The effect of 3d-electron configuration entropy on the temperature coefficient of redox potential in Co1−zMnz Prussian blue analogues

Recently, it was reported that a thermocell can convert temperature into electrical energy by using the difference in the thermal coefficient (α ≡ dV/dT) of the redox potential (V) between the cathode and anode materials. Here, we systematically investigated α of NaxCo1-zMnz[Fe(CN)6]y (Co1-zMnz-PBA) against Mn concentration (z). The z-dependence of α is interpreted in terms of the 3d-electron configuration entropy (ΔS3d) of the redox site. Utilization of S3d is a strategy effective for the design of high-|α| materials for energy harvesting thermocells.