Modification of tetrahedrite Cu12Sb4S13 thermoelectric performance via the combined treatment of mechanochemistry and composite formation

Tetrahedrite Cu12Sb4S13 with its low thermal conductivity represents a flagship in sulphide thermoelectrics. However, to achieve a reasonable figure-of-merit ZT, (measure of thermoelectric efficiency), adequate doping or special sample processing is needed. In this work, a different approach (without doping) is illustrated for the two tetrahedrite-containing systems. In the first approach binary composite tetrahedrite Cu12Sb4S13/chalcopyrite CuFeS2 was prepared by mechanochemical leaching with the aim to obtain partly decomposed tetrahedrite. In this approach, the alkaline leaching medium (Na2S + NaOH) was applied to extract Sb from tetrahedrite thus changing its composition. The obtained composite (formed from its own phases in an intrinsic mode) shows low values of ZT = 0.0022@673 K in comparison with the non-treated tetrahedrite where ZT was 0.0090@673 K. In this case the extremely high electric resistivity (6–20 mΩ cm−1) was documented. In the second approach binary composite tetrahedrite Cu12Sb4S13/muscovite KAl2(AlSi3O10)(OH)2 (formed from its own and foreign phases in an extrinsic mode) was prepared by two-step mechanical activation in which combined treatment of industrial vibratory milling and subsequent laboratory planetary milling was applied. The addition of a foreign phase, muscovite, did not give extraordinary thermoelectric performance results. However, the two-step milling process (without the addition of foreign phase) gives the value of ZT = 0.752@673 K which belongs to the highest in the tetrahedrite thermoelectric community. In this case, the two-times increase in specific surface area and the increased amount of tetrahedrite in comparison to famatinite are suspectable for this effect. Both applied non-traditional approaches to synthesize tetrahedrite composites form a platform for potential modification of its thermoelectric performance.