稳定立方相p型GeMnTe2基热电材料制备

doi:10.15541/jim20250036

无机材料学报 ›› 2025, Vol. 40 ›› Issue (11): 1245-1251.DOI: 10.15541/jim20250036

稳定立方相p型GeMnTe₂基热电材料制备

张海丰¹(), 蒋蒙¹, 孙婷婷³(), 王连军¹(), 江莞¹^,²

1.东华大学材料科学与工程学院, 先进纤维材料全国重点实验室, 上海 201620
2.东华大学功能材料研究中心, 上海 201620
3.东华大学生物与医学工程学院, 上海 201620

收稿日期:2025-01-25 修回日期:2025-03-31 出版日期:2025-11-20 网络出版日期:2025-04-15
通讯作者: 孙婷婷, 讲师. E-mail: tingtingsun@dhu.edu.cn;
王连军, 教授. E-mail: wanglj@dhu.edu.cn
作者简介:张海丰(2000-), 男, 硕士研究生. E-mail: zhanghf2025@163.com
基金资助:
国家自然科学基金(U23A20685);国家自然科学基金(52174343)

Preparation of p-type GeMnTe₂Based Thermoelectric Materials with Stable Cubic Phase

ZHANG Haifeng¹(), JIANG Meng¹, SUN Tingting³(), WANG Lianjun¹(), JIANG Wan¹^,²

1. State Key Laboratory of Advanced Fiber Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
2. Institute of Functional Materials, Donghua University, Shanghai 201620, China
3. College of Biological Science and Medical Engineering, Donghua University, Shanghai 201620, China

Received:2025-01-25 Revised:2025-03-31 Published:2025-11-20 Online:2025-04-15
Contact: SUN Tingting, lecturer. E-mail: tingtingsun@dhu.edu.cn;
WANG Lianjun, professor. E-mail: wanglj@dhu.edu.cn
About author:ZHANG Haifeng (2000-), male, Master candidate. E-mail: zhanghf2025@163.com
Supported by:
National Natural Science Foundation of China(U23A20685);National Natural Science Foundation of China(52174343)

摘要/Abstract

摘要：

p型GeTe基热电材料在中低温区(300~800 K)具有良好的热电性能, 受到了广泛关注。然而, 在600~700 K温度区间, 该化合物易从菱方相转变为立方相, 导致热膨胀系数变化, 这限制了其在热电器件领域的应用。因此, 获得稳定无相变的GeTe基热电材料至关重要。本研究利用高温熔融结合放电等离子体烧结制备了GeMnTe₂材料。合成的样品存在MnTe₂第二相, 导致其总热导率从800 K下的1.34 W·m^-1·K^-1增大到1.81 W·m^-1·K^-1。本研究通过优化不同元素化学计量比, 抑制了MnTe₂第二相的生成, 获得了稳定立方相GeMnTe_1.96材料。制备的GeMnTe_1.96化合物样品最高zT达到~0.85(800 K), 这为中温区废热高效稳定回收利用提供了有发展潜力的热电材料。

关键词: 高温熔融, 立方相, GeMnTe₂基化合物, 热导率

Abstract:

p-type GeTe based thermoelectric (TE) materials have attracted significant attention owing to their remarkable TE performance in medium and low temperature range (300-800 K). However, the material undergoes a phase transition from rhombohedral to cubic in the temperature range of 600-700 K, inducing changes in the coefficient of thermal expansion that limit its application in TE devices. Consequently, it is imperative to develop stable GeTe based thermoelectric material free from phase transitions. In this study, high temperature melting combined with spark plasma sintering was employed to synthesize GeMnTe₂. The as-synthesized samples contain the secondary phase of MnTe₂, which increases total thermal conductivity from 1.34 W·m^-1·K^-1 to 1.81 W·m^-1·K^-1 at 800 K. By optimizing the chemical stoichiometry of different elements, the formation of MnTe₂ secondary phase is suppressed, resulting in stable pure cubic phase GeMnTe_1.96. GeMnTe_1.96 achieves a maximum zT of ~0.85 at 800 K. This TE material exhibits significant potential for efficient and stable waste heat utilization in the medium temperature range.

Key words: high temperature melting, cubic phase, GeMnTe₂ based compound, thermal conductivity

中图分类号:

TQ174

张海丰, 蒋蒙, 孙婷婷, 王连军, 江莞. 稳定立方相p型GeMnTe₂基热电材料制备[J]. 无机材料学报, 2025, 40(11): 1245-1251.

ZHANG Haifeng, JIANG Meng, SUN Tingting, WANG Lianjun, JIANG Wan. Preparation of p-type GeMnTe₂Based Thermoelectric Materials with Stable Cubic Phase[J]. Journal of Inorganic Materials, 2025, 40(11): 1245-1251.

图/表 5

图1 室温下(a)六方相MnTe、(b)菱方相GeTe和(c)立方相GeMnTe2的晶体结构; (d)室温下样品GeMn1-xTe2-2x与GeMnTe2-y的粉末XRD图谱; (e)GeMnTe1.96样品的差示扫描热流曲线和热重曲线

Fig. 1 Room temperature crystal structures for (a) hexagonal MnTe, (b) rhombohedral GeTe and (c) cubic GeMnTe2; (d) Powder XRD patterns of GeMn1-xTe2-2x and GeMnTe2-y at room temperature;(e) Differential scanning calorimetry and thermogravimetric heat flow curves of GeMnTe1.96

图2 (a) GeMnTe2、(b) GeMn0.98Te1.96和(c) GeMnTe1.96样品的BSE照片和EDS面扫描元素分布图

Fig. 2 BSE images and surface scan EDS element distributions of (a) GeMnTe2, (b) GeMn0.98Te1.96 and (c) GeMnTe1.96 samples

表1 图2(a)中对应位置的EDS点扫描元素含量(原子分数)

Table 1 Element contents of the points in Fig. 2(a) by EDS point scanning (in atom)

Point	Mn/%	Ge/%	Te/%
1	34.39	4.04	61.56
2	34.50	/	65.50
3	34.74	5.76	59.49

图3 样品GeMnTe1.96(a)沿[$0\bar{1}1$]方向的(a)FFT图像以及对应的(b)HRTEM照片和(c)元素分布图

Fig. 3 (a) FFT image along [$0\bar{1}1$] zone axes, (b) HRTEM image and (c) elemental distribution images for GeMnTe1.96 sample

图4 样品GeMn1-xTe2-2x与GeMnTe2-y的(a)电阻率、(b) Seebeck系数、(c)功率因子、(d)总热导率、(e)晶格热导率和电子热导率、(f) zT随温度的变化关系

Fig. 4 Temperature dependent (a) electrical resistivity, (b) Seebeck coefficient, (c) power factor, (d) total thermal conductivity, (e) lattice and electronic thermal conductivity, and (f) zT for GeMn1-xTe2-2x and GeMnTe2-y samples

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稳定立方相p型GeMnTe₂基热电材料制备

Preparation of p-type GeMnTe₂Based Thermoelectric Materials with Stable Cubic Phase

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