Fabrication and characterization of doped and porous silicon nanowires as anodes for lithium ion batteries

By using Si(100) with different dopant type (n++-type (As) or p-type (B)), it is shown how metal-assisted chemically (MAC) etched silicon nanowires (Si NWs) can form with rough outer surfaces around a solid NW core for p-type NWs, and a unique, defined mesoporous structure for highly doped n-type NWs. High resolution electron microscopy techniques were used to define the characteristic roughening and mesoporous structure within the NWs and how such structures can form due to a judicious choice of carrier concentration and dopant type. Control of roughness and internal mesoporosity is demonstrated during the formation of Si NWs from highly doped n-type Si(100) during electroless etching through a systematic investigation of etching parameters (etching time, AgNO3 concentration, %HF and temperature). Raman scattering measurements of the transverse optical phonon confirm quantum size effects and phonon scattering in mesoporous wires associated with the etching condition, including quantum confinement effects for the nanocrystallites of Si comprising the internal structure of the mesoporous NWs. Laser power heating of NWs confirms phonon confinement and scattering from internal mesoporosity causing reduced thermal conductivity. The Li+ insertion and extraction characteristics at n-type and p-type Si(100) electrodes with different carrier density and doping type are investigated by cyclic voltammetry and constant current measurements. The insertion and extraction potentials are demonstrated to vary with cycling and the occurrence of an activation effect is shown in n-type electrodes where the charge capacity and voltammetric currents are found to be much higher than p-type electrodes. X-ray photo-electron spectroscopy (XPS) and Raman scattering demonstrate that highly doped n-type Si(100) retains Li as a silicide and converts to an amorphous phase as a two-step phase conversion process. The findings show the succinct dependence of Li insertion and extraction processes for uniformly doped Si(100) single crystals and how the doping type and its effect on the semiconductor-solution interface dominate Li insertion and extraction, composition, crystallinity changes and charge capacity. The effect of dopant, doping density and porosity of MAC etched Si NWs are investigated. The CV response is shown to change in area (current density) with increasing NW length and in profile shape with a changing porosity of the Si NWs. The CV response also changes with scan rate indicative of a transition from intercalation or alloying reactions, to pseudocapactive charge storage at higher scan rates and for p-type NWs. SEM and TEM show a change in structure of the NWs after Li insertion and extraction due to expansion and contraction of the Si NWs. Galvanostatic measurements show the cycling behavior and the Coulombic efficiency of the Si NWs in comparison to their bulk counterparts.

Magnetic materials and soft-switched topologies for high-current DC-DC converters

The thesis is focused on the magnetic materials comparison and selection for high-power non-isolated dc-dc converters for industrial applications or electric, hybrid and fuel cell vehicles. The application of high-frequency bi-directional soft-switched dc-dc converters is also investigated. The thesis initially outlines the motivation for an energy-efficient transportation system with minimum environmental impact and reduced dependence on exhaustible resources. This is followed by a general overview of the power system architectures for electric, hybrid and fuel cell vehicles. The vehicle power sources and general dc-dc converter topologies are discussed. The dc-dc converter components are discussed with emphasis on recent semiconductor advances. A novel bi-directional soft-switched dc-dc converter with an auxiliary cell is introduced in this thesis. The soft-switching cell allows for the MOSFET's intrinsic body diode to operate in a half-bridge without reduced efficiency. The converter's mode-by-mode operation is analysed and closed-form expressions are presented for the average current gain of the converter. The design issues are presented and circuit limitations are discussed. Magnetic materials for the main dc-dc converter inductor are compared and contrasted. Novel magnetic material comparisons are introduced, which include the material dc bias capability and thermal conductivity. An inductor design algorithm is developed and used to compare the various magnetic materials for the application. The area-product analysis is presented for the minimum inductor size and highlights the optimum magnetic materials. Finally, the high-flux magnetic materials are experimentally compared. The practical effects of frequency, dc-bias, and converters duty-cycle effect for arbitrary shapes of flux density, air gap effects on core and winding, the winding shielding effect, and thermal configuration are investigated. The thesis results have been documented at IEEE EPE conference in 2007 and 2008, IEEE APEC in 2009 and 2010, and IEEE VPPC in 2010. A 2011 journal has been approved by IEEE Transactions on Power Electronics.