热处理温度对冷烧结SnSe热电性能的影响研究

doi:10.19799/j.cnki.2095-4239.2024.0501

储能科学与技术 ›› 2024, Vol. 13 ›› Issue (11): 3754-3763.doi: 10.19799/j.cnki.2095-4239.2024.0501

热处理温度对冷烧结SnSe热电性能的影响研究

丁军¹^,²(), 师李洁², 陈翔斌³, 屈相³, 程哲¹, 李秀芬¹(), 蒋曼²(), 陈志权³, 望红玉¹

^1.青海大学机械工程学院，青海西宁 810016
^2.华中科技大学能源与动力工程学院，湖北武汉 430070
^3.武汉大学核固体物理重点实验室，湖北武汉 430070

收稿日期:2024-06-04 修回日期:2024-06-22 出版日期:2024-11-28 发布日期:2024-11-27
通讯作者: 李秀芬,蒋曼 E-mail:dcyywl@outlook.com;lixiufen@qhu.edu.cn;jiangm@hust.edu.cn
作者简介:丁军（1997—），男，硕士研究生，研究方向为热电材料，E-mail：dcyywl@outlook.com；
基金资助:
国家自然科学基金(1217050886)

Impact of heat treatment temperature on the thermoelectric properties of cold-sintered SnSe

Jun DING¹^,²(), Lijie SHI², Xiangbin CHEN³, Xiang QU³, Zhe CHENG¹, Xiufen LI¹(), Man JIANG²(), Zhiquan CHEN³, Hongyu WANG¹

^1.School of Mechanical Engineering, Qinghai University, Xining 810016, Qinghai, China
^2.School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430070, Hubei, China
^3.Hubei Nuclear Solid Physics Key Laboratory, Wuhan University, Wuhan 430070, Hubei, China

Received:2024-06-04 Revised:2024-06-22 Online:2024-11-28 Published:2024-11-27
Contact: Xiufen LI, Man JIANG E-mail:dcyywl@outlook.com;lixiufen@qhu.edu.cn;jiangm@hust.edu.cn

摘要/Abstract

摘要：

SnSe热电材料具有低热导率、低成本、环境友好等优势，成为目前热电领域的研究热点材料之一。本文利用水热法和冷烧结工艺制备了多晶SnSe块体，然后进行热处理，研究热处理温度对合成多晶SnSe热电性能的影响规律。XRD结果显示，各样品的主衍射峰与SnSe卡片相匹配。SEM结果表明，颗粒由块状变为片状结构且材料内部空隙随退火温度升高而降低。正电子湮灭测量结果表明，冷烧结的SnSe样品中可能存在各种空位型缺陷，如V_Se、V_Sn、V_SnSe和大空位团簇，这些空位型缺陷是有效的声子散射中心，导致晶格热导率降低，随着退火温度的升高，空隙减小与空位型缺陷逐渐恢复导致晶界势垒降低使电导率逐渐增大。电导率、功率因子和无量纲热电优值(ZT)的变化趋势几乎相同，都是随着退火温度的升高而增加。在测试温度为773 K时，500 ℃退火样品的电导率σ高达4.1×10³ S/m，功率因子为3.71 μW/(cm·K²)；而热导率随着退火温度的提升减小了声子散射中心而略有升高。最后，计算500 ℃退火样品的ZT值为0.70，比未退火样品的ZT值高出35.7%。因此，表明了冷烧结工艺和热处理在SnSe材料研究中有巨大潜力，为制备出高性能热电材料奠定了理论依据。

关键词: SnSe, 冷烧结, 热处理, 功率因子, 热电优值, 正电子湮没

Abstract:

SnSe thermoelectric materials are promising due to their low thermal conductivity, low cost, and environmental friendliness, making them a focus in thermoelectric research. This study explores the effects of heat treatment temperature on the thermoelectric properties of polycrystalline SnSe blocks prepared via hydrothermal synthesis and cold sintering. X-ray diffraction (XRD) analysis confirmed that the primary diffraction peaks of all samples corresponded with SnSe, while scanning electron microscopy (SEM) revealed a transformation from bulk to lamellar structures with reduced internal voids as annealing temperature increased. Positron annihilation spectroscopy indicated the presence of vacancy-type defects, such as V_Se, V_Sn, V_SnSe, and large vacancy clusters, which serve as phonon scattering centers, thereby reducing lattice thermal conductivity. As the annealing temperature rose, a decrease in voids and partial restoration of these defects lowered the potential barrier at grain boundaries, enhancing electrical conductivity. The electrical conductivity, power factor, and dimensionless thermoelectric figure of merit (ZT) increased consistently with higher annealing temperatures. At a test temperature of 773 K, the sample annealed at 500 ℃ exhibited an electrical conductivity (σ) of 4.1 × 10³ S/m and a power factor of 3.71 μW/(cm·K²). Although thermal conductivity slightly increased with higher annealing temperatures due to reduced phonon scattering centers, the overall ZT value reached 0.7 for the 500 ℃ annealed sample, a 35.7% improvement compared to the unannealed sample. These findings demonstrate that the combination of cold sintering and heat treatment is highly effective for enhancing the thermoelectric performance of SnSe, providing a theoretical basis for the development of high-performance thermoelectric materials.

Key words: SnSe, cold sintering, heat treatment, power factor, thermoelectric merit value, positron annihilation

中图分类号:

TB 34

丁军, 师李洁, 陈翔斌, 屈相, 程哲, 李秀芬, 蒋曼, 陈志权, 望红玉. 热处理温度对冷烧结SnSe热电性能的影响研究[J]. 储能科学与技术, 2024, 13(11): 3754-3763.

Jun DING, Lijie SHI, Xiangbin CHEN, Xiang QU, Zhe CHENG, Xiufen LI, Man JIANG, Zhiquan CHEN, Hongyu WANG. Impact of heat treatment temperature on the thermoelectric properties of cold-sintered SnSe[J]. Energy Storage Science and Technology, 2024, 13(11): 3754-3763.

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参考文献 37

1	ZHENG X F, LIU C X, YAN Y Y, et al. A review of thermoelectrics research-Recent developments and potentials for sustainable and renewable energy applications[J]. Renewable and Sustainable Energy Reviews, 2014, 32: 486-503. DOI: 10.1016/j.rser. 2013. 12.053.
2	FITRIANI, OVIK R, LONG B D, et al. A review on nanostructures of high-temperature thermoelectric materials for waste heat recovery[J]. Renewable and Sustainable Energy Reviews, 2016, 64: 635-659. DOI: 10.1016/j.rser.2016.06.035.
3	SHU G Q, LIANG Y C, WEI H Q, et al. A review of waste heat recovery on two-stroke IC engine aboard ships[J]. Renewable and Sustainable Energy Reviews, 2013, 19: 385-401. DOI: 10. 1016/j.rser.2012.11.034.
4	陈海生, 李泓, 徐玉杰, 等. 2023年中国储能技术研究进展[J]. 储能科学与技术, 2024, 13(5): 1359-1397. DOI: 10.19799/j.cnki.2095-4239.2024.0441.
	CHEN H S, LI H, XU Y J, et al. Research progress on energy storage technologies of China in 2023[J]. Energy Storage Science and Technology, 2024, 13(5): 1359-1397. DOI: 10.19799/j.cnki.2095-4239.2024.0441.
5	KIM T, LEE H, CHUNG I. SnSe: The rise of the ultrahigh thermoelectric performance material[J]. Bulletin of the Korean Chemical Society, 2024, 45(3): 186-199. DOI: 10.1002/bkcs. 12821.
6	ZHOU G, WANG D. High thermoelectric performance from optimization of hole-doped CuInTe₂[J]. Physical Chemistry Chemical Physics, 2016, 18(8): 5925-5931. DOI: 10.1039/c5cp 05129k.
7	CHANG C, WU M H, HE D S, et al. 3D charge and 2D phonon transports leading to high out-of-plane ZT in n-type SnSe crystals[J]. Science, 2018, 360(6390): 778-783. DOI: 10.1126/science.aaq1479.
8	DUONG A T, NGUYEN V Q, DUVJIR G, et al. Achieving ZT=2.2 with bi-doped n-type SnSe single crystals[J]. Nature Communications, 2016, 7: 13713. DOI: 10.1038/ncomms13713.
9	WANG S, HUI S, PENG K L, et al. Low temperature thermoelectric properties of p-type doped single-crystalline SnSe[J]. 2018, 112(14): 142102. DOI: 10.1063/1.5023125.
10	ZHAO L D, LO S H, ZHANG Y S, et al. Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals[J]. Nature, 2014, 508(7496): 373-377. DOI: 10.1038/nature13184.
11	TRITT T M. Holey and unholey semiconductors[J]. Science, 1999, 283(5403): 804-805. DOI: 10.1126/science.283.5403.804.
12	LIU B, HU J Z, ZHOU J, et al. Thermoelectric transport in nanocomposites[J]. Materials, 2017, 10(4): 418. DOI: 10.3390/ma10040418.
13	TAN G J, ZHAO L D, KANATZIDIS M G. Rationally designing high-performance bulk thermoelectric materials[J]. Chemical Reviews, 2016, 116(19): 12123-12149. DOI: 10.1021/acs.chemrev.6b00255.
14	YANG X, WANG Z Y, WANG J, et al. Synthesis of SnSe_1– xSx polycrystals with enhanced thermoelectric properties via hydrothermal methods combined with spark plasma sintering[J]. ACS Applied Energy Materials, 2022, 5(9): 11662-11668. DOI: 10.1021/acsaem.2c02134.
15	LI D, LI J C, QIN X Y, et al. Thermoelectric performance for SnSe hot-pressed at different temperature[J]. Journal of Electronic Materials, 2017, 46(1): 79-84. DOI: 10.1007/s11664-016-4919-1.
16	ZHANG Q, CHERE E K, SUN J Y, et al. Studies on thermoelectric properties of n-type polycrystalline SnSe_1- xSx by iodine doping[J]. Advanced Energy Materials, 2015, 5(12): 1500360. DOI: 10. 1002/aenm.201500360.
17	GRASSO S, BIESUZ M, ZOLI L, et al. A review of cold sintering processes[J]. Advances in Applied Ceramics, 2020, 119(3): 115-143. DOI: 10.1080/17436753.2019.1706825.
18	GUO J, GUO H Z, BAKER A L, et al. Cold sintering: A paradigm shift for processing and integration of ceramics[J]. Angewandte Chemie (International Ed), 2016, 55(38): 11457-11461. DOI: 10.1002/anie.201605443.
19	ZHU B, SU X L, SHU S C, et al. Cold-sintered Bi₂Te₃-based materials for engineering nanograined thermoelectrics[J]. ACS Applied Energy Materials, 2022, 5(2): 2002-2010. DOI: 10.1021/acsaem.1c03540.
20	LU W B, WU S L, DING Q, et al. Cold sintering mediated engineering of polycrystalline SnSe with high thermoelectric efficiency[J]. ACS Applied Materials & Interfaces, 2024, 16(4): 4671-4678. DOI: 10.1021/acsami.3c15970.
21	SHI X, YANG J, SALVADOR J R, et al. Multiple-filled skutterudites: High thermoelectric figure of merit through separately optimizing electrical and thermal transports[J]. Journal of the American Chemical Society, 2011, 133(20): 7837-7846. DOI: 10.1021/ja111199y.
22	ZHAO Z H, PAN Z N, WEI F H, et al. Study on the properties of Ca₉Co₁₂O₂₈ under high pressure[J]. Ceramics International, 2021, 47(24): 34388-34395. DOI: 10.1016/j.ceramint.2021.08.351.
23	MONIKAPANI K, VIJAY V, ABINAYA R, et al. Realizing an enhanced Seebeck coefficient and extremely low thermal conductivity in anharmonic Sb-substituted SnSe nanostructures[J]. Journal of Alloys and Compounds, 2022, 923: 165961. DOI: 10.1016/j.jallcom.2022.165961.
24	TUOMISTO F. Open volume defects[M]//Semiconductors and Semimetals. Amsterdam: Elsevier, 2013: 39-65. DOI: 10.1016/b978-0-12-396489-2.00002-3.
25	LEIPNER H S, MIKHNOVICH V V, BONDARENKO V, et al. Positron annihilation of defects in silicon deformed at different temperatures[J]. Physica B: Condensed Matter, 2003, 340: 617-621. DOI: 10.1016/j.physb.2003.09.119.
26	CHIEN C H, CHANG C C, CHEN C L, et al. Facile chemical synthesis and enhanced thermoelectric properties of Ag doped SnSe nanocrystals[J]. RSC Advances, 2017, 7(54): 34300-34306. DOI: 10.1039/C7RA05819E.
27	HE H F, LI X F, CHEN Z Q, et al. Interplay between point defects and thermal conductivity of chemically synthesized Bi₂Te₃ nanocrystals studied by positron annihilation[J]. The Journal of Physical Chemistry C, 2014, 118(38): 22389-22394. DOI: 10. 1021/jp508085a.
28	LOU X N, LI S, CHEN X, et al. Lattice strain leads to high thermoelectric performance in polycrystalline SnSe[J]. ACS Nano, 2021, 15(5): 8204-8215. DOI: 10.1021/acsnano.1c01469.
29	ZHANG Q K, NING S T, QI N, et al. Enhanced thermoelectric performance of a simple method prepared polycrystalline SnSe optimized by spark plasma sintering[J]. 2019, 125(22): 225109. DOI: 10.1063/1.5095197.
30	LIU H L, ZHANG X, LI S H, et al. Synthesis and thermoelectric properties of SnSe by mechanical alloying and spark plasma sintering method[J]. Journal of Electronic Materials, 2017, 46(5): 2629-2633. DOI: 10.1007/s11664-016-4833-6.
31	MARTIN J, WANG L, CHEN L D, et al. Enhanced Seebeck coefficient through energy-barrier scattering in PbTe nanocomposites[J]. Physical Review B, 2009, 79(11): 115311. DOI: 10.1103/physrevb.79.115311.
32	SHANG P P, DONG J F, PEI J, et al. Highly textured N-type SnSe polycrystals with enhanced thermoelectric performance[J]. Research, 2019, 2019: 9253132. DOI: 10.34133/2019/9253132.
33	LIU D R, WANG D Y, HONG T, et al. Lattice plainification advances highly effective SnSe crystalline thermoelectrics[J]. Science, 2023, 380(6647): 841-846. DOI: 10.1126/science.adg7196.
34	PENG K L, LU X, ZHAN H, et al. Broad temperature plateau for high ZTs in heavily doped p-type SnSe single crystals[J]. Energy & Environmental Science, 2016, 9(2): 454-460. DOI: 10.1039/C5EE03366G.
35	JIN Y, WANG D Y, HONG T, et al. Outstanding CdSe with multiple functions leads to high performance of GeTe thermoelectrics[J]. Advanced Energy Materials, 2022, 12(10): 2103779. DOI: 10.1002/aenm.202103779.
36	WANG J L, WU J, WANG T, et al. T-square resistivity without Umklapp scattering in dilute metallic Bi₂O₂Se[J]. Nature Communications, 2020, 11(1): 3846. DOI: 10.1038/s41467-020-17692-6.
37	HE H F, ZHAO B, QI N, et al. Role of vacancy defects on the lattice thermal conductivity in In₂O₃ thermoelectric nanocrystals: A positron annihilation study[J]. Journal of Materials Science, 2018, 53(18): 12961-12973. DOI: 10.1007/s10853-018-2544-5.

热处理温度对冷烧结SnSe热电性能的影响研究

Impact of heat treatment temperature on the thermoelectric properties of cold-sintered SnSe

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