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Tetrahedrites are promising p-type thermoelectric materials for energy recovery. We present here the first investigation of the structure and thermoelectric properties of copper-rich tetrahedrites, Cu 12+x Sb 4 S 13 (0 < x ≤ 2.0). At room temperature, all samples with x > 0 consist of two tetrahedrite phases. In situ neutron diffraction data demonstrate that on heating, the two tetrahedrite phases coalesce into a single tetrahedrite phase at temperatures between 493 and 553 K and that this transition shows marked hysteresis on cooling. Our structural data indicate that copper ions become mobile above 393 K. Marked changes in the temperature dependence of the electrical and thermal transport properties of the copper-rich phases occur at the onset of copper mobility. Excess copper leads to a significant reduction in the total thermal conductivity, which for the nominal composition Cu 14 Sb 4 S 13 reaches a value as low as 0.44 W m −1 K −1 at room temperature, and to thermoelectric properties consistent with phonon liquid electron crystal (PLEC) behavior.

Bulk polycrystalline samples in the series Ti 1+x S 2 (x = 0 to 0.05) were prepared using high temperature synthesis from the elements and spark plasma sintering. X-ray structure analysis shows that the lattice constant c expands as titanium intercalates between TiS 2 slabs. For x=0, a Seebeck coefficient close to -300 µV/K is observed for the first time in TiS 2 compounds. The decrease in electrical resistivity and Seebeck coefficient that occurs upon Ti intercalation (Ti off stoichiometry) supports the view that charge carrier transfer to the Ti 3d band takes place and the carrier concentration increases. At the same time, the thermal conductivity is reduced by phonon scattering due to structural disorder induced by Ti intercalation. Optimum ZT values of 0.14 and 0.48 at 300K and 700K, respectively, are obtained for x=0.025.

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Polycrystalline samples in the series Ti1-xTaxS2 with x varying from 0 to 1 were prepared using solid-liquid-vapor reaction and spark plasma sintering. Rietveld refinements of X-ray diffraction data are consistent with the existence of a full solid solution for x ≤ 0.4. Transport measurements reveal that tantalum can act as electron donor when substituted in the Ti sites. As a consequence, the electrical resistivity and the absolute value of the Seebeck coefficient decrease with Ta content due to an increase in the carrier concentration. The lattice thermal conductivity being reduced due to mass fluctuation effect, the ZT values in Ti0.95Ta0.05S2 is slightly increased as compared to TiS2.

An effective strategy to enhance thermoelectric performance consists of scattering phonons by point defects, such as the ones intrinsic to the n-type isocubanite CuFe2S3.

No abstract

A univalent copper hyper-stoichiometric stannoidite Cu8+x Fe3–x Sn2S12 with 0 ≤ x ≤ 0.5 has been synthesized using mechanical alloying followed by spark plasma sintering. The X-ray diffraction analysis combined with 57Fe and 119Sn Mössbauer investigations has allowed the charge distribution of the cationic species on the various sites to be established and suggests the possibility of a small tin deficiency. The transport properties show a remarkable crossover from a semiconducting to a metal-like behavior as the copper content increases from x = 0 to x = 0.5, whereas correlatively the Seebeck coefficient decreases moderately, with S values ranging from 310 to 100 μV/K. The thermal conductivity decreases as the temperature increases showing low values at high temperature, far below those reported in related stannite materials. The investigation of the thermoelectric properties shows that the ZT figure of merit is dramatically enhanced by the copper hyper-stoichiometry by a factor of 5 going from 0.07 for x = 0 to 0.35 for x = 0.5 at 630 K. This thermoelectric behavior is interpreted on the basis of a model involving the Cu–S framework as the conducting electronic network where the Fe2+/Fe3+ species play the role of hole reservoir.