铋系化合物改性的新型三元弛豫铁电体的性能研究

人工晶体学报 ›› 2022, Vol. 51 ›› Issue (3): 411-418.

铋系化合物改性的新型三元弛豫铁电体的性能研究

黄江峰, 王涛, 王凤华, 何志兴, 陈哲, 黄音博, 吴文娟

成都信息工程大学光电工程学院,成都 610225

收稿日期:2021-12-01 出版日期:2022-03-15 发布日期:2022-04-11
通讯作者: 吴文娟,副教授。E-mail:wwj@cuit.edu.cn
作者简介:黄江峰(1999—),男,重庆市人。E-mail:744047104@qq.com
基金资助:
四川省科技计划(2021YJ0560);四川省大学生创新创业训练计划(202010621100)

Properties of Novel Ternary Relaxor Ferroelectrics Modified by Bismuth Series Compounds

HUANG Jiangfeng, WANG Tao, WANG Fenghua, HE Zhixing, CHEN Zhe, HUANG Yinbo, WU Wenjuan

College of Optoelectronic Technology, Chengdu University of Information Technology, Chengdu 610225, China

Received:2021-12-01 Online:2022-03-15 Published:2022-04-11

摘要/Abstract

摘要： 钛酸钡(BaTiO₃)陶瓷作为传统的介质电容器材料,其强铁电性会导致储能密度低下,但通过掺杂可以削弱铁电性来获得弛豫铁电体,提高储能性能。利用铋系化合物可增强弛豫特性,本文设计了BiScO₃和(Sr_0.7Bi_0.2)TiO₃取代改性的BaTiO₃基三元陶瓷材料: (0.99-x)Ba(Zr_0.1Ti_0.9)O₃-x(Sr_0.7Bi_0.2)TiO₃-0.01BiScO₃(缩写为BZT-xSBT-BS)。采用传统固相法制备的BZT-xSBT-BS陶瓷,相结构没有因为掺杂发生改变,在室温下均为纯的三方相钙钛矿结构。介电和铁电的测试与分析表明,BZT-xSBT-BS陶瓷具有典型的弛豫铁电特性。由于不等价离子Sr²⁺、Bi³⁺的掺杂导致界面松弛极化,可以增大BZT-xSBT-BS陶瓷的介电常数,但是受制于其慢的响应速度,陶瓷的介电损耗也显著增加。适量(Sr_0.7Bi_0.2)TiO₃可以提升BZT-xSBT-BS陶瓷的介电、铁电、应变和储能性能,x=0.015时的BZT-xSBT-BS陶瓷的综合性能较优:ε_r~10 372,tanδ~0.019,P_max=16.42 μC/cm²,E_c=1.41 kV/cm,S⁺_max=0.12%(@40 kV/cm),W_D=0.181 J/cm³,η=80.4%(@60 kV/cm)。

关键词: BaTiO₃基陶瓷, (Sr_0.7Bi_0.2)TiO₃, 固相法, 弛豫铁电体, 介质电容器, 介电性能, 铁电性能, 储能

Abstract: As a traditional dielectric capacitor material, barium titanate (BaTiO₃) ceramics have strong ferroelectric property, which leads to low energy storage density. However, the relaxation ferroelectric can be obtained through doping to weaken the ferroelectric property and improve the energy storage performance. In this paper, BaTiO₃-based ceramics modified by BiScO₃ and (Sr_0.7Bi_0.2)TiO₃, a ternary ceramic material (0.99-x)Ba(Zr_0.1Ti_0.9)O₃-x(Sr_0.7Bi_0.2)TiO₃-0.01BiScO₃(abbreviated as BZT-xSBT-BS) was designed, owing to the enhanced relaxation properties induced by bismuth series compounds. The phase structure of BZT-xSBT-BS ceramics prepared by traditional solid-state method is not changed due to doping, and they are pure cubic perovskite structure at room temperature. Dielectric and ferroelectric tests and analysis show that BZT-xSBT-BS ceramics have typical relaxor ferroelectric properties. Sr²⁺ and Bi³⁺ ions substitutions produce thermionic relaxation polarization, which contributes to the polarization and increases the dielectric constant of BZT-xSBT-BS ceramics, but the dielectric loss will increase due to its slow response speed. An appropriate amount of (Sr_0.7Bi_0.2)TiO₃ can improve the dielectric, ferroelectric, strain and energy storage properties of BZT-xSBT-BS ceramics. BZT-xSBT-BS ceramics with x=0.015 show excellent properties, ε_r~10 372, tanδ~0.019, P_max=16.42 μC/cm², E_c=1.41 kV/cm, S⁺_max=0.12% (@40 kV/cm), W_D=0.181 J/cm³, η=79.4% (@60 kV/cm).

Key words: BaTiO₃-based dielectric ceramic, (Sr_0.7Bi_0.2)TiO₃, solid-state method, relaxor ferroelectric, dielectric capacitor, dielectric property, ferroelectric property, energy storage

中图分类号:

TQ174.1

黄江峰, 王涛, 王凤华, 何志兴, 陈哲, 黄音博, 吴文娟. 铋系化合物改性的新型三元弛豫铁电体的性能研究[J]. 人工晶体学报, 2022, 51(3): 411-418.

HUANG Jiangfeng, WANG Tao, WANG Fenghua, HE Zhixing, CHEN Zhe, HUANG Yinbo, WU Wenjuan. Properties of Novel Ternary Relaxor Ferroelectrics Modified by Bismuth Series Compounds[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(3): 411-418.

参考文献

[1] 杜红亮,杨泽田,高峰,等.无铅非线性介电储能陶瓷:现状与挑战[J].无机材料学报,2018,33(10):1046-1058.
DU H L, YANG Z T, GAO F, et al. Lead-free nonlinear dielectric ceramics for energy storage applications: current status and challenges[J]. Journal of Inorganic Materials, 2018, 33(10): 1046-1058(in Chinese).
[2] LI D X, ZENG X J, LI Z P, et al. Progress and perspectives in dielectric energy storage ceramics[J]. Journal of Advanced Ceramics, 2021, 10(4): 675-703.
[3] GAO J H, WANG Y, LIU Y B, et al. Enhancing dielectric permittivity for energy-storage devices through tricritical phenomenon[J]. Scientific Reports, 2017, 7: 40916.
[4] WANG T, JIN L, LI C C, et al. Relaxor ferroelectric BaTiO₃-Bi(Mg_2/3Nb_1/3)O₃ ceramics for energy storage application[J]. Journal of the American Ceramic Society, 2015, 98(2): 559-566.
[5] LI X X, CHEN X L, LIU X B, et al. Temperature-stable dielectric properties from -56 ℃ to 248 ℃ in (1-x)BaTiO₃-xBi(Mg_0.5Sn_0.5)O₃ system[J]. Journal of Electronic Materials, 2019, 48(1): 296-303.
[6] LIANG X W, ZHAO Z Y, ZHU Q Y, et al. Lead-free BaTiO₃-based ceramics modified by Bi(Mg_0.5Sn_0.5)O₃ with enhanced energy-storage performance and charge-discharge properties[J]. Journal of Materials Science: Materials in Electronics, 2021, 32(3): 3377-3390.
[7] WU L W, WANG X H, LI L T. Lead-free BaTiO₃-Bi(Zn_2/3Nb_1/3)O₃ weakly coupled relaxor ferroelectric materials for energy storage[J]. RSC Advances, 2016, 6(17): 14273-14282.
[8] HU Q Y, JIN L, WANG T, et al. Dielectric and temperature stable energy storage properties of 0.88BaTiO₃-0.12Bi(Mg_1/2Ti_1/2)O₃ bulk ceramics[J]. Journal of Alloys and Compounds, 2015, 640: 416-420.
[9] OGIHARA H, RANDALL C A, TROLIER-MCKINSTRY S. High-energy density capacitors utilizing 0.7BaTiO₃-0.3BiScO₃Ceramics[J]. Journal of the American Ceramic Society, 2009, 92(8): 1719-1724.
[10] WU L W, LUO B C, TIAN E K. Ferroelectric properties of BaTiO₃-BiScO₃ weakly coupled relaxor energy-storage ceramics from first-principles calculations[J]. Journal of Alloys and Compounds, 2021, 866: 158933.
[11] 何俊峰,梁山,谢帅,等.(Sr_0.7Bi_0.2)TiO₃取代BNT基无铅陶瓷的相变及储能特性[J].人工晶体学报,2017,46(10):1965-1970.
HE J F, LIANG S, XIE S, et al. Phase transition and energy-storage property of (Sr_0.7Bi_0.2)TiO₃ substituted BNT-based lead-free ceramics[J]. Journal of Synthetic Crystals, 2017, 46(10): 1965-1970(in Chinese).
[12] SAKURAI M, KANEHARA K, TAKEDA H, et al. Wideband dielectric spectroscopy of (Sr_0.7Bi_0.2)TiO₃ ceramics and its microscopic mechanism of polarization[J]. Journal of the Ceramic Society of Japan, 2016, 124(6): 664-667.
[13] LI S Y, SHI P, ZHU X P, et al. Enhanced energy storage properties in lead-free NaNbO₃-Sr_0.7Bi_0.2TiO₃-BaSnO₃ ternary ceramic[J]. Journal of Materials Science, 2021, 56(20): 11922-11931.
[14] LI J L, LI F, XU Z, et al. Multilayer lead-free ceramic capacitors with ultrahigh energy density and efficiency[J]. Advanced Materials (Deerfield Beach, Fla), 2018, 30(32): e1802155.
[15] DONG L, STONE D S, LAKES R S. Enhanced dielectric and piezoelectric properties of xBaZrO₃-(1-x)BaTiO₃ ceramics[J]. Journal of Applied Physics, 2012, 111(8): 084107.