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Co-rich skutterudite compounds of FexCo4-xSb12(x=0-1.0) were synthesized by spark plasma sintering (SPS) at 800-1000 K, and the structure, morphologies and thermoelectric properties of the compounds were studied. The lattice constant increased linearly with increasing Fe content, and electric conductivity increased with increasing substitution of Fe for Co sites, while the highest value of Seebeck coefficient shifted towards high temperature range and thermal conductivity further decreased with increasing Fe content. For Co-rich skutterudite compounds of FexCo4-xSb12, the compound of Fe1.0Co3.0Sb12 had a higher thermoelectric property and the maximum value of the dimensionless figure of merit ZT of 0.30 was achieved at 673 K.
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