Graphene is a promising electrode material for electrochemical double-layer capacitors (EDLCs) used for energy storage due to its high electrical conductivity and theoretical specific surface area. However, the intrinsic capacitance of graphene is known to be low and governed by the electronic side of the interface. Furthermore, graphene tends to aggregate and stack together when processed into thick electrode films. This significantly lowers the ion-accessible specific surface area (SSA). Maximizing both the SSA and the intrinsic capacitance are the main problems addressed in this thesis in an effort to improve the specific capacitance and energy density of EDLCs.

In contrast to pristine graphene, functionalized graphene produced by the thermal exfoliation of graphite oxide contains residual functional groups and lattice defects. To study how these properties affect the double-layer capacitance, a model electrode system capable of measuring the intrinsic electrochemical properties of functionalized graphene was developed. To prevent artifacts and uncertainties related to measurements on porous electrodes, the functionalized graphene sheets (FGSs) were assembled as densely tiled monolayers using a Langmuir-Blodgett technique. In this way, charging can be studied in a well-defined 2D geometry. The possibility of measuring and isolating the intrinsic electrochemical properties of FGS monolayers was first demonstrated by comparing capacitance and redox probe measurements carried out on coatings deposited on passivated gold and single crystal graphite substrates.

This monolayer system was then used to follow the double-layer capacitance of the FGS/electrolyte interface as the structure and chemistry of graphene was varied by thermal treatments ranging from 300 °C to 2100 °C. Elemental analysis and Raman spectroscopy were used to determine the resulting chemical and structural transformation upon heat treatment. It was demonstrated that intrinsically defective graphene monolayers can exhibit four-fold higher double-layer capacitance than pristine graphene. High temperature annealing lowered the capacitance until it approached that of pristine graphene. An optimal level of functionalization and lattice disorder is found necessary to retain high double-layer capacitance suggesting that graphene-based materials can be chemically tailored to engineer higher capacitance electrodes.

The second half of this thesis focuses on understanding the factors that control the SSA of FGS aggregates when processed into dense electrodes and the development of a new electrode fabrications strategy to improve the ion-accessible surface area of FGS-based electrodes. Using various processing conditions, it was demonstrated that aggregates can exhibit a wide range of SSAs (1 m²/g to 1750 m²/g) accessible to the adsorption of nitrogen or methylene blue. The effects of capillary forces, van der Waals interactions and aggregation kinetics on the SSA were explored and an aggregation model was proposed to account for these effects.

In order to minimize aggregation, a new strategy for preparing graphene-based electrodes for EDLCs was developed. Colloidal gels of graphene oxide in a water-ethanol-ionic liquid solution were assembled into graphene-ionic liquid laminated structures. Our process involves evaporating the solvents water and ethanol yielding a graphene oxide/ionic liquid composite, followed by thermal reduction of the graphene oxide to electrically conducting functionalized graphene. This yields an electrode in which the ionic liquid serves not only as the working electrolyte but also as a spacer to separate the graphene sheets and to increase their electrolyte-accessible surface area. Using this approach, we achieve an outstanding energy density of 17.5 Wh/kg at a gravimetric capacitance of 156 F/g and 3 V operating voltage, due to a high effective density of the active electrode material of 0.46 g/cm². By increasing the ionic liquid content and degree of thermal reduction, we obtain electrodes that retain >​90% of their capacity at a scan rate of 500 mV/s, illustrating that we can tailor the electrodes towards higher power density if energy density is not the primary goal. The ease of manufacturing, achieved by combining the steps of electrode assembly and electrolyte infiltration, makes this bottom-up assembly approach scalable and well suited for combinations of potentially any graphene material with ionic liquid electrolytes.