Nb/Mg3SbBi界面层热稳定性研究

doi:10.15541/jim20230006

无机材料学报 ›› 2023, Vol. 38 ›› Issue (8): 931-937.DOI: 10.15541/jim20230006 CSTR: 32189.14.10.15541/jim20230006

Nb/Mg₃SbBi界面层热稳定性研究

胡忠良¹(), 傅赟天¹, 蒋蒙¹, 王连军¹, 江莞¹^,²()

1.东华大学材料科学与工程学院, 上海 201620
2.东华大学功能材料研究中心, 上海 201620

收稿日期:2023-01-04 修回日期:2023-03-03 出版日期:2023-08-20 网络出版日期:2023-03-17
通讯作者: 江莞, 教授. E-mail: wanjiang@dhu.edu.cn
作者简介:胡忠良(1997-), 男, 硕士研究生. E-mail: hu676789989@163.com
基金资助:
国家自然科学基金(52174343)

Thermal Stability of Nb/Mg₃SbBi Interface

HU Zhongliang¹(), FU Yuntian¹, JIANG Meng¹, WANG Lianjun¹, JIANG Wan¹^,²()

1. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
2. Institute of Functional Materials, Donghua University, Shanghai 201620, China

Received:2023-01-04 Revised:2023-03-03 Published:2023-08-20 Online:2023-03-17
Contact: JIANG Wan, professor. E-mail: wanjiang@dhu.edu.cn
About author:HU Zhongliang (1997-), male, Master candidate. E-mail: hu676789989@163.com
Supported by:
National Natural Science Foundation of China(52174343)

摘要/Abstract

摘要：

Zintl相Mg₃(Sb,Bi)₂基热电材料因在中低温区(27~500 ℃)表现出优异的热电性能而受到广泛关注。然而, 由于Mg、Sb元素比较活泼, 在长期高温服役下易与电极发生剧烈界面扩散反应, 导致热电器件的性能和服役寿命衰减。因此, 选择能有效阻挡元素剧烈互扩散并且具有低界面接触电阻率阻挡层材料至关重要。本研究首先利用热压工艺制备出300 ℃最高ZT~1.4的n型Mg₃SbBi(Mg_3.2SbBi_0.996Se_0.004)样品, 然后采用Nb粉作为扩散阻挡层一步烧结制备Mg₃SbBi/Nb/Mg₃SbBi“三明治”结构样品, 系统研究界面层的组成、微结构以及电阻随老化时间演变过程。加速老化实验(525 ℃/70 h; 525 ℃/170 h; 525 ℃/360 h)研究发现, Nb阻挡层中的Mg-Sb/Bi组分发生偏析, 表面产生裂纹, 抛光处理后界面连接完好, 无裂纹和孔洞, 界面扩散层厚度随老化时间延长缓慢增加至1.6 μm。Nb/Mg₃SbBi界面电阻率从初始的12.9 μΩ·cm²增大到19.8、27.4和31.8 μΩ·cm², 表明老化导致界面处元素发生微弱扩散, 但Nb阻挡层仍呈现优异的阻挡性能。因此, 在Mg₃(Sb,Bi)₂基热电材料体系中, 选择界面扩散微弱且结构致密的Nb作为阻挡层材料, 可以在确保连接可靠的同时有效阻挡Mg、Sb元素扩散, 从而提升Mg₃(Sb,Bi)₂基器件的稳定性和可靠性, 推动其在中温发电领域的应用。

关键词: Mg₃(Sb,Bi)₂, 扩散阻挡层, 界面稳定性, 界面电阻率

Abstract:

Zintl-phase Mg₃(Sb,Bi)₂-based thermoelectric (TE) compounds have attracted extensive attention due to their excellent TE performance in the medium and low temperature region (27-500 ℃). However, the reactive nature of Mg and Sb elements leads to violent interfacial diffusion reactions with electrodes during long-term high-temperature service, degrading TE performance and shortening lifespan of TE devices. Consequently, it is crucial to select diffusion barrier layer (DBL) with low interfacial contact resistivity to block violent interdiffusion of components. In this work, the n-type Mg₃SbBi (Mg_3.2SbBi_0.996Se_0.004) sample, with ZT~1.4@300 ℃, and the “sandwich” structure of Mg₃SbBi/Nb/ Mg₃SbBi was prepared by hot pressing sintering process. Composition and microstructure of the interfacial layer and evolution of resistance with aging time were investigated systematically. Accelerated aging results (525 ℃/70 h, 525 ℃/170 h, 525 ℃/360 h) indicated that Mg-Sb/Bi components segregation occurred in the Mg₃SbBi-Nb DBL junctions, and cracks formed on the surface. However, the interfaces were well conjunctive after polishing the pellets. And the thickness of diffusion layer slowly increased to 1.6 μm after aging. Besides, resistivity of the Nb/Mg₃SbBi interface slightly increased from initial 12.9 μΩ·cm² to 19.8, 27.4 and 31.8 μΩ·cm², respectively, indicating the Nb DBL still displaying excellent barrier properties except for the faint diffusion during aging. Based on these data, Nb is a better choice to effectively suppress the diffusion of Mg and Sb elements achieving reliable connection, to be the DBL material in the Mg₃(Sb,Bi)₂-based TE families. In conclusion, Nb can effectively improve the Mg₃(Sb,Bi)₂-based devices' thermal stability and promote the application over the medium temperature power generation.

Key words: Mg₃(Sb,Bi)₂, diffusion barrier layer, interface stability, interface resistivity

中图分类号:

TQ174

胡忠良, 傅赟天, 蒋蒙, 王连军, 江莞. Nb/Mg₃SbBi界面层热稳定性研究[J]. 无机材料学报, 2023, 38(8): 931-937.

HU Zhongliang, FU Yuntian, JIANG Meng, WANG Lianjun, JIANG Wan. Thermal Stability of Nb/Mg₃SbBi Interface[J]. Journal of Inorganic Materials, 2023, 38(8): 931-937.

图/表 8

图1 Mg3SbBi/Nb/Mg3SbBi样品的(a)装样示意图和(b)粒子实物照片

Fig. 1 (a) Loading diagram and (b) physical particle picture of Mg3SbBi/Nb/Mg3SbBi sample

图2 Mg3SbBi样品的(a)粉体与块体XRD衍射图谱和(b)块体面扫描元素分布图

Fig. 2 (a) Powder and bulk XRD patterns and (b) block decent scanning element distribution mappings of Mg3SbBi sample

图3 热压750 ℃热压烧结不同时间的样品的热电性能随测试温度的变化曲线

Fig. 3 Thermoelectric properties of hot-pressed 750 ℃ sintered samples with various holding time as a function of test temperature (a) Electrical conductivity; (b) Seebeck coefficient; (c) Lattice thermal conductivity; (d) ZT

图4 老化前Mg3SbBi/Nb/Mg3SbBi样品的(a)背散射电子图和(b, c)图(a)中相应区域的放大图

Fig. 4 (a) BSE image of Mg3SbBi/Nb/Mg3SbBi sample before aging and (b, c) magnified images of corresponding areas in (a)

表1 图4(c)中对应EDS点分析结果(原子分数)

Table 1 EDS point analysis results of the points in Fig.4(c) (in atomic)

Point	Mg/%	Sb/%	Bi/%	Nb/%
1	59.75	9.25	29.64	1.36
2	51.88	8.35	25.57	14.20
3	1.19	0.14	0.13	98.54
4	58.78	19.85	20.22	1.15

图5 Mg3SbBi/Nb/Mg3SbBi结构在525 ℃老化70、160、360 h的背散射电子照片

Fig. 5 BSE images of the interface of Mg3SbBi/Nb/Mg3SbBi after aging at 525 ℃ for 70, 160 and 360 h (a-c) Before polished; (d-f) After polished

图6 Nb/Mg3SbBi界面525 ℃老化不同时间的背散射电子图(上)和线扫描结果(下)

Fig. 6 Backscatter (up) and line sweep (down) results of Nb /Mg3SbBi interface aged at 525℃for different time (a) 70; (b) 170 h; (c) 360 h; Colorful figures are available on website

图7 Nb/Mg3SbBi的界面电阻率

Fig. 7 Interface resistivities of Nb/Mg3SbBi (a) Comparison with literature [13,17⇓-19]; (b) Relationship of interface resistivity with thermal aging time

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Nb/Mg₃SbBi界面层热稳定性研究

Thermal Stability of Nb/Mg₃SbBi Interface

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