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Sr‐doped Ca3Co4O9 thermoelectric thick films have been prepared by dip‐coating technique, followed by sintering and hot uniaxial pressing. XRD patterns are very similar in both types of samples, with only differences in the relative intensity of peaks, pointing out to a better grain orientation in hot‐pressed films. Moreover, SEM observation showed a drastic decrease in the hot‐pressed films thickness. Electrical resistivity is decreased in textured materials due to the higher grain orientation and density, confirmed through Hall measurements. On the other hand, Seebeck coefficient is maintained practically unchanged. Power factor at 800°C is much higher in textured materials (0.44 mW/K2m) than determined in sintered films (0.30 mW/K2m), and in the order of the best typically reported in the literature (0.43 mW/K2m). [ABSTRACT FROM AUTHOR]

Ca0.9Yb0.1MnO3 thermoelectric materials have been prepared, through a classical solid-state sintering method, from attrition- and ball-milled precursors. After calcination step, microstructural observations have shown that attrition-milled precursors possess much smaller particle sizes than the obtained by ball milling. Smaller precursors sizes lead to higher reactivity, producing higher density, hardness, and thermoelectric phase content in the sintered materials. The thermoelectric properties reflect the microstructural features, decreasing electrical resistivity in the attrition milling prepared samples without a drastic decrease in the Seebeck coefficient. As a consequence, power factor values are higher than the obtained in the classical solid-state method samples. Moreover, the highest power factor values at 800°C are much higher than the best results obtained in this CaMnO3 family. As a result, it has been found that it is possible to tailor the thermoelectric properties of Ca0.9Yb0.1MnO3 ceramics by designing the appropriate preparation procedure while keeping in mind its industrial scalability. [ABSTRACT FROM AUTHOR]

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 the strong interplay between the mobility of charge carriers and their concentration, capable of breaking the electron–hole symmetry from the conductive layers. [ABSTRACT FROM AUTHOR]

Attrition milling is an easily scalable and environmentally friendly process used to produce Ca3Co4O9+δ nanoprecursors in a relatively short time. Sintered materials produced through the classical solid-state method, involving ball milling, show much larger grain sizes and slightly lower density than those obtained in samples produced from attrition-milled precursors. On the other hand, electrical resistivity has been drastically decreased, accompanied with a slight decrease in the Seebeck coefficient in samples obtained from these attrition-milled precursors. Moreover, the use of an attrition milling process leads to a very important reduction in processing time (around 75%), together with a slight power factor improvement of around 10%, when compared to the classically prepared samples. [ABSTRACT FROM AUTHOR]