Small polaron hopping conduction mechanism and enhanced thermoelectric power factor in the perovskite LaCoO₃ ceramic

Among the various thermoelectric oxide materials, perovskites offer more flexibility to adjust the interdependent thermoelectric parameters for an improved thermoelectric performance. In this work, we investigated the effect of A-site cation deficiency and Sr-substitution on the thermoelectric properties of the LaCoO₃ ceramic synthesized via a solid-state reaction. A rhombohedral crystal structure with the R3̄c space group was revealed through Rietveld refinement of the XRD data. XPS analysis further confirmed the presence of multiple oxidation states of Co, and the mechanism of charge transport involving these multivalent cations was described using the small polaron hopping model. The La deficiency and Sr-substitution were found to increase the electrical conductivity in the LCO1 and LCO2 compositions, which resulted in a significant increase in the thermoelectric power factor. It was found that the increase in electrical conductivity of LCO1 and LCO2 was caused by a substantial reduction in the activation energy barrier for small polaron hopping conduction and an increase in fractional polaron concentration. The maximum power factor value of 78 μW m^-1 K^-2 was observed for the LCO2 composition at 403 K.