Bi2Te3基热电材料的湿热稳定性研究

doi:10.15541/jim20220736

无机材料学报 ›› 2023, Vol. 38 ›› Issue (7): 800-806.DOI: 10.15541/jim20220736 CSTR: 32189.14.10.15541/jim20220736

所属专题：【能源环境】热电材料(202506)

Bi₂Te₃基热电材料的湿热稳定性研究

肖娅妮¹(), 吕嘉南¹^,², 李振明³, 刘铭扬³, 刘伟³, 任志刚⁴, 刘弘景⁴, 杨东旺¹(), 鄢永高¹()

1.武汉理工大学材料复合新技术国家重点实验室, 武汉430070
2.武汉理工大学纳微结构研究中心, 武汉 430070
3.中国电力科学研究院有限公司储能与电工新技术研究所, 北京100192
4.国网北京市电力公司电力科学研究院, 北京100075

收稿日期:2022-12-05 修回日期:2023-02-23 出版日期:2023-03-15 网络出版日期:2023-03-15
通讯作者: 杨东旺, 助理研究员. E-mail: ydongwang@whut.edu.cn;
鄢永高, 研究员. E-mail: yanyonggao@whut.edu.cn
作者简介:肖娅妮(1999-), 女, 硕士研究生. E-mail: 303587@whut.edu.cn
基金资助:
国家电网有限公司科技项目(5500-202255482A-2-0-KJ)

Hygrothermal Stability of Bi₂Te₃-based Thermoelectric Materials

XIAO Yani¹(), LYU Jianan¹^,², LI Zhenming³, LIU Mingyang³, LIU Wei³, REN Zhigang⁴, LIU Hongjing⁴, YANG Dongwang¹(), YAN Yonggao¹()

1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
2. Nanostructure Research Center, Wuhan University of Technology, Wuhan 430070, China
3. Energy Storage and Electrotechnics Department, China Electric Power Research Institute, Beijing 100192, China
4. SGCC Beijing Electric Power Research Institute, Beijing 100075, China

Received:2022-12-05 Revised:2023-02-23 Published:2023-03-15 Online:2023-03-15
Contact: YANG Dongwang, research assistant. E-mail: ydongwang@whut.edu.cn;
YAN Yonggao, professor. E-mail: yanyonggao@whut.edu.cn
About author:XIAO Yani (1999-), female, Master candidate. E-mail: 303587@whut.edu.cn
Supported by:
The Science and Technology Program from State Grid Corporation of China(5500-202255482A-2-0-KJ)

摘要/Abstract

摘要：

Bi₂Te₃基化合物是目前得到广泛商业应用的热电材料, 其湿热稳定性直接影响着热电器件的服役可靠性。本工作探究了商用n型Bi₂Se_0.21Te_2.79和p型Bi_0.4Sb_1.6Te₃热电材料存储于85 ℃, 85% RH（相对湿度）湿热环境600 h期间的降解行为。在湿热处理600 h后, n型Bi₂Se_0.21Te_2.79和p型Bi_0.4Sb_1.6Te₃材料表面均被氧化, 反应过程分别为Bi₂Te₃+O₂→Bi₂O₃+TeO₂和Bi₂Te₃+Sb₂Te₃+O₂→Bi₂O₃+Sb₂O₃+TeO₂。氧化过程在材料内部产生了纳米级孔洞, 甚至微裂纹, 导致材料的电、热性能全面劣化。在室温时, n型Bi₂Se_0.21Te_2.79材料的电导率从存储前的9.45×10⁴ S·m^-1显著下降到7.79×10⁴ S·m^-1, ZT则从0.97下降至0.79; p型Bi_0.4Sb_1.6Te₃材料的Seebeck系数从243 μV·K^-1明显减小至220 μV·K^-1, ZT则从1.24降低到0.97。综上所述, Bi₂Te₃基热电材料的湿热稳定性极差, 微型热电器件在服役过程中需要进行严格封装, 以阻止热电材料自身与环境中的水汽、空气发生复杂的氧化还原反应。

关键词: Bi₂Te₃, 热电材料, 湿热稳定性

Abstract:

Bi₂Te₃-based thermoelectric (TE) materials have already been commercialized, of which the hygrothermal stability has a direct impact on the service reliability of TE devices, but is still confronted many challenges. This work investigated the degradation behavior of commercial n-type Bi₂Se_0.21Te_2.79 and p-type Bi_0.4Sb_1.6Te₃ TE materials during storage in 85 ℃, 85% RH hygrothermal environment for 600 h. The surfaces of n-type Bi₂Se_0.21Te_2.79 and p-type Bi_0.4Sb_1.6Te₃ TE materials were oxidized with reaction process of Bi₂Te₃+O₂→Bi₂O₃+TeO₂ and Bi₂Te₃+Sb₂Te₃+O₂→Bi₂O₃+Sb₂O₃+TeO₂, respectively. The oxidation process creates nanoscale holes and even microcracks inside the material, which leads to an overall deterioration of the electrical and thermal properties. At room temperature, the electrical conductivity of the n-type Bi₂Se_0.21Te_2.79 material drops from 9.45×10⁴ S·m^-1 to 7.79×10⁴ S·m^-1 after exposure, and ZT decreases from 0.97 to 0.79, while Seebeck coefficient of the p-type Bi_0.4Sb_1.6Te₃ material declines from 243 μV·K^-1to 220 μV·K^-1, correspondingly, ZT decreases from 1.24 to 0.97. In conclusion, Bi₂Te₃-based TE materials have extremely poor hygrothermal stability, and their corresponding micro-TE devices need to be strictly encapsulated in service to prevent complex redox reactions between the TE materials themselves and the environmental water vapor and air.

Key words: Bi₂Te₃, thermoelectric material, hygrothermal stability

中图分类号:

TQ174

肖娅妮, 吕嘉南, 李振明, 刘铭扬, 刘伟, 任志刚, 刘弘景, 杨东旺, 鄢永高. Bi₂Te₃基热电材料的湿热稳定性研究[J]. 无机材料学报, 2023, 38(7): 800-806.

XIAO Yani, LYU Jianan, LI Zhenming, LIU Mingyang, LIU Wei, REN Zhigang, LIU Hongjing, YANG Dongwang, YAN Yonggao. Hygrothermal Stability of Bi₂Te₃-based Thermoelectric Materials[J]. Journal of Inorganic Materials, 2023, 38(7): 800-806.

图/表 9

表1 n型Bi2Se0.21Te2.79和p型Bi0.4Sb1.6Te3材料在湿热环境(85 ℃, 85% RH)存储600 h前后的室温热电性能

Table 1 Room temperature thermoelectric performance of n-type Bi2Se0.21Te2.79 and p-type Bi0.4Sb1.6Te3 materials before and after storage in hygrothermal environment (85 ℃, 85% RH) for 600 h

Parameter at room temperature	n-type Bi₂Se_0.21Te_2.79
Parameter at room temperature	0 h	600 h	0 h	600 h
σ / (×10⁴, S·m^-1)	9.45	7.79	9.12	8.69
S / (μV·K^-1)	219	224	243	220
n / (×10¹⁹, cm^-3)	1.25	1.32	1.52	1.47
μ / (cm²·V^-1·s^-1)	470	369	375	370
PF / (mW·m^-1·K^-2)	4.54	3.90	5.41	4.21
κ / (W·m^-1·K^-1)	1.40	1.48	1.31	1.29
ZT	0.97	0.79	1.24	0.97

图1 (a1, b1)在湿热环境存储不同时间后材料的XRD谱图及(a2, b2)存储600 h后材料的表面EDS能谱

Fig. 1 (a1, b1) XRD patterns of samples after storage in hygrothermal environment for different time with (a2, b2) EDS results of material surface after storage in hygrothermal environment for 600 h (a1, a2) n-type Bi2Se0.21Te2.79; (b1, b2) p-type Bi0.4Sb1.6Te3

图2 n型Bi2Se0.21Te2.79材料在湿热环境存储600 h(a1~b1)前(a2~b2)后的表面XPS谱图

Fig. 2 Surface XPS spectra of n-type Bi2Se0.21Te2.79 material (a1-b1) before and (a2-b2) after storage in hygrothermal environment for 600 h (a1, a2) Bi4f; (b1, b2) Te3d

图3 p型Bi0.4Sb1.6Te3材料在湿热环境存储600 h(a1~c1)前(a2~c2)后的表面XPS谱图

Fig. 3 Surface XPS spectra of p-type Bi0.4Sb1.6Te3 material (a1-c1) before and (a2-c2) after storage in hygrothermal environment for 600 h (a1, a2) Bi4f; (b1, b2) Te3d; (c1, c2) Sb3d

图4 (a1, a2) n型Bi2Se0.21Te2.79和(b1, b2) p型Bi0.4Sb1.6Te3材料在湿热环境存储600 h(a1, b1)前(a2, b2)后的FESEM照片

Fig. 4 FESEM images of (a1, a2) n-type Bi2Se0.21Te2.79 and (b1, b2) p-type Bi0.4Sb1.6Te3 material (a1, b1) before and (a2, b2) after storage in hygrothermal environment for 600 h

图5 (a) 湿热环境存储600 h的n型Bi2Se0.21Te2.79材料靠近表面区域的TEM照片; (b) 图(a)中方框区域的元素面分布图谱; (c) 图(a)中方框区域的HRTEM照片; (d) 图(c)的IFFT图;湿热环境存储600 h的p型Bi0.4Sb1.6Te3材料靠近表面的(e) HAADF-STEM照片和(f)元素面分布图谱

Fig. 5 (a) TEM image of the area close to the surface of n-type Bi2Se0.21Te2.79 material exposed to hygrothermal environment for 600 h; (b) elemental surface distribution profiles of the square region in (a); (c) HRTEM image of the square region in (a); (d) IFFT image of (c); (e) HAADF-STEM image of the area close to the surface of p-type Bi0.4Sb1.6Te3 material exposed to hygrothermal environment and (f) its elemental surface distribution profiles of the region (b1, f1) O; (b2, f2) Bi; (b3, f3) Te; (b4)Se; (f4) Sb

图S1 湿热环境(85 ℃, 85% RH)条件下n型Bi2Se0.21Te2.79的热电性能

Fig. S1 Thermoelectric performance of n-type Bi2Se0.21Te2.79 in hygrothermal environment (85 ℃, 85% RH) (a) Electrical conductivity; (b) Seebeck coefficient; (c) Room temperature carrier concentration and carrier mobility; (d) Power factor; (e) Thermal conductivity; (f) ZT

图S2 湿热环境(85 ℃, 85% RH)条件下p型Bi0.4Sb1.6Te3的热电性能

Fig. S2 Thermoelectric performance of p-type Bi0.4Sb1.6Te3 in hygrothermal environment (85 ℃, 85% RH) (a) Electrical conductivity; (b) Seebeck coefficient; (c) Room temperature carrier concentration and carrier mobility; (d) Power factor; (e) Thermal conductivity; (f) ZT

图S3 n型Bi2Se0.21Te2.79和p型Bi0.4Sb1.6Te3材料在湿热环境存储不同时间的FESEM照片

Fig. S3 FESEM images of samples exposed to hygrothermal environment for different time n-type Bi2Se0.21Te2.79: (a1) 200 h; (a2) 400 h; p-type Bi0.4Sb1.6Te3: (b1) 200 h; (b2) 400 h

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Bi₂Te₃基热电材料的湿热稳定性研究

Hygrothermal Stability of Bi₂Te₃-based Thermoelectric Materials

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