A round robin test aiming at measuring the high-temperature thermoelectric properties was carried out by a group of European (mainly French) laboratories (labs). Polycrystalline skutterudite Co_0.97Ni_0.03Sb₃ was characterized by Seebeck coefficient (8 labs), electrical resistivity (9 labs), thermal diffusivity (6 labs), mass volume density (6 labs), and specific heat (6 labs) measurements. These data were statistically processed to determine the uncertainty on all these measured quantities as a function of temperature and combined to obtain an overall uncertainty on the thermal conductivity (product of thermal diffusivity by density and by specific heat) and on the thermoelectric figure of merit ZT. An increase with temperature of all these uncertainties is observed, in agreement with growing difficulties to measure these quantities when temperature increases. The uncertainties on the electrical resistivity and thermal diffusivity are most likely dominated by the uncertainty on the sample dimensions. The temperature-averaged (300–700 K) relative standard uncertainties at the confidence level of 68% amount to 6%, 8%, 11%, and 19% for the Seebeck coefficient, electrical resistivity, thermal conductivity, and figure of merit ZT, respectively. Thermal conductivity measurements appear as the least accurate. The moderate value of the temperature-averaged relative expanded (confidence level of 95%) uncertainty of 17% on the mean of ZT is essential in establishing Co_0.97Ni_0.03Sb₃ as a high temperature standard n-type thermoelectric material.

Donor-substituted strontium titanate ceramics demonstrate one of the most promising performances among n-type oxide thermoelectrics. Here we report a marked improvement of the thermoelectric properties in rare-earth substituted titanates Sr_0.9R_0.1TiO_3±δ (R = La, Ce, Pr, Nd, Sm, Gd, Dy, Y) to achieve maximal ZT values of as high as 0.42 at 1190 K < T < 1225 K, prepared via a conventional solid state route followed by sintering under strongly reducing conditions (10%H₂–90%N₂, 1773 K). As a result of complex defect chemistry, both electrical and thermal properties were found to be dependent on the nature of the rare-earth cation and exhibit an apparent correlation with the unit cell size. High power factors of 1350–1550 μW m⁻¹ K⁻² at 400–550 K were observed for R = Nd, Sm, Pr and Y, being among the largest reported so far for n-type conducting bulk-ceramic SrTiO₃-based materials. Attractive ZT values at high temperatures arise primarily from low thermal conductivity, which, in turn, stem from effective phonon scattering in oxygen-deficient perovskite layers formed upon reduction. The results suggest that highly-reducing conditions are essential and should be employed, whenever possible, in other related micro/nanostructural engineering approaches to suppress the thermal conductivity in target titanate-based ceramics.

Driven by a need to develop low-cost and thermally stable materials for thermoelectric applications, donor-substituted strontium titanate is considered as a promising alternative to traditional thermoelectrics. The complex defect chemistry of SrTiO₃-based materials imposes various limitations on identifying the relevant effects exerted on the electronic band structure and heat transfer, being a subject of debate and intensive research. Based on combined XRD, SEM/EDS, HRTEM, XPS, and TGA studies and measurements of thermoelectric properties, this work uncovers the particular role of various structural defects in electrical and thermal transport in Sr_1±yTi_0.9Nb_0.1O_3±δ, selected as a model system. Introduction of A-site cation vacancies provides a synergistic effect of combining fast charge transport in the perovskite lattice and suppressing the thermal conductivity mostly due to simultaneous generation of oxygen vacancies. The presence of oxygen vacancies promotes more efficient phonon scattering compared to Ruddlesden–Popper-type layers. These findings provide a link between structural and thermoelectric properties, offering further prospects for seeking highly performing SrTiO₃-based thermoelectrics by tailoring the defect chemistry mechanisms.