硅酸盐学报

Bi₂Te₃基热电材料中的声子工程

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刘志愿 ¹^,² , 管希成 ¹ , 李周 ³ , 马妮 ⁴ , 马俊杰 ¹ , 巴倩 ¹ , 夏爱林 ¹ , 晋传贵 ¹

硅酸盐学报 | 综合评述 2024,52(1): 203-217

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硅酸盐学报 |综合评述 2024 , 52 (1) : 203 -217

Bi₂Te₃基热电材料中的声子工程

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刘志愿¹^,², 管希成¹, 李周³, 马妮⁴, 马俊杰¹, 巴倩¹, 夏爱林¹, 晋传贵¹

作者信息

^1．安徽工业大学材料科学与工程学院，安徽马鞍山 243002

^2．安徽工业大学先进金属材料绿色制备与表面技术教育部重点实验室，安徽马鞍山 243002

^3．安徽大学材料科学与工程学院，合肥 230601

^4．中国科学技术大学化学与材料科学学院，合肥 230026

作者简介:

刘志愿（1982—），男，博士，副教授。

Phonon Engineering in Bi₂Te₃-Based Thermoelectric Materials

Zhiyuan LIU¹^,², Xicheng GUAN¹, Zhou LI³, Ni MA⁴, Junjie MA¹, Qian BA¹, Ailin XIA¹, Chuangui JIN¹

Affiliations

^1.School of Materials Science and Engineering, Anhui University of Technology, Ma'anshan 243002, Anhui, China

^2.Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials, Ministry of Education, Anhui University of Technology, Ma'anshan 243002, Anhui, China

^3.School of Materials Science and Engineering, Anhui University, Hefei 230601, China

^4.School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China

LIU Zhiyuan (1982-), male, Ph.D., Associate Professor. E-mail: zhiyuanliu826@ahut.edu.cn

出版时间: 2024-01-20 doi: 10.14062/j.issn.0454-5648.20230333

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摘要

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Bi₂Te₃基合金因其优异的电输运性能和较低热导率在低温区热电材料中备受关注。然而由Bi₂Te₃基合金制造的热电发电或制冷器件转化效率仍较低，因此进一步提升Bi₂Te₃基材料的热电优值zT是关键。由于晶格热导率与电性能参数关联较少，在热电性能参数中较为独立，因此，在不影响电性能的前提下，通过声子工程降低晶格热导率成为提升zT值的重要方法。本文主要综述了近年来通过纳米改性、超晶格结构、纳米复合、掺杂和引入位错阵列等声子工程优化Bi₂Te₃基材料热电性能的主要研究进展。通过这些优化手段可以显著降低材料的比热容、声子群速度或声子平均自由程，Bi₂Te₃基材料的晶格热导率显著降低，热电性能大幅提升，为热电器件的应用提供科学和技术支撑。

关键词

碲化铋基热电材料 / 声子工程 / 晶格热导率 / 热电性能

Abstract

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Bi₂Te₃ based alloys have attracted considerable attention in low-temperature thermoelectric materials due to their superior electrical transport properties and low thermal conductivity. However, the conversion efficiency of thermoelectric power generation or refrigeration devices made of Bi₂Te₃-based alloys is still low. It is thus crucial to further improve the thermoelectric figure of merit zT of Bi₂Te₃ based materials. There are some correlations between lattice thermal conductivity and electrical performance parameter. Reducing the lattice thermal conductivity by phonon engineering becomes an important method to increase zT without deteriorating the electrical performance. This review summarized the main research progress in recent years to optimize the thermoelectric properties of Bi₂Te₃ based materials by phonon engineering, such as nano-modification, superlattice structure, nanocomposing, doping and adding dislocation arrays. The effect of the optimization method on the specific heat capacity, phonon group velocity and phonon mean free path was discussed. The specific heat capacity, phonon group velocity or phonon mean free path of Bi₂Te₃ based materials can be significantly reduced by the optimization methods. As a result, the lattice thermal conductivity of Bi₂Te₃ based materials is significantly reduced, leading to a significant increase in the thermoelectric properties.

Nano-modification: The interface density is increased via low dimensionalization and grain refinement, resulting in an enhanced scattering of low-frequency phonons, reduced phonon mean free path and phonon group velocity, significantly reducing the lattice thermal conductivity. Nowadays, the grain size and morphology of Bi₂Te₃-based alloys can be precisely controlled by mechanical milling, MBE method, hydrothermal method, chemical vapour deposition and wet chemical method. Bi₂Te₃ nanostructures with a ultra-low grain size can be prepared. However, heat conduction cannot be completely prevented even at rather small sizes due to the incomplete suppression of low-frequency phonons. Therefore, it is difficult to improve zT by a single low-dimensionalisation and grain refinement method. The specific surface area can be increased either by combining the phases of different nanostructures to form a heterogeneous interface or by introducing special nanostructures such as twins and nanopores, which can strongly scatter the low-frequency phonons caused by lattice mismatch and lattice vibration, and further reduce the lattice thermal conductivity.

Bi₂Te₃-based superlattice structure: Furthermore, in the microscopic and mesoscopic scales, the superlattice structure generated by artificially controlling the ordered arrangement of atomic layers of Bi₂Te₃-based materials is considered as the optimum candidate material to achieve the 'phonon glass-electron crystal' thermoelectric material standard. Especifically, the quantum well structure in the thin film superlattice produces an intense boundary scattering effect and a quantum confinement effect on phonons, resulting in a decrease in the mean free path and group velocity of phonons, greatly reducing the thermal conductivity of Bi₂Te₃-based thermoelectric materials. The bulk superlattice structure of the Bi₂Te₃-based alloy relies on its complex crystal structure and acousto-optic coupling effect, causing a low cut-off frequency of phonon mode and an intense phonon resonance scattering, and resulting in a low intrinsic thermal conductivity. In addition, the low phonon group velocity caused by chemical bond softening and lattice anharmonicity is also a reason for the low intrinsic thermal conductivity of the bulk superlattice structure of Bi₂Te₃-based alloy.

Nanocomposites, doping modification and dislocation arrays: Nanocomposite and doping modification are the main approaches to improve the thermoelectric properties of Bi₂Te₃-based materials. In the nanocomposite process, the nanoparticles dispersed in the thermoelectric material do not enter the matrix lattice, but attach onto the surface of the matrix grain, forming a heterogeneous interface with the matrix. Also, introducing nanoparticles increases the grain boundary density, resulting in a further scattering of low frequency phonons. Doping modification is achieved by doping elements entering the Bi₂Te₃ lattice, replacing Bi site (or Te site) or entering the van der Waals gap for interstitial doping. This process can introduce multiple scattering centers such as grain boundaries, point defects, in-situ precipitates and dislocations into Bi₂Te₃-based alloy, enhancing a multi-scale scattering of phonons and effectively reducing the mean free path of phonons. Combined with the preparation process such as sintering, the dislocation array is increased, which leads to a higher scattering intensity of intermediate frequency phonons, further reducing the lattice thermal conductivity.

Summary and prospects

The phonon specific heat capacity, phonon group velocity and mean free path of the Bi₂Te₃-based alloy could be effectively controlled by phonon engineering including nano-modification, superlattice structure, nanocomposite, doping and introduction of the dislocation array to achieve a sufficiently low lattice thermal conductivity. The electrical transport properties were optimized by the carrier engineering and energy band engineering techniques, and the synergistic regulation of the electrical and thermal transport properties was realized. As a result, the thermoelectric properties of Bi₂Te₃-based alloys were significantly improved. This provided a scientific and technical support for the application of thermoelectric devices. However, a lot of work remained in improving the thermoelectric properties of Bi₂Te₃ materials by phonon, carrier and energy band engineering. Nevertheless, the large-scale commercialization of Bi₂Te₃-based alloys as thermoelectric materials still attracts much attention. Also, interdisciplinary research in thermoelectricity and other disciplines becomes popular. The future research and large-scale application of Bi₂Te₃ thermoelectric materials are expected.

Key words

bismuth telluride based thermoelectric materials / phonon engineering / lattice thermal conductivity / thermoelectric properties

引用本文

刘志愿, 管希成, 李周, 马妮, 马俊杰, 巴倩, 夏爱林, 晋传贵. Bi₂Te₃基热电材料中的声子工程. 硅酸盐学报, 2024 , 52 (1) : 203 -217 . DOI: 10.14062/j.issn.0454-5648.20230333

Zhiyuan LIU, Xicheng GUAN, Zhou LI, Ni MA, Junjie MA, Qian BA, Ailin XIA, Chuangui JIN. Phonon Engineering in Bi₂Te₃-Based Thermoelectric Materials[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (1) : 203 -217 . DOI: 10.14062/j.issn.0454-5648.20230333

基金

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安徽省优秀青年项目(2208085Y17)
安徽省高校协同创新项目(GXXT-2022-008)
国家自然科学基金(51872006)

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2024年第52卷第1期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230333

接收时间：2023-05-16
首发时间：2026-10-22
出版时间：2024-01-20

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收稿日期：2023-05-16
修回日期：2023-06-10

基金

安徽省优秀青年项目(2208085Y17)

安徽省高校协同创新项目(GXXT-2022-008)

国家自然科学基金(51872006)

作者信息

^1．安徽工业大学材料科学与工程学院，安徽马鞍山 243002

^2．安徽工业大学先进金属材料绿色制备与表面技术教育部重点实验室，安徽马鞍山 243002

^3．安徽大学材料科学与工程学院，合肥 230601

^4．中国科学技术大学化学与材料科学学院，合肥 230026

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230333

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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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