RESUMO
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.
RESUMO
The strong interplay between magnetism and transport can tune the thermoelectric properties in chalcogenides and oxides. In the case of ferromagnetic CoS2 pyrite, it was previously shown that the power factor is large at room temperature, reaching 1 mW m-1 K-2 and abruptly increases for temperatures below the Curie transition ( TC), an increase potentially due to a magnonic effect on the Seebeck ( S) coefficient. The too large thermal conductivity approximately equal to 10.5 W m-1 K-1 at room temperature prevents this pyrite from being a good thermoelectric material. In this work, samples belonging to the Co1- xFe xS2 pyrite family ( x = 0, 0.15 and 0.30) have thus been investigated in order to modify the thermal properties by the introduction of disorder on the Co site. We show here that the thermal conductivity can indeed be reduced by such a substitution, but that this substitution predominantly induces a reduction of the electronic part of the thermal conductivity and not of the lattice part. Interestingly, the magnonic contribution to S below TC disappears as x increases, while at high T, S tends to a very similar value (close to -42 µV K-1) for all the samples investigated. This article is part of a discussion meeting issue 'Energy materials for a low carbon future'.