Nanomaterials of silicides and silicon for energy conversion and storage

Our consumption of fossil fuels can be reduced to address the pressing concerns of global climate change by maximizing the efficiency of conversion technologies. Since many of the alternative fuel sources also being examined are intermittent in nature, it is imperative that high capacity and high power density storage devices are also developed. The conversion efficiency of current state-of-the-art thermoelectric materials is too low to meet our needs, but it may be possible to increase the conversion efficiency of thermoelectric materials by moving from the bulk to the nanoscale. The transition metal silicides, including CrSi2, beta-FeSi2 , Mg2Si and MnSi1.7, have been explored as environmentally friendly non-toxic thermoelectric materials. I began my research in the group synthesizing silicide nanowires via chemical vapor transport (CVT), and later expanded my research to include the synthesis of silicide nanocomposites for thermoelectrics and mesoporous silicon nanocomposites for use as high capacity lithium battery electrodes. Nanoscale thermoelectrics and the enhanced thermoelectric figure-of-merit ZT reported by thermoelectric researchers are reviewed in Chapter 1. Chapter 2 reviews the progress being made in the research community with nanoscale and nanostructured silicon battery anodes. The synthesis and characterization of CrSi2 nanowires synthesized via CVT is detailed in Chapter 3, followed by hyperbranched epitaxial FeSi nanostructures exhibiting merohedral twinning in Chapter 4. Nanowires are fundamentally interesting and provide insight into the changes in materials properties compared to the bulk. The synthesis of interesting nanostructured silicide materials are detailed in Chapter 5, where the conversion of diatoms into a nanostructured thermoelectric Mg2Si/MgO nanocomposite that retains the basic diatom structure after conversion is detailed. This reaction was then modified to use mesoporous silica instead of diatoms to reduce the nanocrystalline domain size and to synthesize mesoporous silicon/carbon nanocomposites for use as lithium battery anodes. This nanocomposite is presented in Chapter 6, with details of its preliminary electrochemical performance. Chapter 7 details the synthesis of mesoporous Si1-xGe xO2, which has previously been reported only once in the literature.