ABSTRACTWe have synthesized the type II silicon clathrates Na1Si136 and Na8Si136, and report on the electrical and thermal transport in these materials. The crystal structure consists of a covalently bonded silicon framework in which sodium guest atoms are encapsulated inside the silicon host framework. Differential scanning calorimetry measurements show the compounds decompose above 600°C to diamond-structure silicon. Temperature dependant electrical resistivity measurements show the specimens to have an insulating character, with magnitudes that decrease with increasing sodium content. For the first time, thermal conductivity measurements on type II sodium-silicon clathrates are presented. The thermal conductivity is very low for both specimens, and for Na8Si136 exhibits a clear dip in the range from 50 to 70 K. These data suggest that the “rattling” behavior observed in type I clathrates may also be present in type II clathrates.
Structural Origin of Reversible Li Insertion in Guest‐Free, Type II Silicon Clathrates