New bulk p-type skutterudites DD0.7Fe2.7Co1.3Sb12-xXx (X = Ge, Sn) reaching ZT>1.3

The best p-type skutterudites so far are didymium filled, Fe/Co substituted, Sb-based skutterudites. Substitution at the Sb-sites influences the electronic structure, deforms the Sb4-rings, enhances the scattering of phonons on electrons and impurities and this way reduces the lattice thermal conductivity. In this paper we study structural and transport properties of p-type skutterudites with the nominal composition DD0.7Fe2.7Co1.3Sb11.7{Ge/Sn}0.3, which were prepared by a rather fast reaction-annealing-melting technique. The Ge-doped sample showed impurities, which did not anneal out completely and even with ZT > 1 the result was not satisfying. However, the single-phase Sn-doped sample, DD0.7Fe2.7Co1.3Sb11.8Sn0.2, showed a lower thermal and lattice thermal conductivity than the undoped skutterudite leading to a higher ZT=1.3, hitherto the highest ZT for a p-type skutterudite. Annealing at 570 K for 3 days proved the stability of the microstructure. After severe plastic deformation (SPD), due to additionally introduced defects, an enhancement of the electrical resistivity was compensated by a significantly lower thermal conductivity and the net effect led to a record high figure of merit: ZT = 1.45 at 850 K for DD0.7Fe2.7Co1.3Sb11.8Sn0.2.