High-Performance p-Type Bi2Te3-Based Thermoelectric Materials with a Wide Temperature Range Obtained by Direct Sb Doping

doi:10.1007/s40195-024-01794-x

摘要/Abstract

Abstract:

Doping modification is one of the most effective ways to optimize the thermoelectric properties of Bi₂Te₃-based alloys. P-type Bi₂₋_xSb_xTe₃ thermoelectric materials have been successfully prepared by direct Sb doping method. It can be found that doping Sb into Bi₂Te₃ lattice array for Bi-site replacement facilitates the generation of Sb′_Te anti-site defects. This anti-site defects can increase the hole concentration and optimize electrical transport properties of Bi₂₋_xSb_xTe₃ alloys. In addition, the point defects induced by mass and stress fluctuations and the Sb impurities produced during the sintering process can enhance the multi-scale phonon scattering and reduce the lattice thermal conductivity. As a result, the Bi_0.47Sb_1.63Te₃ sample has a maximum thermoelectric figure of merit ZT of 1.04 at 350 K. It is worth noting that the bipolar effect of Bi₂Te₃-based alloys can be weakened with the increase of Sb content. The Bi_0.44Sb_1.66Te₃ sample has a maximum average ZT value (0.93) in the temperature range of 300-500 K, indicating that direct doping of Sb can broaden the temperature range corresponding to the optimal ZT value. This work provides an idea for developing high-performance near room temperature thermoelectric materials with a wide temperature range.

Key words: Bi₂Te₃-based materials, Sb doping, Wide temperature range, Thermoelectric properties

. [J]. 金属学报英文版, 2025, 38(5): 849-858.

Xicheng Guan, Zhiyuan Liu, Ni Ma, Zhou Li, Juan Liu, Huiyan Zhang, Hailing Li, Qian Ba, Junjie Ma, Chuangui Jin, Ailin Xia. High-Performance p-Type Bi₂Te₃-Based Thermoelectric Materials with a Wide Temperature Range Obtained by Direct Sb Doping[J]. Acta Metallurgica Sinica (English Letters), 2025, 38(5): 849-858.

图/表 7

Fig. 1 Structural characterization of Bi2−xSbxTe3 (x = 1.50-1.69) samples: a XRD patterns of Bi2−xSbxTe3 samples, b the enlarged XRD patterns of in the 2θ range of 26-31°, c-g rietveld refinement of XRD patterns of Bi2−xSbxTe3 samples, h Raman spectra of Bi2−xSbxTe3 samples

Fig. 2 Microstructural characterization of Bi2−xSbxTe3 (x = 1.50-1.69) samples. FESEM images of fractured Bi2−xSbxTe3 samples: a BST163, b BST166, c BST169. BEI images of polished Bi2−xSbxTe3 samples: d BST150, e BST160, f BST163, g BST166, h BST169. i EDS spectrum of yellow elliptical region in BST166 sample

Table 1 Nominal compositions, EDS compositions, lattice parameter (a, b, and c), room-temperature Hall coefficients (RH), carrier concentrations (n), carrier mobilities (μH), and effective masses (m*) of Bi2−xSbxTe3 samples

Nominal composition	Bi_0.50Sb_1.50Te₃	Bi_0.40Sb_1.60Te₃	Bi_0.37Sb_1.63Te₃	Bi_0.34Sb_1.66Te₃	Bi_0.31Sb_1.69Te₃
EDS composition	Bi_0.53Sb_1.47Te_2.85	Bi_0.40Sb_1.60Te₃	Bi_0.35Sb_1.65Te_2.88	Bi_0.32Sb_1.68Te_2.72	Bi_0.31Sb_1.69Te_2.74
a or b (Å)	4.3122	4.3005	4.2954	4.2911	4.2878
c (Å)	30.5564	30.5190	30.5086	30.4836	30.4780
R_H (cm³/C)	0.24171	0.22782	0.20878	0.18837	0.16513
n (× 10¹⁹ cm⁻³)	2.58252	2.73997	2.98984	3.3138	3.78017
μ_H (cm²·V⁻¹·s⁻¹)	116	113	108	104	98.9
m^⁎	1.95m_e	1.39m_e	1.35m_e	1.36m_e	1.32m_e

Fig. 3 Electrical transport properties of Bi2−xSbxTe3 (x = 1.50-1.69) samples: a Hall coefficients (RH), b carrier concentrations (n) and Hall mobilities (μH) as a function of Sb content at 300 K; c electrical conductivity and d Seebeck coefficient as a function of temperature for Bi2−xSbxTe3 samples in the temperature range of 300-500 K; e curves of |S| vs. n of Bi2−xSbxTe3 samples at 300 K obtained by Pisarenko relation with m* = 1.32me and m* = 1.95me; f power factor as a function of temperature for Bi2−xSbxTe3 samples in the temperature range of 300-500 K

Fig. 4 Temperature dependence of a total thermal conductivity, b carrier thermal conductivity, and c Lorentz number L of Bi2−xSbxTe3 (x = 1.50-1.69) samples; d the difference between the total thermal conductivity and carrier thermal conductivity as a function of temperature for Bi2−xSbxTe3 samples in the temperature range of 300-500 K; e the calculation process of bipolar thermal conductivity of Bi0.34Sb1.66Te3 sample in the temperature range of 300-500 K, and the blue dashed line is linearly fitting to the lattice thermal conductivity at low temperatures from 300 to 330 K; f temperature dependence of bipolar thermal conductivity for Bi2−xSbxTe3 samples in the range of 300-500 K

Fig. 5 Effect of the Sb doping on the band gap of the Bi2Te3 material: a UV-visible spectra of Bi2−xSbxTe3 (x = 1.50-1.69), b-e (αhv)2 versus hv for the direct bandgap of Bi2−xSbxTe3, f variation in the direct band gap for Bi2−xSbxTe3 with the Sb doping

Fig. 6 Temperature dependence of a ZT values of Bi2−xSbxTe3 samples in the temperature range of 300-500 K, b average ZT (300-500 K) values of Bi2−xSbxTe3 samples, c comparison of the average ZT (300-500 K) of the optimized Bi0.34Sb1.66Te3 in this study and other studies on Sb-doped Bi2Te3-based alloys [9,24,29,45]

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High-Performance p-Type Bi₂Te₃-Based Thermoelectric Materials with a Wide Temperature Range Obtained by Direct Sb Doping

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