TiO2与MnO2复合掺杂Ca0.8(Li0.1Ce0.03Bi0.07)Bi2Nb2O9压电陶瓷优化电学性能
Optimization of Electrical Properties of Ca0.8(Li0.1Ce0.03Bi0.07)Bi2Nb2O9 Piezoelectric Ceramics Doped with TiO2 and MnO2 Composite
摘要: CaBi2Nb2O9(CBNO)压电陶瓷作为一种典型的铋层状结构铁电体，居里温度高达940℃，在高温压电领域展现出巨大的应用潜力，但由于压电性能较低限制了其实际应用。为提升CBNO的电学性能，本文以Ca0.8(Li0.1Ce0.03Bi0.07)Bi2Nb2O9为基体，引入TiO2和MnO2作为掺杂剂取代Nb5+进行多离子复合掺杂改性，采用固相反应法制备得到Ca0.8(Li0.1Ce0.03Bi0.07)Bi2Nb1.99−x(TixMn0.01)O9 (x = 0, 0.01, 0.02, 0.03)，通过多种表征和测试系统探究TiO2和MnO2对陶瓷烧结特性、晶体结构以及电学性能的影响机制。研究表明，适量的TiO2和MnO2复合掺杂可使离子进入晶格占据B位形成稳定的固溶体，引发晶体结构的四方畸变，有效降低陶瓷的烧结温度，在一定程度上抑制了Bi2O3的挥发，并显著促进了晶粒生长，同时还削弱了氧空位对畴壁的钉扎效应，促进铁电畴翻转，使CBNO综合性能得到有效提升。在x = 0.02时，CBNO表现出最佳的综合性能，剩余极化强度为8.0 uC/cm2，机械品质因数为1500，平面机电耦合系数达到12.0%，居里温度为916℃压电系数由17.6 pC/N提升至20.1 pC/N，提升了约14%，且经800℃退火30 min后，仍有18.4 pC/N，仅下降了9%，展现出良好的热稳定性。本文通过实验确立了最佳掺杂范围，实现了CBNO压电陶瓷电学性能的有效改善，为高性能压电陶瓷的设计提供了实验依据和理论指导。
Abstract: CaBi2Nb2O₉ (CBNO) piezoelectric ceramics, as typical bismuth layer-structured ferroelectrics, possess an ultrahigh Curie temperature of 940˚C, showing great potential for high-temperature piezoelectric applications. However, their practical use is limited by relatively low piezoelectric performance. To enhance the electrical properties, this work adopts Ca0.8(Li0.1Ce0.03Bi0.07)Bi2Nb2O9 as the matrix and introduces TiO2 and MnO2 as co-dopants to substitute for Nb5+ at the B‑site through a multi-ion doping strategy. A series of Ca0.8(Li0.1Ce0.03Bi0.07)Bi2Nb1.99−x(TixMn0.01)O9 (x = 0, 0.01, 0.02, 0.03) ceramics were fabricated by a solid-state reaction method. Systematic characterizations were conducted to investigate the effects of TiO2 and MnO2 co-doping on the sintering behavior, crystal structure, and electrical properties. The results indicate that an appropriate amount of TiO2 and MnO2 co-doping enables the dopant ions to enter the lattice and occupy B‑sites, forming a stable solid solution that induces a tetragonal distortion of the crystal structure. This significantly lowers the sintering temperature, suppresses the volatilization of Bi2O3 to a certain extent, and markedly promotes grain growth. Meanwhile, the co-doping weakens the pinning effect of oxygen vacancies on domain walls and facilitates ferroelectric domain switching, leading to an overall improvement in the performance of CBNO ceramics. At x = 0.02, the ceramic exhibits the optimum comprehensive properties: a remnant polarization of 8.0 μC/cm2, a mechanical quality factor of 1500, a planar electromechanical coupling coefficient of 12.0%, a Curie temperature of 916˚C, and a piezoelectric coefficient enhanced from 17.6 pC/N to 20.1 pC/N (an increase of ~14%). After annealing at 800˚C for 30 min, the piezoelectric coefficient remains 18.4 pC/N with only a 9% drop, demonstrating excellent thermal stability. This study experimentally establishes the optimal doping range and achieves effective enhancement of the electrical properties of CBNO piezoelectric ceramics, thereby providing experimental evidence and theoretical guidance for the design of high-performance piezoelectric ceramics.
文章引用：黄靖, 马家峰. TiO2与MnO2复合掺杂Ca0.8(Li0.1Ce0.03Bi0.07)Bi2Nb2O9压电陶瓷优化电学性能[J]. 物理化学进展, 2026, 15(3): 190-201. https://doi.org/10.12677/japc.2026.153019

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