High-yield production of graphene sheets by graphite electro-exfoliation for application in electrochemical power sources

This thesis first aims at developing an electrochemical approach for low temperature, simple, and cost-effective synthesis of graphene microsheets (GNs) using graphitic electrodes in ionic liquid (IL) medium. The second major focus involves the products application as cathode-modifying microporous layers (MPLs) in proton exchange membrane fuel cells (PEMFCs) as well as anode-modifying materials in microbial fuel cells (MFCs). For the electrochemical exfoliation, a novel IL/acetonitrile electrolyte is introduced, and investigated with low concentration of ionic liquids. Using iso-molded graphite rod as the anode, up to 86% of exfoliation was achieved with the majority of the products as graphene flakes in addition to smaller quantities of carbonaceous particles and rolled sheets. Moreover, the simultaneous anodic and cathodic GN production was developed here with a synergistic exfoliation effect. When graphitic anode and cathode were subjected to a constant cell potential, up to 3 times higher exfoliation yields were generated compared to single-electrode studies on each side (~6-fold improvement in total). Thorough materials characterization confirmed the production of ultrathin GNs (< 5 layers) on both electrodes, with cathodic sheets being relatively larger and less functionalized. On the application side, the successful integration of GNs in MPLs resulted in enhanced PEMFC performance over a wide range of operating conditions. GN-based MPLs improved performance in the kinetic and ohmic regions of the polarization curve, while the addition of carbon black (CB), particularly Vulcan XC72, to form a composite GN+CB MPL, further extended the improvement to the mass transport limiting region. This was reflected by an approximate 30% and 70% increase in peak power densities compared to CB and GN MPLs, respectively, at the relative humidity (RH) of 100%. Despite the presence of CB, GN+CB MPLs also retained their superior performance at a much lower RH of 20%, thereby widening the peak power gap with CB MPLs to 80%. On the other side, the functionalized GN-modified carbon cloth anodes integrated within single-chamber MFCs generated an over four-fold improvement in peak power density compared to the plain carbon cloth (2.85 W m-² vs 0.66 W m-², respectively), exceeding the previously reported values with graphene anodes.Applied Science, Faculty ofGraduat