Metal oxides (Ca3Co4O9, CaMnO3, SrTiO3, In2O3), Ti sulfides, and Mn silicides are promising thermoelectric (TE) material candidates for cascade‐type modules that are usable in a temperature range of 300–1200 K in air. In this paper, we review previous studies in the field of TE materials development and make recommendations for each material regarding future research. Furthermore, the R&D of TE modules composed of metal oxide materials and the prospect of their commercialization for energy harvesting is demonstrated.

High-performance thermoelectric bulk sulfide with the colusite structure is achieved by controlling the densification process and forming short-to-medium range structural defects. A simple and powerful way to adjust carrier concentration combined with enhanced phonon scattering through point defects and disordered regions is described. By combining experiments with band structure and phonons calculations, we elucidate, for the first time, the underlying mechanism at the origin of intrinsically low thermal conductivity in colusite samples as well as the effect of S vacancies and antisite defects on the carrier concentration. Our approach provides a controlled and scalable method to engineer high power factors and remarkable figures of merit near the unity in complex bulk sulfide such as CuVSnS colusites.

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Electric resistivity, thermoelectric power and thermal conductivity of a polycrystalline sample of the composite crystal [Ca2CoO3.34]0.614[CoO2], also known as Ca3Co4O9, have been measured below 300 K. Metallic conductivity accompanied by large thermoelectric power has been observed down to 50 K. At 300 K, the sample exhibits a thermoelectric power of S = 133 µV·K-1, resistivity of ρ= 15 mΩ·cm and thermal conductivity of κ= 9.8 mW·K-1·cm-1. The resulting dimensionless figure of merit becomes Z T 300 = 3.5×10-2, which is comparable to the value reported for a polycrystalline sample of NaCo2O4, indicating that the title compound is a potential candidate for a thermoelectric material.

Zintl compound n-type Mg 3 (Sb,Bi) 2 was recently found to exhibit excellent thermoelectric figure of merit zT ($1.5 at around 700 K). To improve the thermoelectric performance in the whole temperature range of operation from room temperature to 720 K, we investigated how the grain size of sintered samples influences electronic and thermal transport. By increasing the average grain size from 1.0 lm to 7.8 lm, the Hall mobility below 500 K was significantly improved, possibly due to suppression of grain boundary scattering. We also confirmed that the thermal conductivity did not change by increasing the grain size. Consequently, the sample with larger grains exhibited enhanced average zT. The calculated efficiency of thermoelectric power generation reaches 14.5% (DT ¼ 420 K), which is quite high for a polycrystalline pristine material.