Charge transport and thermoelectric properties of double-filled Nd1–z Yb z Fe4–x Co x Sb12 skutterudites

Abstract

p-Type Nd1–zYbzFe4–xCoxSb12 (z = 0.25, 0.5, 0.75 and x = 0, 0.5, 1.0) skutterudites were synthesized by using encapsulated melting and hot pressing. The effects of Nd/Yb double filling and Co substitution for Fe (charge compensation) on the microstructure, the charge transport, and the thermoelectric properties of the skutterudite specimens were investigated. All specimens were transformed to the skutterudite phase by the annealing process, and a few secondary phases such as marcasite FeSb2 were formed together with the skutterudite phase, although their formation was suppressed with increasing Co content. The lattice constant changed with the filling ratio of Nd/Yb and Fe/Co substitution, which meant that the double filling of Nd/Yb and the substitution of Co for Fe were successfully performed. All specimens showed p-type conduction at temperatures ranging from 323 K to 823 K and exhibited degenerate semiconductor characteristics, in which the electrical conductivity decreased and the Seebeck coefficient increased with increasing temperature. The Seebeck coefficient increased with increasing Nd and Co contents due to the decreased carrier concentration while the electrical conductivity and the thermal conductivity decreased. The maximum Seebeck coefficient was obtained at temperatures in the range from 723 K to 823 K, and the thermal conductivity significantly increased at temperatures above 623 K due to bipolar conduction. The dimensionless figure of merit, ZT, showed maximum values at temperatures ranging from 723 K to 823 K due to the decrease in the Seebeck coefficient (or the decrease in the power factor) and the increase in the thermal conductivity at high temperatures. The maximum ZT = 0.81 was obtained for Nd0.75Yb0.25Fe4Sb12 at 823 K and for Nd0.75Yb0.25Fe3CoSb12 at 723 K.