热电器件的界面和界面材料

doi:10.15541/jim20180248

无机材料学报 ›› 2019, Vol. 34 ›› Issue (3): 269-278.DOI: 10.15541/jim20180248

所属专题：热电材料与器件

热电器件的界面和界面材料

胡晓凯^1,4, 张双猛¹, 赵府^1,2, 刘勇^1,3, 刘玮书¹

1. 南方科技大学材料科学与工程系, 深圳 518055;
2. 南方科技大学前沿与交叉科学研究院, 深圳 518055;
3. 中国航发北京航空材料研究院, 北京100095;
4. 迪肯大学前沿材料研究所, 吉郎 3216, 澳大利亚

收稿日期:2018-06-21 修回日期:2018-08-23 出版日期:2019-03-20 网络出版日期:2019-02-26
作者简介:胡晓凯(1978-), 男, 博士. E-mail: xiaokai.hu@deakin.edu.au
基金资助:
“千人计划”-青年人才项目;深圳市“孔雀人才计划”;广东省“珠江人才计划”-创新创业团队项目(2016ZT06G587)

Thermoelectric Device: Contact Interface and Interface Materials

HU Xiao-Kai^1,4, ZHANG Shuang-Meng¹, ZHAO Fu^1,2, LIU Yong^1,3, LIU Wei-Shu¹

1. Department of Material Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, China;
2. Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology, Shenzhen 518055, China;
3. AECC Beijing Institute of Aeronautical Materials, Beijing 100095, China;
4. Institute for Frontier Materials, Deakin University, Geelong 3216, Australia;

Received:2018-06-21 Revised:2018-08-23 Published:2019-03-20 Online:2019-02-26
Supported by:
National 1000-Youth Talent;Shenzhen Talent Peacock Plan;Guangdong InnovativeandEntrepreneurialResearch Team Program (2016ZT06G587)

摘要/Abstract

摘要：

基于塞贝克效应的热电转换技术, 在大量分散的低品位废热转换电能方面有着不可替代的优势。以热电优值ZT为性能指标的热电材料研发成为新能源材料领域研究的热点之一。近年来, 大量新型中温热电材料被相继发现, 然而新型热电材料的产业化应用, 尤其是在温差发电方面的进展尤为缓慢, 其中热电器件中的材料界面问题严重制约了热电转换技术的应用进程。本文从Bi₂Te₃型器件在温差发电方面所遇到的技术瓶颈为例, 阐述热电器件中的界面关键技术, 并归纳出电极接触界面需要综合考虑低的界面电阻、高的结合强度、以及好的高温稳定性能。然后总结了与Bi₂Te₃、PbTe、CoSb₃基三种热电材料相关的界面材料研究进展。

关键词: 热电器件, 金属化层, 界面电阻, 高温稳定, 综述

Abstract:

Thermoelectric power generation via Seebeck effect features an unique advantage in converting large amount of distributed and low-grade waste heat into electricity. Thermoelectric materials have become a hot topic of research in the field of new energy materials, guided by the high figure of merit ZT. Although various mid-temperature thermoelectric materials were discovered, the industrial application of these materials, especially in power generation applications, progressed very slowly. The staggering interface technology associated with thermoelectric device restricted the advance of thermoelectric conversion technology. In this review, the bottleneck issues of utilizing Bi₂Te₃-based devices for power generation were used as an example to illustrate the critical interface technologies. The key issues at designing electrode contact interfaces were summarized, including low contact resistance, high bonding strength, and superior thermal chemical stability at high temperature. The recent progress on the metallization and interfacial barrier layer for typical materials of Bi₂Te₃, PbTe and CoSb₃ were also reviewed.

Key words: thermoelectric device, metallization, contact resistance, high-temperature stability, review

中图分类号:

TN37

胡晓凯, 张双猛, 赵府, 刘勇, 刘玮书. 热电器件的界面和界面材料[J]. 无机材料学报, 2019, 34(3): 269-278.

HU Xiao-Kai, ZHANG Shuang-Meng, ZHAO Fu, LIU Yong, LIU Wei-Shu. Thermoelectric Device: Contact Interface and Interface Materials[J]. Journal of Inorganic Materials, 2019, 34(3): 269-278.

图/表 10

图1 热电器件结构示意图(a)和电极界面结构示意图(b)

Fig.1 Schematic diagram of structure of thermoelectric device (a) and electrode interface (b)

表1 一些焊料的成分和液相线、固相线温度[16]

Table 1 Compositions of some solders as well as the temperature (T) at liquidus and solidus[16]

T range /℃	Compositions/wt%	Liquidus T/℃	Solidus T/℃
100-200	52 In+48 Sn	118	118
	85 Sn+10 Bi+5 Zn	190	168
	63 Sn+37 Pb	183	183
	91.2 Sn+8.8 Zn	198.5	198.5
200-300	50 Sn+50 Pb	212	183
	96.5 Sn+3 Ag+0.5 Cu	220	217
	95 Sn+5 Sb	240	232
300-400	5 Sn+95 Pb	312	305
	95 Pb+5 Ag	364	305
	75 Sn+0.25 Sb+ 0.25 Bi+24.5 Pb	380	370
400-500	94 Sn+0.2 Pb+5.8 Sb	461	450
400-500	88 Pb+11.75 Sb+0.25 Bi	473	473
500-600	97 Pb+0.4 Sb + 2.35 Ag+0.25 Bi	580	580
500-600	8.5 Sn+90 Pb+1.5 Ag	588	588

图2 商业Bi2Te3制冷片用于温差发电热循环测试后接触界面的形貌[17]

Fig.2 Interface micrograph of commercial Bi2Te3 refrigeration device after the thermal cycle test[17]

图3 方钴矿器件热电偶臂的界面开裂与氧化(图片由上海硅酸盐研究所热电材料器件课题组提供)(Skutterudite, SKD)

Fig.3 Interface cracking and oxidation images of Skutterudite thermoelectric legs

图4 通过粉末热压法连接的Ni/Bi2Te3界面接触电阻的扫描探针测试方法示意图(a)(插图为Bi2Te3基接触脚照片), Ni/Bi2Te2.7Se0.3/Ni和Ni/Bi0.4Sb1.6Te3/Ni的电势曲线以及接触电阻计算方法(b)[21]

Fig. 4 Schematic diagram of a scanning voltage probe for contact resistance measurement, and a Bi2Te3-based leg (inset) (a); contact resistance measurement for both n-type Ni/Bi2Te2.7Se0.3/Ni and p-type Ni/Bi0.4Sb1.6Te3/Ni(b)[21]

图5 Ni/Bi0.4Sb1.6Te3界面(a)和Ni/Bi2Te2.7Se0.3界面(b)附近元素百分浓度分布[21]

Fig.5 Comparison of composition profile between Ni/Bi0.4Sb1.6Te3 interface (a)and Ni/Bi2Te2.7Se0.3Interface (b) obtained from a selected area SEM-EDS[21]IRL: interface reaction layer, TDR: Te-deficient region

图6 Bi2Te3基热电臂电极界面高温反应模型[21]

Fig.6 High-temperature reaction model of electrode interface of Bi2Te3-based thermoelectric leg[21]

图7 聚光太阳能热电发电器件: 新型NiFe基合金用于n型Bi2Te3的金属化[12]

Fig. 7 Concentrating solar thermoelectric generators: new type of NiFe-based alloy applied to metallization of n-type Bi2Te3[12]

图8 虚拟的碲化铋热电偶臂最大输出功率(a)和效率(b)随界面接触电阻率的变化情况, 其中l为热电臂高度

Fig.8 The maximum output power (a) and efficiency (b) vs. interface contact resistivity for the simulated Bi2Te3 leg (l is the leg height)

图9 碲化铋-方钴矿两段式热电器件的发电效率(a)和器件热端SKD/Ti0.88Al0.12/Ni界面与电极扫描电镜照片(b) [13]

Fig.9 (a) Power generation efficiency of segmented BT/SKD modules and (b) scanning electron microscopy image of SKD/Ti0.88Al0.12/Ni interface and electrode on hot side[13]

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热电器件的界面和界面材料

Thermoelectric Device: Contact Interface and Interface Materials

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