In this study, we investigate the effect of an Sb-deficiency on the thermoelectric properties of double-filled n-type skutterudite (In_0.05Yb_0.15Co₄Sb_12-x). Samples were prepared by encapsulated induction melting, consecutive long-time annealing, and finally spark plasma sintering processes. The Sb-deficient sample contained a CoSb₂ secondary phase. Both the double-filled n-type skutterudite pristine and Sb-deficient samples showed metallic behavior in electrical conductivity with increasing temperature. The carrier concentration of the Sb-deficient sample decreased compared with that of the pristine sample. Due to a decrease in carrier concentration, the Sb deficient sample showed decreased electrical conductivity and an increased Seebeck coefficient compared with the conductivity and coefficient of the pristine sample. Furthermore, the Sb deficient sample showed an increase in the power factor (σ·S²); the power factor maximum shifted to athe lower temperature side than ones of the pristine sample. As a result, the Sb-deficient sample represents an improved average figure of merit (ZT) and a ZT_max temperature lower than that of the pristine sample. Therefore, we propose that Sb-deficient double-filled n-type skutterudite thermoelectric material (In_0.05Yb_0.15Co₄Sb_12-x) be used in the 573~673 K temperature range.

In this study, we investigate the effect of high-energy ball milling on thermoelectric transport properties in double-filled CoSb3 skutterudite (In0.2Yb0.1Co4Sb12). In0.2Yb0.1Co4Sb12 powders are milled using high-energy ball milling for different periods of time (0, 5, 10, and 20 min), and the milled powders are consolidated into bulk samples by spark plasma sintering. Microstructure analysis shows that the high-energy ball milled bulk samples are composed of nano- and micro-grains. Because the filling fractions are reduced in the bulk samples due to the kinetic energy of the high-energy ball milling, the carrier concentration of the bulk samples decreases with the ball milling time. Furthermore, the mobility of the bulk samples also decreases with the ball milling time due to enhanced grain boundary scattering of electrons. Reduction of electrical conductivity by ball milling has a decisive effect on thermoelectric transport in the bulk samples, power factor decreases with the ball milling time.