Mechanosynthesis and Thermoelectric Properties of Fe, Zn, and Cd-Doped P-Type Tetrahedrite: Cu12-xMxSb4S13.

This contribution deals with the mechanochemical synthesis, characterization, and thermoelectric properties of tetrahedrite-based materials, Cu12-xMxSb4S13 (M = Fe2+, Zn2+, Cd2+; x = 0, 1.5, 2). High-energy mechanical milling allows obtaining pristine and substituted tetrahedrites, after short milling under ambient conditions, of stoichiometric mixtures of the corresponding commercially available binary sulfides, i.e., Cu2S, CuS, Sb2S3, and MS (M = Fe2+, Zn2+, Cd2+). All the target materials but those containing Cd were obtained as single-phase products; some admixture of a hydrated cadmium sulfate was also identified by XRD as a by-product when synthesizing Cu10Cd2Sb4S13. The as-obtained products were thermally stable when firing in argon up to a temperature of 350-400 °C. Overall, the substitution of Cu(II) by Fe(II), Zn(II), or Cd(II) reduces tetrahedrites' thermal and electrical conductivities but increases the Seebeck coefficient. Unfortunately, the values of the thermoelectric figure of merit obtained in this study are in general lower than those found in the literature for similar samples obtained by other powder processing methods; slight compositional changes, undetected secondary phases, and/or deficient sintering might account for some of these discrepancies.