Abstract
The Cu–S compounds have been reported as promising thermoelectric materials with abundant element composition, low price, and low toxicity. In this work, SnxCu1.8−xS samples with different Sn contents (x = 0.005, 0.01, 0.03, and 0.05) were fabricated by mechanical alloying combined with spark plasma sintering. The phase structure and microstructure of all the bulk samples were checked by X-ray diffraction (XRD) and field emission scanning electron microscopy respectively. The thermoelectric transport properties, such as electrical conductivity, Seebeck coefficient, carrier concentration, carrier mobility, and thermal conductivity, were measured. The effect of second phase introduced by Sn addition on the thermoelectric properties of Cu–S system was investigated. The thermoelectric properties of samples were improved by the precipitations of two different second phases (Cu2SnS3 and Cu4SnS4). The second phase species depend on the Sn contents. Finally, the Sn0.01Cu1.79S bulk sample obtained the highest ZT value of 0.81 at 773 K, which is 1.6-fold higher than that of the pristine Cu1.8S sample due to the significantly reduced thermal conductivity by second phase and nanopores scattering.
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G.J. Snyder and E.S. Toberer: Complex thermoelectric materials. Nat. Mater. 7, 105 (2008).
M.G. Kanatzidis: Nanostructured thermoelectrics: The new paradigm?Chem. Mater. 22, 648 (2010).
B.C. Sales: Smaller is cooler. Science 295, 1248 (2002).
F.J. Disalvo: Thermoelectric cooling and power generation. Science 285, 703 (1999).
G. Chen, M.S. Dresselhaus, and G. Dresselhaus: Recent developments in thermoelectric materials. Int. Mater. Rev. 1, 45 (2003).
L.D. Zhao, B.P. Zhang, W.S. Liu, and J.F. Li: Effect of mixed grain sizes on thermoelectric performance of Bi2Te3 compound. J. Appl. Phys. 105, 023704 (2009).
M. Zhou, J.F. Li, and T. Kita: Nanostructured AgPb(m)SbTe(m +2) system bulk materials with enhanced thermoelectric performance. J. Am. Chem. Soc. 130, 4527 (2008).
H. Wang, J.F. Li, C.W. Nan, M. Zhou, W.S. Liu, B.P. Zhang, and T. Kita: Enhanced thermoelectric properties in CoSb3−xTex alloys prepared by mechanical alloying and spark plasma sintering. Appl. Phys. Lett. 88, 092104 (2006).
X. Shi, J. Yang, S.Q. Bai, J.H. Yang, H. Wang, M.F. Chi, J.R. Salvador, W.Q. Zhang, L.D. Chen, and W. Wong-Ng: On the design of high-efficiency thermoelectric clathrates through a systematic cross-substitution of framework elements. Adv. Funct. Mater. 20, 755 (2010).
W.S. Liu, B.P. Zhang, L.D. Zhao, H.L. Zhang, and J.F. Li: Improvement of thermoelectric performance of CoSb3−xTex skutterudite compounds by additional substitution of IVB-group elements for Sb. Chem. Mater. 20, 7526 (2008).
L.D. Zhao, J. He, D. Berardan, Y. Lin, J.F. Li, C.W. Nan, and N. Dragoe: BiCuSeO oxyselenides: New promising thermoelectric materials. Energy Environ. Sci. 7, 2900 (2014).
A. Samarelli, L. Llin, S. Cecchi, J. Frigerio, D. Chrastina, G. Isella, E. Müller Gubler, T. Etzelstorfer, J. Stangl, Y. Zhang, J.M.R. Weaver, P.S. Dobson, and D.J. Paul: Prospects for SiGe thermoelectric generators. Solid-State Electron. 98, 70 (2014).
B.A. Mansour: Electrical and thermoelectric properties of in and Cd doped Cu1.8S. Phys. Status Solidi A 136, 153 (1993).
L.D. Zhao, S.H. Lo, Y.S. Zhang, H. Sun, G.J. Tan, C. Uher, C. Wolvrton, V.P. Dravid, and M.G. Kanatzidis: Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals. Nature 508, 373 (2014).
Z.H. Ge, K. Wei, H. Lewis, J. Martin, and G.S. Nolas: Bottom-up processing and low temperature transport properties of polycrystalline SnSe. J. Solid State Chem. 225, 354 (2015).
H.L. Liu, X. Shi, F.F. Xu, L.L. Zhang, W.Q. Zhang, L.D. Chen, Q. Li, C. Uher, T. Day, and G.J. Snyder: Copper ion liquid-like thermoelectrics. Nat. Mater. 11, 422 (2012).
B. Zhong, Y. Zhang, W. Li, Z. Chen, J. Cui, W. Li, Y. Xie, Q. Hao, and Q. He: High superionic conduction arising from aligned large lamellae and large figure of merit in bulk Cu1.94Al0.02Se. Appl. Phys. Lett. 105, 123902 (2014).
Z.H. Ge, B.P. Zhang, Z.X. Yu, Y. Liu, and J.F. Li: Synthesis and transport property of Cu1.8S as a promising thermoelectric compound. Chem. Commun. 47, 12697 (2012).
Y. He, T. Day, T. Zhang, H. Liu, X. Shi, L. Chen, and G.J. Snyder: High thermoelectric performance in non-toxic earth-abundant copper sulfide. Adv. Mater. 26, 3974 (2014).
Q. Jiang, H. Yan, Y. Shen, K. Simpson, and M.J. Reece: Enhancement of thermoelectric properties by atomic-scale percolation in digenite CuxS. J. Mater. Chem. A 2, 9486 (2014).
S.N. Guin, J. Pan, A. Bhowmik, D. Sanyal, U.V. Waghmare, and K. Biswas: Temperature dependent reversible p–n–p type conduction switching with colossal change in thermopower of semiconducting AgCuS. J. Am. Chem. Soc. 136, 12712 (2014).
S.N. Guin, D. Sanyal, and K. Biswas: The effect of order–disorder phase transitions and band gap evolution on the thermoelectric properties of AgCuS nanocrystals. Chem. Sci. 7, 534 (2016).
S.N. Guin and K. Biswas: Temperature driven p–n–p type conduction switching materials: Current trends and future directions. Phys. Chem. Chem. Phys. 17, 10316 (2015).
Y.B. Lou, A.C.S. Samia, J. Cowen, K. Banger, X. Chen, H. Lee, and C. Burda: Evaluation of the photoinduced electron relaxation dynamics of Cu1.8S quantum dots. Phys. Chem. Chem. Phys. 5, 1091 (2003).
N. Morimoto and G. Kullerud: Polymorphism in digenite. Am. Mineral. 48, 110 (1963).
Z.H. Ge, X.Y. Liu, D. Feng, J.Y. Lin, and J.Q. He: High-performance thermoelectricity in nanostructured earth-abundant copper sulfides bulk materials. Adv. Energy Mater. 6, 1600607 (2016).
L.D. Zhao, B.P. Zhang, W.S. Liu, H.L. Zhang, and J.F. Li: Enhanced thermoelectric properties of bismuth sulfide polycrystals prepared by mechanical alloying and spark plasma sintering. J. Solid State Chem. 181, 3278 (2008).
L.J. Zheng, B.P. Zhang, H.Z. Li, J. Pei, and J.B. Yu: CuxS superionic compounds: Electronic structure and thermoelectric performance enhancement. J. Alloys Compd. 722, 17 (2017).
Z.H. Ge, B.P. Zhang, P.P. Shang, Y-Q. Yu, C. Chen, and J-F. Li: Enhancing thermoelectric properties of polycrystalline Bi2S3 by optimizing a ball-milling process. J. Electron. Mater. 40, 1087 (2011).
L. Zhao, X. Wang, F.Y. Fei, J. Wang, and Z. Cheng: High thermoelectric and mechanical performance in highly dense Cu2−xS bulks prepared by a melt-solidification technique. J. Mater. Chem. A, 3, 9432–9437 (2015).
L. Zhao, B. Zhang, J. Li, M. Zhou, W. Liu, and J. Liu: Thermoelectric and mechanical properties of nano-SiC-dispersed Bi2Te3 fabricated by mechanical alloying and spark plasma sintering. J. Alloys Compd. 455, 259 (2008).
Y. Gelbstein, G. Gotesman, Y. Lishzinker, Z. Dashevsky, and M.P. Dariel: Mechanical properties of PbTe-based thermoelectric semiconductors. Scr. Mater. 58, 251 (2008).
ACKNOWLEDGMENT
This work was supported by the National Natural Science Foundation of China (Grant No. 51501086).
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Qin, P., Ge, ZH. & Feng, J. Effects of second phases on thermoelectric properties in copper sulfides with Sn addition. Journal of Materials Research 32, 3029–3037 (2017). https://doi.org/10.1557/jmr.2017.288
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DOI: https://doi.org/10.1557/jmr.2017.288