| Batteries with higher volumetric and specific energy capacities are needed. Silicon is a promising candidate to replace graphite as the negative electrode material in Li-ion batteries. Silicon alloys with lithium, meaning its structure changes significantly during lithiation. Unlike other lithium alloys, lithiated silicon is amorphous when created electrochemically at room temperature. However, when lithiated at 415°C, crystalline Li-Si phases are experimentally found.;Density functional theory calculations yielded formation energies for the crystalline and amorphous structures, from which potential-composition curves were calculated and compared to experiment. Good agreement with experiment was found, providing validation of the calculation methods and proposed protocol. Charge transfer studies and calculations of electronic densities of states for crystalline and amorphous structures were also completed. These confirmed the understanding of Li-Si structures as Zintl phases and quantified the charge transferred from Li to Si atoms. Phonon studies were completed for the crystalline Li-Si phases and helped explain their stability as a function of temperature. The phonon studies revealed that the Li15Si4 phase is unstable with respect to the other crystalline phases at elevated temperature, in agreement with experiment.;Finally, experimental thermal studies of lithiated Si were used to obtain activation energies of the various crystallization events that occur when heating lithiated Si.;This thesis focused on the study of the Li-Si crystalline phases and the lithiation of amorphous LixSi using first-principles calculations. A novel protocol to model the lithiation of amorphous silicon was developed, yielding results in good agreement with experiment. This represents the first time the lithiation of an amorphous alloy material has been modeled using first-principles calculations. |
