Ag掺杂Cu2SnSe3致相反热电性能及其复合提升

doi:10.15541/jim20180295

无机材料学报 ›› 2019, Vol. 34 ›› Issue (3): 301-309.DOI: 10.15541/jim20180295

Ag掺杂Cu₂SnSe₃致相反热电性能及其复合提升

周一鸣¹, 周玉玲², 庞前涛³, 邵建伟⁴, 赵立东¹

1. 北京航空航天大学材料科学与工程学院, 北京 100191;
2. 中航沈飞民用飞机有限责任公司, 沈阳 110034;
3. 中国石油天然气股份有限公司辽宁铁岭销售分公司, 铁岭 112000;
4. 中国航发沈阳黎明航发发动机有限责任公司, 沈阳 110043

收稿日期:2018-07-02 修回日期:2018-07-25 出版日期:2019-03-20 网络出版日期:2019-02-26
作者简介:周一鸣(1994-), 男, 硕士研究生. E-mail: zhouym@buaa.edu.cn
基金资助:
国家重点研发计划(2018YFB0703600);国家自然科学基金(51571007, 51772012);北京市科学技术委员会(Z171100002017002);深圳市孔雀计划(KQTD2016022619565911);111计划 (B17002)

Different Doping Sites of Ag on Cu₂SnSe₃ and Their Thermoelectric Property

ZHOU Yi-Ming¹, ZHOU Yu-Ling², PANG Qian-Tao³, SHAO Jian-Wei⁴, ZHAO Li-Dong¹

1. School of Materials Science and Engineering, Beihang University, Beijing 100191, China;
2. AVIC SAC Commercial Aircraft Company Ltd., Shenyang 110034, China;
3. Liaoning Tieling Sales Branch, Petro China Co. Ltd., Tieling 112000, China;
4. Shenyang Liming Areo-Engine Co. Ltd., Shenyang 110043, China;

Received:2018-07-02 Revised:2018-07-25 Published:2019-03-20 Online:2019-02-26
About author:ZHOU Yi-Ming. E-mail: zhouym@buaa.edu.cn
Supported by:
National Key R&D Program of China(2018YFB0703600);National Natural Science Foundation of China(51571007, 51772012);Beijing Municipal Science & Technology Commission(Z171100002017002);Shenzhen Peacock Plan Team(KQTD2016022619565911);111 Project(B17002)

摘要/Abstract

摘要：

热电材料可有效回收废热并将其转化为电能, 然而转换效率受复杂耦合热电参数的限制。高效热电材料需要具有优异的电传输和良好的隔热性能。具有类金刚石结构的Cu₂SnSe₃是一种潜在的中温区热电材料, 本研究通过在Sn位和Cu引入Ag离子, 分别获得了高电传输相Cu₂Sn_0.93Ag_0.07Se₃和低热传输相Cu_1.91Ag_0.09SnSe₃, 然后通过机械混合和烧结制备了Cu₂Sn_0.93Ag_0.07Se₃和Cu_1.91Ag_0.09SnSe₃两相复合的材料。利用两相材料的晶体结构相同和晶格常数匹配的特点, 在高温段有效地协同调控了Cu₂SnSe₃材料的电输运和热输运性能, 从而使材料的高温热电性能得到优化, 用有效介质理论很好地描述了高性能的两相复合材料的电和热传输行为。

关键词: 热电, 有效介质理论, 类金刚石结构, Cu₂SnSe

Abstract:

Thermoelectric materials enable the direct inter-conversion between electrical energy and thermal energy. However, the conversion efficiency is limited by complex interdependent thermoelectric parameters, while the high performance thermoelectrics should simultaneously possess excellent electrical transport properties and poor thermal conductivities. The diamond-like compound Cu₂SnSe₃ is a promising middle-temperature thermoelectric material. In this work, the phase (Cu₂Sn_0.93Ag_0.07Se₃) with excellent electrical transport properties and the phase (Cu_1.91Ag_0.09SnSe₃) with poor thermal conductivities were obtained just through Ag doping on the Sn and Cu sites, respectively. Meanwhile, their Seebeck coefficients were also quite different. To combine their advantages, the composites of Cu₂Sn_0.93Ag_0.07Se₃ and Cu_1.91Ag_0.09SnSe₃ were fabricated through mechanical mixing and sintering. Benefited from the same crystal structure and the similar lattice parameters for these two phases, the small-mismatch phase interface is supposed to scatter phonons with little influence to the electrons, especially at high temperature. Therefore, the thermoelectric performance is improved due to the synergistically optimized electrical and thermal transport properties, which are well supported by the effective media theory for the composite.

Key words: thermoelectric, effective medium theory, diamond-like, Cu₂SnSe₃

中图分类号:

TQ174

周一鸣, 周玉玲, 庞前涛, 邵建伟, 赵立东. Ag掺杂Cu₂SnSe₃致相反热电性能及其复合提升[J]. 无机材料学报, 2019, 34(3): 301-309.

ZHOU Yi-Ming, ZHOU Yu-Ling, PANG Qian-Tao, SHAO Jian-Wei, ZHAO Li-Dong. Different Doping Sites of Ag on Cu₂SnSe₃ and Their Thermoelectric Property[J]. Journal of Inorganic Materials, 2019, 34(3): 301-309.

图/表 7

图1 Cu2Sn1-xAgxSe3 (x=0~0.09)的XRD图像及25°~45°的放大图谱

Fig. 1 XRD patterns and enlarged XRD patterns between 25° to 45°of Cu2Sn1-xAgxSe3 (x=0-0.09)

图2 Cu2Sn1-xAgxSe3 (x=0~0.07)的热电性能随温度的变化曲线

Fig. 2 Temperature dependence of thermoelectric properties of Cu2Sn1-xAgxSe3 (x = 0-0.07)(a) Electrical conductivity; (b) Seebeck coefficient; (c) Power factor; (d) Total thermal conductivity; (e) Lattice thermal conductivity; (f) Thermoelectric figure of merit (ZT)

图3 Cu2-yAgySnSe3 (y=0~0.09) 的XRD图谱

Fig. 3 XRD patterns of Cu2-yAgySnSe3 (y=0-0.09)

表1 Cu2-yAgySnSe3的晶格常数和平均晶胞体积

Table 1 Lattice parameters and average volume of unit cell of Cu2-yAgySnSe3

y	a/nm	b/nm	c/nm	β/(°)	V/nm³
0	0.69919	1.20763	0.69667	109.26	0.55533
0.01	0.69714	1.20586	0.69671	109.20	0.55310
0.03	0.69812	1.20641	0.69551	109.21	0.55314
0.05	0.69973	1.20578	0.69819	109.47	0.55539
0.07	0.70011	1.20749	0.70033	109.47	0.55817
0.09	0.70019	1.21247	0.69674	109.46	0.55772

图4 Cu2-yAgySnSe3 (y=0~0.09)的热电性能随温度的变化曲线

Fig. 4 Temperature dependence of thermoelectric properties of Cu2-yAgySnSe3 (y=0-0.09)(a) Electrical conductivity; (b) Seebeck coefficient; (c) Power factor; (d) Total thermal conductivity;(e) Lattice thermal conductivity; (f) Thermoelectric figure of merit (ZT)

图5 Cu2Sn0.93Ag0.07Se3和Cu1.91Ag0.09SnSe3复合样品的热电性能随温度的变化曲线

Fig. 5 Temperature dependence of thermoelectric properties of composites of Cu2Sn0.93Ag0.07Se3 and Cu1.91Ag0.09SnSe3(a) Electrical conductivity; (b) Seebeck coefficient; (c) Power factor; (d) Total thermal conductivity;(e) Lattice thermal conductivity; (f) Thermoelectric figure of merit (ZT)

图6 Cu2Sn0.93Ag0.07Se3和Cu1.91Ag0.09SnSe3复合样品的有效介质理论计算结果

Fig. 6 Calculations by effective medium theory for composites of Cu2Sn0.93Ag0.07Se3 and Cu1.91Ag0.09SnSe3

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Ag掺杂Cu₂SnSe₃致相反热电性能及其复合提升

Different Doping Sites of Ag on Cu₂SnSe₃ and Their Thermoelectric Property

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