Energy crisis and thermal management related issues have been highlighted in the modern century due to escalating demands for energy consumption and global warming from fossil fuels. Sustainable and alternative energy sources are an ever growing global concern. Thermoelectric (TE) materials have gained significant interest, due to effective solid-state energy conversion from waste heat to useful electrical energy and vice versa. Clean, noise-free, and environment-friendly operation of TE devices has triggered great attention in viable technologies including automotive, military equipment, aerospace, and industries to scavenge waste heat into power. To date, conventional TE materials have shown limited energy conversion efficiency, i.e. TE Figure of Merit (ZT). However, the concept of nanostructuring and development of novel TE materials have opened excellent avenues to improve significantly the ZT values. Nano-engineered bulk TE materials allow effective phonon scattering at the high density of grain boundaries, which offer a way of lowering the thermal conductivity.
Large-scale synthesis of TE nanomaterials is a challenge for the TE industry because of expensive fabrication processes involved. This thesis reports several nano-engineering approaches for fabricating large quantities of bulk nanostructured TE materials. We have developed bottom-up chemical synthesis routes, as well as top-down mechanical alloying methodologies, to produce highly pure, homogenous and highly crystalline TE nanomaterials. State of the art chalcogenide, iron antimonide, and silicide based TE materials have been investigated in this thesis. Chalcogenide are the best candidates for TE devices operating at temperature range up to 450 K. Iron antimonide (FeSb2) have shown attractive performance below room temperature. Earth abundant and environment friendly, silicide based materials have better ZT performance in the range of 600-900 K. Spark plasma sintering (SPS) was utilized to preserve the nanostructuring and to achieve the highest compaction density. Comprehensive physiochemical characterizations were performed on as-prepared and SPS compacted samples. Detailed TE evaluation of the fabricated materials showed significant improvement in ZT for all categories of TE materials.