Ge1-xInxTe微观结构对热电性能的影响

doi:10.15541/jim20190641

无机材料学报 ›› 2020, Vol. 35 ›› Issue (8): 916-922.DOI: 10.15541/jim20190641 CSTR: 32189.14.10.15541/jim20190641

所属专题：能源材料论文精选(三)：热电与燃料电池(2020)；【虚拟专辑】热电材料(2020~2021)

Ge_1-_xIn_xTe微观结构对热电性能的影响

邱小小¹(),周细应¹(),傅赟天²,孙晓萌²,王连军³(),江莞²

1.上海工程技术大学材料工程学院, 上海 201620
2.东华大学材料科学与工程学院, 纤维材料改性国家重点实验室, 上海 201620
3.东华大学先进玻璃制造技术教育部工程研究中心, 上海 201620

收稿日期:2019-12-18 修回日期:2020-01-10 出版日期:2020-08-20 网络出版日期:2020-03-06
作者简介:邱小小(1994–), 男, 硕士研究生. E-mail: 1511921567@qq.com
QIU Xiaoxiao(1994–), male, Master candidate. E-mail: 1511921567@qq.com
基金资助:
国家自然科学基金(51774096);国家自然科学基金(51871053);上海市科委科技创新行动计划基础研究领域项目(18JC1411200)

Influence of Ge_1-_xIn_xTe Microstructure on Thermoelectric Properties

QIU Xiaoxiao¹(),ZHOU Xiying¹(),FU Yuntian²,SUN Xiaomeng²,WANG Lianjun³(),JIANG Wan²

1. School of Materials Engineering, Shanghai University of Engineering and Science, Shanghai 201620, China
2. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
3. Engineering Research Center of Advanced Glasses Manufacturing Technology, Ministry of Education, Donghua University, Shanghai 201620, China

Received:2019-12-18 Revised:2020-01-10 Published:2020-08-20 Online:2020-03-06
Supported by:
National Natural Science Foundation of China(51774096);National Natural Science Foundation of China(51871053);Basic Research Project of Science and Technology Innovation Action Plan of Shanghai Science and Technology Commission(18JC1411200)

摘要/Abstract

摘要：

在GeTe中掺杂In能够引入共振能级, 但其微观结构对热电性能的影响还不明确。本研究采用熔炼-淬火-退火并结合放电等离子体烧结(SPS)的方法制备了系列Ge_1-_xIn_xTe样品, 采用XRD、SEM、激光导热仪和热电性能分析系统(ZEM-3)对其微观结构和热电性能进行了研究。结果表明, 随着In元素的掺入, Ge_1-_xIn_xTe的晶胞体积减小、人字鱼骨结构变小、晶界增多, 导致晶格热导率降低, 获得的最低热导率为2.16 W·m ^-1·K ^-1。同时, 掺杂In引入了共振能级, 降低了载流子浓度, 使塞贝克系数以及功率因子增大。当In掺杂量x为0.03时, Ge_1-_xIn_xTe在600 K时获得最大ZT值1.15, 比GeTe提升了26.4%, 表明调整Ge_1-_xIn_xTe的微观结构可以有效提升热电性能。

关键词: 掺杂In, 热导率, GeTe, 热电材料

Abstract:

The resonant levels can be introduced into GeTe by In element, however, the effect of its microstructure on thermoelectric properties still remained unclear. In this study, a series of Ge_1-_xIn_xTe samples were prepared by smelting-quenching-annealing combined with spark plasma sintering (SPS). The XRD, SEM, laser thermal conductivity instrument and thermoelectric performance analysis system (ZEM-3) were applied to study the microstructure and thermoelectric properties. Results show that, with the incorporation of In content, the unit cell volume decreases, and Herringbone structure has become smaller and grain boundaries increase, which result in a decrease in the lattice thermal conductivity. Thereby, a minimum thermal conductivity of 2.16 W·m ^-1·K ^-1 is obtained. Meanwhile, In doping introduces the resonant levels and decreases the carrier concentration, so the Seebeck coefficient and the power factor increase. Consequently, the maximum ZT value of 1.15 is obtained in the 0.03 sample at 600 K, which is 26.4% higher than that of GeTe. This indicates that the thermoelectric properties of Ge_1-_xIn_xTe can be effectively improved by the microstructure regulation.

Key words: In doping, thermal conductivity, GeTe, thermoelectric materials

中图分类号:

TB34
O472

邱小小,周细应,傅赟天,孙晓萌,王连军,江莞. Ge_1-_xIn_xTe微观结构对热电性能的影响[J]. 无机材料学报, 2020, 35(8): 916-922.

QIU Xiaoxiao,ZHOU Xiying,FU Yuntian,SUN Xiaomeng,WANG Lianjun,JIANG Wan. Influence of Ge_1-_xIn_xTe Microstructure on Thermoelectric Properties[J]. Journal of Inorganic Materials, 2020, 35(8): 916-922.

图/表 10

图1 Ge1-xInxTe的XRD图谱

Fig. 1 XRD patterns of Ge1-xInxTe compounds (a) Before SPS; (b) After SPS

表1 Ge1-xInxTe晶格常数及晶胞体积

Table 1 Lattice parameters and volume of Ge1-xInxTe

x	a/nm	b/nm	c/nm	V/nm³
0	0.4165	0.4165	1.0667	0.160284
0.01	0.4167	0.4167	1.0656	0.160234
0.02	0.4170	0.4170	1.0639	0.160204
0.03	0.4173	0.4173	1.0627	0.160278
0.05	0.4175	0.4175	1.0604	0.160037
0.10	0.4192	0.4192	1.0449	0.159058

图2 Ge1-xInxTe样品的X射线光电子能谱图

Fig. 2 XPS patterns of Ge1-xInxTe (a) Full scan spectrum; (b) Binding energy of Ge3d; (c) Binding energy of In3d; (d) Binding energy of Te3d

图3 Ge0.97In0.03Te的EDS分析结果

Fig. 3 EDS mapping of the elements in Ge0.97In0.03Te (a)Fractured surface of Ge0.97In0.03Te; (b-d) Corresponding compositional mapping

表2 Ge0.97In0.03Te的元素信息表

Table 2 Information of different elements of Ge0.97In0.03Te

Element	Atomic number	Mass/ %	Normalized quality/%	Atom/ %	Abs. error/ %
Te	52	64.25	64.28	50.38	1.89
Ge	32	34.24	34.26	47.18	1.91
In	49	1.43	1.46	1.27	0.07

图4 Ge1-xInxTe的断面SEM照片

Fig. 4 Fructure surface SEM images of Ge1-xInxTe (a) x=0; (b)x=0.01; (c) x=0.02; (d) x=0.03; (e)x=0.05; (f) x=0.10

表3 室温下Ge1-xInxTe的电学输运性能

Table 3 Electrical transport properties of Ge1-xInxTe at room temperature

Sample	ρ/(g·cm^-3)	d/%	σ/(×10⁴, S·m^-1)	S/(μV·K^-1)	n_H/(×10²⁰, cm^-3)	m_H/(cm²·V^-1·s^-1)	L₀/(×10^-8, V²·K^-2)
x=0	6.176	99.27	74.92	38.4	16.32	35.31	2.22
x =0.005	6.168	99.00	54.75	49.7	—	—	2.15
x =0.010	6.184	99.16	49.75	54.5	—	—	2.13
x =0.015	6.193	99.20	37.72	64.3	13.05	25.44	2.07
x =0.020	6.185	98.95	30.61	66.8	—	—	2.05
x =0.025	6.170	98.59	26.80	77.9	—	—	2.01
x =0.030	6.183	98.75	22.49	86.0	10.55	22.54	1.98
x =0.050	6.162	97.86	11.47	125	9.818	12.40	1.84
x =0.100	6.240	97.48	1.02	267	4.083	5.521	1.60

图5 Ge1-xInxTe的热电性能

Fig. 5 Thermoelectric properties of Ge1-xInxTe (a) Electrical conductivity; (b) Seebeck coefficient; (c) Power factor; (d) Total thermal conductivity; (e) Lattice thermal conductivity; (f) Figure of merit

图6 Ge1-xInxTe的热容

Fig. 6 Heat capacity of Ge1-xInxTe

图7 微观结构对热电性能影响的机理示意图

Fig. 7 Mechanism of the effect of structure on thermoelectric performance

参考文献 32

[1]	MAO J, LIU Z, ZHOU J, et al. Advances in thermoelectrics. Advances in Physics, 2018,67(2):69-147.
[2]	ZHANG X, ZHAO L. Thermoelectric materials: energy conversion between heat and electricity. Journal of Materiomics, 2015,1(2):92-105. DOI URL
[3]	LU X, ZHENG Q, GU S, et al. Enhanced Te properties of Cu@Ag/Bi₂Te₃ nanocomposites by decoupling electrical and thermal properties. Chinese Chemical Letters, 2019. in press, doi: 10.1016/j.cclet.2019.07.034. URL PMID
[4]	ZHANG Q H, BAI S Q, CHEN L D. Technologies and applications of thermoelectric devices: current status, challenges and prospects. Journal of Inorganic Materials, 2019,34(3):279-293. DOI URL
[5]	ZHOU Z X, LI J L, FAN Y C, et al. Uniform dispersion of SiC in Yb-filled skutterudite nanocomposites with high thermoelectric and mechanical performance. Scripta Materialia, 2019,162:166-171. DOI URL
[6]	SAJID M, HASSAN I, RAHMAN A. An overview of cooling of thermoelectric devices. Renewable and Sustainable Energy Reviews, 2017,78:15-22. DOI URL
[7]	LI W, PENG J, XIAO W, et al. The temperature distribution and electrical performance of fluid heat exchanger-based thermoelectric generator. Applied Thermal Engineering, 2017,118:742-747. DOI URL
[8]	ZHU T J. Recent advances in thermoelectric materials and devices. Journal of Inorganic Materials, 2019,34(3):233-235. DOI URL
[9]	HONG M, ZOU J, CHEN Z G. Thermoelectric GeTe with diverse degrees of freedom having secured superhigh performance. Advanced Materials, 2019,31(14):e1807071. DOI URL PMID
[10]	TANG C M, LIANG D D, LI H Z, et al. Preparation and thermoelectric properties of Cu_1.8S/CuSbS₂ composites. Journal of Advanced Ceramics, 2019,8(2):209-217. DOI URL
[11]	ZHANG X, LI J, WANG X, et al. Vacancy manipulation for thermoelectric enhancements in GeTe alloys. Journal of the American Chemical Society, 2018,140(46):15883-15888. DOI URL PMID
[12]	OKAMOTO H. Ge-Te (germanium-tellurium). Journal of Phase Equilibria, 2000,21(5):496-496. DOI URL
[13]	DONG J F, SUN F H, TANG H C, et al. Medium-temperature thermoelectric GeTe: vacancy suppression and band structure engineering leading to high performance. Energy & Environmental Science, 2019,12(4):1396-1403.
[14]	PERUMAL S, ROYCHOWDHURY S, NEGI D S, et al. High thermoelectric performance and enhanced mechanical stability of p-type Ge_1-xSb_xTe. Chemistry of Materials, 2015,27(20):7171-7178. DOI URL
[15]	GELBSTEIN Y, DAVIDOW J, LESHEM E, et al. Significant lattice thermal conductivity reduction following phase separation of the highly efficient Ge_xPb_1-xTe thermoelectric alloys. Physica Status Solidi (b), 2014,251(7):1431-1437. DOI URL
[16]	CHEN Z, ZHANG X, PEI Y. Manipulation of phonon transport in thermoelectrics. Advanced Materials, 2018,30(17):e1705617. DOI URL PMID
[17]	HEREMANS J P, JOVOVIC V, TOBERER E S, et al. Enhancement of thermoelectric efficiency in PbTe by distortion of the electronic density of states. Science, 2008,321(5888):554-557. DOI URL PMID
[18]	WU L H, LI X, WANG S Y, et al. Resonant level-induced high thermoelectric response in indium-doped GeTe. NPG Asia Materials, 2017,9(1):e343. DOI URL
[19]	SRINIVASAN B, GELLE A, HALET J F, et al. Detrimental effects of doping Al and Ba on the thermoelectric performance of GeTe. Materials (Basel), 2018,11(11):2237. DOI URL
[20]	LEE H S, KIM B S, CHO C W, et al. Herringbone structure in GeTe-based thermoelectric materials. Acta Materialia, 2015,91:83-90. DOI URL
[21]	ZHENG Z, SU X, DENG R, et al. Rhombohedral to cubic conversion of GeTe via MnTe alloying leads to ultralow thermal conductivity, electronic band convergence, and high thermoelectric performance. Journal of the American Chemical Society, 2018,140(7):2673-2686. DOI URL PMID
[22]	ZHOU Y M, ZHOU Y L, PANG Q T, et al. Different doping sites of Ag on Cu₂SnSe₃ and their thermoelectric property. Journal of Inorganic Materials, 2019,34(3):301-309. DOI URL
[23]	KIM S, LEE H S. Effects of addition of Si and Sb on the microstructure and thermoelectric properties of GeTe. Metals and Materials International, 2018,25(2):528-538. DOI URL
[24]	HONG M, WANG Y, LIU W, et al. Arrays of planar vacancies in superior thermoelectric Ge_1-x-yCd_xBi_yTe with band convergence. Advanced Energy Materials, 2018,8(30):1801837. DOI URL
[25]	DESOUZA L, ZAMIAN J, DAROCHAFILHO G, et al. Blue pigments based on Co_xZn_1-xAl₂O₄ spinels synthesized by the polymeric precursor method. Dyes and Pigments, 2009,81(3):187-192. DOI URL
[26]	ALLRED A L. Electronegativity values from thermochemical data. Journal of Inorganic and Nuclear Chemistry, 1961,17(3):215-221. DOI URL
[27]	SRINIVASAN B, GELLÉ A, GUCCI F, et al. Realizing a stable high thermoelectric ZT~2 over a broad temperature range in Ge_1-x-yGa_xSb_yTe via band engineering and hybrid flash-SPS processing. Inorganic Chemistry Frontiers, 2019,6(1):63-73. DOI URL
[28]	SRINIVASAN B, GAUTIER R, GUCCI F, et al. Impact of coinage metal insertion on the thermoelectric properties of GeTe solid- state solutions. The Journal of Physical Chemistry C, 2017,122(1):227-235. DOI URL
[29]	YUE L, FANG T, ZHENG S, et al. Cu/Sb codoping for tuning carrier concentration and thermoelectric performance of GeTe-based alloys with ultralow lattice thermal conductivity. ACS Applied Energy Materials, 2019,2(4):2596-2603. DOI URL
[30]	LI J, ZHANG X, CHEN Z, et al. Low-symmetry rhombohedral gete thermoelectrics. Joule, 2018,2(5):976-987. DOI URL
[31]	ROYCHOWDHURY S, BISWAS K. Slight symmetry reduction in thermoelectrics. Chem., 2018,4(5):939-942. DOI URL
[32]	WANG S, YANG J, TOLL T, et al. Conductivity-limiting bipolar thermal conductivity in semiconductors. Scientific Reports, 2015,5:10136. DOI URL PMID

Ge_1-_xIn_xTe微观结构对热电性能的影响

Influence of Ge_1-_xIn_xTe Microstructure on Thermoelectric Properties

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Ge1-xInxTe微观结构对热电性能的影响

Influence of Ge1-xInxTe Microstructure on Thermoelectric Properties

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Ge_1-_xIn_xTe微观结构对热电性能的影响

Influence of Ge_1-_xIn_xTe Microstructure on Thermoelectric Properties