Zr4+掺杂对钛酸钡基热释电陶瓷性能的影响
Effect of Zr4+ Doping on the Properties of Barium Titanate-Based Pyroelectric Ceramics
DOI: 10.12677/ms.2026.167157, PDF,   
作者: 潘昊昱：浙江师范大学工学院，浙江 金华
关键词: 热释电陶瓷；热释电性能；离子掺杂；Pyroelectric Ceramics； Pyroelectric Property； Ion Doping
摘要: 我国低品位波动性余热资源丰富，但传统热电技术难以高效利用。热释电技术可直接将温度波动转化为电能，极具回收潜力。然而，现有高性能热释材料存在成本高、污染大、对随机热源适应性差等核心瓶颈。为开发高性能环保无铅热释电材料，研究以钛酸锶钡(BST)陶瓷为基底，选用Zr4+作为掺杂离子，采用传统固相反应法进行制备，并通过铁电性能测试、介电温谱测试及热释电系数测试等方法，系统研究Zr4+掺杂量对陶瓷铁电性能、介电性能及热释电性能的影响规律。结果表明，适量掺杂能够有效调节居里温度并改善介电温度稳定性，显著提升热释电系数。其中，Zr4+掺杂量为0.06 mol%的BSZT陶瓷在Olsen循环和Stirling循环下的峰值能量密度分别达到296.4 mJ/cm³和106.0 mJ/cm³，较无Zr4+体系有明显提升。该研究结果为高性能无铅热释电陶瓷的组分设计与工艺优化提供了实验依据。
Abstract: China is rich in low-grade fluctuating waste heat resources, yet traditional thermoelectric technologies struggle to utilize them efficiently. Pyroelectric technology can directly convert temperature fluctuations into electric energy, which has great recovery potential. However, the existing high-performance pyroelectric materials have the core bottlenecks of high cost, high pollution, and poor adaptability to random heat sources. In order to develop lead-free pyroelectric materials with high performance and environmental protection, barium strontium titanate (BST) ceramics were prepared by the traditional solid-state reaction method with Zr4+ as the doping ion. The effects of Zr4+ doping amount on the ferroelectric, dielectric, and pyroelectric properties of the ceramics were systematically studied by means of ferroelectric properties test, dielectric temperature spectrum test, and pyroelectric coefficient test. The results show that proper doping can effectively adjust the Curie temperature, improve the dielectric temperature stability, and significantly increase the pyroelectric coefficient. Among them, the peak energy density of BSZT ceramics doped with 0.06 mol% Zr4+ reached 296.4 MJ/cm and 106.0 MJ/cm under the Olsen cycle and the Stirling cycle, respectively, which was obviously improved compared with the system without Zr4+. The research results provide an experimental basis for composition design and process optimization of high-performance lead-free pyroelectric ceramics.
文章引用：潘昊昱. Zr4+掺杂对钛酸钡基热释电陶瓷性能的影响[J]. 材料科学, 2026, 16(7): 72-80. https://doi.org/10.12677/ms.2026.167157

参考文献

[1] 杨步云, 刘云, 熊彦翀. 碳中和愿景下超低品位余热回收利用技术分析[J]. 广州化工, 2025, 53(16): 127-129.
[2] 王驿凯, 赵栋霖, 杨曙川, 等. 区域能源系统中热泵储能技术研究与应用综述[J]. 东南大学学报(自然科学版), 2025, 55(3): 839-848.
[3] Cao, T., Shi, X.L. and Chen, Z.G. (2023) Advances in the Design and Assembly of Flexible Thermoelectric Device. Progress in Materials Science, 131, Article 101003. [Google Scholar] [CrossRef] 
[4] 张金平. 无铅铁电陶瓷的晶格振动及电子跃迁特性研究[D]: [博士学位论文]. 上海: 华东师范大学, 2014.
[5] Wang, Y., Yang, L., Shi, X., Shi, X., Chen, L., Dargusch, M.S., et al. (2019) Flexible Thermoelectric Materials and Generators: Challenges and Innovations. Advanced Materials, 31, Article 1807916. [Google Scholar] [CrossRef] [PubMed]
[6] Olsen, R.B., Bruno, D.A., Briscoe, J.M. and Jacobs, E.W. (1985) Pyroelectric Conversion Cycle of Vinylidene Fluoride-Trifluoroethylene Copolymer. Journal of Applied Physics, 57, 5036-5042. [Google Scholar] [CrossRef] 
[7] Zhang, D., Wu, H., Bowen, C.R. and Yang, Y. (2021) Recent Advances in Pyroelectric Materials and Applications. Small, 17, Article 2103960. [Google Scholar] [CrossRef] [PubMed]
[8] Srikanth, K.S., Singh, V.P. and Vaish, R. (2018) Pyroelectric Performance of Porous Ba0.85Sr0.15Tio3 Ceramics. International Journal of Applied Ceramic Technology, 15, 140-147. [Google Scholar] [CrossRef] 
[9] Pandya, S., Wilbur, J., Kim, J., Gao, R., Dasgupta, A., Dames, C., et al. (2018) Pyroelectric Energy Conversion with Large Energy and Power Density in Relaxor Ferroelectric Thin Films. Nature Materials, 17, 432-438. [Google Scholar] [CrossRef] [PubMed]
[10] 李佳妮. 四方PMN-PT及Mn掺杂单晶的畴结构与热释电性能研究[D]: [硕士学位论文]. 上海: 上海师范大学, 2024.
[11] Wei, Y., Wang, X., Zhu, J., Wang, X. and Jia, J. (2013) Dielectric, Ferroelectric, and Piezoelectric Properties of BiFeO3-BaTiO3 Ceramics. Journal of the American Ceramic Society, 96, 3163-3168. [Google Scholar] [CrossRef] 
[12] 余文孜. Ba1-xSrxTiO3基无铅铁电陶瓷电卡效应研究[D]: [硕士学位论文]. 重庆: 西南大学, 2023.
[13] Kishore, R.A. and Priya, S. (2018) A Review on Low-Grade Thermal Energy Harvesting: Materials, Methods and Devices. Materials, 11, 1433-1445. [Google Scholar] [CrossRef] [PubMed]
[14] Cohen, R.E. (1992) Origin of Ferroelectricity in Perovskite Oxides. Nature, 358, 136-138. [Google Scholar] [CrossRef] 
[15] Roundy, S., Wright, P.K. and Rabaey, J. (2003) A Study of Low Level Vibrations as a Power Source for Wireless Sensor Nodes. Computer Communications, 26, 1131-1144. [Google Scholar] [CrossRef] 
[16] Davis, W.R., Zhang, N., Camera, K., Markovic, D., Smilkstein, T., Ammer, M.J., et al. (2002) A Design Environment for High-Throughput Low-Power Dedicated Signal Processing Systems. IEEE Journal of Solid-State Circuits, 37, 420-431. [Google Scholar] [CrossRef] 
[17] Mondal, R., Hasan, M.A.M., Baik, J.M. and Yang, Y. (2023) Advanced Pyroelectric Materials for Energy Harvesting and Sensing Applications. Materials Today, 66, 273-301. [Google Scholar] [CrossRef] 
[18] Li, X., Lu, S., Chen, X., Gu, H., Qian, X. and Zhang, Q.M. (2013) Pyroelectric and Electrocaloric Materials. Journal of Materials Chemistry C, 1, 23-37. [Google Scholar] [CrossRef] 
[19] Wang, Q., Bowen, C.R., Lewis, R., Chen, J., Lei, W., Zhang, H., et al. (2019) Hexagonal Boron Nitride Nanosheets Doped Pyroelectric Ceramic Composite for High-Performance Thermal Energy Harvesting. Nano Energy, 60, 144-152. [Google Scholar] [CrossRef] 
[20] Lheritier, P., Torelló, A., Usui, T., Nouchokgwe, Y., Aravindhan, A., Li, J., et al. (2022) Large Harvested Energy with Non-Linear Pyroelectric Modules. Nature, 609, 718-721. [Google Scholar] [CrossRef] [PubMed]
[21] Zhou, X., Gong, H., Zhang, J., Liu, J., Zhang, D. and Zhang, Y. (2025) Pore Structure-Dependent Pyroelectric Properties of Porous PZT Ceramics Fabricated by Template Method. Journal of Materials Chemistry A, 13, 40689-40697. [Google Scholar] [CrossRef] 
[22] Meng, Y., Zhao, Y. and Liu, Z. (2023) Enhanced Pyro-/Photo Catalysis of the Pyroelectric PZT/CDS Heterostructure for Dye Decomposition Driven by Visible Light and Cold-Hot Cycles. Ceramics International, 49, 31144-31151. [Google Scholar] [CrossRef] 
[23] Ngo, N.C.T., Sugiyama, H., Sodige, B.A.K., Wiff, J.P., Yamanaka, S., Kim, Y., et al. (2022) Enhancing Low‐Temperature Energy Harvesting by Lead‐Free Ferroelectric Ba(Zr0.1Ti0.9)O3. Journal of the American Ceramic Society, 106, 201-212. [Google Scholar] [CrossRef] 
[24] Qiu, K. and Hayden, A.C.S. (2014) Direct Thermal to Electrical Energy Conversion Using Very Low Bandgap TPV Cells in a Gas-Fired Furnace System. Energy Conversion and Management, 79, 54-58. [Google Scholar] [CrossRef] 

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