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.
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BiSe with intrinsic low thermal conductivity has considered as a promising thermoelectric (TE) material at nearly room temperature. To improve its low thermoelectric figure of merit (zT), in this work, Sb and Te isovalent co-alloying was performed and significantly optimized its TE property with weakly anisotropic characteristic. After substituting Sb on Bi sites, the carrier concentration is suppressed by introduction of Sb- Se site defects, which contributes to the increased absolute value of Seebeck coefficient (|S|). Further co-alloying Te on Se of the optimized composition Bi0.7Sb0.3Se, the carrier concentration increased without affecting the |S| due to the enhanced effective mass, which leads to a highest power factor of 12.8 μW/(cm·K2) at 423 K. As a result, a maximum zT of ~0.54 is achieved for Bi0.7Sb0.3Se0.7Te0.3 along the pressing direction and the average zT (zTave) (from 300 K to 623 K) are drastically improved from 0.24 for pristine BiSe sample to 0.45. Moreover, an energy conversion efficiency ~4.0% is achieved for a single leg TE device of Bi0.7Sb0.3Se0.7Te0.3when applied the temperature difference of 339 K, indicating the potential TE application.