方钴矿热电材料/Ti88Al12界面稳定性研究

doi:10.15541/jim20170517

无机材料学报 ›› 2018, Vol. 33 ›› Issue (8): 889-894.DOI: 10.15541/jim20170517

所属专题：庆祝上海硅酸盐所独立建所60周年虚拟专刊！；热电材料与器件；乘风破浪的新能源材料

方钴矿热电材料/Ti₈₈Al₁₂界面稳定性研究

张骐昊^{1, 2}, 廖锦城¹, 唐云山¹, 顾明¹, 刘睿恒¹, 柏胜强¹, 陈立东¹

1. 中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050;
2. 中国科学院大学,北京 100049

收稿日期:2017-11-02 修回日期:2017-12-27 出版日期:2018-08-28 网络出版日期:2018-07-17
作者简介:张骐昊(1988-), 男, 博士研究生. E-mail: zqh378@163.com
基金资助:
国家自然科学基金(51632010, 51572282, 51404236)

Interface Stability of Skutterudite Thermoelectric Materials/Ti₈₈Al₁₂

ZHANG Qi-Hao^{1, 2}, LIAO Jin-Cheng¹, TANG Yun-Shan¹, GU Ming¹, LIU Rui-Heng¹, BAI Sheng-Qiang¹, CHEN Li-Dong¹

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China;
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2017-11-02 Revised:2017-12-27 Published:2018-08-28 Online:2018-07-17
About author:ZHANG Qi-Hao. E-mail: zqh378@163.com
Supported by:
National Natural Science Foundation of China (51632010, 51572282, 51404236)

摘要/Abstract

摘要：

热电器件的界面稳定性是决定其服役可靠性和寿命的关键因素。对于方钴矿热电器件, 为了抑制高温电极与方钴矿材料之间的相互扩散, 需要在两者之间加入阻挡层。本工作选用Ti₈₈Al₁₂作为阻挡层, 利用一步法热压烧结制备n型Yb_0.3Co₄Sb₁₂/Ti₈₈Al₁₂/Yb_0.3Co₄Sb₁₂和p型CeFe_3.85Mn_0.15Sb₁₂/Ti₈₈Al₁₂/CeFe_3.85Mn_0.15Sb₁₂样品, 研究Ti₈₈Al₁₂阻挡层与热电材料间的界面接触电阻率及微结构在加速老化实验中的演化规律。结果表明: 在相同的老化条件下, n型样品的界面接触电阻率增加速度比p型样品慢, 其激活能分别为84.1 kJ/mol和68.8 kJ/mol。对于n型样品, 由元素扩散反应生成的金属间化合物中间层的增长及最终AlCo/TiCoSb层的开裂是导致界面接触电阻率增加的主要原因; 而p型热电材料与Ti₈₈Al₁₂的热膨胀系数的差异加速了p型样品中界面裂纹的产生。

关键词: 方钴矿, 界面稳定性, 阻挡层, 接触电阻率

Abstract:

Interface stability is one of the key issues determining the service reliability and life of thermoelectric devices. For skutterudite-based thermoelectric devices, the barrier layer is required in order to restrain the inter-diffusion between the hot-side electrode and skutterudite matrix. In this work, Ti₈₈Al₁₂was selected as the barrier layer. N-type Yb_0.3Co₄Sb₁₂/Ti₈₈Al₁₂/Yb_0.3Co₄Sb₁₂ and p-type CeFe_3.85Mn_0.15Sb₁₂/Ti₈₈Al₁₂/CeFe_3.85Mn_0.15Sb₁₂thermoelectric joints were prepared by one-step hot pressing sintering method. The evolution processes of contact resistivity and microstructure were studied through accelerated aging experiments. The results show that the contact resistivity of n-type joints increases slower than that of p-type joints under the same aging condition. Activation energy for n-type and p-type joints is 84.1 kJ/mol and 68.8 kJ/mol, respectively. Growth of the inter-metallic compound layer and cracking at the AlCo/TiCoSb interface result in rapidly increased contact resistivity of n-type joints. For p-type joints, the difference of coefficient of thermal expansion between CeFe_3.85Mn_0.15Sb₁₂ and Ti₈₈Al₁₂ becomes the main reason for the cracks.

Key words: skutterudite, interface stability, barrier layer, contact resistivity

中图分类号:

TQ174

张骐昊, 廖锦城, 唐云山, 顾明, 刘睿恒, 柏胜强, 陈立东. 方钴矿热电材料/Ti₈₈Al₁₂界面稳定性研究[J]. 无机材料学报, 2018, 33(8): 889-894.

ZHANG Qi-Hao, LIAO Jin-Cheng, TANG Yun-Shan, GU Ming, LIU Rui-Heng, BAI Sheng-Qiang, CHEN Li-Dong. Interface Stability of Skutterudite Thermoelectric Materials/Ti₈₈Al₁₂[J]. Journal of Inorganic Materials, 2018, 33(8): 889-894.

图/表 9

图1 界面接触电阻率(ρc)随老化时间和温度的变化曲线: (a)n型Yb0.3Co4Sb12/Ti88Al12/Yb0.3Co4Sb12; (b)p型CeFe3.85Mn0.15Sb12/Ti88Al12/CeFe3.85Mn0.15Sb12; lnk随1000/T的变化关系: (c) n型; (d) p型

Fig. 1 Variation of specific contact resistivity (ρc) with thermal aging time and temperature: (a) n-type Yb0.3Co4Sb12/Ti88Al12/Yb0.3Co4Sb12; (b) p-type CeFe3.85Mn0.15Sb12/Ti88Al12/CeFe3.85Mn0.15Sb12; Variation of lnk with 1000/T: (c) n-type; (d) p-type

图2 n型Yb0.3Co4Sb12/Ti88Al12/Yb0.3Co4Sb12界面老化前的(a)扫描电镜照片; 不同元素成分的面扫描结果: (b) Co; (c) Sb; (d) Ti; (e) Al; (f) EDS点分析采集图

Fig. 2 As-prepared n-type Yb0.3Co4Sb12/Ti88Al12/Yb0.3Co4Sb12 interface (a) SEM image; EDS mapping results of (b) Co; (c) Sb; (d) Ti; (e) Al and (f) EDS point analysis location

表1 EDS点分析结果

Table 1 EDS point analysis results

Point	Co/at%	Sb/at%	Ti/at%	Al/at%
1	0	36.74	63.26	0
2	0	59.19	33.87	6.94
3	30.11	31.01	33.23	5.65
4	48.04	0.49	3.75	47.72
5	0	56.36	33.14	10.50
6	0	66.92	33.08	0

图3 n型Yb0.3Co4Sb12/Ti88Al12/Yb0.3Co4Sb12界面在550℃下经历不同老化时间后的扫描电镜照片

Fig. 3 SEM images of n-type Yb0.3Co4Sb12/Ti88Al12/Yb0.3Co4Sb12 interface after thermal aging at 550℃ for different days(a) 0 d; (b) 8 d; (c) 18 d; (d) 38 d

图4 n型Yb0.3Co4Sb12/Ti88Al12/Yb0.3Co4Sb12界面经历不同老化过程后的扫描电镜照片

Fig. 4 SEM images of n-type Yb0.3Co4Sb12/Ti88Al12/Yb0.3Co4Sb12 interface after thermal aging(a) 550℃, 38 d; (b) 575℃, 38 d; (c) 600℃, 38 d

图5 p型CeFe3.85Mn0.15Sb12/Ti88Al12/CeFe3.85Mn0.15Sb12界面老化前的(a)扫描电镜照片; 不同元素成分的面扫描结果(b)Ti; (c)Al; (d)Fe; (e)Sb; (f)Mn; (g)EDS线扫描采集图和(h)对应的线扫描结果

Fig. 5 As-prepared p-type CeFe3.85Mn0.15Sb12/Ti88Al12/ CeFe3.85Mn0.15Sb12 interface (a) SEM image; EDS mapping results of (b) Ti; (c) Al; (d) Fe; (e) Sb; (f) Mn; (g) EDS line scanning location, and (h) the corresponding result

图6 p型CeFe3.85Mn0.15Sb12/Ti88Al12/CeFe3.85Mn0.15Sb12界面在550℃下经历不同老化时间后的扫描电镜照片

Fig. 6 SEM images of p-type CeFe3.85Mn0.15Sb12/Ti88Al12/CeFe3.85Mn0.15Sb12 interface after thermal aging at 550℃ for different days(a) 0 d; (b) 2 d and (c) the corresponding EDS mapping result; (d) 12 d and (e) the corresponding EDS mapping result; (f) 38 d

图7 p型CeFe3.85Mn0.15Sb12/Ti88Al12/CeFe3.85Mn0.15Sb12界面经历不同老化后的扫描电镜照片

Fig. 7 SEM images of p-type CeFe3.85Mn0.15Sb12/Ti88Al12/CeFe3.85Mn0.15Sb12 interface after thermal aging

图8 材料的热膨胀系数随温度的变化曲线

Fig. 8 The variation of thermal expansion coefficient of different materials as function of the temperature

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方钴矿热电材料/Ti₈₈Al₁₂界面稳定性研究

Interface Stability of Skutterudite Thermoelectric Materials/Ti₈₈Al₁₂

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