Enhancement of Electrical Properties of the Thermoelectric Compound Ca₃Co₄O₉ through Use of Large-grained Powder

Hot-forged Ca₃Co₄O₉ (Co349) ceramics were synthesized using large-grained powders prepared by a flux-growth method, and their thermoelectric properties and degree of grain alignment were evaluated. Neutron-diffraction experiments evidenced the effect of grain size on the development of the c-axis grain alignment. The optimum grain size was around 7 μm in our hot-forging method. The electrical resistivity (ρ) in the direction parallel to the pressed-plane was more reduced at higher degrees of orientation. Since ρ was reduced without lowering the Seebeck coefficient (S), the power factor (PF = S²/ρ) of the Co349 sample was improved and reached 0.8 mW/mK² at 1073 K using Co349 grains with average size of around 7 μm. The thermal conductivity (κ) in the direction parallel to the pressed-plane slightly increased with the increase of the grain size, however the improvement of PF owing to use of large-grained powder outweighed this negative impact on the κ component of the thermoelectric figure of merit (Z = S²/ρκ).