Structural properties and thermoelectric performance of the double-filled skutterudite (Sm,Gd)_y(Fe_xNi_1-x)₄Sb₁₂

The structural and thermoelectric properties of the filled skutterudite (Sm,Gd)_y(Fe_xNi_1-x)₄ Sb₁₂ were investigated and critically compared to the ones in the Sm-containing system with the aim of unravelling the effect of double filling on filling fraction and thermal conductivity. Several samples (x = 0.50-0.90 and y = 0.15-0.48) were prepared by melting-sintering, and two of them were densified by spark plasma sintering in order to study their thermoelectric features. The crystallographic study enables the recognition of the role of the filler size in ruling the filling fraction and the compositional location of the p/n crossover: It has been found that the former lowers and the latter moves toward lower x values with the reduction of the filler ionic size, as a consequence of the progressively weaker interaction of the filler with the Sb₁₂ cavity. The analysis of thermoelectric properties indicates that, despite the Sm³⁺/Gd³⁺ small mass difference, the contemporary presence of these ions in the 2a site significantly affects the thermal conductivity of both p- and n-compositions. This occurs by reducing its value with respect to the Sm-filled compound at each temperature considered, and making the overall thermoelectric performance of the system comparable to several multi-filled (Fe, Ni)-based skutterudites described in the literature.