A pristine colusite Cu26V2Sn6S32 was successfully synthesised on a 100 g scale via a mechanochemical reaction in an industrial eccentric vibratory ball mill followed by spark plasma sintering (SPS) at 873 K. The milling of elemental precursors from 1 up to 12 hours was performed and the prepared samples were investigated in detail by X-ray powder diffraction, Mössbauer spectroscopy, scanning electron microscopy, and thermoelectric property measurements. The results point to the formation of a high purity and high crystallinity non-exsoluted colusite phase after the SPS process (P4[combining macron]3n, a = 10.7614(1) Å) in the case of a 12 h milled sample. In comparison, samples milled for 1-6 h displayed small quantities of binary Cu-S phases and vanadium core-shell inclusions, leading to a V-poor/Sn-rich colusite with a higher degree of structural disorder. These samples exhibit lower electrical conductivity and Seebeck coefficient while an increase in the total thermal conductivity is observed. This phenomenon is explained by a higher reactivity and grain size reduction upon prolonged milling and by a weak evolution of the chemical composition from a partly disordered V-poor/Sn-rich colusite phase to a well-ordered stoichiometric Cu26V2Sn6S32 colusite, which leads to a decrease in carrier concentration. For all samples, the calculated PF values, around 0.7-0.8 mW m-1 K-2 at 700 K, are comparable to the values previously achieved for mechanochemically synthesised Cu26V2Sn6S32 in laboratory mills. This approach thus serves as an example of scaling-up possibility for sulphur-based TE materials and supports their future large-scale deployment.

CRISMAT CNRS Normandie Univ ENSICAEN UNICAEN 14000 Caen France

Institut Jean Lamour UMR 7198 CNRS Université de Lorraine 2 allée André Guinier Campus ARTEM BP 50840 54011 Nancy Cedex France

Institute of Geotechnics Slovak Academy of Sciences Watsonova 45 04001 Košice Slovakia

Normandie Univ INSA Rouen UNIROUEN CNRS GPM 76000 Rouen France

Synthon s r o Brněnská 32 678 01 Blansko Czech Republic

Univ Rennes CNRS ISCR UMR 6226 F 35000 Rennes France

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