Abstract
The interplay of crystal structure and thermoelectric properties of A- or B-site substituted high-density calcium manganese oxide ceramics, Ca1-zAzMn1-zMzO3-δ (A = Bi, Gd, Yb/Gd or M = W with 0 ≤ z ≤ 0.08) is investigated. For the same degree of substitution z, smaller sized substituents cause a unit cell volume contraction and higher electrical conductivity, whereas the Seebeck coefficients are not affected. Evaluation along with results from published reports shows that this is valid for both, A- and B-site substitutions. The mean tolerance factor is used to describe this dependency qualitatively. The high-density ceramics show large power factors (S2σ > 400 μW/mK2) and moderate figures of merit zT ≈ 0.15 at 700 °C. The best thermoelectric performance is anticipated for calcium manganese oxide, substituted heterovalently as well as homovalently with small substituents, due to higher electrical conductivity and lower thermal conductivity.
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