(Ba0.85Ca0.15)(Ti0.9Zr0.1-xSnx)O3无铅压电陶瓷的相结构与压电性能

doi:10.15541/jim20210416

无机材料学报 ›› 2022, Vol. 37 ›› Issue (5): 513-519.DOI: 10.15541/jim20210416

所属专题：【信息功能】电介质材料

(Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1-_xSn_x)O₃无铅压电陶瓷的相结构与压电性能

王新健¹(), 朱逸璇¹, 张鹏¹, 杨文龙¹, 王挺², 郇宇¹()

1. 济南大学材料科学与工程学院, 济南 250022
2. 惠州学院广东省电子功能材料与器件重点实验室, 惠州 516001

收稿日期:2021-07-02 修回日期:2021-08-18 出版日期:2022-05-20 网络出版日期:2021-10-21
通讯作者: 郇宇, 副教授. E-mail: mse_huany@ujn.edu.cn
作者简介:王新健(1996-), 男, 硕士研究生. E-mail: wangxinjian_ujn@163.com
基金资助:
国家自然科学基金(52072150);广东省电子功能材料与器件重点实验室开放基金项目(EFMD202100Z)

Phase Structure and Piezoelectric Property of (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1-_xSn_x)O₃ Lead-free Piezoceramics

WANG Xinjian¹(), ZHU Yixuan¹, ZHANG Peng¹, YANG Wenlong¹, WANG Ting², HUAN Yu¹()

1. School of Material Science and Engineering, University of Jinan, Jinan 250022, China
2. Guangdong Provincial Key Laboratory of Electronic Functional Materials and Devices, Huizhou University, Huizhou 516001, China

Received:2021-07-02 Revised:2021-08-18 Published:2022-05-20 Online:2021-10-21
Contact: HUAN Yu, associate professor. E-mail: mse_huany@ujn.edu.cn
About author:WANG Xinjian (1996-), male, Master candidate. E-mail: wangxinjian_ujn@163.com
Supported by:
National Natural Science Foundation of China(52072150);Open Fund Foundation of Guangdong Provincial Key Laboratory of Electronic Functional Materials and Devices(EFMD202100Z)

摘要/Abstract

摘要：

钙锆共掺钛酸钡陶瓷(BCZT)具有优异的介电性能和压电性能, 是一类具有发展潜力的无铅压电陶瓷, 但其压电性能仍无法与铅基陶瓷媲美。为提高压电性能, 本研究对陶瓷材料进行Sn元素掺杂改性((Ba_0.85Ca_0.15)- (Ti_0.9Zr_0.1-_xSn_x)O₃, x=0.02~0.07))。晶体结构分析证实所有组分的陶瓷无杂相, 处于正交相与四方相两相共存状态, 并具有较大的c/a; 显微结构分析发现所有陶瓷都很致密, 且平均晶粒尺寸随着Sn含量的增加而增大。当x=0.04时, 陶瓷最致密, 且室温处于准同型相界附近, 因此拥有最佳的电学性能: d₃₃=590 pC•N ^-1, k_p=52.2%, tanδ=0.016, ε ^T₃₃=5372, d ^*₃₃=734 pm•V ^-1, IR=57.8 GΩ•cm。本研究表明: Sn掺杂的BCZT基无铅压电陶瓷具有优异的压电性能, 有望在换能器、机电传感器和驱动器等方面得到应用。

关键词: (BaCa)(TiZr)O₃基无铅压电陶瓷, Sn掺杂, 准同型相界, 晶粒尺寸效应

Abstract:

Zr and Ca co-doped brium titanate (BCTZ) based ceramics have attracted much attention due to their excellent dielectric and piezoelectric properties, which are potential candidates for lead-free piezoelectric materials. However, the piezoelectric property of BCTZ-based ceramics are still lower than that of commercial lead-based ceramics. Therefore, Sn elements are doped in (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1-_xSn_x)O₃ (x = 0.02-0.07) ceramics to improve their piezoelectric property in this work. First, all ceramics exhibit a pure perovskite structure without any secondary phase. Furthermore, orthorhombic and tetragonal phases coexist at room temperature for all counterparts. Second, all ceramics display a dense microstructure. And the grain size gradually increases with Sn content increasing. The crystal structure of x=0.04 ceramic locates in morphotropic phase boundary. Meanwhile, the x=0.04 ceramic exhibits the most dense microstructure. Hence, x=0.04 ceramic has the best piezoelectric property with d₃₃ = 590 pC•N ^-1, k_p = 52.2%, tanδ = 0.016, ε ^T₃₃= 5372, d ^*₃₃= 734 pm•V ^-1, and IR = 57.8 GΩ•cm. This work demonstrates that the Sn-doped BCZT based lead-free piezoelectric ceramics could be applied in transducers, electromechanical sensors and actuators.

Key words: (BaCa)(TiZr)O₃ based lead-free piezoceramics, Sn doping, morphotropic phase boundary, grain size effect

中图分类号:

TQ174

王新健, 朱逸璇, 张鹏, 杨文龙, 王挺, 郇宇. (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1-_xSn_x)O₃无铅压电陶瓷的相结构与压电性能[J]. 无机材料学报, 2022, 37(5): 513-519.

WANG Xinjian, ZHU Yixuan, ZHANG Peng, YANG Wenlong, WANG Ting, HUAN Yu. Phase Structure and Piezoelectric Property of (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1-_xSn_x)O₃ Lead-free Piezoceramics[J]. Journal of Inorganic Materials, 2022, 37(5): 513-519.

图/表 8

图1 BCZTSn陶瓷样品表面的SEM照片

Fig. 1 SEM images of the surface of BCZTSn ceramic samples (a) x=0.02; (b) x=0.03; (c) x=0.04; (d) x=0.05; (e) x=0.06; (f) x=0.07

图2 BCZTSn陶瓷样品的(a)XRD图谱和(b)局位放大图

Fig. 2 (a) XRD patterns of BCZTSn ceramic samples and (b) partial magnified views

图3 BCZTSn陶瓷样品的XRD精修结果

Fig. 3 XRD rietveld refinements of BCZTSn ceramic samples (a) x=0.02; (b) x=0.03; (c) x=0.04; (d) x=0.05; (e) x=0.06; (f) x=0.07

表1 BCZT陶瓷样品的晶格参数

Table 1 Lattice parameters of BCZTSn ceramic samples

Sample	Lattice parameter							Phase ratio/%		R_wp/%
	Tetragonal phase				Orthorhombic phase
	a/nm	c/nm	V/nm³	c/a	a/nm	b/nm	c/nm	Tetragonal phase	Orthorhombic phase
x=0.02	0.39986	0.40071	0.06406	1.0021	0.39968	0.56622	0.56836	35	65	7.48
x=0.03	0.39982	0.40070	0.06405	1.0022	0.39949	0.56638	0.56771	37	63	5.91
x=0.04	0.39970	0.40069	0.06401	1.0024	0.39950	0.56597	0.56789	47	53	9.08
x=0.05	0.39909	0.40000	0.06370	1.0022	0.39989	0.56565	0.56669	47	53	6.49
x=0.06	0.39929	0.39960	0.06370	1.0007	0.39935	0.56606	0.56680	54	46	7.61
x=0.07	0.39901	0.39981	0.06365	1.0002	0.39923	0.56707	0.56528	58	42	7.94

图4 BCZTSn陶瓷样品的介电温谱和相转变温度图

Fig. 4 Temperature dielectric spectra and phase transition temperature diagram of BCZTSn ceramic samples (a) Temperature dielectric spectra; (b) Phase transition temperature diagram Colorful figures are available on website

图5 BCZTSn陶瓷样品的电滞回线以及数据汇总

Fig. 5 P-E hysteresis loops of BCZTSn ceramic samples (a) P-E hysteresis loops at 1 Hz; (b) Data summary of Pmax, Pr and Ec Colorful figures are available on website

图6 BCZTSn陶瓷样品的应力-应变曲线

Fig. 6 S-E curves of BCZTSn ceramic samples (a) Bipolar S-E curves; (b) Unipolar S-E curves Colorful figures are available on website

表2 BCZTSn陶瓷样品的基本电学性能

Table 2 Basic electric property of BCZTSn ceramic samples

Component	d₃₃/(pC×N^-1)	k_p/%	tanδ	ε^T₃₃	d^*₃₃/(pm×V^-1)	IR/(GW×cm)
x=0.02	493	45.6	0.019	4773	678	55.5
x=0.03	545	47.5	0.017	5083	729	56.3
x=0.04	590	52.2	0.016	5372	734	57.8
x=0.05	464	42.1	0.018	5152	669	56.8
x=0.06	430	41.3	0.019	5446	660	53.9
x=0.07	364	32.5	0.02	6237	504	53.4

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(Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1-_xSn_x)O₃无铅压电陶瓷的相结构与压电性能

Phase Structure and Piezoelectric Property of (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1-_xSn_x)O₃ Lead-free Piezoceramics

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