The development of high performance ion conducting membranes is crucial to the commercialization of polymer electrolyte membrane fuel cells (PEMFCs) and solid oxide fuel cells (SOFCs). This thesis work addresses some of the issues for improving the performance of ion conducting membranes in PEMFCs and SOFCs through engineering membrane microstructures. Electric-field directed particle assembly shows promise as a route to control the structure of polymer composite membranes in PEMFCs. The application of electric fields results in the aggregation of proton conducting particles into particle chains spanning the thickness of composite membranes. The field-induced structure provides improved proton conductivity, selectivity for protons over methanol, and mechanical stability compared to membranes processed without electric field.

Hydrothermal deposition is developed as a route to grow electrolyte crystals into membranes (material is hydroxyapatite) with aligned proton conductive pathways that significantly enhance proton transport by eliminating grain boundary resistance. By varying deposition parameters such as reactant concentration, reaction time, or adding crystal growth modifiers, dense hydroxyapatite electrolyte membranes with a range of thickness are produced. The microstructurally engineered hydroxyapatite membranes are promising electrolyte candidates for intermediate temperature fuel cells. The microstructural engineering of ceramics by hydrothermal deposition can potentially be applied to create other ion conducting materials with optimized transport properties.

To understand how to control the crystal growth habit by adding growth modifiers, growth of unusual calcite rods was investigated in a microemulsion-based synthesis prior to the investigation of hydrothermal deposition of hydroxyapatite membranes. The microemulsions act as crystal growth modifier to mediate crystal nucleation and subsequent growth. The small microemulsion droplets confine nucleation sites and the surfactants of microemulsions adsorb onto a specific face of growing crystals, which causes crystals to grow in anisotropic shapes. The as-obtained elongated shape of the calcite crystals facilitates assembly into hierarchical structures under electric fields, and can allow the crystals to be used as templates for fabricating advanced materials such as composite calcite/titania (core/shell) rods and titania tubes by removing the calcite core off with dilute hydrochloric acid.