Tuning Thermoelectric Properties of Type I Clathrate K8–xBaxAl8+xSi38–x through Barium Substitution

The thermal stability and thermoelectric properties of type I clathrate K8Al8Si38 up to 873 K are reported. K8Al8Si38 possesses a high absolute Seebeck coefficient value and high electrical resistivity in the temperature range of 323 to 873 K, which is consistent with previously reported low temperature thermoelectric properties. Samples with Ba partial substitution at the K guest atom sites were synthesized from metal hydride precursors. The samples with the nominal chemical formula of K8–xBaxAl8+xSi38–x (x = 1, 1.5, 2) possess type I clathrate structure (cubic, Pm3n), confirmed by X-ray diffraction. The guest atom site occupancies and thermal motions were investigated with Rietveld refinement of synchrotron powder X-ray diffraction. Transport properties of Ba-containing samples were characterized from 2 to 300 K. The K–Ba alloy phases showed low thermal conductivity and improved electrical conductivity compared to K8Al8Si38. Electrical resistivity and Seebeck coefficients were measured over the tempera...