Abstract
In-containing skutterudites have long attracted much attention and debate partly due to the solubility limit issue of indium in CoSb3. The isothermal section of the equilibrium phase diagram for the In-Co-Sb system at 873 K is proposed using knowledge of the related binary phase diagrams and experimental data, which explains the debated indium solubility that depends on Sb content. In this paper, a series of In-containing skutterudite samples (InxCo4Sb12-x/3 with x varying from 0.075 to 0.6 and In0.3Co4-ySb11.9+y with y changing from -0.20 to 0.20) are synthesized and characterized. X-ray analysis and scanning electron microscopy images indicate that, up to x = 0.27, single-phase skutterudites are obtained with lattice constant increasing with In fraction x. A fixed-composition skutterudite In0.27±0.01Co 4Sb11.9 was determined for the Co-rich side of In-CoSb3 which is in coexistence with liquid InSb and CoSb 2. Indium, like Ga, is expected, from DFT calculations, to form compound defects in In-containing skutterudites. However, relatively higher carrier concentrations of In-containing skutterudites compared to Ga-containing skutterudites indicate the existence of not fully charge-compensated compound defects, which can also be explained by DFT calculations. The net n-type carrier concentration that naturally forms from the complex defects is close to the optimum for thermoelectric performance, enabling a maximum zT of 1.2 for the fixed skutterudite composition In0.27Co4Sb11.9 at 750 K. © The Royal Society of Chemistry.