通过Bi3+自掺杂增强CaBi4Ti4O15基陶瓷压电性能

doi:10.15541/jim20240537

无机材料学报 ›› 2025, Vol. 40 ›› Issue (6): 719-728.DOI: 10.15541/jim20240537

通过Bi³⁺自掺杂增强CaBi₄Ti₄O₁₅基陶瓷压电性能

周阳阳¹^,²(), 张艳艳¹^,², 于子怡¹, 傅正钱¹, 许钫钫¹, 梁瑞虹¹, 周志勇¹()

1.中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 201899
2.中国科学院大学材料科学与光电工程中心, 北京 100049

收稿日期:2024-12-26 修回日期:2025-02-17 出版日期:2025-06-20 网络出版日期:2025-02-19
通讯作者: 周志勇, 研究员. E-mail: zyzhou@mail.sic.ac.cn
作者简介:周阳阳(1999-), 男, 博士研究生. E-mail: zhouyangyang21@mails.ucas.ac.cn

Enhancement of Piezoelectric Properties in CaBi₄Ti₄O₁₅-based Ceramics through Bi³⁺ Self-doping Strategy

ZHOU Yangyang¹^,²(), ZHANG Yanyan¹^,², YU Ziyi¹, FU Zhengqian¹, XU Fangfang¹, LIANG Ruihong¹, ZHOU Zhiyong¹()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2024-12-26 Revised:2025-02-17 Published:2025-06-20 Online:2025-02-19
Contact: ZHOU Zhiyong, professor. E-mail: zyzhou@mail.sic.ac.cn
About author:ZHOU Yangyang (1999-), male, PhD candidate. E-mail: zhouyangyang21@mails.ucas.ac.cn
Supported by:
National Natural Science Foundation of China(51932010)

摘要/Abstract

摘要：

高温压电振动传感器是高温、复杂振动等严苛环境下用于结构健康监测的首选传感器。具有高居里温度(T_C)的铋层状结构CaBi₄Ti₄O₁₅(CBT)高温压电陶瓷是500 ℃及以上压电振动传感器的核心元件, 但其压电系数d₃₃低, 极大限制了其高温应用。本研究采用独特的Bi³⁺自掺杂策略, 提高了CBT压电陶瓷内部晶界数量, 增加了空间电荷的聚集位点, 促进了空间电荷极化的形成。进一步地, 基于空间电荷极化主要在低频下产生的特性, 利用不同频率介电温谱阐明了空间电荷极化提升CBT压电陶瓷压电性能的重要机制。最终获得了综合性能优异的CBT基高温压电陶瓷: T_C高达778 ℃; d₃₃提高了30%以上, 达到20.1 pC/N; 电阻率提高了1个数量级(在500 ℃下达到6.33×10⁶ Ω·cm)。本工作为500 ℃及以上压电振动传感器的实际应用提供了性能优异的关键功能材料。

关键词: 高温压电陶瓷, 铋层状结构, 自掺杂, 空间电荷极化, 氧空位

Abstract:

High-temperature piezoelectric vibration sensors are the preferred choice for structural health monitoring in harsh environments such as high temperatures and complex vibrations. Bismuth layer-structured CaBi₄Ti₄O₁₅ (CBT) high-temperature piezoelectric ceramics, with high Curie temperature (T_C), are the key components for piezoelectric vibration sensors operating at temperatures exceeding 500 ℃. However, their low piezoelectric coefficient (d₃₃) greatly limits their high-temperature applications. In this work, a novel Bi³⁺ self-doping strategy was employed to enhance the piezoelectric performance of CBT ceramics. The enhancement is attributed to an increase in the number of grain boundaries, providing more sites for space charge accumulation and promoting formation of space charge polarization. Furthermore, given that space charge polarization predominantly occurs at low frequencies, dielectric temperature spectra at different frequencies were used to elucidate the mechanism by which space charge polarization enhances piezoelectric properties of CBT ceramics. Excellent overall performance was achieved for the CBT-based high-temperature piezoelectric ceramics. Among them, T_C reached 778 ℃, d₃₃ increased by more than 30%, reaching 20.1 pC/N, and the electrical resistivity improved by one order of magnitude (reaching 6.33×10⁶ Ω·cm at 500 ℃). These advancements provide a key functional material with excellent performance for practical applications of piezoelectric vibration sensors at 500 ℃ and above.

Key words: high-temperature piezoelectric ceramic, bismuth layer structure, self-doping, space charge polarization, oxygen vacancy

中图分类号:

O482

周阳阳, 张艳艳, 于子怡, 傅正钱, 许钫钫, 梁瑞虹, 周志勇. 通过Bi³⁺自掺杂增强CaBi₄Ti₄O₁₅基陶瓷压电性能[J]. 无机材料学报, 2025, 40(6): 719-728.

ZHOU Yangyang, ZHANG Yanyan, YU Ziyi, FU Zhengqian, XU Fangfang, LIANG Ruihong, ZHOU Zhiyong. Enhancement of Piezoelectric Properties in CaBi₄Ti₄O₁₅-based Ceramics through Bi³⁺ Self-doping Strategy[J]. Journal of Inorganic Materials, 2025, 40(6): 719-728.

图/表 8

Fig. 1 (a-e) Surface SEM images of CBT-xBi ceramics after thermal etching; (f) XRD patterns of CBT-xBi ceramics and corresponding localized enlarged patterns (a) x=0; (b) x=0.02; (c) x=0.04; (d) x=0.06; (e) x=0.08

Fig. 2 Dielectric properties of CBT-xBi ceramics (a-c) Dielectric constant as a function of temperature at different frequencies after polarization: (a) x=0, (b) x=0.04 and (c) x=0.06; (d-f) Dielectric constant as a function of temperature at 100 Hz before and after polarization: (d) x=0, (e) x=0.04 and (f) x=0.06

Fig. 3 XPS core-level spectra of CBT-xBi ceramics (a) O1s; (b) Bi4f; (c) Bi4d3/2 and Ti2p

Table 1 Results of CBT-xBi ceramics O1s XPS peak fitting analysis

x	S₁ (Oxygen vacancy area)	S₂ (Lattice oxygen area)	S (Total area, S₁+S₂)	S₁/S₂	S₁/S
0	5581.86	23546.90	29128.76	0.24	0.19
0.04	5635.40	28758.79	34394.19	0.20	0.16
0.06	5078.49	27836.63	32915.12	0.18	0.15
0.06 (Oxygen sintering)	3969.83	24463.16	28432.99	0.16	0.14

Fig. 4 Characterization of CBT-0.06Bi ceramic sintered in a flowing oxygen atmosphere (a) XRD patterns; (b) SEM image of the thermal etching surface; (c) O1s XPS spectrum; (d) Dielectric temperature spectra at 100 Hz before and after polarization

Fig. 5 (a) Dielectric temperature spectra of CBT-xBi ceramics; (b) Temperature dependence of DC resistivity of CBT-xBi ceramics; (c) Effect of heat treatment on the piezoelectric constants of CBT-xBi ceramics (set temperature annealing 2 h); (d) In-situ XRD patterns of CBT-0.06Bi ceramic; (e) Relationship between lattice constants and unit cell volume with temperature; (f) (119) peak position and I(200)/I(020) changed with temperature

Fig. 6 (a) XRD refinement results of CBT-xBi ceramics; (b) Visual crystal structures of CBT-xBi ceramics; (c) Raman scattering spectra in the range of 80-900 cm-1; (d) Wavenumber displacements of B2g, B3g, A1g, and B1g modes

Fig. 7 PFM characterization of CBT-xBi ceramics (a-c) PFM phase images for (a) x=0, (b) x=0.04, and (c) x=0.06; (d-f) PFM amplitude distribution histograms for (d) x=0, (e) x=0.04, and (f) x=0.06; (g) TEM image of CBT-0.06Bi; (h) 5 μm×5 μm PFM phase image of CBT-0.06Bi; (i) Hysteresis loops of CBT-xBi ceramics after polarizing at 180 ℃ and 1 Hz. Colorful figures are available on website

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通过Bi³⁺自掺杂增强CaBi₄Ti₄O₁₅基陶瓷压电性能

Enhancement of Piezoelectric Properties in CaBi₄Ti₄O₁₅-based Ceramics through Bi³⁺ Self-doping Strategy

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