硅酸盐学报

热电制冷材料研究进展

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周敏 ¹ , 苏浩健 ¹^,² , 师莉 ¹ , 李来风 ¹

硅酸盐学报 | 综合评述 2024,52(10): 3311-3326

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硅酸盐学报 |综合评述 2024 , 52 (10) : 3311 -3326

热电制冷材料研究进展

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周敏¹, 苏浩健¹^,², 师莉¹, 李来风¹

作者信息

^1．低温科学与技术重点实验室，中国科学院理化技术研究所，北京 100190

^2．中国科学院大学材料科学与光电技术学院，北京 100049

通讯作者:

师莉（1970—），女，博士，研究员。

作者简介:

周敏（1976—），女，博士，研究员。

Progress on Thermoelectric Cooling Materials

Min ZHOU¹, Haojian SU¹^,², Li SHI¹, Laifeng LI¹

Affiliations

^1.Key Laboratory of Cryogenic Science and Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China

^2.Centre of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding Author:

SHI Li (1970-), female, Ph.D., Professor. E-mail: shili@mail.ipc.ac.cn

ZHOU Min (1976-), female, Ph.D., Professor. E-mail: mzhou@mail.ipc.ac.cn

出版时间: 2024-10-20 doi: 10.14062/j.issn.0454-5648.20240129

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摘要

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热电制冷是一种基于Peltier效应的新型固态制冷技术，具有体积小、重量轻、可靠性高、无机械运动部件等特点，在5G芯片制冷、红外探测器制冷、高精度温控等高科技和航空航天领域具有广阔的应用前景。近年来，对新型固态制冷技术的需求越来越迫切，热电制冷技术和热电制冷材料的研究引起越来越多的关注。简要介绍了热电制冷的基本原理，对热电制冷材料，包括近室温区热电材料，低温区热电材料等的研究现状进行了综述，分析了研究中存在的问题，并对未来的研究发展进行了展望。

关键词

热电制冷 / 热电材料 / 热电性能 / 热电优值

Abstract

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Conventional vapor compression cooling technologies become a challenge because of the high global warming risks. In addition, most of the refrigerant fluids working in vapor compression plants is environmentally harmful. The thermoelectric solid-state cooling is realized by electricity without mechanically moving parts or emissions, offering a sustainable solution to overcome the environmental pollution. However, the thermoelectric cooling efficiency is not competitive, compared with the conventional vapor compression cooling. To improve the efficiency of thermoelectric refrigeration and enhance the competitiveness of thermoelectric refrigeration technology, it is of great significance to develop high-performance thermoelectric refrigeration materials.

Recent research work fcous on the thermoelectric refrigeration materials like conventional Bi₂Te₃-based materials, Mg₃(Sb, Bi)₂-based materials, IV-VI semiconductors at near room temperature, and Bi_1-_xSb_x, CsBi₄Te₆, FeSb₂ alloys at low temperatures.

At near room temperatures, Bi₂Te₃-based alloy is a kind of conventional thermoelectric material, which has excellent thermoelectric properties. The zT value of Bi₂Te₃-based thermoelectric materials prepared by the Bridgman method or zone melting method is approximately 1. The thermoelectric properties of Bi₂Te₃-based alloys are greatly improved, and the zT value of Bi₂Te₃-based thermoelectric materials is increased based on developed concepts, mechanisms and preparation methods. The zT value of some p-type (Bi, Sb)₂Te₃ is >1.5. The zT value of some n-type Bi₂(Te, Se)₃ is >1. However, the crust abundance of Te is rather low, the tellurium resources are scattered and the cost is high. Mg₃X₂ (X=Sb, Bi) compound is a kind of layered Zintl phase, which has the characteristics of "phonon glass-electron crystal (PGEC)", non-toxicity and high abundance of constituent elements. Recent studies indicate that the band gap of Mg₃(Sb, Bi)₂ alloy decreases with the increase of Bi content, and the peak value of zT also moves to the near room temperature region. Bi-rich Mg₃(Sb, Bi)₂ alloy shows the excellent thermoelectric properties in the near room temperature region, which is comparable to the thermoelectric properties of conventional Bi₂Te₃-based materials. The IV-VI compounds such as SnSe have good mid-temperature thermoelectric properties and extremely competitive thermoelectric properties in the near room temperature region.

Bi_1-_xSb_x is one of the low temperature thermoelectric materials, which has good thermoelectric properties in the temperatures below room temperature. Bi_1-_xSb_x single crystal has good low temperature thermoelectric properties, but poor mechanical properties, which is easy to cleavage during use. In recent years, Bi_1-_xSb_x polycrystalline materials are developed, whose the mechanical properties are better than those of single crystals, but the thermoelectric properties are difficult to reach the level of single crystals. CsBi₄Te₆ is a kind of p-type low-temperature thermoelectric material with the excellent properties, but in the preparation process, element Cs with an intense activity is usually used, and toxic formaldehyde is required for cleaning. FeSb₂ is an only deep low-temperature thermoelectric material that shows a good prospect near 50 K, and its deep low-temperature electric transmission performance is excellent, but the thermal conductivity is high, and its deep low-temperature thermoelectric performance needs to be further investigated.

Summary and prospects

The thermoelectric cooling technology has a potential in the field of refrigeration for 5G chips, infrared detector, and temperature controlling, etc.. To improve the efficiency of thermoelectric refrigeration and enhance the competitiveness of thermoelectric refrigeration technology, it is of great significance to develop high-performance thermoelectric refrigeration materials. However, the refrigeration temperature of the first-stage refrigerator is 230 K based on commercial Bi₂Te₃-based alloy, and the refrigeration temperature of the multi-stage refrigerator is as low as 150 K, while the thermoelectric performance of the commercial Bi₂Te₃-based alloy is sharply reduced at below room temperature, which is difficult to meet the needs of low-temperature refrigeration. It is thus necessary to develop high-performance low-temperature thermoelectric cooling materials to meet the low-temperature refrigeration in the future.

Key words

thermoelectric cooling / thermoelectric material / thermoelectric performance / thermoelectric figure of merit

引用本文

周敏, 苏浩健, 师莉, 李来风. 热电制冷材料研究进展. 硅酸盐学报, 2024 , 52 (10) : 3311 -3326 . DOI: 10.14062/j.issn.0454-5648.20240129

Min ZHOU, Haojian SU, Li SHI, Laifeng LI. Progress on Thermoelectric Cooling Materials[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (10) : 3311 -3326 . DOI: 10.14062/j.issn.0454-5648.20240129

基金

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国家自然科学基金面上项目(51872299)
低温科学与技术重点实验室自主项目(CRYO20230203)

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2024年第52卷第10期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240129

接收时间：2024-02-21
首发时间：2026-10-22
出版时间：2024-10-20

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出版历史

收稿日期：2024-02-21
修回日期：2024-04-09

基金

国家自然科学基金面上项目(51872299)

低温科学与技术重点实验室自主项目(CRYO20230203)

作者信息

^1．低温科学与技术重点实验室，中国科学院理化技术研究所，北京 100190

^2．中国科学院大学材料科学与光电技术学院，北京 100049

通讯作者:

师莉（1970—），女，博士，研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240129

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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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