Gd/Bi0.5Sb1.5Te3热电磁梯度复合材料的服役稳定性

doi:10.15541/jim20220637

无机材料学报 ›› 2023, Vol. 38 ›› Issue (6): 663-670.DOI: 10.15541/jim20220637 CSTR: 32189.14.10.15541/jim20220637

所属专题：【能源环境】热电材料(202409)

Gd/Bi_0.5Sb_1.5Te₃热电磁梯度复合材料的服役稳定性

汪波¹(), 余健¹^,²(), 李存成¹^,³, 聂晓蕾¹, 朱婉婷¹, 魏平¹, 赵文俞¹(), 张清杰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
2.九江学院材料科学与工程学院, 九江 332005
3.山东理工大学材料科学与工程学院, 淄博 255000

收稿日期:2022-10-28 修回日期:2022-12-15 出版日期:2023-06-20 网络出版日期:2022-12-28
通讯作者: 余健, 讲师. E-mail: jianyujju@126.com;
赵文俞, 教授. E-mail: wyzhao@whut.edu.cn
作者简介:汪波(1996-), 男, 硕士研究生. E-mail: bowang@whut.edu.cn
基金资助:
国家重点研发计划(2019YFA0704903);国家自然科学基金(91963207);国家自然科学基金(52130203);国家自然科学基金(11834012);国家自然科学基金(52201256);佛山仙湖实验室开放基金(XHT2020-004)

Service Stability of Gd/Bi_0.5Sb_1.5Te₃ Thermo-electro-magnetic Gradient Composites

WANG Bo¹(), YU Jian¹^,²(), LI Cuncheng¹^,³, NIE Xiaolei¹, ZHU Wanting¹, WEI Ping¹, ZHAO Wenyu¹(), ZHANG Qingjie¹

1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
2. School of Materials Science and Engineering, Jiujiang University, Jiujiang 332005, China
3. School of Materials Science and Engineering, Shandong University of Technology, Zibo 255000, China

Received:2022-10-28 Revised:2022-12-15 Published:2023-06-20 Online:2022-12-28
Contact: YU Jian, lecturer. E-mail: jianyujju@126.com;
ZHAO Wenyu, professor. E-mail: wyzhao@whut.edu.cn
About author:WANG Bo (1996-), male, Master candidate. E-mail: bowang@whut.edu.cn
Supported by:
National Key Research and Development Program of China(2019YFA0704903);National Natural Science Foundation of China(91963207);National Natural Science Foundation of China(52130203);National Natural Science Foundation of China(11834012);National Natural Science Foundation of China(52201256);Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory(XHT2020-004)

摘要/Abstract

摘要：

将热电材料与磁卡材料复合, 发展基于热电制冷和磁制冷耦合增强的热电磁能源转换全固态制冷新技术, 有望实现从热电制冷向热电磁制冷的技术变革, 但目前热电磁复合材料在服役环境下的稳定性还有待研究。本研究采用放电等离子体烧结技术将Bi_0.5Sb_1.5Te₃(BST)热电材料和Gd磁卡材料复合, 制备了一系列Gd/BST热电磁梯度复合材料, 系统研究了该复合材料在338 K、80%相对湿度(RH)的环境下老化12 d过程中的物相组成、显微结构、热电性能及制冷性能的演变特征。结果显示, Gd/BST热电磁梯度复合材料的物相组成和显微结构具有良好的服役稳定性, Gd/BST异质界面的Gd-Te扩散层化学成分和厚度(~4.5 µm)在老化过程中未发生明显变化。测试不同Gd浓度梯度方向热电性能和单臂器件制冷性能发现, 老化前后材料的ZT变化非常小, 单臂器件制冷温差在2.5 A阀值电流下稳定在6.5 K左右, 表明Gd/BST热电磁梯度复合材料具有良好的热电性能和制冷性能服役稳定性。

关键词: 热电磁梯度复合, 热电性能, 制冷性能, 服役稳定性

Abstract:

Combining thermoelectric materials with magnetocaloric materials enables a potential new all-solid-state cooling technology based on coupling enhancement of thermoelectric cooling and magnetic cooling, which is highly expected to achieve a technological change from thermoelectric cooling to thermoelectromagnetic cooling. However, the stability of thermal-electro-magnetic composites in service environment is still unknown. Herein, a series of Gd/BST thermo-electro-magnetic gradient composites were prepared by combining Bi_0.5Sb_1.5Te₃ (BST) thermoelectric material and Gd magnetocaloric material via spark plasma sintering technology. Evolution of phase composition, microstructure, thermoelectric, and cooling performance of the gradient composites during the 12 d aging process at 338 K and 80% relative humidity(RH) were systematically studied. The results show that the phase composition and microstructure of Gd/BST thermal-electro-magnetic gradient composites have excellent service stability. The chemical composition and average thickness (~4.5 μm) of Gd-Te diffusion layer at Gd/BST heterogeneous interface doesn’t exhibit obvious change during the aging process. The test of thermoelectric and cooling performance along different Gd concentration gradient indicates that ZT of the materials negligibly changed before and after aging treatment, and the cooling temperature difference of the single-leg device is stable at about 6.5 K under the threshold current of 2.5 A. These results show that thermoelectric and cooling performance of the Gd/BST gradient composites have excellent service stability.

Key words: thermo-electro-magnetic gradient composites, thermoelectric performance, cooling performance, service stability

中图分类号:

TB34

汪波, 余健, 李存成, 聂晓蕾, 朱婉婷, 魏平, 赵文俞, 张清杰. Gd/Bi_0.5Sb_1.5Te₃热电磁梯度复合材料的服役稳定性[J]. 无机材料学报, 2023, 38(6): 663-670.

WANG Bo, YU Jian, LI Cuncheng, NIE Xiaolei, ZHU Wanting, WEI Ping, ZHAO Wenyu, ZHANG Qingjie. Service Stability of Gd/Bi_0.5Sb_1.5Te₃ Thermo-electro-magnetic Gradient Composites[J]. Journal of Inorganic Materials, 2023, 38(6): 663-670.

图/表 10

图1 用于结构和性能表征样品的切割部位示意图

Fig. 1 Schematic diagram of the cutting positions for the structure and performance characterization of samples

图2 Gd/BST梯度复合材料电性能测试示意图

Fig. 2 Schematic diagram of the electrical performance test of Gd/BST gradient composite

图3 不同时间老化后Gd/BST梯度复合材料的XRD图谱

Fig. 3 XRD patterns of Gd/BST gradient composites with different aging time

图4 老化处理12d后样品的(a)二次电子像、(b, c) 背散射电子像及(d)元素EPMA面扫图

Fig. 4 (a) Secondary electron image (SEI), (b, c) backscattered electron images (BEI) and (d) EPMA elemental mapping images of the samples after aging for 12 d

图5 Gd/BST异质界面扩散层厚度与老化时间变化关系

Fig. 5 Change of thickness of the diffusion layer of Gd/BST heterojunction interface with aging time

图6 (a, b)未老化和(c, d)老化12 d后样品中从Gd球到BST基体方向各元素的EPMA波谱线扫结果

Fig. 6 EPMA element line analysis from Gd ball to BST matrix for (a, b) as-prepared sample and (c, d) sample after aging for 12 d

图7 Gd/BST梯度复合材料老化不同时间后正向(实心图标)和反向(空心图标)测试的(a)电导率和(b)Seebeck系数与温度的关系曲线, 插图为300、350和500 K条件下的电导率和Seebeck系数与老化时间之间的关系曲线

Fig. 7 Temperature dependence of (a) electrical conductivity and (b) Seebeck coefficient for forward (solid icon) and reverse (hollow icon) testing of Gd/BST gradient composites for different aging time with insets showing change of electrical conductivity and Seebeck coefficient with aging time at 300, 350 and 500 K

图8 Gd/BST梯度复合材料老化不同时间后正向(实心图标)和反向(空心图标)测试的(a)热导率、(b)载流子热导率、(c)晶格热导率和(d)ZT与与温度的关系曲线, 图中的插图为300、350和500 K时的热导率、载流子热导率、晶格热导率和ZT与老化时间之间的关系曲线

Fig. 8 Temperature dependence of (a) thermal conductivity, (b) carrier thermal conductivity, (c) lattice thermal conductivity, and (d) ZT for forward (solid icon) and reverse (hollow icon) testing of Gd/BST gradient composites with different aging time with insets showing changes of thermal conductivity, carrier thermal conductivity, lattice thermal conductivity, and ZT with aging time at 300, 350 and 500 K

图9 老化不同时间后Gd/BST梯度复合材料单臂器件在不同正向电流下的制冷端和散热端的温度变化

Fig. 9 Cooling performance of the Gd/BST gradient composite device with different aging time under different forward currents ΔT: Difference of working temperatures; ΔTC: Difference of cooling temperatures Colorful figures are available on website

表1 Gd/BST梯度复合材料单臂器件老化不同时间后的制冷性能/K

Table 1 Cooling performance of Gd/BST gradient composite device with different ageing time/K

Sample	I = 1.5 A				I=2.0 A				I=2.5 A				I=3.0 A
	I_forward		I_reverse		I_forward		I_reverse		I_forward		I_reverse		I_forward		I_reverse
	ΔT	ΔT_C	ΔT	ΔT_C	ΔT	ΔT_C	ΔT	ΔT_C	ΔT	ΔT_C	ΔT	ΔT_C	ΔT	ΔT_C	ΔT	ΔT_C
t00	14.6	5.4	15.8	5.5	18.7	6.1	21.1	6.3	24.1	6.6	27.3	7.0	28.4	6.1	33.3	7.0
t04	15.6	5.4	16.6	5.7	20.1	6.3	22.2	6.2	24.6	6.8	28.3	6.7	28.8	6.7	34.9	6.5
t08	14.4	5.2	15.5	5.4	19.3	6.1	21.0	6.3	24.1	6.4	27.0	6.9	29.2	6.2	33.2	7.0
t12	15.3	5.4	15.9	5.6	19.1	6.2	21.2	6.2	23.2	6.5	26.5	6.5	27.0	6.3	31.6	6.6

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Gd/Bi_0.5Sb_1.5Te₃热电磁梯度复合材料的服役稳定性

Service Stability of Gd/Bi_0.5Sb_1.5Te₃ Thermo-electro-magnetic Gradient Composites

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