published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Thesis (Ph. D.)--University of Hong Kong, 2002. / Includes bibliographical references (leaves 219-222).

Electrochemical energy storage has been widely used in various areas, including new energy sources, auto industry, and information technology. However, the performance of current electrochemical energy storage devices does not meet the requirements of these areas that include both high energy and power density, fast recharge time, and long lifetime. One solution to meet consumer demands is to discover new materials that can substantially enhance the performance of electrochemical energy storage devices. In this dissertation we report four transition metal materials systems with potential applications in electrochemical energy storage. Nanoscale and nanostructured materials are expected to play important roles in energy storage devices because of their enhanced and sometimes unique physical and chemical properties. Studied here is the comparative electrochemical cation insertion into a nanostructured vanadium oxide, a promising electrode material candidate, for the alkali metal ions Li+, Na+ and K+ and the organic ammonium ion, in aqueous electrolyte solutions. Observed are the distinctive insertion processes of the different ions, which yield a correlation between physical degradation of the material and a reduction of the calculated specific charge. The results reveal the potential of this nanostructured vanadium oxide material for energy storage. Vanadium based electrochemical systems are of general interest, and as models for vanadium based solid-state electrochemical processes, the solution state and the solid-state electrochemical properties of two cryolite-type compounds, (NH4)3VxGa1-xF6, and Na3VF6, are studied. The electrochemical behavior of (NH4)3VxGa1-xF6 explored the possibility of using this material as an electrolyte for solid state energy storage systems. Zeolite-like materials have large surface to volume ratios, with ions and neutral species located in the nanometer sized pores of the 3-dimensional framework, potentially yielding high energy density storage capabilities. Yet the insulating nature of known zeolite-like materials has limited their use for electrical energy storage. Studied here are two vanadium based zeolite-like structures, the oxo-vanadium arsenate [(As6V15O51)-9]∞, and the oxo-vanadium phosphate [(P6V15O51)-9]∞, where the former shows electronic conduction in the 3-dimensional framework. Mixed electronic and ionic conductivity, from the framework and from the cations located within the framework, respectively, is measured in the oxo-vanadium arsenate, and allows the use of this material in electrochemical double-layer capacitor configuration for energy storage. By contrast, the oxo-vanadium phosphate shows ionic conduction only. Lastly, a new strontium manganese vanadate with a layered structure exhibiting mixed protonic and electronic conductivity is studied. The various transition metal compounds and materials systems experimentally studied in this thesis showcase the importance of novel materials in future energy storage schemes. / Ph. D.