This thesis focuses on liquid redox electrolytes in dye-sensitized solar cells (DSCs). A liquid redox electrolyte, as one of the key constituents in DSCs, typically consists of a redox mediator, additives and a solvent. This thesis work concerns all these three aspects of liquid electrolytes, aiming through fundamental insights to enhance the photovoltaic performances of liquid DSCs. Initial attention has been paid to the iodine concentration effects in ionic liquid (IL)-based electrolytes. It has been revealed that the higher iodine concentration required in IL-based electrolytes can be attributed to both triiodide mobility associated with the high viscosity of the IL, and chemical availability of triiodide. The concept of incompletely solvated ionic liquids (ISILs) has been introduced as a new type of electrolyte solvent for DSCs. It has been found that the photovoltaic performance of ISIL-based electrolytes can even rival that of organic solvent-based electrolytes. And most strikingly, ISIL-based electrolytes provide highly stable DSC devices under light-soaking conditions, as a result of the substantially lower vapor pressure of the ISIL system. A significant synergistic effect has been observed when both guanidinium thiocyanate and N-methylbenzimidazole are employed together in an IL-based electrolyte, exhibiting an optimal overall conversion efficiency. Tetrathiafulvalene (TTF) has been investigated as an organic iodine-free redox couple in electrolytes for DSCs. An unexpected worse performance has been observed for the TTF system, albeit it possesses a particularly attractive positive redox potential. An organic, iodine-free thiolate/disulfide system has also been adopted as a redox couple in electrolytes for organic DSCs. An impressive efficiency of 6.0% has successfully been achieved by using this thiolate/disulfide redox couple in combination with a poly (3, 4-ethylenedioxythiophene) (PEDOT) counter electrode material under full sunlight illumination (AM 1.5G, 100 mW/cm2). Such high efficiency can even rival that of its counterpart DSC using a state-of-the-art iodine-based electrolyte in the systems studied.The cation effects of lithium, sodium and guanidinium ions in liquid electrolytes for DSCs have been scrutinized. The selection of the type of cations has been found to exert quite different impacts on the conduction band edge (CB) of the TiO2 and also on the electron recombination kinetics, therefore resulting in different photovoltaic behavior. / QC 20120124

Potential electrolytes for dye-sensitized photoelectrochemical solar cells have been synthesized and their applicability has been investigated. Different experimental techniques were used in order to characterize the synthesized electrolytes, such as elemental analysis, electrospray ionisation/mass spectrometry, cyclic voltammetry, dynamic viscosity measurements, as well as impedance, Raman and NMR spectroscopy. Some crystal structures were characterized by using single crystal X-ray diffraction. In order to verify the eligibility of the ionic compounds as electrolytes for photoelectrochemical solar cells, photocurrent density/photovoltage and incident photon-to-current conversion efficiency measurements were performed, using different kinds of light sources as solar simulators. In electron kinetic studies, the electron transport times in the solar cells were investigated by using intensitymodulated photocurrent and photovoltage spectroscopy. The accumulated charge present in the semiconductor was studied in photocurrent transient measurements. The ionic liquids were successfully used as solar cell electrolytes, especially those originating from the diethyl and dibutyl-alkylsulphonium iodides. The highest overall conversion efficiency of almost 4 % was achieved by a dye-sensitized, nanocrystalline solar cell using (Bu2MeS)I:I2 (100:1) as electrolyte (Air Mass 1.5 spectrum at 100 W m-2), quite compatible with the standard efficiencies provided by organic solvent-containing cells. Several solar cells with iodine-doped metal-iodidebased electrolytes reached stable efficiencies over 2 %. The (Bu2MeS)I:I2-containing cells showed better long-term stabilities than the organic solvent-based cells, and provided the fastest electron transports as well as the highest charge accumulation. Several polypyridyl-ruthenium complexes were tested as solar cell sensitizers. No general improvements could be observed according to the addition of amphiphilic co-adsorbents to the dyes or nanopartices of titanium dioxide to the electrolytes. For ionic liquid-containing solar cells, a saturation phenomena in the short-circuit current densities emerged at increased light intensities, probably due to inherent material transport limitation within the systems. Some iodoargentates and -cuprates were structurally characterized, consisting of monomeric or polymeric entities with anionic networks or layers. A system of metal iodide crownether complexes were employed and tested as electrolytes in photoelectrochemical solar cells, though with poorer results. Also, the crystal structure of a copper-iodide-(12-crown-4) complex has been characterized / QC 20101013

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Abstract The polymer electrolytes (ion conducting polymers) consist of macromolecules (usually in the form of polyethereal units) that are doped with alkali mental salts. The polymer electrolytes are being used in Li-polymer buttery. It is suggested that conductivity in these systems takes place through two distinct events. The first is associated with the charge migration of ions between coordination sites in the host material, and the second is that the conductivity is generally observed to rise with increasing flexibility of the polymer chains. Rayleigh-Brillouin scattering spectra of molecular liquids will provide mechanical relaxation information in the frequency range from 10^8 to 10^11 Hz. We have carried out the Brillouin scattering study of PEG400/LiCl mixtures to probe its elastic properties. The change in the flexibility of polymer chains at different temperatures, the fraction of free ion, and their interactions with polymer all effect the Brillouin spectrum and the present work suggests the usefulness of this technique as an useful tool to probe the various interactions in polymer electrolytes.

<p>Potential electrolytes for dye-sensitized photoelectrochemical solar cells have been synthesized and their applicability has been investigated. Different experimental techniques were used in order to characterize the synthesized electrolytes, such as elemental analysis, electrospray ionisation/mass spectrometry, cyclic voltammetry, dynamic viscosity measurements, as well as impedance, Raman and NMR spectroscopy. Some crystal structures were characterized by using single crystal X-ray diffraction.</p><p>In order to verify the eligibility of the ionic compounds as electrolytes for photoelectrochemical solar cells, photocurrent density/photovoltage and incident photon-to-current conversion efficiency measurements were performed, using different kinds of light sources as solar simulators. In electron kinetic studies, the electron transport times in the solar cells were investigated by using intensitymodulated photocurrent and photovoltage spectroscopy. The accumulated charge present in the semiconductor was studied in photocurrent transient measurements.</p><p>The ionic liquids were successfully used as solar cell electrolytes, especially those originating from the diethyl and dibutyl-alkylsulphonium iodides. The highest overall conversion efficiency of almost 4 % was achieved by a dye-sensitized, nanocrystalline solar cell using (Bu₂MeS)I:I₂ (100:1) as electrolyte (Air Mass 1.5 spectrum at 100 W m^-2), quite compatible with the standard efficiencies provided by organic solvent-containing cells. Several solar cells with iodine-doped metal-iodidebased electrolytes reached stable efficiencies over 2 %. The (Bu₂MeS)I:I₂-containing cells showed better long-term stabilities than the organic solvent-based cells, and provided the fastest electron transports as well as the highest charge accumulation.</p><p>Several polypyridyl-ruthenium complexes were tested as solar cell sensitizers. No general improvements could be observed according to the addition of amphiphilic co-adsorbents to the dyes or nanopartices of titanium dioxide to the electrolytes. For ionic liquid-containing solar cells, a saturation phenomena in the short-circuit current densities emerged at increased light intensities, probably due to inherent material transport limitation within the systems.</p><p>Some iodoargentates and -cuprates were structurally characterized, consisting of monomeric or polymeric entities with anionic networks or layers. A system of metal iodide crownether complexes were employed and tested as electrolytes in photoelectrochemical solar cells, though with poorer results. Also, the crystal structure of a copper-iodide-(12-crown-4) complex has been characterized</p>

Thesis (Ph. D.)--University of Chicago, Department of Chemistry, 2002. / Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1960. / Includes bibliographical references (leaves 72-73).

The study was designed to test the hypothesis that P excretion in manure of dairy cattle could be reduced by manipulating electrolyte balance of the diet. Feces was the main route of P excretion, but fecal P was not affected by dietary cation-anion (DCAB) (P > 0.05). Plasma concentration of P tended (P < 0.10) to be higher at lower DCAB levels, implying that DCAB may have influenced P homeostasis. The overall P balance was not affected by the different DCAB levels. The range of DCAB where both P excretion and animal performance could be optimised is very narrow (+250 to +350 mEq/kg DM), so using DCAB to control P excretion in dairy cattle requires caution. (Abstract shortened by UMI.)

The live export of cattle is an important industry for Australia. Concerns have arisen about animal welfare and in particular heat stress which may cause production losses and death. Cattle shipped live to the Middle East from a southern Australian winter can face continuous and prolonged periods of high heat and humidity as they cross the equator and arrive into a northern hemisphere summer, leading to heat stress and excessive heat load. Some live animal exporters treat heat stressed cattle with electrolyte supplements, but no scientific data exists as to whether this is beneficial to cattle in these unique environmental conditions. In response to industry’s concerns, the experiments described here monitored the physiological responses of Bos taurus and Bos indicus to conditions similar to those experienced by cattle being shipped from southern Australian to the Middle East. Initial experiments were conducted in climate controlled rooms at Murdoch University where intensive monitoring was possible. In the Bos taurus, increases in core body temperature, reductions in feed intake, and increased water intake were measured. There were also changes in blood gas variables consistent with the observed panting causing a compensated respiratory alkalosis. Following the heating period, there were decreases in blood and urinary pH. Bos indicus showed similar responses to the heat, but the changes were less pronounced at the temperatures tested. A pair feeding experiment was conducted to separate the effects of heat from the reductions in feed intake, and this indicated that the major measured effects were due to the responses to heat. On the basis of the measured responses, an electrolyte supplement was formulated and tested on Bos taurus, in the climate controlled rooms, and then on a commercial live export vessel. Results from these experiments indicated improved buffering capacity and a weight advantage for supplemented cattle, even in the absence of extreme heat stress. A final experiment investigated the effects of amount and quality of roughage in a pelleted feed on core and rumen temperature and feed intakes in Bos taurus subjected to hot environmental conditions in climate controlled rooms at Murdoch University. Both pelleted feeds had approximately the same metabolisable energy and crude protein but differed in content and type of roughage. There were no differences in feed intake, core temperature or rumen temperature between diets. This work has led to a greater understanding of the physiological responses of cattle to prolonged and continuous high heat and humidity, the requirements and effects of supplemental electrolytes in these conditions, and the effect of manipulating export diets. The demonstration of advantages in weight and buffering capacity with the electrolyte supplement highlights future areas of research to investigate electrolyte doses, route and types of supplementation, and dietary manipulation.

Thesis (Ph.D.) - School of Engineering and Science, Swinburne University of Technology, 2002. / Submitted in fulfillment of the requirements for the degree of Doctor of Philosophy, School of Engineering and Science, Swinburne University of Technology, 2002. Typescript. Includes bibliographical references (p. 229-239).