基于分步式双重调控n型(PbTe)1-x-y(PbS)x(Sb2Se3)y体系的热电传输特性

doi:10.15541/jim20200635

摘要/Abstract

摘要：

PbTe在中温区热电材料中广受关注, 然而, n型PbTe因其较低的载流子浓度和复杂的能带结构, 其热电性能难以大幅提升。本研究通过分步式添加PbS、Sb₂Se₃组元以调控n型PbTe基体的热、电传输性能。研究发现, PbS与Sb₂Se₃组元可分别提升功率因子和降低热导率。通过扩大带隙、增加点缺陷、第二相弥散等途径可改善能带, 加剧散射, 从而有效提升热电优值ZT。其中(PbTe)_0.94(PbS)_0.05(Sb₂Se₃)_0.01表现出最佳的热电性能, 700 K时ZT最大值为1.7, 且ZT平均值较PbTe基体显著提高, 这表明分步式双组元调控可为改善其它材料体系的热电性能提供技术途径。

关键词: 热电材料, n型PbTe, 双重组元, 分步式调控

Abstract:

PbTe recently attracted extensive attentions as potential candidates for applications at intermediate temperatures. However, it is difficult to significantly improve the thermoelectric performance of n-type PbTe due to its relatively low carrier concentration and complicated band structures. In this study, the stepwise addition of dual components was utilized to verify the possibility for modulating the thermal and electrical transport characteristics of n-type PbTe-based materials. The results indicated that PbS and Sb₂Se₃ can improve the power factor and reduce thermal conductivity of PbTe, respectively. Optimization of band structures and enhancement of phonon scattering were realized by means of expanding band gap, producing point defects and secondary dispersoids. As a result, the merit of figure ZT was remarkably improved. In particular, (PbTe)_0.94(PbS)_0.05(Sb₂Se₃)_0.01 exhibited the highest value of ZT=1.7 at 700 K simultaneously with almost doubled average ZT compared to the pristine PbTe. Accordingly, it seems that the stepwise addition of adequate dual components provides possible technological approach for improving thermoelectric performance of other materials.

Key words: thermoelectric material, n-type PbTe, dual-component, stepwise modulation

中图分类号:

O472

张岑岑, 王雪, 彭良明. 基于分步式双重调控n型(PbTe)_1-_x_-_y(PbS)_x(Sb₂Se₃)_y体系的热电传输特性[J]. 无机材料学报, 2021, 36(9): 936-942.

ZHANG Cencen, WANG Xue, PENG Liangming. Thermoelectric Transport Characteristics of n-type (PbTe)_1-_x_-_y(PbS)_x(Sb₂Se₃)_y Systems via Stepwise Addition of Dual Components[J]. Journal of Inorganic Materials, 2021, 36(9): 936-942.

图/表 8

表1 (PbTe)1-x-y(PbS)x(Sb2Se3)y的编号、室温下的霍尔系数、载流子浓度与迁移率

Table 1 Sample ID, Hall coefficients, carrier concentrations and mobilities at room temperature for (PbTe)1-x-y(PbS)x(Sb2Se3)y

Nominal composition		Sample ID	R_H/(cm³∙C^-1)	n_H/(´10¹⁹, cm^-3)	μ_H/(cm²∙V^-1∙s^-1)
Matrix	PbTe	A	-0.203	3.075	82.691
Dual component	(PbTe)_0.97(PbS)_0.03	AB₃	-0.099	6.319	104.962
	(PbTe)_0.95(PbS)_0.05	AB₅	-0.115	5.918	98.805
	(PbTe)_0.93(PbS)_0.07	AB₇	-0.087	7.223	40.345
Triple component	(PbTe)_0.945(PbS)_0.05(Sb₂Se₃)_0.005	AB₅C_0.5	-0.071	8.752	89.784
	(PbTe)_0.94(PbS)_0.05(Sb₂Se₃)_0.01	AB₅C₁	-0.116	5.406	51.586
	(PbTe)_0.935(PbS)_0.05(Sb₂Se₃)_0.015	AB₅C_1.5	-0.106	5.924	30.806

图1 (PbTe)1-x-y(PbS)x(Sb2Se3)y粉末的XRD图谱

Fig. 1 XRD patterns of (PbTe)1-x-y(PbS)x(Sb2Se3)y powders

图2 多组元体系中PbTe晶格常数a和峰偏移角度Δ2θ随组元含量的变化关系

Fig. 2 Lattice parameters a and migration angle Δ2θ of PbTe varied as functions of contents of different components (a) Matrix, dual-component; (b) Triple-component systems

图3 (a)AB7和(b)AB5C1.5样品在N2环境下的热重分析

Fig. 3 Thermogravimetric analysis results of (a) AB7 and (b) AB5C1.5 in N2 atmosphere

图4 双组元样品ABm的热电性能曲线

Fig. 4 Temperature dependences of thermoelectric properties for dual-component samples ABm (a) Electrical conductivity; (b) Seebeck coefficient; (c) Power factor; (d) Total thermal conductivity; (e) Lattice thermal conductivity; (f) ZT

图5 三组元样品AB5Cn的热电性能曲线

Fig. 5 Temperature dependences of thermoelectric properties for triple-component samples AB5Cn (a) Electrical conductivity; (b) Seebeck coefficient; (c) Power factor; (d) Total thermal conductivity; (e) Lattice thermal conductivity; (f) ZT

图6 样品AB5的(a)断面形貌(SEM)、(b)背散射(BSE)图像, 样品AB5C1的(c)断面形貌(SEM)、(d)背散射(BSE)图像以及(e)EDS面扫结果

Fig. 6 (a) Fractured surfure SEM and (b) back-scattered electron (BSE) images for sample AB5, (c) fractured surfure SEM image, (d) back-scattered electron (BSE) image and (e) EDS mappings for sample AB5C1

图7 样品AB5C1的EBSD数据

Fig. 7 EBSD images of AB5C1 sample (a) Phase; (b) IPF Z; (c) Diffraction band; (d) Pole figure (111)

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基于分步式双重调控n型(PbTe)_1-_x_-_y(PbS)_x(Sb₂Se₃)_y体系的热电传输特性

Thermoelectric Transport Characteristics of n-type (PbTe)_1-_x_-_y(PbS)_x(Sb₂Se₃)_y Systems via Stepwise Addition of Dual Components

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