硅酸盐学报

Zr掺杂对Sr_0.7Bi_0.2TiO₃铁电陶瓷储能性能的影响

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刘建博 ¹ , 郑鹏 ¹ , 白王峰 ² , 盛林生 ³

硅酸盐学报 | 电介质储能材料专刊—研究论文 2024,52(4): 1345-1354

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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) : 1345 -1354

Zr掺杂对Sr_0.7Bi_0.2TiO₃铁电陶瓷储能性能的影响

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刘建博¹, 郑鹏¹, 白王峰², 盛林生³

作者信息

^1．杭州电子科技大学电子科学与技术系纳米电子学与纳电子器件实验室，杭州 310018

^2．杭州电子科技大学传感器新型材料浙江省重点实验室，杭州 310012

^3．嘉兴南湖学院信息工程学院，浙江嘉兴 314001

通讯作者:

郑鹏（1983—），男，博士，副教授；

白王峰（1985—），男，博士，副教授。

作者简介:

刘建博（1999—），男，硕士研究生。

Effect of Zr Doping on Energy Storage Performance of Sr_0.7Bi_0.2TiO₃ Ferroelectric Ceramics

Jianbo LIU¹, Peng ZHENG¹, Wangfeng BAI², Linsheng SHENG³

Affiliations

^1.Lab for Nanoelectronics and Nanoelectronic Devices, Department of Electronics Science and Technology, Hangzhou Dianzi University, Hangzhou 310018, China

^2.Key Laboratory of Novel Materials for Sensor of Zhejiang Province, Hangzhou Dianzi University, Hangzhou 310012, China

^3.College of Information Engineering, Jiaxing Nanhu University, Jiaxing 314001, Zhejiang, China

Corresponding Author:

ZHENG Peng (1983-), male, Ph.D., Associate Professor; E-mail: zhengpeng@hdu.edu.cn;

BAI Wangfeng (1985-), male, Ph.D., Associate Professor. bwf@hdu.edu.cn

LIU Jianbo (1999-), male, Master candidate. E-mail: liujianbo0921@163.com

出版时间: 2024-04-20 doi: 10.14062/j.issn.0454-5648.20230757

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摘要

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高功率、高能量密度的介质储能电容器在脉冲功率系统小型化和轻量化的过程中具有重要意义。采用固相反应法制备了无铅改性的Sr_0.7Bi_0.2TiO₃（SBT）基储能陶瓷，研究了掺杂不同含量ZrO₂对该陶瓷的相结构、微观结构、介电性能、铁电性能、击穿机制的影响。结果表明：Zr元素部分以Zr⁴⁺形式溶解于SBT晶格中，其余以ZrO₂形式存在晶界和晶粒表面；储能密度的提升主要依赖于介电击穿强度（E_b）的增强，可能的物理机制，包括晶粒尺寸、带隙、阻抗和激活能等，协同促进了E_b的提高。在所研究的材料中，SBT-2%（质量分数）ZrO₂陶瓷具有最好的储能性能，可恢复储能密度W_rec=5.57 J/cm³，能量效率η=88.97%；即使在经过5×10⁴次循环后也能表现出良好的性能稳定性（W_rec变化幅度<1%），是一种非常有前景的脉冲功率储能电容器候选材料。

关键词

钛酸锶铋基陶瓷 / 储能 / 介电击穿强度 / 物理机制

Abstract

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Introduction

Dielectric ceramic capacitors are essential components in next-generation advanced pulse power systems due to their ultra-fast charging/discharging rates and remarkable power density. As a typical lead-free perovskite material, Sr_0.7Bi_0.2TiO₃ (SBT) has a larger permittivity rather than SrTiO₃ because Bi modification favors producing a high polarization due to the intense hybridization between the 6s² orbitals of Bi³⁺ and O 2p orbitals. Moreover, it also has a superior ferroelectric relaxor behavior with a diffused maximum dielectric constant in a wide temperature range, benefiting from Bi³⁺ off centering and Sr site vacancies. However, SBT ceramic still has a critical challenge for improving dielectric breakdown strength (E_b). Some previous studies indicate that adding some oxides can effectively inhibit grain growth and increase E_b. In this paper, the SBT ceramics were synthesized by a conventional solid-state sintering method with ZrO₂ as an additive. A part of Zr⁴⁺ was deposited on the grain boundary in the form of oxides to inhibit grain growth. The breakdown strength and the energy storage density of the ceramics with different ZrO₂ contents were analyzed.

Materials and method

Bi₂O₃(99.5%, in mass. The same below), SrCO₃(99.5%), TiO₂(99.8%), and ZrO₂(99.9%) were used as raw materials. The raw materials were weighed according to the stoichiometric ratio. The materials were mixed with anhydrous ethanol and ground in a ball mill with zirconium balls for 12 h. The slurry was dried in an oven. After pre-firing at 850 ℃ for 5 h, the powder was further ground for 24 h according to the corresponding mass ratio Sr_0.7Bi_0.2TiO₃+xZrO₂ (SBT-xZr, x= 0, 0.5%, 1.0%, 2.0%, 5.0%, in mass fraction). The dried ground powder was pressed into sheets with a thickness of 0.8 mm and a diameter of 12 mm, and then sintered at a rate of 4 ℃/min at 1 200-1 250 ℃ for 3 h, and then cooled down naturally.

Results and discussion

Based on the XRD patterns and mapping energy spectra, element Zr partially dissolves in the SBT lattice in the form of Zr⁴⁺, and the rest exists in the form of ZrO₂ on the grain boundary and surface, showing the formation of a 0-3 type composite structure. The dielectric constant of SBT-2%Zr ceramic consistently exhibits a high value, while the low dielectric loss mitigates excess waste heat, which is beneficial to the energy storage performance. The heightened energy storage density primarily stems from the increased E_b value. With the augmentation of ZrO₂ content, the E_b value of the SBT-2%Zr increases, reaching a peak of 580 kV/cm, which is 27.6% higher than that of pure SBT ceramic. Consequently, the recoverable energy storage density (W_rec) experiences an elevation from 4.07 J/cm³ for the ceramic without x to 5.57 J/cm³ for the ceramic with x of 2%, while energy efficiency (η) maintains 88.97%. However, for the ceramic with x of 5%, despite achieving a high E_b value, the introduction of excessive ZrO₂ leads to a notable reduction in maximum polarization (P_max), preventing the attainment of the maximum W_rec value. The average grain size decreases from 2.30 μm to 1.31 μm, facilitating the attainment of more highly insulated grain boundaries. Also, the band gap energy (E_g) increases from 2.94 eV for the SBT ceramic to 3.02 eV for the SBT-5%Zr ceramic. This signifies that electrons require a larger applied electric field to achieve the valence band and conduction band transition. The expansion of the impedance circle indicates a higher resistivity of the material, and the elevated activation energy (E_a) effectively restrains the transmission of charged carriers. These interrelated mechanisms are crucial factors contributing to the substantial enhancement of E_b. In addition, SBT-2%Zr ceramic also shows an excellent fatigue stability (i.e, 5×10⁴ cycles, W_rec change <1%) and a good charge-discharge performance (i.e., discharge energy density W_d=2.15 J/cm³, current density C_D=1 060.51 A/cm² and power density P_D=169.68 MW/cm³).

Conclusions

A lead-free 0-3 type relaxation ferroelectric ceramic based on SBT was prepared by a stable solid-state reaction method. The ceramics doped with different concentrations of ZrO₂ exhibited an original crystal structure with some Zr⁴⁺ in the lattice. The remaining Zr⁴⁺ existed in the form of a second phase, predominantly appearing at the boundaries and surfaces of grains. The increase of energy storage density mainly depended on the increase of E_b, and the possible physical mechanisms (i.e., grain size, band gap, impedance and activation energy) cooperated to promote the increase of E_b. SBT-2%Zr ceramic had the optimum energy storage performance, i.e., recoverable energy storage density (W_rec=5.57 J/cm³) and energy efficiency (η=88.97%). After 5×10⁴ cycles, SBT-2%Zr ceramic with a good performance stability (i.e., W_rec change amplitude <1%) could be used as a promising candidate material for pulse power energy storage capacitors.

Key words

strontium bismuth titanate based ceramics / energy storage / dielectric breakdown strength / physical mechanisms

引用本文

刘建博, 郑鹏, 白王峰, 盛林生. Zr掺杂对Sr_0.7Bi_0.2TiO₃铁电陶瓷储能性能的影响. 硅酸盐学报, 2024 , 52 (4) : 1345 -1354 . DOI: 10.14062/j.issn.0454-5648.20230757

Jianbo LIU, Peng ZHENG, Wangfeng BAI, Linsheng SHENG. Effect of Zr Doping on Energy Storage Performance of Sr_0.7Bi_0.2TiO₃ Ferroelectric Ceramics[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (4) : 1345 -1354 . DOI: 10.14062/j.issn.0454-5648.20230757

基金

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浙江省自然科学基金(LY22E020006; LQ22A040012)

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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.0454-5648.20230757

接收时间：2023-10-06
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：2023-10-06
修回日期：2023-11-23

基金

浙江省自然科学基金(LY22E020006; LQ22A040012)

作者信息

^1．杭州电子科技大学电子科学与技术系纳米电子学与纳电子器件实验室，杭州 310018

^2．杭州电子科技大学传感器新型材料浙江省重点实验室，杭州 310012

^3．嘉兴南湖学院信息工程学院，浙江嘉兴 314001

通讯作者:

郑鹏（1983—），男，博士，副教授；

白王峰（1985—），男，博士，副教授。

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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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