Journal Home > Volume 13 , Issue 5

In situ phase separation precipitates play an important role in enhancing the thermoelectric properties of copper sulfides by suppressing phonon transmission. In this study, Cu1.8S composites were fabricated by melting reactions and spark plasma sintering. The complex structures, namely, micron-PbS, Sb2S3, nano-FeS, and multiscale pores, originate from the introduction of FePb4Sb6S14 into the Cu1.8S matrix. Using effective element (Fe) doping and multiscale precipitates, the Cu1.8S+0.5 wt% FePb4Sb6S14 bulk composite reached a high dimensionless figure of merit (ZT) value of 1.1 at 773 K. Furthermore, the modulus obtained for this sample was approximately 40.27 GPa, which was higher than that of the pristine sample. This study provides a novel strategy for realizing heterovalent doping while forming various precipitates via in situ phase separation by natural minerals, which has been proven to be effective in improving the thermoelectric and mechanical performance of copper sulfides and is worth promoting in other thermoelectric systems.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Highly enhanced thermoelectric and mechanical performance of copper sulfides via natural mineral in-situ phase separation

Show Author's information Xi YanHongjiang Pan( )Yixin ZhangTianyu YangYangwei WangKun HuangChongyu WangJing Feng( )Zhenhua Ge( )
Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, China

Abstract

In situ phase separation precipitates play an important role in enhancing the thermoelectric properties of copper sulfides by suppressing phonon transmission. In this study, Cu1.8S composites were fabricated by melting reactions and spark plasma sintering. The complex structures, namely, micron-PbS, Sb2S3, nano-FeS, and multiscale pores, originate from the introduction of FePb4Sb6S14 into the Cu1.8S matrix. Using effective element (Fe) doping and multiscale precipitates, the Cu1.8S+0.5 wt% FePb4Sb6S14 bulk composite reached a high dimensionless figure of merit (ZT) value of 1.1 at 773 K. Furthermore, the modulus obtained for this sample was approximately 40.27 GPa, which was higher than that of the pristine sample. This study provides a novel strategy for realizing heterovalent doping while forming various precipitates via in situ phase separation by natural minerals, which has been proven to be effective in improving the thermoelectric and mechanical performance of copper sulfides and is worth promoting in other thermoelectric systems.

Keywords: thermoelectric, copper sulfides, jamesonite, natural mineral, in situ precipitates

References(53)

[1]

Bell LE. Cooling, heating, generating power, and recovering waste heat with thermoelectric systems. Science 2008, 321: 1457–1461.

[2]

He J, Tritt TM. Advances in thermoelectric materials research: Looking back and moving forward. Science 2017, 357: eaak9997.

[3]

Basit A, Xin JW, Murtaza G, et al. Recent advances, challenges, and perspective of copper-based liquid-like thermoelectric chalcogenides: A review. EcoMat 2023, 5: e12391.

[4]

Yang X, Wang CY, Lu R, et al. Progress in measurement of thermoelectric properties of micro/nano thermoelectric materials: A critical review. Nano Energy 2022, 101: 107553.

[5]

Ge ZH, Zhang YX, Yang TY, et al. Highly stabilized thermoelectric performance in natural minerals. Joule 2024, 8: 129–140.

[6]

Xu WJ, Zhang ZW, Liu CY, et al. Substantial thermoelectric enhancement achieved by manipulating the band structure and dislocations in Ag and La co-doped SnTe. J Adv Ceram 2021, 10: 860–870.

[7]

Liu HL, Shi X, Xu FF, et al. Copper ion liquid-like thermoelectrics. Nat Mater 2012, 11: 422–425.

[8]

Guo Z, Wu G, Tan XJ, et al. Enhanced thermoelectric performance in GeTe by synergy of midgap state and band convergence. Adv Funct Mater 2023, 33: 2212421.

[9]

Tian ZT. Anderson localization for better thermoelectrics. ACS Nano 2019, 13: 3750–3753.

[10]

Zhang WY, Zhou ZF, Yang YY, et al. Enhanced thermoelectric performance of n-type PbTe through introducing PbSe by a fast preparation method. Mater Today Phys 2023, 38: 101231.

[11]

Qin BC, Wang DY, Hong T, et al. High thermoelectric efficiency realized in SnSe crystals via structural modulation. Nat Commun 2023, 14: 1366.

[12]

Zhang YX, Tang YQ, Ma Z, et al. Achievement of excellent thermoelectric properties in Cu–Se–S compounds via in situ phase separation. Inorg Chem 2021, 60: 13269–13277.

[13]

Aminorroaya Yamini S, Santos R, Fortulan R, et al. Room-temperature thermoelectric performance of n-type multiphase pseudobinary Bi2Te3–Bi2S3 compounds: Synergic effects of phonon scattering and energy filtering. ACS Appl Mater Inter 2023, 15: 19220–19229.

[14]

Vineis CJ, Shakouri A, Majumdar A, et al. Nanostructured thermoelectrics: Big efficiency gains from small features. Adv Mater 2010, 22: 3970–3980.

[15]

Peng PP, Wang C, Cui SQ, et al. Achieving ultralow lattice thermal conductivity and high thermoelectric performance in SnTe by alloying with MnSb2Se4. ACS Appl Mater Inter 2023, 15: 45016–45025.

[16]

Chen P, Zhang B, Zhou ZZ, et al. Anionic regulation and valence band convergence boosting the thermoelectric performance of Se-alloyed GeSb2Te4 single crystal. Acta Mater 2023, 254: 118999.

[17]

Taneja V, Das S, Dolui K, et al. High thermoelectric performance in phonon-glass electron-crystal like AgSbTe2. Adv Mater 2024, 36: 2307058.

[18]

Shi XL, Zou J, Chen ZG. Advanced thermoelectric design: From materials and structures to devices. Chem Rev 2020, 120: 7399–7515.

[19]

Ahmad A, Zhu B, Wang ZB, et al. Largely enhanced thermoelectric performance in p-type Bi2Te3-based materials through entropy engineering. Energy Environ Sci 2024, 17: 695–703.

[20]

Qin Y, Xiong T, Zhu JF, et al. Realizing high thermoelectric performance of Cu and Ce co-doped p-type polycrystalline SnSe via inducing nanoprecipitation arrays. J Adv Ceram 2022, 11: 1671–1686.

[21]

Zhao LD, Tan GJ, Hao SQ, et al. Ultrahigh power factor and thermoelectric performance in hole-doped single-crystal SnSe. Science 2016, 351: 141–144.

[22]

Ge ZH, Zhao LD, Wu D, et al. Low-cost, abundant binary sulfides as promising thermoelectric materials. Mater Today 2016, 19: 227–239.

[23]

Zhang R, Pei J, Han ZJ, et al. Optimal performance of Cu1.8S1− x Te x thermoelectric materials fabricated via high-pressure process at room temperature. J Adv Ceram 2020, 9: 535–543.

[24]

Ge ZH, Liu XY, Feng D, et al. High-performance thermoelectricity in nanostructured earth-abundant copper sulfides bulk materials. Adv Energy Mater 2016, 6: 1600607.

[25]

Yang TY, Gu SW, Zhang YX, et al. Pseudopolymorphic phase engineering for improved thermoelectric performance in copper sulfides. Adv Mater 2024, 36: e2308353.

[26]

Xiang SQ, Liang YH, Han X, et al. Controlling the thermal stability, threshold voltage, and thermoelectric properties of cuprous sulfide thermoelectrics. Inorg Chem 2022, 61: 14973–14986.

[27]

Dennler G, Chmielowski R, Jacob S, et al. Are binary copper sulfides/selenides really new and promising thermoelectric materials. Adv Energy Mater 2014, 4: 1301581.

[28]

Ge ZH, Chong X, Feng D, et al. Achieving an excellent thermoelectric performance in nanostructured copper sulfide bulk via a fast doping strategy. Mater Today Phys 2019, 8: 71–77.

[29]

Zhang YX, Lou Q, Ge ZH, et al. Excellent thermoelectric properties and stability realized in copper sulfides based composites via complex nanostructuring. Acta Mater 2022, 233: 117972.

[30]

Zhang YX, Ma Z, Ge ZH, et al. Highly enhanced thermoelectric properties of Cu1.8S by introducing PbS. J Alloys Compd 2018, 764: 738–744.

[31]

Li ZG, Gu SW, Zhang YX, et al. Highly enhanced thermoelectric performance of copper sulfide by compositing with CNT & CuO. J Alloys Compd 2023, 953: 169954.

[32]

Qin P, Ge ZH, Chen YX, et al. Achieving high thermoelectric performance of Cu1.8S composites with WSe2 nanoparticles. Nanotechnology 2018, 29: 345402.

[33]

Zhou ZF, Huang Y, Wei B, et al. Compositing effects for high thermoelectric performance of Cu2Se-based materials. Nat Commun 2023, 14: 2410.

[34]

Li L, Yang M, Xiong H, et al. Extracting antimony trisulfide from complex lead-antimony sulfide ore by two-step vacuum distillation. J Cent South Univ 2023, 30: 132–141.

[35]

Derakhshan S, Assoud A, Soheilnia N, et al. Electronic structure and thermoelectric properties of the thioantimonate FePb4Sb6S14. J Alloys Compd 2005, 390: 51–54.

[36]

Léone P, André G, Doussier C, et al. Neutron diffraction study of the magnetic ordering of jamesonite (FePb4Sb6S14). J Magn Magn Mater 2004, 284: 92–96.

[37]

Zhao YH, Shan ZH, Zhou W, et al. Enhanced thermoelectric performance of Bi–Se co-doped Cu1.8S via carrier concentration regulation and multiscale phonon scattering. ACS Appl Energy Mater 2022, 5: 5076–5086.

[38]

Ren JJ, Zheng LC, Su YM, et al. Competitive adsorption of Cd(II), Pb(II) and Cu(II) ions from acid mine drainage with zero-valent iron/phosphoric titanium dioxide: XPS qualitative analyses and DFT quantitative calculations. Chem Eng J 2022, 445: 136778.

[39]

Liu RD, Zhang YY, Duan LB, et al. Effect of Fe2+/Fe3+ ratio on photocatalytic activities of Zn1− x Fe x O nanoparticles fabricated by the auto combustion method. Ceram Int 2020, 46: 1–7.

[40]

Kwon DW, Nam KB, Hong SC. The role of ceria on the activity and SO2 resistance of catalysts for the selective catalytic reduction of NO x by NH3. Appl Catal B Environ 2015, 166–167: 37–44.

[41]

Yadav S, Chaudhary S, Pandya DK. Enhancing thermoelectric properties of p-type CoSb3 skutterudite by Fe doping. Mater Sci Semicond Proc 2021, 127: 105721.

[42]

Ge ZH, Zhang BP, Liu Y, et al. Nanostructured Bi2− x Cu x S3 bulk materials with enhanced thermoelectric performance. Phys Chem Chem Phys 2012, 14: 4475–4481.

[43]

Kim W, Zide J, Gossard A, et al. Thermal conductivity reduction and thermoelectric figure of merit increase by embedding nanoparticles in crystalline semiconductors. Phys Rev Lett 2006, 96: 045901.

[44]

Zhuang HL, Hu HH, Pei J, et al. High ZT in p-type thermoelectric (Bi,Sb)2Te3 with built-in nanopores. Energy Environ Sci 2022, 15: 2039–2048.

[45]

Zhu B, Wang W, Cui J, et al. Point defect engineering: Co-doping synergy realizing superior performance in n-type Bi2Te3 thermoelectric materials. Small 2021, 17: 2101328.

[46]

Sundari RS, Vijay V, Shalini V, et al. Effective decoupling of grain boundaries and secondary phase interfaces for enhanced thermoelectric performance of Cu1.8S/WS2 nanocomposites. J Alloys Compd 2023, 960: 170796.

[47]

Liang DD, Zhang BP, Zou L. Enhanced thermoelectric properties of Cu1.8S by Ti-doping induced secondary phase. J Alloys Compd 2018, 731: 577–583.

[48]

Liang DD, Ge ZH, Li HZ, et al. Enhanced thermoelectric property in superionic conductor Bi-doped Cu1.8S. J Alloys Compd 2017, 708: 169–174.

[49]

Zhou Y, Ge ZH, Gan GY, et al. Enhanced thermoelectric properties of Pb-doped Cu1.8S polycrystalline materials. Solid State Sci 2019, 95: 105953.

[50]

Qin P, Ge ZH, Feng J. Effects of second phases on thermoelectric properties in copper sulfides with Sn addition. J Mater Res 2017, 32: 3029–3037.

[51]

Qin P, Ge ZH, Feng J. Enhanced thermoelectric properties of SiC nanoparticle dispersed Cu1.8S bulk materials. J Alloys Compd 2017, 696: 782–787.

[52]

Zhao Z, Liang DD, Pei J, et al. Enhanced thermoelectric properties of Mn x Cu1.8S via tuning band structure and scattering multiscale phonons. J Materiomics 2021, 7: 556–562.

[53]

Taneike M, Abe F, Sawada K. Creep-strengthening of steel at high temperatures using nano-sized carbonitride dispersions. Nature 2003, 424: 294–296.

File
JAC0885_ESM.pdf (2.6 MB)
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 31 January 2024
Revised: 06 March 2024
Accepted: 25 March 2024
Published: 28 May 2024
Issue date: May 2024

Copyright

© The Author(s) 2024.

Acknowledgements

Acknowledgements

This work was supported by the National Key R&D Program of China (No. 2022YFF0503804), the National Natural Science Foundation of China (No. 52162029), the Yunnan Provincial Natural Science Key Fund (No. 202101AS070015), the Basic Research Project of Yunnan Science and Technology Program (No. 202401AT070403), and the Outstanding Youth Fund of Yunnan Province (No. 202201AV070005).

Rights and permissions

This is an open access article under the terms of the Creative Commons Attribution 4.0 International License (CC BY 4.0, http://creativecommons.org/licenses/by/4.0/).

Return