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

研究成果: ジャーナルへの寄稿記事

6 引用 (Scopus)

抄録

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.

元の言語英語
記事番号1803249
ジャーナルAdvanced Energy Materials
9
発行部数6
DOI
出版物ステータス出版済み - 2 7 2019

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Cations
Positive ions
Sulfides
Transport properties
Electronegativity
Sulfur
Structural analysis
Relaxation time
Electronic structure
Copper
Thermal conductivity
cupric sulfide
zinc sulfide

All Science Journal Classification (ASJC) codes

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

これを引用

High Power Factors of Thermoelectric Colusites Cu26T2Ge6S32 (T = Cr, Mo, W) : Toward Functionalization of the Conductive “Cu–S” Network. / Pavan Kumar, Ventrapati; Supka, Andrew R.; Lemoine, Pierric; Lebedev, Oleg I.; Raveau, Bernard; Suekuni, Koichiro; Nassif, Vivian; Al Rahal Al Orabi, Rabih; Fornari, Marco; Guilmeau, Emmanuel.

:: Advanced Energy Materials, 巻 9, 番号 6, 1803249, 07.02.2019.

研究成果: ジャーナルへの寄稿記事

Pavan Kumar, V, Supka, AR, Lemoine, P, Lebedev, OI, 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, 巻. 9, 番号 6, 1803249. https://doi.org/10.1002/aenm.201803249
Pavan Kumar, Ventrapati ; Supka, Andrew R. ; Lemoine, Pierric ; Lebedev, Oleg I. ; Raveau, Bernard ; Suekuni, Koichiro ; Nassif, Vivian ; Al Rahal Al Orabi, Rabih ; Fornari, Marco ; Guilmeau, Emmanuel. / High Power Factors of Thermoelectric Colusites Cu26T2Ge6S32 (T = Cr, Mo, W) : Toward Functionalization of the Conductive “Cu–S” Network. :: Advanced Energy Materials. 2019 ; 巻 9, 番号 6.
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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 {\AA} for W to 2.71 {\AA} for Cr. The interactions between these complexes are responsible for the outstanding electronic transport properties. By contrast, the thermal conductivity is not significantly affected.",
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T2 - Toward Functionalization of the Conductive “Cu–S” Network

AU - Pavan Kumar, Ventrapati

AU - Supka, Andrew R.

AU - Lemoine, Pierric

AU - Lebedev, Oleg I.

AU - Raveau, Bernard

AU - Suekuni, Koichiro

AU - Nassif, Vivian

AU - Al Rahal Al Orabi, Rabih

AU - Fornari, Marco

AU - Guilmeau, Emmanuel

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