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Attrition-milling process has been applied to Ce-doped CaMnO3 precursors to obtain small grain-size powders. The use of Ce4+ as dopant instead a Rare Earth3+ has allowed decreasing by 50% the atomic proportion of dopant, to obtain equivalent charge carrier concentration, which is required for attaining promising properties for thermoelectric applications. An impressive decrease in thermal processing time was achieved, together with an increase in thermoelectric performances, when compared to classically prepared materials. XRD and SEM analysis have confirmed that the final material is nearly single phase. Moreover, grain sizes and density increase with the sintering duration. These microstructural differences are reflected in a significant decrease in electrical resistivity, when compared to the samples prepared from ball-milled precursors (used as reference), without drastically modifying the Seebeck coefficient values. On the other hand, despite of their high electrical conductivity, thermal conductivity is decreased for short time sintered materials, leading to the highest ZT values at 800 °C (∼0.27) in samples sintered for 1 h at 1310 °C. These values are among the best reported in the literature, but they have been obtained in very short time using a simple, and easily scalable process. The suggested approach presented in this work appears particularly promising for large-scale production of oxide-based thermoelectric modules for power generation.

This work assesses the feasibility of processing CuFe1-xNixO2 (x = 0, 0.02) using the Laser Floating Zone (LFZ) technique to grow fibres with different pulling rates, to tune their thermoelectric performance. Structural analysis showed CuFeO2 as the major phase. Formation of secondary phases is promoted by Ni addition, diminishing with decreasing pulling rate. Grain alignment and crystallite size of the fibres increase with the puling rate and doping. Electrical conductivity is enhanced by decreasing the pulling rate, while Ni-doping decreases the conductivity, and Seebeck coefficient demonstrates quite complex behaviour. Thermal conductivity decreases with temperature and with the pulling rate and Ni-doping. A maximum ZT value of 0.17 was achieved for 10 mm h-1 sample at 1000 K for pure, and 700 K for Ni-doped samples. These ZT values are higher than found in the literature, demonstrating the feasibility of the LFZ method for processing thermoelectric delafossites, indicating a proper optimisation process.

Aliovalent substitutions in Ca3Co4O9 often result in complex effects on the electrical properties and the solubility, and impact of the substituting cation also depends largely on the preparation and processing method. It is also well-known that the monoclinic symmetry of this material’s composite crystal structure allows for a significant hole transfer from the rock salt-type Ca2CoO3 buffer layers to the hexagonal CoO2 ones, increasing the concentration of holes and breaking the electron–hole symmetry from the latter layers. This work explored the relevant effects of relatively low La-for-Ca substitutions, for samples prepared and processed through a conventional ceramic route, chosen for its simplicity. The obtained results show that the actual substitution level does not exceed 0.03 (x < 0.03) in Ca3−xLaxCo4O9 samples with x = 0.01, 0.03, 0.05 and 0.07 and that further introduction of lanthanum results in simultaneous Ca3Co4O9 phase decomposition and secondary Ca3Co2O6 and (La,Ca)CoO3 phase formation. The microstructural effects promoted by this phase evolution have a moderate influence on the electronic transport. The electrical measurements and determined average oxidation state of cobalt at room temperature suggest that the present La substitutions might only have a minor effect on the concentration of charge carriers and/or their mobility. The electrical resistivity values of the Ca3−xLaxCo4O9 samples with x = 0.01, 0.03 and 0.05 were found to be ~1.3 times (or 24%) lower (considering mean values) than those measured for the pristine Ca3Co4O9 samples, while the changes in Seebeck coefficient values were only moderate. The highest power factor value calculated for Ca2.99La0.01Co4O9 (~0.28 mW/K2m at 800 °C) is among the best found in the literature for similar materials. The obtained results suggest that low rare-earth substitutions in the rock salt-type layers can be a promising pathway in designing and improving these p-type thermoelectric oxides, provided by