High Power Factors of Thermoelectric Colusites Cu26T2Ge6S32 (T = Cr, Mo, W): Toward Functionalization of the Conductive “Cu–S” Network

The introduction of hexavalent T6+ cations in p‐type thermoelectric colusites Cu26T2Ge6S32 (T = Cr, Mo, W) leads to the highest power factors among iono‐covalent sulfides, ranging from 1.17 mW m−1 K−2 at 700 K for W to a value of 1.94 mW m−1 K−2 for Cr. In Cu26Cr2Ge6S32, ZT reaches values close to unity at 700 K. The improvement of the transport properties in these new sulfides is explained on the basis of electronic structure and transport calculations keeping in mind that the relaxation time is significantly influenced by the size and the electronegativity of the interstitial T cation. The rationale is based on the concept of a conductive “Cu–S” network, which in colusites corresponds to the more symmetric parent structure sphalerite. A detailed structural analysis of these colusites shows that the distortion of the conductive network is influenced by the presence in the structure of mixed octahedral–tetrahedral [TS4]Cu6 complexes where the T cations are underbonded to sulfur and form metal–metal interactions with copper, Cu–T distances decreasing from 2.76 Å for W to 2.71 Å for Cr. The interactions between these complexes are responsible for the outstanding electronic transport properties. By contrast, the thermal conductivity is not significantly affected. The introduction of hexavalent Cr6+ cation in colusite, Cu26Cr2Ge6S32, allows a new p‐type thermoelectric with high power factors to be synthesized. Considering the concept of a conductive network as an ion sublattice which dominates the electronic states active in transport, these results open the route to the functionalization of these materials for the achievement of high power factors in sulfides.