硅酸盐学报

La/Ce共掺对CaBi₄Ti₄O₁₅高温压电陶瓷电性能的影响

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贺菁菁 ¹ , 李威 ¹ , 姚赟峰 ² , 沈超 ² , 盛林生 ¹ , 郑鹏 ³ , 白王峰 ⁴

硅酸盐学报 | 研究论文 2026,54(6): 1963-1972

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硅酸盐学报 |研究论文 2026 , 54 (6) : 1963 -1972

La/Ce共掺对CaBi₄Ti₄O₁₅高温压电陶瓷电性能的影响

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贺菁菁¹, 李威¹, 姚赟峰², 沈超², 盛林生¹, 郑鹏³, 白王峰⁴

作者信息

^1．嘉兴南湖学院信息工程学院，浙江嘉兴 314001

^2．嘉兴南湖学院机电工程学院，浙江嘉兴 314001

^3．杭州电子科技大学电子科学与技术系纳米电子学与纳电子器件实验室，杭州 310018

^4．杭州电子科技大学，传感器新型材料浙江省重点实验室，杭州 310012

通讯作者:

盛林生（1993—），男，硕士，助理实验师。

作者简介:

贺菁菁（1987—），女，博士，讲师。

Effect of La/Ce Co-Doping on Electrical Properties of CaBi₄Ti₄O₁₅ High-Temperature Piezoelectric Ceramics

Jingjing HE¹, Wei LI¹, Yunfeng YAO², Chao SHEN², Linsheng SHENG¹, Peng ZHENG³, Wangfeng BAI⁴

Affiliations

^1.College of Information Engineering, Jiaxing Nanhu University, Jiaxing 314001, China

^2.School of Mechanical and Electrical Engineering, Jiaxing Nanhu University, Jiaxing 314001, Zhejiang, China

^3.Lab for Nanoelectronics and Nanoelectronic Devices, Department of Electronics Science and Technology, Hangzhou Dianzi University, Hangzhou 310018, China

^4.Key Laboratory of Novel Materials for Sensor of Zhejiang Province, Hangzhou Dianzi University, Hangzhou 310012, China

Corresponding Author:

{SHENG} Linsheng (1993-), male, Master, Assistant Experimentalist. E-mail: shenglinsheng@jxnhu.edu.cn

HE Jingjing (1987-), female, Ph.D., Lecturer. E-mail: hejingjing@whu.edu.cn

出版时间: 2026-05-12 doi: 10.14062/j.issn.0454-5648.20250544

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摘要

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钛酸铋钙（CaBi₄Ti₄O₁₅，CBT）因其高的居里温度（约790 ℃），在高温无铅压电陶瓷中具有良好应用前景；然而，其压电性能常因Bi挥发导致缺陷及极化困难而受到限制。为解决这一问题，本研究采用La与Ce共掺策略，通过固相反应法合成了CBT基高温压电陶瓷，并系统探究了掺杂对晶体结构、缺陷行为及电学性能的调控机制。结果表明，La/Ce共掺不仅改善了陶瓷的晶体结构，还有效抑制了Bi的挥发，从而显著增强了压电性能。最优组分x = 0.075样品居里温度保持在791 ℃的同时，d₃₃提升至19 pC/N，电阻率与介电损耗亦显著改善。研究表明，A位稀土双离子掺杂策略能够有效突破CBT陶瓷性能瓶颈，推动其在高温压电器件中的应用。

关键词

无铅压电陶瓷 / 钛酸铋钙 / 镧铈共掺杂 / 高温性能

Abstract

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Introduction

Piezoelectric ceramics are widely used in the fields such as electronics, telecommunications, sensing, and acoustic due to their capability for bidirectional conversion between electrical and mechanical energy. The existing lead zirconate titanate ceramics dominate a wide range of practical applications due to their excellent piezoelectric properties and good manufacturability. However, lead is toxic to human-being health and environment during the processing, application, and disposal. Furthermore, their low Curie temperature (T_C<400 ℃) limits their application potential in the field of high temperature environment. CaBi₄Ti₄O₁₅ (CBT) is one of the piezoceramics with the T_C of < 790 ℃ and high thermal stability, which makes it a leading candidate for high-temperature applications. The potential ultrahigh temperature employment of CBT-based ceramics is, nevertheless, constrained by a low piezoelectric coefficient (d₃₃ < 10 pC/N), small dielectric constant, and poor poling capability. It is difficult to fully pole these ceramics in high electric fields because the volatilization of Bi during high-temperature sintering results in a stoichiometric deviation, a higher density of lattice defects, and reduced electrical resistivity. Recently, numerous researchers use chemical doping strategy to tailor the crystal structure and modify microdefects, yielding an initial success. The A-site doping of rare-earth ions (e.g., Er³⁺, Nd³⁺, and Ce³⁺) or alkali metal ions (e.g., Na⁺, K⁺, and Li⁺) is a practical way of improving the piezoelectric property via suppressing Bi volatilization, inducing lattice distortion and tailoring densification. According to some previous reports, rare-earth element doping promotes the d₃₃ of CBT-based ceramics to 20 pC/N. It is reported that Nd/Ce co-doping substantially elevates the d₃₃ to 28 pC/N in Na_0.5Bi_4.5Ti₄O₁₅, demonstrating that synergistic rare-earth element co-doping plays a critical role in enhancing crystal structure stability and defect control. Despite the promising progress of rare-earth element doping in bismuth layer-structured ferroelectrics, there is still little systematic research regarding the synergistic mechanisms of La/Ce co-doping in regulating the microstructure and piezoelectric properties of CBT ceramics. La³⁺ can incorporate into the A-site in CBT-based ceramics due to the similar ionic radius of La³⁺ and Bi³⁺, enhancing the lattice stability. Meanwhile, Ce can reduce oxygen vacancy concentration by charge compensation mechanism and improve densification. The synergistic interaction between them can boost polarization and piezoelectric property. In this work, CBT-based ceramics with La/Ce co-doping were prepared via conventional solid-state reaction. Moreover, the effect of doping concentration on the crystal structure, microstructure, and various electrical properties, including dielectric, ferroelectric, and piezoelectric characteristics was systematically investigated.

Methods

Ca(La_1/2Ce_1/2)_xBi_4-_xTi₄O₁₅(CLaCe-x, x = 0.000, 0.025, 0.050, 0.075, 0.100) ceramics were synthesized via solid-state reaction. The raw materials were CaCO₃(99.99%)、Bi₂O₃(99.99%)、TiO₂(99.8%)、CeO₂(99.99%) and La₂O₃(99.99%). First, all the starting materials were weighed according to different stoichiometric ratios and ground in a ball mill with alcohol for 12 h. Then, the wet slurries were dried at 80 ℃ and calcined at 82 ℃ for 4 h. Afterwards, the powder was further ground. Consecutively, the dried powder with 0.5% polyvinyl alcohol was pressed into discs with a thickness of 0.7 mm and a diameter of 12 mm. The pellets were sintered at 1025-1075 ℃ for 1 h.

Results and discussion

An improved piezoelectric coefficient of 19 pC/N is obtained, along with an outstanding Curie temperature of 791 ℃ can be achieved in the ceramic. The XRD patterns and SEM images confirm that all the ceramics show a pure single phase, indicating that La/Ce ions are dissolved into the original crystal lattice. Furthermore, the influence of doping ions on the grain size is negligible. The co-doping bigger radius ions at the A-site induce the expansion of lattice, which can improve the crystal structure. The dielectric loss of the ceramic is reduced, and its impedance is increased by over one order of magnitude at a high temperature due to this structure modification. The activation energy is calculated with the Arrhenius relation, manifesting that the oxygen vacancy concentration can reduce. Consequently, the ceramic resistivity is a boosted result from a lower concentration of hole carriers. This improved resistivity facilitates the poling process in high electric fields, leading to a sharp increase in the piezoelectric coefficient. Subsequently, P-E hysteresis loops are measured at 100 ℃. The CLaCe-0.075 ceramic exhibits a larger remanent polarization (P_r) than pure CBT, which is consistent with the enhancement in piezoelectric property. In summary, the La/Ce co-doping ceramics demonstrate the superior d₃₃, T_C, resistivity, and thermal stability, compared to most bismuth-layered piezoelectric ceramics. This work confirms that the rare-earth element co-doping is an efficient strategy for elevating the electrical performance of CBT-based ferroelectrics.

Conclusions

La/Ce co-doping CBT ceramics were fabricated via a solid-state reaction. The effect of rare-earth element doping on the structure and properties of bismuth-layered ceramics was systematically investigated. The results revealed that the ceramics remained phase-pure Aurivillius structures with a high relative density and a negligible variation in grain size. The high d₃₃ of 19 pC/N and T_C of 791 ℃ of the CLaCe-0.075 ceramic were achieved. In addition, the dielectric loss reduced to 1.62%, and the resistivity increased to 2.4 × 10⁸ Ω·cm at 400 ℃. The impedance spectroscopy analysis revealed that La/Ce co-doping effectively inhibited Bi volatilization, leading to a reduced oxygen vacancy concentration, which was responsible for the enhanced piezoelectric property. This work demonstrated that La/Ce co-doping could be an effective strategy for enhancing piezoelectric property of bismuth layer-structured ferroelectrics, providing valuable insights for the development of novel high-temperature piezoelectric materials.

Key words

lead-free piezoelectric ceramics / calcium bismuth titanate / lanthanum/cerium co-doping / high-temperature performance

引用本文

贺菁菁, 李威, 姚赟峰, 沈超, 盛林生, 郑鹏, 白王峰. La/Ce共掺对CaBi₄Ti₄O₁₅高温压电陶瓷电性能的影响. 硅酸盐学报, 2026 , 54 (6) : 1963 -1972 . DOI: 10.14062/j.issn.0454-5648.20250544

Jingjing HE, Wei LI, Yunfeng YAO, Chao SHEN, Linsheng SHENG, Peng ZHENG, Wangfeng BAI. Effect of La/Ce Co-Doping on Electrical Properties of CaBi₄Ti₄O₁₅ High-Temperature Piezoelectric Ceramics[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (6) : 1963 -1972 . DOI: 10.14062/j.issn.0454-5648.20250544

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嘉兴市科技计划公益性研究专项(2025CGZ047)

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2026年第54卷第6期

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doi: 10.14062/j.issn.0454-5648.20250544

接收时间：2025-07-10
首发时间：2026-10-22
出版时间：2026-05-12

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收稿日期：2025-07-10
修回日期：2025-09-09

基金

嘉兴市科技计划公益性研究专项(2025CGZ047)

作者信息

^1．嘉兴南湖学院信息工程学院，浙江嘉兴 314001

^2．嘉兴南湖学院机电工程学院，浙江嘉兴 314001

^3．杭州电子科技大学电子科学与技术系纳米电子学与纳电子器件实验室，杭州 310018

^4．杭州电子科技大学，传感器新型材料浙江省重点实验室，杭州 310012

通讯作者:

盛林生（1993—），男，硕士，助理实验师。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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