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

Ventrapati Pavan Kumar, Andrew R. Supka, Pierric Lemoine, Oleg I. Lebedev, Bernard Raveau, Koichiro Suekuni, Vivian Nassif, Rabih Al Rahal Al Orabi, Marco Fornari, Emmanuel Guilmeau

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

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.

Original languageEnglish
Article number1803249
JournalAdvanced Energy Materials
Volume9
Issue number6
DOIs
Publication statusPublished - Feb 7 2019

All Science Journal Classification (ASJC) codes

  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

Fingerprint Dive into the research topics of 'High Power Factors of Thermoelectric Colusites Cu<sub>26</sub>T<sub>2</sub>Ge<sub>6</sub>S<sub>32</sub> (T = Cr, Mo, W): Toward Functionalization of the Conductive “Cu–S” Network'. Together they form a unique fingerprint.

  • Cite this

    Pavan Kumar, V., Supka, A. R., Lemoine, P., Lebedev, O. I., Raveau, B., Suekuni, K., Nassif, V., Al Rahal Al Orabi, R., Fornari, M., & Guilmeau, E. (2019). High Power Factors of Thermoelectric Colusites Cu26T2Ge6S32 (T = Cr, Mo, W): Toward Functionalization of the Conductive “Cu–S” Network. Advanced Energy Materials, 9(6), [1803249]. https://doi.org/10.1002/aenm.201803249