Copper-Rich Thermoelectric Sulfides: Size-Mismatch Effect and Chemical Disorder in the [TS4]Cu6 Complexes of Cu26T2Ge6S32 (T=Cr, Mo, W) Colusites

Ventrapati Pavan Kumar, Gabin Guélou, Pierric Lemoine, Bernard Raveau, Andrew R. Supka, Rabih Al Rahal Al Orabi, Marco Fornari, Koichiro Suekuni, Emmanuel Guilmeau

研究成果: ジャーナルへの寄稿記事

2 引用 (Scopus)

抄録

Herein, we investigate the Mo and W substitution for Cr in synthetic colusite, Cu26Cr2Ge6S32. Primarily, we elucidate the origin of extremely low electrical resistivity which does not compromise the Seebeck coefficient and leads to outstanding power factors of 1.94 mW m−1 K−2 at 700 K in Cu26Cr2Ge6S32. We demonstrate that the abnormally long iono-covalent T–S bonds competing with short metallic Cu–T interactions govern the electronic transport properties of the conductive “Cu26S32” framework. We address the key role of the cationic size-mismatch at the core of the mixed tetrahedral–octahedral complex over the transport properties. Two essential effects are identified: 1) only the tetrahedra that are directly bonded to the [TS4]Cu6 complex are significantly distorted upon substitution and 2) the major contribution to the disorder is localized at the central position of the mixed tetrahedral–octahedral complex, and is maximized for x=1, i.e. for the highest cationic size-variance, σ2.

元の言語英語
ページ(範囲)15455-15463
ページ数9
ジャーナルAngewandte Chemie - International Edition
58
発行部数43
DOI
出版物ステータス出版済み - 10 21 2019

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Sulfides
Transport properties
Copper
Substitution reactions
Covalent bonds
Seebeck coefficient

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

これを引用

Copper-Rich Thermoelectric Sulfides : Size-Mismatch Effect and Chemical Disorder in the [TS4]Cu6 Complexes of Cu26T2Ge6S32 (T=Cr, Mo, W) Colusites. / Pavan Kumar, Ventrapati; Guélou, Gabin; Lemoine, Pierric; Raveau, Bernard; Supka, Andrew R.; Al Rahal Al Orabi, Rabih; Fornari, Marco; Suekuni, Koichiro; Guilmeau, Emmanuel.

:: Angewandte Chemie - International Edition, 巻 58, 番号 43, 21.10.2019, p. 15455-15463.

研究成果: ジャーナルへの寄稿記事

Pavan Kumar, V, Guélou, G, Lemoine, P, Raveau, B, Supka, AR, Al Rahal Al Orabi, R, Fornari, M, Suekuni, K & Guilmeau, E 2019, 'Copper-Rich Thermoelectric Sulfides: Size-Mismatch Effect and Chemical Disorder in the [TS4]Cu6 Complexes of Cu26T2Ge6S32 (T=Cr, Mo, W) Colusites', Angewandte Chemie - International Edition, 巻. 58, 番号 43, pp. 15455-15463. https://doi.org/10.1002/anie.201908579
Pavan Kumar, Ventrapati ; Guélou, Gabin ; Lemoine, Pierric ; Raveau, Bernard ; Supka, Andrew R. ; Al Rahal Al Orabi, Rabih ; Fornari, Marco ; Suekuni, Koichiro ; Guilmeau, Emmanuel. / Copper-Rich Thermoelectric Sulfides : Size-Mismatch Effect and Chemical Disorder in the [TS4]Cu6 Complexes of Cu26T2Ge6S32 (T=Cr, Mo, W) Colusites. :: Angewandte Chemie - International Edition. 2019 ; 巻 58, 番号 43. pp. 15455-15463.
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abstract = "Herein, we investigate the Mo and W substitution for Cr in synthetic colusite, Cu26Cr2Ge6S32. Primarily, we elucidate the origin of extremely low electrical resistivity which does not compromise the Seebeck coefficient and leads to outstanding power factors of 1.94 mW m−1 K−2 at 700 K in Cu26Cr2Ge6S32. We demonstrate that the abnormally long iono-covalent T–S bonds competing with short metallic Cu–T interactions govern the electronic transport properties of the conductive “Cu26S32” framework. We address the key role of the cationic size-mismatch at the core of the mixed tetrahedral–octahedral complex over the transport properties. Two essential effects are identified: 1) only the tetrahedra that are directly bonded to the [TS4]Cu6 complex are significantly distorted upon substitution and 2) the major contribution to the disorder is localized at the central position of the mixed tetrahedral–octahedral complex, and is maximized for x=1, i.e. for the highest cationic size-variance, σ2.",
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AU - Al Rahal Al Orabi, Rabih

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