CoSb3 Skutterudites materials have high potential for thermoelectric application at mid-temperature range because of their superior thermoelectric properties via control of charge carrier density and substitution of foreign atoms. Improvement of thermoelectric properties is expected for the ternary solid solution developed by substitution of foreign atoms having different valances into the CoSb3 matrix. In this study, ternary solid solutions with a stoichiometry of Co1-xNixSb3 x = 0.01, 0.05, 0.1, 0.2, CoSb3-yTey, y = 0.1, 0.2, 0.3 were prepared by the Spark Plasma Sintering (SPS) system. Before the SPS synthesis, the ingots were synthesized by vacuum induction melting and followed by annealing. For phase analysis X-ray powder diffraction patterns were checked. All the samples were confirmed as single phase; however, with samples that were more doped than the solubility limit some secondary phases were detected. All the samples doped with Ni and Te atoms showed a negative Seebeck coefficient and their electrical conductivities increased with the doping amount up to the solubility limit. For the samples prepared by SPS the maximum value for dimensionless figure of merit reached 0.26, 0.42 for Co0.9Ni0.1Sb3, CoSb2.8Te0.2 at 690 K, respectively. These results show that the SPS method is effective in this system and Ni/Te dopants are also effective for increasing thermoelectric properties of this system.

Fe doped skutterudite CoSb3 with a nominal composition of FexCo1-xSb12 (0≤x≤2.5) have been synthesized by mechanical alloying (MA) of elemental powders, followed by vacuum hot pressing. Phase transformations during mechanical alloying and vacuum hot pressing were systematically investigated using XRD. Single phase skutterudite was successfully produced by vacuum hot pressing using as-milled powders without subsequent annealing. However, second phase of FeSb2 was found to exist in case of x≥2, suggesting the solubility limit of Fe with Co in this system. Thermoelectric properties as functions of temperature and Fe contents were evaluated for the hot pressed specimens. Fe doping up to x=1.5 with Co in FexCo4-xSb12 appeared to increase thermoelectric figure of merit (ZT) and the maximum ZT was found to be 0.78 at 525K in this study.

Undoped powders were synthesized by mechanical alloying (MA) of elemental powders using a nominal stoichiometric composition. Nano-structured, single-phase skutterudite was successfully produced by vacuum hot pressing (VHP) using MA powders without subsequent annealing. Phase transformations during synthesis were investigated using XRD, and microstructure was observed using SEM and TEM. Thermoelectric properties in terms of Seebeck coefficient, electrical conductivity, thermal conductivity and figure of merit(ZT) were systematically measured and compared with the results of analogous studies. Lattice thermal conductivity was reduced owing to increasing phone scattering in nano-structured MA , leading to enhancement in the thermoelectric figure of merit. MA associated with VHP technique offers an alternative potential processing route for the process of skutterudite.

Fe-doped skutterudite with a nominal composition of has been synthesized by mechanical alloying (MA) of elemental powders, followed by hot pressing. Phase transformations during mechanical alloying and hot pressing were systematically investigated using XRD. Single phase skutterudite was successfully produced by vacuum hot pressing using as-milled powders without subsequent annealing. However, second phase in the form of marcasite structure was found to exist in case of , suggesting the solubility limit of Fe with Co in this system. Thermoelectric properties as functions of temperature and Fe contents were evaluated for the hot pressed specimens. Fe substitution up to x=1.5 with Co in appeared to increase thermoelectric figure of merit (ZT) and the maximum ZT was found to be 0.78 at 525K in this study.