粉体还原对硒化亚铜热电性能的影响

摘要/Abstract

摘要： 硒化亚铜(Cu₂Se)作为一种典型的类液体热电材料,不仅拥有较好的电传输性能,而且具有较低的晶格热导率。纳米工程是实现热电材料高热电性能的有效手段,然而在合成纳米级Cu₂Se颗粒时,材料极其容易被氧化,从而影响其热电性能。为了研究粉体还原对Cu₂Se热电性能的影响,本文用水热法合成了纳米尺度的Cu₂Se粉体,分别采用氢氩混合气(氢气体积分数为5%)和纯氩气吹扫粉体,并结合放电等离子烧结技术制备了致密度95%以上的Cu₂Se块体材料。结果表明,粉体还原后,Cu₂Se块体中的氧含量明显降低,并且在800 K时热导率降低了41%,ZT值提高了16%。

关键词: 水热法, 粉体还原, 硒化亚铜, 热电性能, 晶格热导率

Abstract: As a typical liquid-like thermoelectric material, Cu₂Se not only has good electrical transport performance, but also has low lattice thermal conductivity. Nanoengineering is an effective method to achieve high thermoelectric properties for thermoelectrics. However, nanoscale Cu₂Se particles are extremely easy to be oxidized in the process of synthesizing, thus affecting its thermoelectric performance. In order to study the effect of powder reduction on the thermoelectric performance of Cu₂Se, nano-sized Cu₂Se powders were synthesized by hydrothermal method. Hydrogen argon mixed gas (hydrogen volume fraction of 5%) and pure argon were used to purge the powders, respectively. Cu₂Se bulk materials with density above 95% were prepared by spark plasma sintering. The results show that the oxygen content of Cu₂Se bulk is significantly reduced after powder reduction, and there is a 41% decrease in thermal conductivity at 800 K, with a 16% increase in ZT value.

Key words: hydrothermal method, powder reduction, Cu₂Se, thermoelectric performance, lattice thermal conductivity

中图分类号:

陈继虎, 路亚妮. 粉体还原对硒化亚铜热电性能的影响[J]. 人工晶体学报, 2024, 53(8): 1464-1470.

CHEN Jihu, LU Yani. Effect of Powder Reduction on the Thermoelectric Performance of Cu₂Se[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(8): 1464-1470.

参考文献

[1] SNYDER G J, TOBERER E S. Complex thermoelectric materials[J]. Nature Materials, 2008, 7: 105-114.
[2] TAN G J, ZHAO L D, KANATZIDIS M G. Rationally designing high-performance bulk thermoelectric materials[J]. Chemical Reviews, 2016, 116(19): 12123-12149.
[3] FALEEV S V, LEONARD F. Theory of enhancement of thermoelectric properties of materials with nanoinclusions[J]. Physical Review B, 2008, 77(21): 214304.
[4] PEI Y Z, SHI X Y, LALONDE A, et al. Convergence of electronic bands for high performance bulk thermoelectrics[J]. Nature, 2011, 473: 66-69.
[5] ZHU T J, LIU Y T, FU C G, et al. Compromise and synergy in high-efficiency thermoelectric materials[J]. Advanced Materials, 2017, 29(14): 1605884.
[6] PEI Y Z, MAY A F, SNYDER G J. Self-tuning the carrier concentration of PbTe/Ag₂Te composites with excess Ag for high thermoelectric performance[J]. Advanced Energy Materials, 2011, 1(2): 291-296.
[7] YOU L, ZHANG J Y, PAN S S, et al. Realization of higher thermoelectric performance by dynamic doping of copper in n-type PbTe[J]. Energy & Environmental Science, 2019, 12(10): 3089-3098.
[8] YANG L, CHEN Z G, HAN G, et al. High-performance thermoelectric Cu₂Se nanoplates through nanostructure engineering[J]. Nano Energy, 2015, 16: 367-374.
[9] HU Q J, ZHU Z, ZHANG Y W, et al. Remarkably high thermoelectric performance of Cu_2-xLi_xSe bulks with nanopores[J]. Journal of Materials Chemistry A, 2018, 6(46): 23417-23424.
[10] ZHANG K M, ZHANG Q H, WANG L J, et al. Enhanced thermoelectric performance of Se-doped PbTe bulk materials via nanostructuring and multi-scale hierarchical architecture[J]. Journal of Alloys and Compounds, 2017, 725: 563-572.
[11] GAHTORI B, BATHULA S, TYAGI K, et al. Giant enhancement in thermoelectric performance of copper selenide by incorporation of different nanoscale dimensional defect features[J]. Nano Energy, 2015, 13: 36-46.
[12] HE Y, DAY T, ZHANG T S, et al. High thermoelectric performance in non-toxic earth-abundant copper sulfide[J]. Advanced Materials, 2014, 26(23): 3974-3978.
[13] LIU H L, SHI X, XU F F, et al. Copper ion liquid-like thermoelectrics[J]. Nature Materials, 2012, 11: 422-425.
[14] LIU H L, YUAN X, LU P, et al. Ultrahigh thermoelectric performance by electron and phonon critical scattering in Cu₂Se_1-xI_x[J]. Advanced Materials, 2013, 25(45): 6607-6612.
[15] CHEN Z H, ZHANG J H, DENG S Q, et al. Morphology-controlled synthesis of Cu₂O encapsulated phase change materials: photothermal conversion and storage performance in visible light regime[J]. Chemical Engineering Journal, 2023, 454: 140089.
[16] ZHOU C J, LEE Y K, YU Y, et al. Polycrystalline SnSe with a thermoelectric figure of merit greater than the single crystal[J]. Nature Materials, 2021, 20: 1378-1384.
[17] NIERODA P, KUSIOR A, LESZCZYŃSKI J, et al. Thermoelectric properties of Cu₂Se synthesized by hydrothermal method and densified by SPS technique[J]. Materials, 2021, 14(13): 3650.
[18] LIU W D, SHI X L, MOSHWAN R, et al. Solvothermal synthesis of high-purity porous Cu_1.7Se approaching low lattice thermal conductivity[J].Chemical Engineering Journal, 2019, 375: 121996.
[19] KONG F F, BAI J, BI P, et al. Size effect enhanced thermoelectric properties of nanoscale Cu_2-xSe[J]. Ceramics International, 2019, 45(7): 8866-8872.
[20] ZHAO K P, QIU P F, SONG Q F, et al. Ultrahigh thermoelectric performance in Cu_2-ySe_0.5S_0.5 liquid-like materials[J]. Materials Today Physics, 2017, 1: 14-23.
[21] BISWAS K, HE J Q, BLUM I D, et al. High-performance bulk thermoelectrics with all-scale hierarchical architectures[J]. Nature, 2012, 489: 414-418.
[22] HE J, TRITT T M. Advances in thermoelectric materials research: looking back and moving forward[J]. Science, 2017, 357(6358): eaak9997.
[23] NUNNA R, QIU P F, YIN M J, et al. Ultrahigh thermoelectric performance in Cu₂Se-based hybrid materials with highly dispersed molecular CNTs[J]. Energy & Environmental Science, 2017, 10(9): 1928-1935.