| 引用本文: | 马燕,况志祥,韩学武,胡晓明,李亚伟,樊希安.热喷涂制Ni阻挡层在碲化铋热电器件中的应用*[J].中国表面工程,2023,36(3):214~222 |
| MA Yan,KUANG Zhixiang,HAN Xuewu,HU Xiaoming,LI Yawei,FAN Xian.Application of Thermal Spray Ni Barrier Layer in Bismuth Telluride Thermoelectric Devices[J].China Surface Engineering,2023,36(3):214~222 |
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| 热喷涂制Ni阻挡层在碲化铋热电器件中的应用* |
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马燕1,2, 况志祥1,2, 韩学武3, 胡晓明1,2, 李亚伟1,2, 樊希安1,2
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1.武汉科技大学省部共建耐火材料与冶金国家重点实验室 武汉 430081;2.武汉科技大学钢铁冶金及资源利用省部共建教育部重点实验室 武汉 430081;3.湖北赛格瑞新能源科技有限公司 鄂州 436000
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| 摘要: |
| 在碲化铋热电制冷器件的服役过程中，焊料与热电材料间的元素扩散将严重制约器件的正常使用，目前最常用在两者间加 Ni 阻挡层的方法来改善这种问题，以往采用电镀、等离子烧结等制备 Ni 镀层的方法会产生界面镀层厚度不易控制、镀层易氧化的问题，而热喷涂由于其镀速快、镀层厚度易控制和镀后表面较平整、耐氧化、结合强度高等优点，可作为制备 Ni 阻挡层的更好选择。采用热喷涂技术制备不同厚度的 Ni 阻挡层，并对其分别进行 200 ℃下 24、72 和 144 h 的退火试验。 首先探究不同 Ni 层厚度的 p 型(Bi0.4Sb1.6Te3)和 n 型(Bi2Te2.7Se0.3)碲化铋材料退火前后对镀层硬度和防扩散效果的影响， 并将不同 Ni 层厚度的 p、n 型碲化铋材料制备成热电器件进行服役性能测试。结果表明：退火对 p 型材料镀 Ni 层硬度影响较小，其值变化在 10%以内，但对 n 型材料镀 Ni 层的硬度影响较大，其最大硬度值下降 56.36%；Ni 是 p 型碲化铋材料较好的扩散阻挡层，能显著减少 Bi0.4Sb1.6Te3中所有元素的扩散，但其对于 n 型材料的阻挡效果不明显，仅能较弱地阻挡 Bi2Te2.7Se0.3 中除 Te 之外的元素扩散；正常工作时，镀 Ni 器件在热循环 2.5 万次后，内阻变化小于 5%，相较于无镀 Ni 器件，其服役寿命得到显著提高。 |
| 关键词: 碲化铋 防扩散层 镀 Ni 热喷涂 |
| DOI：10.11933/j.issn.1007?9289.20220813002 |
| 分类号:TB34;TB64 |
| 基金项目:国家自然科学基金资助项目(51674181) |
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| Application of Thermal Spray Ni Barrier Layer in Bismuth Telluride Thermoelectric Devices |
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MA Yan1,2, KUANG Zhixiang1,2, HAN Xuewu3, HU Xiaoming1,2, LI Yawei1,2, FAN Xian1,2
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1.State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology,Wuhan 430081 , China;2.Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education,Wuhan University of Science and Technology, Wuhan 430081 , China;3.Hubei Saigrui New Energy Technology Co.Ltd, Ezhou 436000 , China
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| Abstract: |
| In recent years, some studies have found that thermoelectric materials exhibit ideal characteristics to realize energy efficiency. Among thermoelectric materials, Bi2Te3 compounds, discovered in the 1950s, exhibit the highest thermoelectric conversion performance at room temperature, and their alloys have been widely applied in many fields, such as radioisotope thermoelectric generators and polymerase chain reaction amplifiers. The compounds have become the most widely used commercial materials. The connection between the electrode and thermoelectric material is typically achieved by welding in a thermoelectric cooling device. If the thermoelectric element is in direct contact with a solder, they readily diffuse into each other. With a vigorous diffusion reaction at the interface, many dislocations are generated, decreasing the shear stress and interface adhesion strength; and eventually leading to the failure of the thermoelectric device. The addition of a Ni-based alloy barrier layer between the two materials is the most widely used method for solving this problem. However, the preparation of Ni-based alloys has the problem of incompatible properties during the previous preparation process, which may produce defects and uneven coatings. Using a single element as a barrier layer can reduce or even prevent these phenomena. The thermal spraying process has received increasing attention owing to the advantages of simple operation, uniform coating, and large-area spraying, in large-scale projects, the thermal spraying process can significantly facilitate construction progress. However, few studies on applying thermal sprays to synthesizes Ni plating as a barrier layer have been conducted. Other, traditional methods of adding a Ni barrier layer, such as electroplating and plasma sintering, may cause difficulty in controlling the interface coating thickness, and frequent oxidization of the coatings. The effect of Ni-spray coatings of different thicknesses on the interface of bismuth telluride was evaluated by accelerating the aging methods, and some problems arising from thermoelectric devices in the operating process were investigated based on the degree of diffusion of the material interface through annealing and thermal cycling experiments. Ni layers with various thicknesses were prepared by thermal spraying, and annealing experiments were performed for 24, 72, and 144 h at 200 ℃. First, the effects of p-type and n-type bismuth telluride materials with various Ni layer thicknesses on the coating hardness and anti-diffusion effect were investigated, and p-type and n-type samples were prepared in thermoelectric devices for operating performance tests. The results show that the annealing process minimally influences the Ni coating hardness of p-type materials, with the hardness fluctuating within 10%. In contrast, the process can significantly decrease the Ni coating hardness of n-type materials by 56.36%, indicating that Ni is a superior choice as a diffusion barrier in p-type bismuth telluride materials of almost all the elements in Bi0.4Sb1.6Te3. However the blocking effect of the n-type material is not evident, and the Ni barrier can only weakly block the diffusion of elements except Te in Bi2Te2.7Se0.3. The electrical resistance in the internal resistance of Ni-plated devices can change by less than 5% after 25 000 thermal cycles, significantly increasing the service life compared to non-Ni-plated devices. |
| Key words: Bismuth telluride non-diffusion layer Ni plating thermal spraying |
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