Dual porous structures are observed for the first time on a metallic Cu surface underneath anodic Cu oxide by the application of an anodizing voltage to Cu in oxalic acid. The as-prepared porous Cu surface contains macropores of less than 1 μm diameter and mesopores of about tens of nanometers diameter with circular shapes. The size and density (number of pores/area) of the macropores are dependent on the applied voltage. It is likely that the localized dissolution (corrosion) of Cu in oxalic acid under the anodizing voltages is responsible for the formation of the mesopores, and the combination of a number of the mesopores might create the macropores, especially under a relatively high anodizing voltages or a prolonged anodizing time. The variations of pore structure (especailly macropores) with applied voltage and time are reasonably explained on the basis of the proposed mechanism of pore formation.

Cobalt nano-rods were fabricated using a template-free electrochemical-deposition process. The structure of cobalt electro-deposits strongly depends on the electrolyte composition and on the density of the applied current. In particular, as the content of boric acid increased in the electrolyte, deposits of semi-spherical nuclei formed, and then grew into one-dimensional nano-rods. From analysis of the electro-deposits created under the conditions of continuous and pulsed current, it is suggested that the distribution of the active species around the electrode/electrolyte interface, and their transport, might be an important factor affecting the shape of the deposits. When transport of the active species was suppressed by lowering the deposition temperature, more of the well-defined nano-rod structures were obtained. The optimal conditions for the preparation of well-defined nano-rods were determined by observing the morphologies resulting from different deposition conditions. The maximum height of the cobalt nano-rods created in this work was 1μm and it had a diameter of 200 nm. Structural analysis proved that the nano-rods have preferred orientations of (111).

Tungsten oxide films were prepared by an electrochemical deposition method for use as the anode in rechargeable lithium batteries. Continuous potentiostatic deposition of the film led to numerous cracks of the deposits while pulsed deposition significantly suppressed crack generation and film delamination. In particular, a crack-free dense tungsten oxide film with a thickness of ca. 210 nm was successfully created by pulsed deposition. The thickness of tungsten oxide was linearly proportional to deposition time. Compositional and structural analyses revealed that the as-prepared deposit was amorphous tungsten oxide and the heat treatment transformed it into crystalline triclinic tungsten oxide. Both the as-prepared and heat-treated samples reacted reversibly with lithium as the anode for rechargeable lithium batteries. Typical peaks for the conversion processes of tungsten oxides were observed in cyclic voltammograms, and the reversibility of the heat-treated sample exceeded that of the as-prepared one. Consistently, the cycling stability of the heat-treated sample proved to be much better than that of the as-prepared one in a galvanostatic charge/discharge experiment. These results demonstrate the feasibility of using electrolytic tungsten oxide films as the anode in rechargeable lithium batteries. However, further works are still needed to make a dense film with higher thickness and improved cycling stability for its practical use.

Silicon-based thin film was prepared at room temperature by an electrochemical deposition method and a feasibility study was conducted for its use as an anode material in a rechargeable lithium battery. The growth of the electrodeposits was mainly concentrated on the surface defects of the Cu substrate while that growth was trivial on the defect-free surface region. Intentional formation of random defects on the substrate by chemical etching led to uniform formation of deposits throughout the surface. The morphology of the electrodeposits reflected first the roughened surface of the substrate, but it became flattened as the deposition time increased, due primarily to the concentration of reduction current on the convex region of the deposits. The electrodeposits proved to be amorphous and to contain chlorine and carbon, together with silicon, indicating that the electrolyte is captured in the deposits during the fabrication process. The silicon in the deposits readily reacted with lithium, but thick deposits resulted in significant reaction overvoltage. The charge efficiency of oxidation (lithiation) to reduction (delithiation) was higher in the relatively thick deposit. This abnormal behavior needs to clarified in view of the thickness dependence of the internal residual stress and the relaxation tendency of the reaction-induced stress due to the porous structure of the deposits and the deposit components other than silicon.

Thin film electrode consisting purely of porous anodic tin oxide with well-defined nano-channeled structure was fabricated for the first time and its electrochemical properties were investigated for application to an anode in a rechargeable lithium battery. To prepare the thin film electrode, first, a bi-layer of porous anodic tin oxides with well-defined nano-channels and discrete nano-channels with lots of lateral micro-cracks was prepared by pulsed and continuous anodization processes, respectively. Subsequent to the Cu coating on the layer, well-defined nano-channeled tin oxide was mechanically separated from the specimen, leading to an electrode comprised of porous tin oxide and a Cu current collector. The porous tin oxide nearly maintained its initial nano-structured character in spite of there being a series of fabrication steps. The resulting tin oxide film electrode reacted reversibly with lithium as an anode in a rechargeable lithium battery. Moreover, the tin oxide showed far more enhanced cycling stability than that of powders obtained from anodic tin oxides, strongly indicating that this thin film electrode is mechanically more stable against cycling-induced internal stress. In spite of the enhanced cycling stability, however, the reduction in the initial irreversible capacity and additional improvement of cycling stability are still needed to allow for practical use.

A nano-porous structure of tin oxide was prepared using an anodic oxidation process and the sample's electrochemical properties were evaluated for application as an anode in a rechargeable lithium battery. Microscopic images of the as-anodized sample indicated that it has a nano-porous structure with an average pore size of several tens of nanometers and a pore wall size of about 10 nanometers; the structural/compositional analyses proved that it is amorphous stannous oxide (SnO). The powder form of the as-anodized specimen was satisfactorily lithiated and delithiated as the anode in a lithium battery. Furthermore, it showed high initial reversible capacity and superior rate performance when compared to previous fabrication attempts. Its excellent electrode performance is probably due to the effective alleviation of strain arising from a cycling-induced large volume change and the short diffusion length of lithium through the nano-structured sample. To further enhance the rate performance, the attempt was made to create porous tin oxide film on copper substrate by anodizing the electrodeposited tin. Nevertheless, the full anodization of tin film on a copper substrate led to the mechanical disintegration of the anodic tin oxide, due most likely to the vigorous gas evolution and the surface oxidation of copper substrate. The adhesion of anodic tin oxide to the substrate, together with the initial reversibility and cycling stability, needs to be further improved for its application to high-power electrode materials in lithium batteries.

A porous nickel-tin nano-dendritic electrode, for use as the anode in a rechargeable lithium battery, has been prepared by using an electrochemical deposition process. The adjustment of the complexing agent content in the deposition bath enabled the nickel-tin alloys to have specific stoichiometries while the amount of acid, as a dynamic template for micro-porous structure, was limited to a certain amount to prevent its undesirable side reaction with the complexing agent. The ratios of nickel to tin in the electro-deposits were nearly identical to the ratios of nickel ion to tin ion in the deposition bath; the particle changed from spherical to dendritic shape according to the tin content in the deposits. The nickel to tin ratio and the dendritic structure were quite uniform throughout the thickness of the deposits. The resulting nickel-tin alloy was reversibly lithiated and delithiated as an anode in rechargeable lithium battery. Furthermore, the resulting anode showed much more stable cycling performance up to 50 cycles, as compared to that resulting from dense electro-deposit with the same atomic composition and from tin electrodeposit with a similar porous structure. From the results, it is expected that highly-porous nickel-tin alloys presented in this work could provide a promising option for the high performance anode materials for rechargeable lithium batteries.

The morphology of three-dimensional (3D) cross-linked electrodeposits of copper and tin was investigated as a function of the content of metal sulfate and acetic acid in a deposition bath. The composition of copper sulfate had little effect on the overall copper network structure, whereas that of tin sulfate produced significant differences in the tin network structure. The effect of the metal sulfate content on the copper and tin network is discussed in terms of whether or not hydrogen evolution occurs on electrodeposits. In addition, the hydrophobic additive, i.e., acetic acid, which suppresses the coalescence of evolved hydrogen bubbles and thereby makes the pore size controllable, proved to be detrimental to the formation of a well-defined network structure. This led to a non-uniform or discontinuous copper network. This implies that acetic acid critically retards the electrodeposition of copper.

Carbon nanotube (CNT) cathodes were fabricated using nano-sized silver (Ag) powders as a bonding material between the CNTs and cathode electrodes. The effects of the powder size on the sintering behavior, the current density and emission image for CNT cathodes were investigated. As the diameter of the Ag powders decreases to 10 nm, the sintering temperature of the CNT cathode was lowered primarily due to the higher specific surface area of the Ag powders. In this study, it was demonstrated that nano-sized Ag powders can be feasibly used as a bonding material for a screen-printed CNT cathode, yielding a high current density and a uniform emission image.