Ionic conductivity studies of solid oxide fuel cell electrolytes and theoretical modeling of an entire solid oxide fuel cell

Because of the steep increase in oil prices, the global warming effect and the drive for energy independence, alternative energy research has been encouraged worldwide. The sustainable fuels such as hydrogen, biofuel, natural gas, and solar energy have attracted the attention of researchers. To convert these fuels into a useful energy source, an energy conversion device is required. Fuel cells are one of the energy conversion devices which convert chemical potentials into electricity. Due to their high efficiency, the ease to scale from 1 W range to megawatts range, no recharging requirement and the lack of CO2 and NOx emission (if H2 and air/O 2 are used), fuel cells have become a potential candidate for both stationary power generators and portable applications. This thesis has been focused primarily on solid oxide fuel cell (SOFC) studies due to its high efficiency, varieties of fuel choices, and no water management problem.; At the present, however, practical applications of SOFCs are limited by high operating temperatures that are needed to create the necessary oxide-ion vacancy mobility in the electrolyte and to create sufficient electrode reactivities. This thesis introduces several experimental and theoretical approaches to lower losses both in the electrolyte and the electrodes. Yttria stabilized zirconia (YSZ) is commonly used as a solid electrolyte for SOFCs due to its high oxygen-ion conductivity. To improve the ionic conductivity for low temperature applications, an approach that involves dilating the structure by irradiation and introducing edge dislocations into the electrolyte was studied. Secondly, to understand the activation loss in SOFC, the kinetic Monte Carlo (KMC) technique was implemented to model the SOFC operation to determining the rate-limiting step due to the electrodes on different sizes of Pt catalysts.; The isotope exchange depth profiling technique was employed to investigate the irradiation effect on the ionic transport in different orientations of single crystal YSZ and polycrystalline thin film YSZ deposited by pulsed laser deposition. The results indicate enhanced ionic conductivity and decreased activation energy of oxygen self-diffusion coefficients in the (100) Xe 3+ irradiated samples. However, a reduction in ionic conductivity was found in (100), (110), (111) Ar+ irradiated, and (111) Xe3+ irradiated single crystal YSZ, and Ar+ irradiated thin film YSZ.; To gain insight into the diffusion mechanism of vacancies in YSZ, quantum simulations using Density Functional Theory (DFT) complemented with the KMC technique were employed. Quantum simulations were used to calculate the migration energy barriers at different dopant arrangements surrounding a diffusing oxygen vacancy in the bulk and dislocation core regions. KMC was then used to simulate a random walk process in a randomly distributed landscape of vacancies and Y atoms in a YSZ supercell containing different types of dislocations. Subsequently, the diffusion coefficients and the activation energies of the simulated diffusion process were extracted as a function of dislocation densities and doping concentrations.; Furthermore, the similar simulation technique was modified to model impedance measurements in YSZ. The purpose of this study was to gain insight into the oxide ion diffusion process and the space charge double layer at the electrode-electrolyte interface subject to applied alternating potentials, as well as the dependence of impedance and double layer capacitance on the thickness of the electrolyte. KMC simulations were performed to simulate the movement of oxide ions using the migration barrier database obtained from previous DFT calculations with potential energy corrections under applied alternating potentials in different frequency domains.; Combining the electrolyte studies with experimental studies of the cathode and anode reaction rates, a complete solid oxide fuel cell can be modeled using KMC. To study the effect of...