Enhanced Thermoelectric Properties of Hydrothermal Synthesized BiCl3/Bi2S3 Composites

doi:10.15541/jim20180261

Abstract

Abstract:

Hierarchical spherical Bi₂S₃ particles with nanorod were synthesized by hydrothermal method, and then BiCl₃/Bi₂S₃ composite powders with different molar ratios were consolidated into bulk samples by spark plasma sintering (SPS) technique. The addition of BiCl₃ with appropriate amount not only increased the electrical conductivity, but also decreased the thermal conductivity of Bi₂S₃. The Bi₂S₃ sample doped with 0.5mol% BiCl₃ shows a maximum electrical conductivity of 45.1 S·cm^-1 at 762 K, which is much higher than that of pure Bi₂S₃at 762 K (12.9 S·cm^-1). The minimum thermal conductivity is 0.31 W·m^-1·K^-1 for the Bi₂S₃ sample doped with 0.25mol% BiCl₃ at 762 K, which is lower than that of pure Bi₂S₃(0.47 W·m^-1·K^-1)at the same temperature. The maximum ZT value of 0.63 at 762 K was achieved by Bi₂S₃ doped with 0.25mol% BiCl₃, which is almost two times higher than that of pure Bi₂S₃(0.22).

Key words: Bi₂S₃, hydrothermal method, spherical particle, spark plasma sintering, thermoelectric

CLC Number:

TB34

WANG Wei, LUO Shi-Jie, XIAN Cong, XIAO Qun, YANG Yang, OU Yun, LIU Yun-Ya, XIE Shu-Hong. Enhanced Thermoelectric Properties of Hydrothermal Synthesized BiCl₃/Bi₂S₃ Composites[J]. Journal of Inorganic Materials, 2019, 34(3): 328-334.

Figures/Tables 6

Fig. 1 XRD patterns (a) and the enlarged patterns of 2θ in the range of 24°-32.5°(b) with peaks of crystal plane (211) in the inset for BiCl3/Bi2S3 powders with different xmol% (x= 0, 0.25, 0.5, and 1.0) BiCl3

Fig. 2 SEM images of Bi2S3 powders (a), fractured surfaces of SPSed samples of Bi2S3 doped with xmol% BiCl3 ((b) x=0, (c) x=0.25, (d) x=0.5, (e) x=1.0); TEM images of sintered samples of Bi2S3 doped with xmol% BiCl3 ((f) x=0, (h) x=1.0); HRTEM image of Bi2S3 powder after SPS (g)

Fig. 3 SEM image of the fractured surfaces of Bi2S3 doped with 1.0mol% BiCl3 bulk after SPS (a), corresponding elemental mappings of Bi, S and Cl (b-d)

Table 1 Thermoelectric performance of BiCl3/Bi2S3 samples at 762 K

Sample	ρ/%	S/(µV·K^-1)	σ/(S·cm^-1)	PF/(μW·m^-1·K^-2)	κ/(W·m^-1·K^-1)	ZT
Bi₂S₃	89%	-326.0	12.9	136.9	0.47	0.22
Bi₂S₃+0.25% BiCl₃	90%	-304.0	27.6	255.0	0.31	0.63
Bi₂S₃+0.5% BiCl₃	89%	-279.0	45.1	350.2	0.58	0.46
Bi₂S₃+1.0% BiCl₃	92%	-273.5	25.4	189.7	0.49	0.30

Fig. 4 Temperature dependence of thermoelectric performances for BiCl3/Bi2S3 composite samples (a) Seebeck coefficient; (b) Electrical conductivity; (c) Power factor; (d) Total thermal conductivity; (e) Lattice thermal conductivity; (f) Figure of merit (ZT)

Table 2 Carrier concentration of BiCl3/Bi2S3 samples at room temperature

Sample	Bi₂S₃	Bi₂S₃+0.25% BiCl₃	Bi₂S₃+0.5% BiCl₃	Bi₂S₃+1.0% BiCl₃
Carrierconcentration/(×10¹⁵, cm^-3)	1.82	2.13	4.31	6.83

References 34

[1]	PEI Y, SHI X, LALONDE A, et al.Convergence of electronic bands for high performance bulk thermoelectrics. Nature, 2011, 473(7345): 66-69.
[2]	BELL L E.Cooling, heating, generating power, and recovering waste heat with thermoelectric systems. Science, 2008, 321(5895): 1457-1461.
[3]	DISALVO F J.Thermoelectric cooling and power generation. Science, 1999, 285(5428): 703-706.
[4]	LI J F, LIU W S, ZHAO L D, et al.High-performance nanostructured thermoelectric materials. NPG Asia Materials, 2010, 2(4): 152-158.
[5]	SNYDER G J, TOBERER E S.Complex thermoelectric materials. Nature Materials, 2008, 7(2): 105-114.
[6]	YANG Y, MA F Y, LEI C H, et al. Is thermoelectric conversion efficiency of a composite bounded by its constituents? Applied Physics Letters, 2013, 102(5): 053905-1-4.
[7]	YANG Y, XIE S H, MA F Y, et al. On the effective thermoelectric properties of layered heterogeneous medium. Journal of Applied Physics, 2012, 111(1): 013510-1-7.
[8]	KIM W, ZIDE J, GOSSARD A, et al. Thermal conductivity reduction and thermoelectric figure of merit increase by embedding nanoparticles in crystalline semiconductors. Physical Review Letters,2006, 96(4): 045901-1-4.
[9]	MUTA H, IEDA A, KUROSAKI K, et al.Substitution effect on the thermoelectric properties of alkaline earth titanate. MaterialsLetters,2004, 58(30): 3868-3871.
[10]	NASR ESFAHANI E, MA F, WANG S, et al.Quantitative nanoscale mapping of three-phase thermal conductivities in filled skutterudites via scanning thermal microscopy. National Science Review, 2017, 5(1): 59-69.
[11]	LIU Y, CHEN L, LI J.Precipitate morphologies of pseudobinary Sb2Te3-PbTe thermoelectric compounds. Acta Materialia, 2014, 65: 308-315.
[12]	YANG Y, MA F Y, LEI C H, et al.Nonlinear asymptotic homogenization and the effective behavior of layered thermoelectric composites. Journal of the Mechanics and Physics of Solids, 2013, 61(8): 1768-1783.
[13]	WANG C, NIU Y, JIANG J, et al.Hybrid thermoelectric battery electrode FeS2 study. Nano Energy, 2018, 45: 432-438.
[14]	DUGHAISH Z H.Lead telluride as a thermoelectric material for thermoelectric power generation. Physica B: Condensed Matter, 2002, 322(1/2): 205-223.
[15]	HEREMANS J P, JOVOVIC V, TOBERER E S, et al.Enhancement of thermoelectric efficiency in PbTe by distortion of the electronic density of states. Science, 2008, 321(5888): 554-557.
[16]	POUDEL B, HAO Q, MA Y, et al.High-thermoelectric performance of nanostructured bismuth antimony telluride bulk alloys. Science, 2008, 320(5876): 634-638.
[17]	CAO Y Q, ZHAO X B, ZHU T J, et al. Syntheses and thermoelectric properties of Bi2Te3/Sb2Te3 bulk nanocomposites with laminated nanostructure. Applied Physics Letters,2008, 92(14): 143106-1-3.
[18]	CANTARERO A, MARTINEZ-PASTOR J, SEGURA A, et al.Transport properties of bismuth sulfide single crystals. Physical Review B, 1987, 35(18): 9586-9590.
[19]	BISWAS K, ZHAO L D, KANATZIDIS M G.Tellurium-free thermoelectric: the anisotropic n-type semiconductor Bi2S3. Advanced Energy Materials, 2012, 2(6): 634-638.
[20]	LIU W, GUO C F, YAO M, et al.Bi2S3 nanonetwork as precursor for improved thermoelectric performance. Nano Energy, 2014, 4: 113-122.
[21]	CHEN B, UHER C, IORDANIDIS L, et al.Transport properties of Bi2S3 and the ternary bismuth sulfides KBi6.33S10 and K2Bi8S13. Chemistry of Materials, 1997, 9(7): 1655-1658.
[22]	LIUFU S C, CHEN L D, YAO Q, et al. Assembly of one-dimensional nanorods into Bi2S3 films with enhanced thermoelectric transport properties. Applied Physics Letters,2007, 90(11): 112106-1-3.
[23]	GE Z H, ZHANG B P, LIU Y, et al.Nanostructured Bi2-xCuxS3 bulk materials with enhanced thermoelectric performance. Physical Chemistry Chemical Physics, 2012, 14(13): 4475-4481.
[24]	YU Y Q, ZHANG B P, GE Z H, et al.Thermoelectric properties of Ag-doped bismuth sulfide polycrystals prepared by mechanical alloying and spark plasma sintering. Materials Chemistry and Physics,2011, 131(1/2): 216-222.
[25]	DU X, CAI F, WANG X.Enhanced thermoelectric performance of chloride doped bismuth sulfide prepared by mechanical alloying and spark plasma sintering. Journal of Alloys and Compounds, 2014, 587: 6-9.
[26]	YANG X X, ZHOU Z F, WANG Y, et al. Raman spectroscopy determination of the Debye temperature and atomic cohesive energy of CdS, CdSe, Bi2Se3,Sb2Te3 nanostructures. Journal of Applied Physics, 2012, 112(8): 083508-1-6.
[27]	PHURUANGRAT A, THONGTEM T, THONGTEM S.Characterization of Bi2S3 nanorods and nano-structured flowers prepared by a hydrothermal method. Materials Letters, 2009, 63(17): 1496-1498.
[28]	ZHAO L D, ZHANG B P, LIU W S, et al.Enhanced thermoelectric properties of bismuth sulfide polycrystals prepared by mechanical alloying and spark plasma sintering. Journal of Solid State Chemistry, 2008, 181(12): 3278-3282.
[29]	ZHAO L D, LO S H, ZHANG Y, et al.Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals. Nature, 2014, 508(7496): 373-377.
[30]	HAN Y M, ZHAO J, ZHOU M, et al.Thermoelectric performance of SnS and SnS-SnSe solid solution. Journal of Materials Chemistry A, 2015, 3(8): 4555-4559.
[31]	TAN G, ZHAO L D, KANATZIDIS M G.Rationally designing high-performance bulk thermoelectric materials. Chemical Reviews, 2016, 116(19): 12123-12149.
[32]	GE Z H, QIN P, HE D S, et al.Highly enhanced thermoelectric properties of Bi/Bi2S3 nanocomposites. ACS Applied Materials & Interfaces, 2017, 9(5): 4828-4834.
[33]	YANG J, LIU G, YAN J, et al.Enhanced the thermoelectric properties of n-type Bi2S3 polycrystalline by iodine doping. Journal of Alloys and Compounds, 2017, 728: 351-356.
[34]	ZHANG L J, ZHANG B P, GE Z H, et al.Fabrication and properties of Bi2S3-xSex thermoelectric polycrystals. Solid State Communications, 2013, 162: 48-52.

Enhanced Thermoelectric Properties of Hydrothermal Synthesized BiCl₃/Bi₂S₃ Composites

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