Tetrahedrites synthesized via scalable mechanochemical process and spark plasma sintering

In this study, we demonstrate the use of elemental precursors (Cu,Sb,S) to synthesize tetrahedrite Cu12Sb4S13 using an industrial eccentric vibratory mill. Mechanochemical synthesis of tetrahedrite leads to the formation of covellite (CuS), skinnerite (Cu3SbS3) or famatinite (Cu3SbS4) in dependence on milling time. However, the composite product can be modified in favour of prevailing tetrahedrite when Spark Plasma Sintering (SPS) treatment is applied after milling. The as-synthesized and sintered products are composed of polydisperse nanosized particles with dimensions up to 250 nm. The thermoelectric measurements reveal a maximum value of figure-of-merit ZT = 0.67 @ 700 K, as a consequence of a relatively high power factor (1.07 mW m(-1) K-2) and a low thermal conductivity (1.12 W m(-1) K-1). The obtained zT values of products prepared in an industrial mill are comparable to the ones reported for compounds synthesized using laboratory mills. The synthesis of ternary and quatemary sulphides by a scalable and industrializable milling process represents a prospective route for mass production of thermoelectric materials.