Preparation and thermoelectric properties of Cu_(1.8)S/CuSbS_2 composites
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摘要
Chalcostibite(CuSbS_2)is composed of earth-abundant elements and has a proper band gap(E_g=1.05 eV)as a thermoelectric(TE)material.Herein,we report the TE properties in the CuSbS_2 based composites with a mole ratio of(1–x)CuSbS_2–x Cu_(1.8)S(x=0,0.1,0.2,0.3),which were prepared by mechanical alloying(MA)combined with spark plasma sintering(SPS).X-ray diffraction(XRD)and back-scattered electron image(BSE)results indicate that a single phase of CuSbS_2 is synthesized at x=0 and the samples consist of CuSbS_2,Cu_3SbS_4,and Cu_(12)Sb_4S_(13) at 0.1≤x≤0.3.The correlation between the phase structure,microstructure,and TE transport properties of the bulk samples is established.The electrical conductivity increases from 0.14 to 50.66 S·cm~(–1) at 723 K and at0≤x≤0.03,while the Seebeck coefficient holds an appropriate value of 190.51μV·K~(–1).The highest ZT value of 0.17 is obtained at 723 K and at x=0.3 owing to the combination of a high PF183μW·m~(–1)·K~(–2) and a lowκ0.8 W·m~(–1)·K~(–1).
Chalcostibite(CuSbS_2)is composed of earth-abundant elements and has a proper band gap(E_g=1.05 eV)as a thermoelectric(TE)material.Herein,we report the TE properties in the CuSbS_2 based composites with a mole ratio of(1–x)CuSbS_2–x Cu_(1.8)S(x=0,0.1,0.2,0.3),which were prepared by mechanical alloying(MA)combined with spark plasma sintering(SPS).X-ray diffraction(XRD)and back-scattered electron image(BSE)results indicate that a single phase of CuSbS_2 is synthesized at x=0 and the samples consist of CuSbS_2,Cu_3SbS_4,and Cu_(12)Sb_4S_(13) at 0.1≤x≤0.3.The correlation between the phase structure,microstructure,and TE transport properties of the bulk samples is established.The electrical conductivity increases from 0.14 to 50.66 S·cm~(–1) at 723 K and at0≤x≤0.03,while the Seebeck coefficient holds an appropriate value of 190.51μV·K~(–1).The highest ZT value of 0.17 is obtained at 723 K and at x=0.3 owing to the combination of a high PF183μW·m~(–1)·K~(–2) and a lowκ0.8 W·m~(–1)·K~(–1).
Chalcostibite(CuSbS_2)is composed of earth-abundant elements and has a proper band gap(E_g=1.05 eV)as a thermoelectric(TE)material.Herein,we report the TE properties in the CuSbS_2 based composites with a mole ratio of(1–x)CuSbS_2–x Cu_(1.8)S(x=0,0.1,0.2,0.3),which were prepared by mechanical alloying(MA)combined with spark plasma sintering(SPS).X-ray diffraction(XRD)and back-scattered electron image(BSE)results indicate that a single phase of CuSbS_2 is synthesized at x=0 and the samples consist of CuSbS_2,Cu_3SbS_4,and Cu_(12)Sb_4S_(13) at 0.1≤x≤0.3.The correlation between the phase structure,microstructure,and TE transport properties of the bulk samples is established.The electrical conductivity increases from 0.14 to 50.66 S·cm~(–1) at 723 K and at0≤x≤0.03,while the Seebeck coefficient holds an appropriate value of 190.51μV·K~(–1).The highest ZT value of 0.17 is obtained at 723 K and at x=0.3 owing to the combination of a high PF183μW·m~(–1)·K~(–2) and a lowκ0.8 W·m~(–1)·K~(–1).
引文
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[21]Zheng LJ,Zhang BP,Li HZ,et al.CuxS superionic compounds:Electronic structure and thermoelectric performance enhancement.J Alloys Compd 2017,722:17-24.
[22]Ge ZH,Zhang BP,Yu YQ,et al.Fabrication and properties of Bi2-xAg3xS3 thermoelectric polycrystals.J Alloys Compd2012,514:205-209.
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[2]Ge ZH,Zhao LD,Wu D,et al.Low-cost,abundant binary sulfides as promising thermoelectric materials.Mater Today 2016,19:227-239.
[3]Gassoumi A,H.-E MMS,Alfaify S,et al.The investigation of crystal structure,elastic and optoelectronic properties of Cu Sb S2 and CuBiS2 compounds for photovoltaic applications.J Alloys Compd 2017,725:181-189.
[4]Chen K.Synthesis and thermoelectric properties of Cu-Sb-S compounds.Ph.D.Thesis.London(UK):Queen Mary,University of London,2016.
[5]Du BL,Zhang RZ,Chen K,et al.The impact of lone-pair electrons on the lattice thermal conductivity of the thermoelectric compound CuSbS2.J Mater Chem A 2017,5:3249-3259.
[6]Chen K,Du BL,Bonini N,et al.Theory-guided synthesis of an eco-friendly and low-cost copper based sulfide thermoelectric material.J Phys Chem C 2016,120:27135-27140.
[7]Heo J,Laurita G,Muir S,et al.Enhanced thermoelectric performance of synthetic tetrahedrites.Chem Mater 2014,26:2047-2051.
[8]Lu X,Morelli DT,Xia Y,et al.High performance thermoelectricity in earth-abundant compounds based on natural mineral tetrahedrites.Adv Energy Mater 2013,3:342-348.
[9]Lu X,Morelli D.The effect of Te substitution for Sb on thermoelectric properties of tetrahedrite.J Electron Mater2014,43:1983-1987.
[10]Kumar Gudelli V,Kanchana V,Vaitheeswaran G,et al.Thermoelectric properties of chalcopyrite type CuGaTe2and chalcostibite CuSbS2.J Appl Phys 2013,114:223707.
[11]Rodr??guez-Lazcano Y,Nair MTS,Nair PK.Cu Sb S2 thin film formed through annealing chemically deposited Sb2S3-CuS thin films.J Cryst Growth 2001,223:399-406.
[12]Rodríguez-Lazcano Y,Nair MTS,Nair PK.Photovoltaic p-i-N structure of Sb2S3 and CuSbS2 absorber films obtained via chemical bath deposition.J Electrochem Soc2005,152:G635.
[13]Rabhi A,Kanzari M.Structural,optical and electrical properties of CuSbS2 these amorphous films:effect of the thickness variation.Chalcogenide Lett 2011,8:383-390.
[14]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.
[15]Ge ZH,Zhang BP,Chen YX,et al.Synthesis and transport property of Cu1.8S as a promising thermoelectric compound.Chem Commun 2011,47:12697-12699.
[16]Yao Y,Zhang BP,Pei J,et al.Improved thermoelectric transport properties of Cu1.8S with NH4Cl-derived mesoscale-pores and point-defects.Ceram Int 2016,42:17518-17523.
[17]Li JF,Pan Y,Wu CF,et al.Processing of advanced thermoelectric materials.Sci China Technol Sci 2017,60:1347-1364.
[18]Saal JE,Kirklin S,Aykol M,et al.Materials design and discovery with high-throughput density functional theory:The open quantum materials database(OQMD).JOM 2013,65:1501-1509.
[19]Kirklin S,Saal JE,Meredig B,et al.The open quantum materials database(OQMD):Assessing the accuracy of DFT formation energies.npj Comput Mater 2015,1:15010.
[20]Zou L,Zhang BP,Ge ZH,et al.Size effect of SiO2 on enhancing thermoelectric properties of Cu1.8S.Phys Status Solidi A 2013,210:2550-2555.
[21]Zheng LJ,Zhang BP,Li HZ,et al.CuxS superionic compounds:Electronic structure and thermoelectric performance enhancement.J Alloys Compd 2017,722:17-24.
[22]Ge ZH,Zhang BP,Yu YQ,et al.Fabrication and properties of Bi2-xAg3xS3 thermoelectric polycrystals.J Alloys Compd2012,514:205-209.
[23]Goldsmid HJ.Introduction to Thermoelectricity.Berlin(Germany):Springer-Verlag Berlin Heidelberg,2010.
[24]Pei J,Zhang BP,Li JF,et al.Maximizing thermoelectric performance of AgPbmSb Tem+2 by optimizing spark plasma sintering temperature.J Alloys Compd 2017,728:694-700.