Thesis (Ph. D.)--State University of New York at Binghamton, Materials Science and Engineering Program, 2009. / Includes bibliographical references.

Thesis (M.S.)--University of Wyoming, 2008. / Title from PDF title page (viewed on Mar. 11, 2010). Includes bibliographical references (p. 42-45).

Thesis (Ph. D.)--University of Hong Kong, 2002. / Includes bibliographical references (leaves 281-283).

The existence of Room Temperature Ionic Liquids (RTILs) has been known for a long time, but only recently have they been pulled to the forefront of chemical research. This increase in attention can be attributed to a keen interest in their intrinsic properties for a wide variety of potential applications. RTILs have been used as alternative solvents for organic synthesis as well as catalysis, as well as supports for the purification or extraction of metals. Being ionic in nature and liquid at temperatures below 100°C, RTILs lend themselves to the electrochemist. As a result, they have been looked at for use in electrochemical systems such as high capacity batteries and supercapacitors. Due to their extremely high density of charge carriers relative to more well-known aqueous electrochemical systems, a new theoretical approach must be taken. Currently, a large gap exists between theoretical approaches and experimental results. The work contained within this thesis aims to provide insight into the interface between a RTIL and an electrified gold electrode.

Electrogenerated chemiluminescence (ECL) studies were performed on several interesting compounds. A series of BODIPY derivatives was examined to understand the structural effects on the electrochemical, spectroscopic, and ECL behavior. Stable electrochemistry and high fluorescence in the green to the red regions were observed. PB, MCPB, DCPB and PM580 produced intense ECL, strong enough to be seen with the naked eye in a lighted room. Unlike MCPB and DCPB, PB produced the multiple ECL peaks. Totally blocked BODIPY compound showed the improvement of fluorescence and ECL quantum yield due to the stability of radicals. Strong signal of EPR data during the oxidative electrolysis was obtained by simultaneous electrochemical-electron paramagnetic resonance technique with home-made cell. Several new antrhacene derivatives such as a variety of 2- and 4-fold anthracene-functionalized tetraarylbimesityls and a series of 9-naphthylanthracene based dimer and trimer were studied. They showed one wave on the oxidation and reduction because of a sequence, two or more electron transfers during the annihilation of the radical ions. Depended on the structure, some of them exhibited excimer formation on ECL spectra. Azide-BTA compound which consists of two triphenylamine and 2,1,3-benzothiadiazole groups at the ends bridged by a fluorene moiety was synthesized and examined. The compound is a newly synthesized D-A-[pi]-A-D molecule which had reversibility upon electrochemical oxidation and reduction, and also showed intense red fluorescence and stable red ECL emission. Using a simple reprecipitation method, well-dispersed and spherical organic nanoparticles of Azide-BTA and 9-naphthylanthracene based dimer were prepared in an aqueous solution. Controlling the preparation condition, the size of nanoparticles can be minimized to 15 nm. Especially we prepared the organic nanoparticles of 9-naphthylanthracene based dimer dispersed in organic solvent, MeCN, one of the preferred solvents for electrochemical studies and ECL. / text

This work presents the first electrochemical observation of single polystyrene microbead collisions with an electrode within a microchannel. We have observed that detecting single microbead collisions is facile with this system. Additionally, we have shown that by increasing flow within the channel, one can increase both the frequency and magnitude of collision signals. This technique may provide a means of signal amplification in future sensing work. / text

Manganese spinel cathodes LiMn₂O₄ offer the advantage of a strong, edge-shared octahedral framework with fast, 3-dimensional Li⁺-ion conduction. To better understand the safety of these materials, the thermal stability characteristics of spinel oxide and oxyfluoride cathodes Li[subscript 1.1]Mn[subscript 1.9-y]M[subscript y]O₄[subscript-z]F[subscript z] (M = Ni and Al, 0 ≤ y ≤ 0.3, and 0 ≤ z ≤ 0.2) have been investigated systematically. The thermal characteristics are assessed in terms of the onset temperature and reaction enthalpy for the exothermic reaction. The thermal stability increases with decreasing lithium content in the cathode in the charged state. High-voltage spinel cathodes LiMn[subscript 1.5]Ni[subscript 0.5]O₄ are promising candidates for electric vehicles and stationary storage of electricity produced by renewable energies due to their high power capability. However, widespread adoption of this high-voltage spinel cathode is hampered by severe capacity fade resulting from aggressive reaction with the electrolyte to form a thick solid-electrolyte interphase (SEI) layer. The synthesis conditions of the co-precipitation method are found to influence the microstructure and morphology through nucleation and growth of crystals in solution. Two samples prepared by similar wet-chemical routes have been characterized by microscopy and electrochemical methods to determine the role of microstructure and morphology on the electrochemical performance. It is found that the surface crystal planes play a key role in the capacity retention and rate performance. In order to achieve consistent electrochemical properties essential for the commercialization of the high-voltage spinel cathode LiMn[subscript1.5]Ni[subscript 0.5]O₄, the relationship between cation ordering, presence of impurity phase, and particle morphology must be elucidated. Accordingly, comparison of the stoichiometric LiMn[subscript1.5]Ni[subscript 0.5]O₄ cathodes with a Mn/Ni ratio of 3.0 prepared by different methods having varying morphologies and degrees of cation ordering is presented. It is found that although an increase in the degree of cation ordering decreases the rate capability, the crystallographic planes in contact with the electrolyte have a dominant effect on the electrochemical properties. To examine the effect of cation substitution on morphology, an investigation of the nucleation and growth of doped co-precipitated mixed-metal hydroxide precursor particles and the resulting stabilization of preferred crystallographic surface planes in the final spinel samples are presented. It is found that doping with certain cations stabilizes the growth of low-energy (111) surface planes, facilitating a long cycle life and fast high-rate performance. With an aim to develop a better understanding of the factors influencing the electrochemical properties, a systematic investigation of LiMn[subscript 1.5]Ni[subscript0.5-x]M[subscript x]O₄ (M = Cu and Zn and x = 0.08 and 0.16), in which Ni²⁺ ions are substituted by divalent Cu2+ and Zn2+ ions, is presented. It is found that although both Zn and Cu are divalent with ionic radii similar to that of Ni2+, they behave quite differently with respect to cation ordering and site occupancy, and higher levels of doping leads to distinct differences in cycling and rate performances. / text

Photoelectrochemical studies were performed on bismuth vanadate (BiVO₄) to understand chemical and physical properties of the photocatalysts, and to improve the photoactivity for water oxidation. Scanning electrochemical microscopy (SECM) was used to screen various dopants for BiVO₄, to calculate the photoconversion efficiencies to chemical energy at BiVO₄ electrodes, and to study the water oxidation intermediate radicals at the surface of BiVO₄. Tungsten and molybdenum doped BiVO₄ (W/Mo-BiVO₄) shows a photocurrent for water oxidation that is more than 10 times higher than undoped BiVO₄. Photoelectrochemical measurements and material analysis were done to discuss the factors that affect performance of BiVO₄. Finite elements analysis was also performed to explain the electron-hole transport and electrochemical reactions at W/Mo-BiVO₄ electrodes in solutions. Addition of conductive or electron accepting materials, e.g. reduced graphene oxide, into BiVO₄ was tried to study the electron-hole transport phenomena in the metal oxide electrodes. Surface adsorbed radicals produced during the water oxidation at W/Mo-BiVO₄ were interrogated by using SECM that the surface coverage and decay kinetics of adsorbed hydroxyl radicals at W/Mo-BiVO₄ were measured. The quantum efficiencies of the injected photon conversion to chemical energy were obtained from the photoelectrochemical measurements by using SECM. SECM techniques and finite elements analysis were also used to measure the faradaic efficiency of water oxidation at W/Mo-BiVO₄ under irradiation. Finally, unbiased water splitting to generate hydrogen and oxygen from water splitting only using photon energy at W/Mo-BiVO₄ electrodes was demonstrated in a dual n-type semiconductor or Z-scheme device. / text

abstract / Chemistry / Doctoral / Doctor of Philosophy

Lithium-ion technology has revolutionized the electronics and electric vehicle industry in the past two decades. First commercialized by Sony in 1991, the lithium-ion battery is composed of three main components: (i) the cathode, (ii) the anode, and (iii) the electrolyte. Graphitic carbon remains the most widely used anode material due to its low voltage vs. the Li/Li+ redox couple and high specific capacity. However, there are several popular cathode materials, including layered oxides, spinel oxides, and polyanion materials. In an effort to increase the energy density of lithium-ion batteries, much focus is given to improving the gravimetric charge capacity and the overall cell voltage. The latter must be accomplished by employing high-voltage cathodes, the most promising of which is the lithium manganese nickel oxide spinel with a specific capacity of 146 mAh/g and a redox voltage of 4.7 V vs. Li/Li+. However, there are still several problems with this material that must be understood and overcome in order to develop high-voltage spinel as a viable commercial cathode. Physical property measurements can reveal the underlying electronic and atomic interactions in the solid in order to better understand high-voltage spinel and its odd behavior. Novel magnetic techniques have been developed, which reliably indicate the degree of Mn-Ni ordering and quantitative determination of the concentration of the Mn3+ ion. Measurements of several physical properties as a function of lithium content were also undertaken to determine the effects of Mn-Ni ordering on the electronic conductivity and the importance of electron-ion interactions. In addition to understanding the physical properties of high voltage spinel, the understanding of the solid state chemistry and unique structure was utilized to realize a new full cell construction technique. The spinel structure offers a unique way to deal with first cycle irreversible capacity loss in full cells stemming from solid-electrolyte interphase (SEI) layer growth on the anode surface. To that end, a novel microwave-assisted chemical lithiation process was developed using non-toxic and air-stable chemicals. New composite anode chemistry was combined with a pre-lithiated spinel cathode to demonstrate the feasibility of this approach to realizing practical next-generation Li-ion cells. / text