Shibin WANG, Weiqiu LI, Houzhu HE, Xiaobo ZHAO, Yingbang YAO, Tao TAO, Bo LIANG, Sheng Guo LU. Low-Temperature Sintering and Energy Storage Properties of Lead Lanthanum Zirconate Stannate-Titanate Antiferroelectric Ceramics[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (4) : 1403 -1412 . DOI: 10.14062/j.issn.0454-5648.20230938

基金

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国家自然科学基金(51872053; 52272105)
国家自然科学基金委-广东省联合基金(U1501246)
广东省自然科学基金(2015A030308004)
东莞市核心技术攻关前沿项目(2019622101006)
先进能源科学与技术广东省实验室佛山分中心佛山仙湖实验室开放基金(XHT2020-011)
国家自然科学基金面上项目(51372042)

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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.0454-5648.20230938

接收时间：2023-12-05
首发时间：2026-10-22
出版时间：2024-04-20

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收稿日期：2023-12-05
修回日期：2024-01-12

基金

国家自然科学基金(51872053; 52272105)

国家自然科学基金委-广东省联合基金(U1501246)

广东省自然科学基金(2015A030308004)

东莞市核心技术攻关前沿项目(2019622101006)

先进能源科学与技术广东省实验室佛山分中心佛山仙湖实验室开放基金(XHT2020-011)

国家自然科学基金面上项目(51372042)

作者信息

^1．广东工业大学材料与能源学院，广东省智能材料和能量转化器件工程技术研究中心，广州 510006

^2．东莞华南设计创新院，广东东莞 523830

通讯作者:

鲁圣国（1963—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230938

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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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