Abstract/Summary

The incorporation of lithium as a filler species in Co1-2xFexNixSb3 skutterudites was accomplished by intercalation at 60 C, using n-BuLi as a reducing agent. Solid state 7Li NMR and ICP-MS analysis confirm the presence of lithium in the product phases and provide an estimate of the lithium content. The maximum uptake of lithium increases as cobalt is progressively substituted by an equimolar mixture of iron and nickel. Difference Fourier maps, calculated during Rietveld structure refinement using powder neutron diffraction data, locate the lithium cations at the 2a (0,0,0) sites within the cavities of the skutterudite framework. The intercalation of lithium results in reductions in thermal conductivity of up to 47 %, indicative of phonon glass electron crystal (PGEC) type behaviour. Charge transfer from lithium to the framework that accompanies intercalation results in a substantial decrease in electrical resistivity in lithiated phases and a more metal-like temperature dependence. The increased carrier concentration also decreases the Seebeck coefficient, with the consequence that modest increases in the figure of merit occur, despite the reduced thermal conductivity.