Enhanced thermoelectric properties of Ca3Co4O9+δ ceramics by Sr substitution

Ca3-xSrxCo4O9+δ (CCO-Srx) with varying strontium (Sr) content (x = 0.4, 0.5, 0.6, and 0.7) were synthesized by solid-state method. The crystal structures and morphologies of Ca3-xSrxCo4O9+δ thermoelectric ceramics were analyzed by XRD and SEM. Micro structural characterizations have shown that all samples are composed by the same oriented plate-like grains with similar sizes about 1–3 μm diameters and 0.2–0.5 μm thicknesses. The results of XRD have shown that no secondary phases have been produced, which indicated that Sr has been incorporated into the Ca3Co4O9 phase. The diffraction peak (00l) shifted to a lower angle and the offset is increasing with the increase of Sr content, which indicated that the Sr cations can enter the Ca-sites of the Ca3-xSrxCo4O9+δ, and cause increase of the length of the C axis. Slight improvements in the Seebeck coefficient (S) and electrical resistivity (ρ) were observed across all Sr-substitution samples when the mol% of Sr was adjusted. The improvement in both electrical resistivity and Seebeck coefficient leads to higher power factor (PF) values for the ceramics. The measured results show that the highest power factor value around 0.21 mW m−1K−2 can be obtained in Ca2.4Sr0.6Co4O9+δ at 650 °C, which is 16.7% higher than the undoped sample, The ZT value of 0.37 at 650°Cfor the CCO–Sr0.6 sample is significantly higher than that of the pure CCO sample. The results show that Sr can be as an effective doping element to reduce the thermal conductivity and enhance the Seebeck coefficient for the CCO system. It can be concluded that x = 0.6 is the optimal Sr for Ca substitution in this material system.