| Summary: | Thesis advisor: Chia-Kuang Tsung === Electrochemical energy storage and conversion applications benefit from the integration of nanostructures into the devices, as they have many more active sites per gram which enables excellent mass utilization of the active species. By controlling the surface of fuel cell catalysts, higher activity and efficiency can be achieved as compared to the bulk counterpart, with multiple catalyst facets of varying activity and efficiency. Nanostructured electrochemical capacitors have enhanced electrolyte diffusion over the surface of the electrode, facilitating high rate capability. Nanostructured materials for energy storage and conversion devices, such as electrochemical capacitors and proton exchange membrane fuel cells, can perform even better with the incorporation of carbon. High surface area carbon can enhance the activity of electrochemical capacitors by improving the conductivity of the electrode and/or enhancing the double layer capacitance. Carbon supports for fuel cell catalysts enable proper dispersion of active material without sacrificing conductivity. The work reported in this thesis is aimed toward improving the performance of electrochemical energy storage and conversion devices through novel incorporation of carbon. Carbon was first used to enhance the performance of electrocatalysts. By wrapping fuel cell catalysts in a porous carbon shell, the activity was increased over its bare and CNT-supported counterparts. The carbon shell synthetic method reported here is a good route to the production of a conductive host for Pd electrocatalysts with good contact and in one step with the formation of the Pd nanoparticles. Carbon was also used to enhance the performance of pseudocapacitors, first by incorporating it into the precursor spray solution in the generation of mesoporous metal oxides and then as a metal-organic framework-derived carbon host with dispersed electrochemically active metal oxides. A carbon network was generated from the pyrolysis of pore directing agents during the decomposition of precursor metal nitrates in the generation of mesoporous manganese oxides in a modified spray pyrolysis approach. The addition of Super P to the precursor spray solution further enhanced the conductivity of the material, enabling the formation of high-performing pseudocapacitors. Lastly, nitrogen-doped carbon cubes produced from thermally-treated parent ZIF-8 cubes were tested as electrochemical capacitors and found to have higher specific capacitance than the nitrogen-doped carbon generated from the parent ZIF-8 rhombic dodecahedra. ZIF-67 cubes were then thermally treated to yield cubic nitrogen-doped carbon hosts for the generated cobalt nanoparticles. Once the cobalt particles were oxidized, the cobalt oxide/carbon hybrid structure exhibited the best pseudocapacitive performance of the ZIF-derived carbon materials tested, exhibiting high specific capacitance and good capacitance retention with increased scan rates and prolonged cycling. Each of the materials tested for electrochemical energy storage and conversion saw an enhancement in performance with the addition of carbon. The results reported here illustrate the importance of carbon in electrochemical cells and the importance of continuing research to modify and improve the methods for carbon production and integration. === Thesis (PhD) — Boston College, 2016. === Submitted to: Boston College. Graduate School of Arts and Sciences. === Discipline: Chemistry.
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