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Bi4Ti3O12铋层状压电陶瓷的A/B位掺杂及其电学性能

张家维1,2, 陈宁1, 程原2, 王博2, 朱建国1, 金城2   

  1. 1.四川大学 材料科学与工程学院,成都 610065;
    2.成都凯天电子股份有限公司,成都 610083
  • 收稿日期:2024-11-13 修回日期:2025-01-08
  • 通讯作者: 朱建国,教授.E-mail: nic0400@scu.edu.cn; 金城,高级工程师. E-mail: jin_int@163.com
  • 作者简介:张家维(1999-),男,硕士研究生.E-mail: 2451220096@qq.com
  • 基金资助:
    国家自然科学基金(51932010); 四川省科技项目(2023YFG0042)

Structure and Electrical Properties of High-Temperature Bismuth Layered Piezoelectric Bi4Ti3O12 Ceramics

ZHANG Jiawei1,2, CHEN Ning1, CHENG Yuan2, WANG Bo2, ZHU Jianguo1, JIN Cheng2   

  1. 1. College of Material Science and Engineering, Sichuan University, Chengdu 610065, China;
    2. AVIC Chengdu CAIC Electronics CO., LTD, Chengdu 610083, China
  • Received:2024-11-13 Revised:2025-01-08
  • Contact: ZHU Jianguo, Professor. E-mail: nic0400@scu.edu.cn; JIN Cheng, Senior Engineer. E-mail: jin_int@163.com
  • About author:ZHANG Jiawei(1999-), male, Master Candidate.E-mail: 2451220096@qq.com
  • Supported by:
    National Natural Science Foundation of China(51932010); The Sichuan Province Science and Technology Plan(2023YFG0042)

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摘要： 近年来,随着航天、航空和核能领域的快速发展,对能够在450 ℃及以上温度正常工作的压电陶瓷材料的需求日益迫切。钛酸铋(Bi4Ti3O12,简写BIT)是铋层状结构铁电陶瓷中具有较高居里温度(TC~650 ℃)的压电陶瓷,是能够在高温环境下工作的候选压电陶瓷之一。但是纯相BIT陶瓷压电系数和高温电阻率较低,阻碍了其在高温环境下的应用。本工作采用固相反应法制备了A位Ce离子和B位W/Ta/Sb离子共同取代的Bi4Ti3O12基压电陶瓷(简记为BCTWTaS-100x,x=0-0.04),系统研究了Ce掺杂对Bi4Ti3O12基陶瓷结构和电学性能的影响。引入Ce离子造成BIT基陶瓷晶格畸变以及畴结构变化,显著增强了陶瓷的压电性能(x = 0.03时,压电常数d33 = 37 pC/N)。随着离子掺杂浓度的增大,TiO6八面体顶部氧原子的相对位移增大,BIT 基陶瓷的晶格畸变程度相应增加。BCTWTaS-0.03陶瓷具有较高的居里温度(TC = 673 ℃)以及高温电阻率(500 ℃时陶瓷的电阻率保持在106Ω·cm数量级)。此外,该陶瓷还表现出良好的压电系数热稳定性,在 600 ℃退极化2 h后,d33仍能保持其初始值的85%以上。结果表明,BCTWTaS-100x陶瓷在450 ℃以上的高温环境具有很大的应用潜力。

关键词: Bi4Ti3O12, 高居里温度, 压电陶瓷, 晶格畸变

Abstract: In recent years, driven by the rapid development of technologies such as aerospace and nuclear power generation, there is an urgent need for piezoelectric ceramic material capable of operating at temperatures of 450 ℃ and above, served as a piezoelectric sensing element in high-temperature piezoelectric vibration sensors. Bi4Ti3O12, abbreviated as BIT, is a piezoelectric ceramic with a high Curie temperature (TC~650 ℃) within the family of bismuth-layered ferroelectric ceramics, making it a promising candidate for high-temperature applications.However, the inherent low piezoelectric coefficient and low high-temperature resistivity of pure phase BIT ceramics limit their application in such environments. This work used solid-phase reaction method to prepare Bi4Ti3O12-based piezoelectric ceramics with substitutions at A-site by Ce ions and at the B-site by W/Ta/Sb ions(abbreviated as BCTWTaS-100x, where x=0-0.04). The effect of Ce doping on the structure and electrical properties of Bi4Ti3O12 based ceramics was systematically studied.The introduction of Ce ions induces lattice distortion and modifies domain structure of BIT-based ceramics, thereby enhancing their piezoelectric properties (with a piezoelectric constant d33 = 37 pC/N at x = 0.03). With the doping concentration of ions increasing, the relative displacement of oxygen atoms at the apex of TiO6 octahedra increases, resulting in increased lattice distortion within BIT-based ceramic. Furthermore, BCTWTaS-0.03 ceramics demonstrate a high Curie temperature (TC = 673 ℃) and high-temperature resistivity, maintaining resistivity on the order of 106 Ω·cm at 500 ℃. In addition, these ceramics also exhibit good piezoelectric coefficient thermal stability of the piezoelectric coefficient and excellent piezoelectric sensitivity. Notably, after depolarization at 600 ℃ for 2 h, d33 can still maintain over 85% of its initial value. These finds indicate that BCTWTaS-100x ceramics have great potential for application in high-temperature environments exceeding 450 ℃.

Key words: Bi4Ti3O12, high Curie temperature, piezoelectric ceramics, lattice distortion