p型多晶Bi0.5Sb1.5Te3合金类施主效应与热电性能

doi:10.15541/jim20230121

无机材料学报 ›› 2023, Vol. 38 ›› Issue (11): 1331-1337.DOI: 10.15541/jim20230121

p型多晶Bi_0.5Sb_1.5Te₃合金类施主效应与热电性能

鲁志强¹^,²(), 刘可可¹^,², 李强¹^,², 胡芹¹^,², 冯利萍¹^,², 张清杰², 吴劲松²^,³, 苏贤礼¹^,²(), 唐新峰¹^,²()

1.武汉理工大学襄阳示范区, 湖北隆中实验室, 襄阳 441000
2.武汉理工大学材料复合新技术国家重点实验室, 武汉 430070
3.武汉理工大学纳微结构研究中心, 武汉 430070

收稿日期:2023-03-09 修回日期:2023-05-09 出版日期:2023-06-02 网络出版日期:2023-06-02
通讯作者: 唐新峰, 教授. E-mail: tangxf@whut.edu.cn;
苏贤礼,研究员. E-mail: suxianli@whut.edu.cn
作者简介:鲁志强(1996-), 男, 硕士研究生. E-mail: luzhiqiangmail@whut.edu.cn
基金资助:
国家自然科学基金(52122108);国家自然科学基金(51972256);国家重点研发计划(2018YFB0703600);湖北隆中实验室自主创新项目(2022ZZ-07)

Donor-like Effect and Thermoelectric Performance in p-Type Bi_0.5Sb_1.5Te₃ Alloy

LU Zhiqiang¹^,²(), LIU Keke¹^,², LI Qiang¹^,², HU Qin¹^,², FENG Liping¹^,², ZHANG Qingjie², WU Jinsong²^,³, SU Xianli¹^,²(), TANG Xinfeng¹^,²()

1. Longzhong Laboratory in Hubei Province, Xiangyang Demonstration Zone of Wuhan University of Technology, Xiangyang 441000, China
2. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
3. Nanostructure Research Center, Wuhan University of Technology, Wuhan 430070, China

Received:2023-03-09 Revised:2023-05-09 Published:2023-06-02 Online:2023-06-02
Contact: TANG Xinfeng, professor. E-mail: tangxf@whut.edu.cn;
SU Xianli, professor. E-mail: suxianli@whut.edu.cn
About author:About author: LU Zhiqiang (1996-), male, Master candidate. E-mail: luzhiqiangmail@whut.edu.cn
Supported by:
National Natural Science Foundation of China(52122108);National Natural Science Foundation of China(51972256);National Key Research and Development Program(2018YFB0703600);Independent and Innovative Project of Longzhong Laboratory in Hubei Province(2022ZZ-07)

摘要/Abstract

摘要：

晶粒细化是提高Bi_0.5Sb_1.5Te₃合金力学性能的有效途径, 但是粉末冶金过程中晶粒细化导致的类施主效应会严重劣化材料热电性能, 制约了Bi_0.5Sb_1.5Te₃基合金在微型热电器件中的应用。本研究围绕p型Bi_0.5Sb_1.5Te₃基合金, 采用实验结合理论计算系统研究了粉末冶金制备过程中研磨和脱附气氛对烧结样品中类施主效应和电热输运性能的影响规律和机制。Bi_0.5Sb_1.5Te₃基合金破碎研磨过程中粉体表面产生缺陷$~\text{V}_{\text{Te}}^{\cdot \cdot }$和${{\text{{V}'''}}_{\text{Sb}}}$并物理吸附空气中的O₂, 在烧结过程中与吸附的O₂发生缺陷化学反应, 产生大量$\text{V}_{\text{Te}}^{\cdot \cdot }$空位和自由电子, 导致类施主效应, 使空穴浓度大幅降低。在保护气氛下(Ar气氛)研磨避免接触空气或在空气中研磨后放置在保护气氛下脱附O₂, 都可以有效抑制类施主效应, 使样品保持较高的载流子浓度和电导率, 且性能在473 K下保持稳定。在空气中研磨后直接烧结的样品和放置在空气中粉体烧结的样品表现出明显的类施主效应, 样品的载流子浓度从保护气氛处理样品的4.49×10¹⁹ cm⁻³下降至3.21×10¹⁹ cm⁻³, 采用保护气氛处理的粉体烧结样品在402 K下获得最高的热电优值ZT为1.03, 平均ZT_ave为0.92。该研究为调控p型多晶Bi₂Te₃基化合物的类施主效应和优化其热电性能提供了新思路。

关键词: Bi_0.5Sb_1.5Te₃合金, 类施主效应, 载流子浓度, 热电性能

Abstract:

Grain refinement is an effective way to improve the mechanical properties of Bi_0.5Sb_1.5Te₃based alloys. However, the donor-like effect caused by the grain refinement during powder metallurgy severely degrades the thermoelectric properties of the material, which limits the application of Bi_0.5Sb_1.5Te₃-based alloys in micro thermoelectric devices. Therefore, in this study, focusing on p-type Bi_0.5Sb_1.5Te₃-base alloy, the impact of grinding and desorption atmosphere on donor-like effect and thermoelectric transport properties of sintered samples during powder metallurgy process were systematically studied through experiments combined with theoretical calculations. Surface defects $~\text{V}_{\text{Te}}^{\cdot \cdot }$ and ${{\text{{V}'''}}_{\text{Sb}}}$^， generated by the grinding process of Bi_0.5Sb_1.5Te₃-based alloy, reacts with the adsorbed O₂ during sintering process. This generates a large number of $\text{V}_{\text{Te}}^{\cdot \cdot }$ vacancies and free electrons, leading to a donor-like effect and a significant decrease in carrier concentration. The use of protective atmosphere (Ar atmosphere) during grinding to avoid exposure to air or O₂ desorption under protective atmosphere after grinding effectively suppresses the donor-like effect, maintaining high carrier concentration and electrical conductivity of the sample. Moreover, the performance is stable up to 473 K. The samples treated in air or sintered using powder placed in air exhibit a significant donor-like effect, and the carrier concentration decreases from 4.49×10¹⁹cm^–3 to 3.21×10¹⁹ cm^–3. The maximum thermoelectric ZT of 1.03 is obtained at 402 K for the samples sintered with the powders treated under protective atmosphere, and the overall average ZT_ave reaches 0.92. This study provides a new avenue to regulate the donor-like effect of p-type polycrystalline Bi₂Te₃-based compounds and to optimize their thermoelectric properties.

Key words: Bi_0.5Sb_1.5Te₃ alloy, donor-like effect, carrier concentration, thermoelectric property

中图分类号:

TQ174

鲁志强, 刘可可, 李强, 胡芹, 冯利萍, 张清杰, 吴劲松, 苏贤礼, 唐新峰. p型多晶Bi_0.5Sb_1.5Te₃合金类施主效应与热电性能[J]. 无机材料学报, 2023, 38(11): 1331-1337.

LU Zhiqiang, LIU Keke, LI Qiang, HU Qin, FENG Liping, ZHANG Qingjie, WU Jinsong, SU Xianli, TANG Xinfeng. Donor-like Effect and Thermoelectric Performance in p-Type Bi_0.5Sb_1.5Te₃ Alloy[J]. Journal of Inorganic Materials, 2023, 38(11): 1331-1337.

图/表 7

图1 (a)不同气氛处理烧结样品的粉体XRD图谱和(b)垂直于烧结压力方向的块体XRD图谱

Fig. 1 (a) Powder XRD patterns of sintered samples with powders treated in different atmospheres, and (b) XRD patterns of bulk samples measured perpendicular to the sintered pressing direction

表1 不同气氛处理粉体烧结样品室温下的取向因子(F)、电导率(σ)、Seebeck系数(S)、载流子浓度(n)、迁移率(μ)、总热导率(κ)、有效质量(m*/m0)、热电优值ZT以及平均热电优值ZTave

Table 1 Orientation factor (F), conductivity (σ), Seebeck coefficient (S), carrier concentration (n), mobility (μ), total thermal conductivity(κ), effective mass (m*/m0), and thermoelectric value ZT of the samples treated with different atmospheres at room temperature and average thermoelectric value ZTave

Sample	F	σ/(×10⁴, S•m⁻¹)	S/(μV•K⁻¹)	n/(×10¹⁹, cm⁻³)	μ/(cm²•V⁻¹•s⁻¹)	κ/(W•m⁻¹•K⁻¹)	m^/m*₀	ZT	ZT_ave
In-Ar	0.076	17.50	150	4.49	243	1.49	0.93	0.78	0.92
Out-Ar	0.074	15.55	160	3.88	249	1.45	0.91	0.82	0.86
In-Air	0.078	12.92	172	3.31	243	1.28	0.89	0.90	0.81
Out-Air	0.072	12.36	177	3.21	240	1.23	0.89	0.94	0.87

图2 In-Ar样品(a)垂直和(b)平行烧结压力方向的FESEM照片

Fig. 2 FESEM images for In-Ar sample along the direction (a) perpendicular and (b) parallel to sintering pressure

图3 In-Ar样品垂直于烧结压力方向抛光表面的(a)背散射电子像以及(b)Bi、(c)Sb和(d)Te元素的面扫描EDS能谱图

Fig. 3 (a) Backscattered electron images, (b) Bi, (c) Sb, and (d) Te elemental distribution mappings on the polished surface of In-Ar sample via EDS along the direction perpendicular to the sintering pressure

图4 不同Te化学势条件下Bi0.5Sb1.5Te3合金中存在的复杂缺陷的形成能

Fig. 4 Formation energy with complex defects presented in Bi0.5Sb1.5Te3 alloys at different Te chemical potentials

图5 不同气氛处理样品垂直烧结压力方向的(a)电导率、(b)Seebeck系数、(c)功率因子随温度变化的关系曲线, (d) 室温下Bi-Sb-Te合金的Seebeck系数与载流子浓度的关系曲线(Pisarenko曲线)

Fig. 5 Temperature dependence of (a) electrical conductivity, (b) Seebeck coefficient, (c) power factor for samples treated with different atmospheres along the direction perpendicular to the sintering pressure, (d) relationship between Seebeck coefficient and carrier concentration (Pisarenko curve) at room temperature for Bi-Sb-Te alloy

图6 不同气氛处理样品垂直烧结压力方向的(a)总热导率、(b)晶格热导率与双极热导率之和以及(c)热电优值ZT随温度变化曲线

Fig. 6 Temperature dependence of (a) total thermal conductivity, (b) sum of lattice thermal conductivity and bipolar thermal conductivity, (c) thermoelectric merit ZT for samples treated with different atmospheres along the direction perpendicular to the sintering pressure

参考文献 41

[1]	IMASATO K, KANG S D, SNYDER G J. Exceptional thermoelectric performance in Mg₃Sb_0.6Bi_1.4 for low-grade waste heat recovery. Energy & Environmental Science, 2019, 12(3): 965.
[2]	YANG X, SU X, YAN Y, et al. Structures and thermoelectric properties of (GeTe)_nBi₂Te₃. Journal of Inorganic Materials, 2021, 36(1): 75. DOI URL
[3]	GONG H, SU X, YAN Y, et al. Ultra-fast synthesis of Cu₂S thermoelectric materials under pulsed electric field. Journal of Inorganic Materials, 2019, 34(12): 1295. DOI
[4]	REN P, WANG C, ZI P, et al. Effect of Te and In co-doping on thermoelectric properties of Cu₂SnSe₃compounds. Journal of Inorganic Materials, 2022, 37(10): 1079. DOI URL
[5]	SHI W, WANG D, SHUAI Z. High-performance organic thermoelectric materials: theoretical insights and computational design. Advanced Electronic Materials, 2019, 5(11): 1079.
[6]	CHEN L D, XIONG Z, BAI S Q. Recent progress of thermoelectric nano-composites. Journal of Inorganic Materials, 2010, 25(6): 561. DOI URL
[7]	CHEN Y, HOU X, MA C, et al. Review of development status of Bi₂Te₃-based semiconductor thermoelectric power generation. Advances in Materials Science and Engineering, 2018, 2018: 1210562.
[8]	KAJIHARA T, MAKINO K, LEE Y H, et al. Study of thermoelectric generation unit for radiant waste heat. Materials Today: Proceedings, 2015, 2(2): 804. DOI URL
[9]	TANG X, LI Z, LIU W, et al. A comprehensive review on Bi₂Te₃- based thin films: thermoelectrics and beyond. Interdisciplinary Materials, 2022, 1(1): 88. DOI URL
[10]	KIM F, KWON B, EOM Y, et al. 3D printing of shape-conformable thermoelectric materials using all-inorganic Bi₂Te₃-based inks. Nature Energy, 2018, 3(4): 301. DOI
[11]	ZHU Y K, WU P, GUO J, et al. Achieving a fine balance in mechanical properties and thermoelectric performance in commercial Bi₂Te₃ materials. Ceramics International, 2020, 46(10): 14994. DOI URL
[12]	DAI Y J, HU H M, GE T S, et al. Investigation on a mini-CPC hybrid solar thermoelectric generator unit. Renewable Energy, 2016, 92: 83. DOI URL
[13]	CHAO W H, TSENG S C, YANG P H, et al. Enhanced thermoelectric properties of Bi₂Te₃ doping Zn₄Sb₃ by combinatorial approach. Surface and Coatings Technology, 2013, 231: 34. DOI URL
[14]	FANG T, LI X, HU C, et al. Complex band structures and lattice dynamics of Bi₂Te₃-based compounds and solid solutions. Advanced Functional Materials, 2019, 29(28): 1900677. DOI URL
[15]	SHI Q, LI J, ZHAO X, et al. Comprehensive insight into p-type Bi₂Te₃-based thermoelectrics near room temperature. ACS Applied Materials & Interfaces, 2022, 14(44): 49425.
[16]	LI Y, CAI K, HUANG B, et al. Use of molecular dynamics simulations to study the effects of nanopores and vacancies on the mechanical properties of Bi₂Te₃. Journal of Electronic Materials, 2013, 43(6): 1824. DOI URL
[17]	REN F, MENCHHOFER P, KIGGANS J, et al. Development of thermoelectric fibers for miniature thermoelectric devices. Journal of Electronic Materials, 2015, 45(3): 1412. DOI URL
[18]	TANG X, YAN Y, XIAO Y, et al. Effect of surface treatment of n-type Bi₂Te₃-based materials on the properties of thermoelectric units. Journal of Inorganic Materials, 2023, 38(2): 163. DOI URL
[19]	ZHENG Y, TAN X Y, WAN X, et al. Thermal stability and mechanical response of Bi₂Te₃-based materials for thermoelectric applications. ACS Applied Materials & Interfaces, 2019, 3(3): 2078.
[20]	FAN X A, YANG J Y, ZHU W, et al. Effect of nominal Sb₂Te₃ content on thermoelectric properties of p-type (Bi₂Te₃)_x(Sb₂Te₃)_1-_x alloys by MA-HP. Journal of Physics D: Applied Physics, 2006, 39(23): 5069. DOI URL
[21]	GÜLER E, GÜLER M. Theoretical prediction of the structural, elastic, mechanical and phonon properties of bismuth telluride under pressure. International Journal of Modern Physics B, 2015, 29(31): 1550222. DOI URL
[22]	IVANOVA L D, PETROVA L I, GRANATKINA Y V, et al. Thermoelectric materials based on Sb₂Te₃-Bi₂Te₃ solid solutions with optimal performance in the range 100-400 K. Inorganic Materials, 2007, 43(9): 933. DOI URL
[23]	KIM H S, HEINZ N A, GIBBS Z M, et al. High thermoelectric performance in (Bi_0.25Sb_0.75)₂Te₃ due to band convergence and improved by carrier concentration control. Materials Today, 2017, 20(8): 452. DOI URL
[24]	STEPANOV N P, KALASHNIKOV A A, ULASHKEVICH Y V. Plasma screening of the fundamental absorption edge in crystals of Bi₂Te₃-Sb₂Te₃ solid solutions with more than 80mol% Sb₂Te₃. Optics and Spectroscopy, 2014, 117(3): 401. DOI URL
[25]	FAN X A, YANG J Y, CHEN R G, et al. Phase transformation and thermoelectric properties of p-type (Bi₂Te₃)_0.25(Sb₂Te₃)_0.75prepared by mechanical alloying and hot pressing. Materials Science and Engineering: A, 2006, 438: 190.
[26]	ALIEV I I, MAMEDOVA N A, SADYGOV F M, et al. Investigation of the chemical interaction in the Sb₂Te₃-InSe system and the properties of the obtained phases. Russian Journal of Inorganic Chemistry, 2020, 65(10): 1585. DOI
[27]	FENG S K, LI S M, FU H Z. Probing the thermoelectric transport properties of n-type Bi₂Te₃ close to the limit of constitutional undercooling. Chinese Physics B, 2014, 23(11): 117202. DOI URL
[28]	WANG S Y, XIE W J, TANG X F. Effects of preparation techniques on the thermoelectric properties and pressive strengths of n-type B₂Te₃ based materials. Journal of Inorganic Materials, 2010, 25(6): 609. DOI URL
[29]	YE S, HWANG J D, CHEN C M. Strong anisotropic effects of p-type Bi₂Te₃ element on the Bi₂Te₃/Sn interfacial reactions. Metallurgical and Materials Transactions A, 2015, 46(6): 2372. DOI URL
[30]	ZHAO L D, ZHANG B P, LI J F, et al. Thermoelectric and mechanical properties of nano-SiC-dispersed Bi₂Te₃ fabricated by mechanical alloying and spark plasma sintering. Journal of Alloys and Compounds, 2008, 455(1/2): 259. DOI URL
[31]	KIM H C, OH T S, HYUN D B. Thermoelectric properties of the p-type Bi₂Te₃-Sb2Te₃-Sb₂Se₃alloys fabricated by mechanical alloying and hot pressing. Journal of Physics and Chemistry of Solids, 2000, 61(5): 743. DOI URL
[32]	NAVRÁTIL J, STARÝ Z, PLECHÁČEK T. Thermoelectric properties of p-type antimony bismuth telluride alloys prepared by cold pressing. Materials Research Bulletin, 1996, 31(12): 1559. DOI URL
[33]	SHIN H S, HA H P, HYUN D B, et al. Thermoelectric properties of 25%Bi₂Te₃-75%Sb₂Te₃ solid solution prepared by hot-pressing method. Journal of Physics and Chemistry of Solids, 1997, 58(4): 671. DOI URL
[34]	SCHULTZ J M, MCHUGH J P, TILLER W A. Effects of heavy deformation and annealing on the electrical properties of Bi₂Te₃. Journal of Applied Physics, 1962, 33(8): 2443. DOI URL
[35]	ZHANG Q, GU B, WU Y, et al. Evolution of the intrinsic point defects in bismuth telluride-based thermoelectric materials. ACS Applied Materials & Interfaces, 2019, 11(44): 41424.
[36]	TAO Q, WU H, PAN W, et al. Removing the oxygen-induced donor-like effect for high thermoelectric performance in n-type Bi₂Te₃-based compounds. ACS Applied Materials & Interfaces, 2021, 13(50): 60216.
[37]	LOTGERING F K. Topotactical reactions with ferrimagnetic oxides having hexagonal crystal structures. Journal of Inorganic and Nuclear Chemistry, 1959, 9(2): 113. DOI URL
[38]	STORDEUR M, STÖLZER M, SOBOTTA H, et al. Investigation of the valence band structure of thermoelectric (Bi_1-_xSb_x)₂Te₃single crystals. Physica Status Solidi B, 1988, 150(1): 165. DOI URL
[39]	EROFEEV R S, OVECHKINA V N. Energy spectrum of solid solutions of Bi₂Te₃-Sb₂Te₃system. Inorganic Materials, 1981, 17(10): 1316.
[40]	GAIDUKOVA V S, EROFEEV R S, OVECHKINA V N. Characteristics of the energy spectrum of solid solutions in the SbTe-BiTe system. Inorganic Materials, 1981, 17(2): 169.
[41]	HAO F, QIU P, SONG Q, et al. Roles of Cu in the enhanced thermoelectric properties in Bi_0.5Sb_1.5Te₃. Materials (Basel), 2017, 10(3): 251. DOI URL

p型多晶Bi_0.5Sb_1.5Te₃合金类施主效应与热电性能

Donor-like Effect and Thermoelectric Performance in p-Type Bi_0.5Sb_1.5Te₃ Alloy

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