Current and potential distribution in electrolyte cells. A cell has been built which has two Luggin capillaries mounted on micrometer drives so that the current and potential distribution around a working electrode can be measured. The current and potential distributions for a variety of electrode geometries have been measured. Experiments have been performed which show the effect of electrode geometry, current density and electrolyte conductivity on the current and potential distribution. Experimentally measured current distributions are compared with those calculated from existing theory.^8 Kinetic measurements of the electrolytic formation of argentous oxides in potassium hydroxide. Cyclic current step measurements during the Ag-Ag_2O oxidation plateau have been made. The results of measurements are very similar to those obtained from systems (Ag-Ag(NH_3)_2^+, (Fe^+2-Fe^+3) where the concentration of the electroactive species is diffusion controlled. The exchange current density, i_0, calculated from the relationship developed by Wijnen and Smit^49 decreased from 1.44 ma/cm^2 to 0.75 ma/cm^2 along the Ag-Ag_2O plateau. The changes in the ohmic resistance of the silver oxide film formed in 0.0543, 0.109, 1.09, 5.43, and 10.9 F KOH have been measured. The maximum resistance of the oxide measured in these electrolytes was 0.31, 0.28, 2.44, 5.15, and 0.16ohm-cm^2. Evidence for a proposed explanation of the changes which occurs in the oxide film resistance is presented.

Pentafluorosulfur (VI) bromide (SF5Br) adds to olefins of the form CX2=CX2, where X= H or F, with the pentafluorosulfur group usually adding to the carbon with more hydrogens attached to it. This series of compounds was used in an attempt to prepare the corresponding sulfonic acid hydrates of the general formula SF5CX2CX2SO3H·nH2O, in order to have these compounds tested as possible fuel cell electrolytes. The reaction scheme involved reflux of the SF5Br adduct with an equimolar amount of sodium sulfite in 50% ethanol for two days, followed by acidification of the recovered solid material using HCl or H2SO4.

No description available.

As global energy consumption moves away from fossil fuel sources to alternative energy, the concern for energy storage is paramount. Through lithium ion batteries (LIBs), secondary battery storage has been secured for both large applications of electric vehicles, solar storage, and smaller items like personal cell phones and laptops. However, LIBs use flammable liquid electrolytes and due to engineering defects or dendritic short-circuits have the potential to swell, catch on fire, or even explode because of the volatile organic solvents within the battery. In the pursuit of new commercial lithium ion battery technologies that are safe, nonflammable, and highly conductive, solid-state electrolytes (SSE) are promising candidates for these critical innovations. To achieve SSEs with electrochemically and functionally desirable properties such as ease of manufacturing, good adherence to electrodes, and high ionic conductivities, continued efforts are devoted to improving electrolyte materials. The two main electrolyte types of interest are polymer electrolytes and ceramic electrolytes. Although polymer electrolytes have desirable physical flexibility to form good contact with electrode surfaces, they continually suffer from low ionic conductivities comparatively. Meanwhile ceramic electrolytes have high ionic conductivities (especially high cationic conductivities) but suffer from both poor electrode contact and brittleness. Single-ion conductive materials (like most ceramic conductors) are necessary to increase lifetime performance of batteries. An avenue to access these necessary attributes in LIB-SSEs is explored through novel boron-containing polymers and polymer-ceramic hybrids with the focus to synthesize a material with a high lithium transference number. By exploiting the Lewis basic nature of borane centers to form negatively charged polymer backbones, novel solid-state electrolytes were synthesized with the goal of creating only cation-conductive polymer networks by incorporating the anionic component within the polymer matrix. The synthesis, chemical and electrochemical characterization of these types of polymers and polymer-ceramic hybrids are analyzed by various techniques including x-ray diffraction, thermal gravimetric analysis, nuclear magnetic spectroscopy, gel permeation chromatography, electrochemical impedance spectroscopy and lithium transference number characterization. / Chemistry

No description available.

In this study we develop a computational approach to the solution of an inverse modelling problem concerning the material properties of electrolytes used in Lithium-ion batteries. The dependence of the diffusion coefficient and the transference number on the concentration of Lithium ions is reconstructed based on the concentration data obtained from an in-situ NMR imaging experiment. This experiment is modelled by a 1D time-dependent PDE describing the evolution of the concentration of Lithium ions with prescribed initial concentration and fluxes at the boundary. The material properties that appear in this model are reconstructed by solving a variational optimization problem in which the least-square error between the experimental and simulated concentration values is minimized. This optimization problem is solved using an innovative gradient-based method in which the gradients are obtained with adjoint analysis. In the thesis we develop and validate a computational framework for this reconstruction problem. Reconstructed material properties are presented for a lab-manufactured and a commercial battery electrolyte providing insights which complement available experimental results. / Thesis / Master of Science (MSc)

Thesis (M.Sc. (Physics)) -- University of Limpopo, 2020. / This dissertation presents the results of the ab-initio based computational studies of spinel lithium manganese oxide (LiMn2O4) bulk, surfaces, and the adsorption of an organic electrolyte, ethylene carbonate. The spinel LiMn2O4 is one of the most promising cathode materials for Lithium-ion batteries because of its affordability, nontoxicity, and improved safety compared to commercially used LiCoO2. However, it also suffers from the irreversible capacity due to the electrolyte-cathode interactions which lead to manganese (Mn) dissolution. Using the spin-polarized density functional theory calculations with on site Coulomb interactions and long-range dispersion corrections [DFT+U−D3−(BJ)], we investigated the bulk properties, surface stability and surface reactivity towards the ethylene carbonate (EC) during charge/discharge processes. Firstly, we explored the structural, electronic, and vibrational bulk properties of the spinel LiMn2O4. It was found that the bulk structure is a stable face-centred cubic structure with a bandgap of 0.041 eV and pseudo-gap at the Fermi level indicating electronic stability. Calculated elastic constants show that the structure is mechanically stable since they obey the mechanical stability criteria. The plotted phonon curves show no imaginary vibrations, indicating vibrational stability. To study the charge/discharge surfaces, we modelled the fully lithiated and the partially delithiated slabs and studied their stability. For the fully lithiated slabs, Li-terminated (001) surface was found to be the most stable facet, which agrees with the reported experimental and theoretical data. However, upon surface delithiation, the surface energies increase, and eventually (111) surface becomes the most stable slab as shown by the reduction of the plane in the particle morphologies. Finally, we explored the surface reactivity towards the ethylene carbonate during charge/discharge processes. The ethylene carbonate adsorption on the fully lithiated and partly delithiated facets turn to enhance the stability of (111) surface. Besides the strong interaction with the (111) surfaces, a negligible charge transfer was calculated, and it was attributed by a large charge rearrangement that takes place within the surfactant upon adsorption. The wavenumbers of the C=O stretching showed a red shifting concerning the isolated EC molecule

No description available.

The purpose of this study was to compare the efficacy of two dose levels of L-Alanyl-LGlutamine in a commercially available sports drink to the sports drink only on time to exhaustion, neuromuscular fatigue and physiological measures during prolonged endurance exercise. Twelve endurance-trained males (23.5±3.7 yrs; 175.5±5.4 cm; 70.7±7.6 kg) performed four trials, each consisting of 1 hr treadmill runs at 75% of VO2peak followed by a run to exhaustion at 90% of VO2peak. The trials differed in type of hydration. One trial consisted of no hydration (NHY), another required ingestion of only a sports drink (ET), and two trials required ingestion of a low dose (LD) (300 mg∙500 ml-1) and high dose (HD) of L-Alanyl-L-Glutamine (1 g∙500 ml-1) mixed in the sports drink. During the fluid ingestion trials 250 ml were consumed every 15 min. Plasma glutamine, glucose, electrolytes, and osmolality were measured prior to the run (PRE), and at 30, 45, and 60 min. VO2, RQ, and HR were measured every 15 min and surface electromyography (EMG) of the vastus lateralis and rectus femoris were measured every 10 min during the 1 hr run. Time to exhaustion was significantly longer during the LD and HD trials compared with NHY. Plasma glutamine concentrations were significantly elevated at 45 min in LD and HD trials, and remained elevated at 60 min during HD. Sodium concentrations increased with the beginning of exercise and remained stable for the duration of the 1 hr run. At 60 min plasma sodium was significantly lower in all trials compared with NHY. The results from this study indicated that ingestion of the alanine-glutamine dipeptide at either the low or high dose significantly improved time to exhaustion during high intensity exercise compared to a no hydration trial. These differences were not noted between ET and NHY.

Abstract Specifics included in thesis. / Thesis / Master of Engineering (MEngr)