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High-temperature instability of the Ca₃Co 4- y  O 9+ δ  and CaMnO 3- δ  direct p-n junction causing the formation of Ca₃Co 2- x  Mn  x  O₆ has motivated the investigation of the thermoelectric performance of this intermediate phase. Here, the thermoelectric properties comprising Seebeck coefficient, electrical conductivity, and thermal conductivity of Ca₃Co 2- x  Mn  x  O₆ with x = 0.05, 0.2, 0.5, 0.75, and 1 are reported. Powders of the materials were synthesized by the solid-state method, followed by conventional sintering. The material Ca₃CoMnO₆ ( x = 1) demonstrated a large positive Seebeck coefficient of 668 μV/K at 900 °C, but very low electrical conductivity. Materials with compositions with x &lt; 1 had lower Seebeck coefficients and higher electrical conductivity, consistent with small polaron hopping with an activation energy for mobility of 44 ± 6 kJ/mol and where both the concentration and mobility of hole charge carriers were proportional to 1- x . The conductivity reached about 11 S·cm -1 at 900 °C for x = 0.05. The material Ca₃Co 1.8 Mn 0.2 O₆ ( x = 0.2) yielded a maximum zT of 0.021 at 900 °C. While this value in itself is not high, the thermodynamic stability and self-assembly of Ca₃Co 2- x  Mn  x  O₆ layers between Ca₃Co 4- y  O 9+ δ  and CaMnO 3- δ  open for new geometries and designs of oxide-based thermoelectric generators.

Thermoelectric Properties of Ca3Co2−xMnxO6 (x = 0.05, 0.2, 0.5, 0.75, and 1)