Optimization of electrical and thermal transport properties of Fe0.25Co0.75Sb3 Skutterudite employing the isoelectronic Bi-doping

The practical applications of unfilled CoSb3-based Skutterudites for thermoelectric (TE) devices have been limited primarily owing to their bipolar conduction behaviour, which is detrimental for the TE performance. In the present studies, a peak TE figure-of-merit (ZT)max ~ 0.7 at 860 K has been realized with a pioneering (ZT)average ~ 0.34 in p-type CoSb3 co-doped by Fe and Bi at an optimal composition of Fe0.25Co0.75Sb2.995Bi0.005. The synthesis route for the alloy was the combination of arc melting and the spark plasma sintering. The TE properties measurement results suggest that the Fe doping at the Co site in CoSb3 lead to the unipolar p-type conduction while Bi substitution at Sb site helps in reducing the thermal conductivity via enhanced point defect induced phonon scattering. The synthesized samples were characterised for phase, morphology and structure using X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy, based on which some TE properties of the synthesized samples have also been discussed. In addition, the effect of magnetic entropy on the TE performance has also been studied experimentally as well as theoretically. The first-principles based density functional theory has been employed for the theoretical calculation of the electronic band-structure, electrical transport properties and the magnetic moment, which are found to be in fair agreement with the experimental observations. [Display omitted] •Combination of fast and effective arc melting and the spark plasma sintering was utilized for synthesis.•A peak TE figure-of-merit (ZT)max ~ 0.7 at 860K and pioneering (ZT)average ~ 0.34 are realized for the optimal composition.•The effect of magnetic entropy on the TE performance has also been studied experimentally as well as theoretically.•DFT has been used to calculate electronic band-structure and transport properties coinciding with experimental results.