Effects of Yttrium and Iron co-doping on the high temperature thermoelectric properties of Ca₃Co₄O_9+δ

A series of Y and Fe co-doped Ca_3−xY_xCo_4−yFe_yO_9+δ (0 ⩽ x ⩽ 0.3, 0 ⩽ y ⩽ 0.1) samples synthesized by auto-combustion reaction and followed by a spark plasma sintering (SPS) processing with the effects of Fe and Y doping on the high temperature (RT to 800 °C) thermoelectric properties were systematically investigated. For the Fe-doped system (x = 0, y ⩽ 0.1), the electrical resistivity (ρ) decreased over the whole measured temperature range, while the Seebeck coefficient (S) remained almost the same. For the co-doped system, at any fixed Fe doping content, both ρ and S tended to increase with increasing Y dopants, however, the effect is more substantial on ρ than on S, particularly in the low temperature regime. In contrast to ρ and S, the in-plane thermal conductivity (κ) is only slightly influenced by Y and Fe substitutions. Among all the investigated samples, the co-doped sample with x = 0.1 and y = 0.03 showed a decrease of ρ, enhanced power factor over the measured temperature range, and improved ZT at 800 °C as compared to un-doped Ca₃Co₄O_9+δ.