The synthesis, characterisation and performance of lithium manganese oxide spinels have been studied in terms of their application as cathode materials in rechargeable lithium batteries. A new air stable synthesis based on a solution route has been proposed. Powder X-ray diffraction demonstrates that formation of single phase spinel is possible at temperatures as low as 200 &deg;C. Chemical analysis indicates that the compositions of the spinels prepared by the new solution route depend on the firing temperature. A temperature of 200 &deg;C gives a composition of LiMn2O4.1 and the oxygen content decreases with increasing firing temperature, reaching LiMn2O4 .02 at 600 &deg;C and LiMn2O4 at 800 &deg;C. TEM indicates that the solution based spinels possess small particle sizes, less than 1 ?m. All these characteristics differ markedly from the highly stoichiometric and crystalline spinel prepared by traditional solid state reaction over 800 &deg;C. Electrochemical cells based on the new spinel cathodes were constructed and subjected to galvanostatical cycling at a high discharge rate of C/2 for 300 cycles (charging at C/4). The material fired at 200 &deg;C exhibits excellent performance at 3 V cells. An initial capacity of around 140 mAhg-1 is obtained, very close to the theoretical capacity (148 mAhg-1 ) expected for LiMn2O4 . An enhancement of capacity retention by nearly 50 % after 300 cycles is obtained if < 1 wt % of carbon is added to the solution during synthesis. After 300 cycles, 64 % of the initial capacity remains. The spinel prepared by the solution route and fired at 600 &deg;C gives excellent performance in 4 V cells. An initial capacity of 120 mAhg-1 is obtained and around 75 % of capacity remains after 300 cycles. Ex-situ X-ray diffraction and electrochemical studies such as ac impedance and cyclic voltammetry including the use of microelectrodes were carried out to understand self-discharge and capacity loss on cycling. Spinel dissolution in the electrolyte as well as layer formed on the electrode surface may play an important part in the cycle life of the 4 V spinel cathode. The capacity loss in the 3 V cells arises from incomplete reversibility of the phase transition between cubic and tetragonal spinel which accompanies each cycle.

This thesis identifies and discusses physical mechanisms in intercalation batteries. The effects of interactions and ordering of intercalated atoms on the voltage behaviour of intercalation cells is described, largely in terms of the lattice gas model of intercalation. Particular emphasis is given to the mean field solutions of the lattice gas model, which are compared to more exact solutions for several cases. Two types of interaction between intercalated atoms are discussed, namely electronic and elastic interactions; it is found that both can be important in intercalation compounds. The kinetics of intercalation batteries is also discussed, with emphasis on overpotentials due to diffusion of the intercalated atoms in the host lattice. Experimental studies of the voltage behaviour of three types of lithium intercalation cells, Li[sub=x]TiS₂, Li[sub=x]MoO₂, and Li[sub=x]MoS₂, are presented, which illustrate the variety of voltage behaviour found in intercalation cells. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

published_or_final_version / Environmental Management / Master / Master of Science in Environmental Management

published_or_final_version / abstract / Electrical and Electronic Engineering / Doctoral / Doctor of Philosophy

Thesis (Ph. D.)--University of Texas at Austin, 2002. / Vita. Includes bibliographical references. Available also from UMI Company.

Proefschrift--Utrecht, 1937. / "Stellingen," 2 l. inserted. Includes bibliographical references.

Proefschrift--Utrecht, 1937. / "Stellingen," 2 l. inserted. Includes bibliographical references.

A physical model for redox flow batteries is developed to estimate performance for any chemistry using parameters such as electrolyte conductivity and kinetic rate constants. The model returns the performance as a function of flow rate, current density, and state of charge. Two different models are developed to estimate the current density distribution throughout the electrode in order to evaluate physical performance of the battery. This is done using electrochemical parameters such as conductivity and kinetic rate constant. The models are analytical in order to produce a computationally cheap algorithm that can be used in optimization routines. This allows for evaluating the economic performance of redox flow batteries, and optimization of cost. The models are validated vs data and found to accurately predict performance in a V-V system for a wide variety of operating conditions.

Thesis (Nav. E. and S.M.)--Massachusetts Institute of Technology, Dept. of Ocean Engineering, 2004. / Includes bibliographical references (p. 111-115). / The utility of present Autonomous Underwater Vehicles (AUVs) is limited by their on-board energy storage capability. Research indicates that rechargeable batteries will continue to be the AUV power source of choice for at least the near future. Thus, a need exists in both military and commercial markets for a universal, industry-standard underwater AUV recharge system. A novel solution using a linear coaxial wound transformer (LCWT) inductive coupling mounted on the AUV and a vertical docking cable is investigated. The docking cable may be deployed from either a fixed docking station or a mobile "tanker AUV". A numerical simulation of the simplified system hydrodynamics was created in MATLAB and used to evaluate the mechanical feasibility of the proposed system. The simulation tool calculated cable tension and AUV oscillation subsequent to the docking interaction. A prototype LCWT coupling was built and tested in saltwater to evaluate the power transfer efficiency of the system. The testing indicated that the surrounding medium has little effect on system performance. / (cont.) Finally, an economic analysis was conducted to determine the impact of the proposed system on the present military and commercial AUV markets. The recharge system creates substantial cost-savings, mainly by reducing support ship requirements. An effective AUV recharge system will be an important element of the Navy's net-centric warfare concept, as well as a valuable tool for commercial marine industries. / by Lynn Andrew Gish. / Nav.E.and S.M.

As the world's power needs grow, the demand for power from renewable resources, such as wind or solar is increasing. One major drawback associated with these renewable resources is that the power output is dependent on environmental factors, such as cloud cover and wind speeds. This allows the possibility of either power output exceeding or falling short of forecast levels that may lead to grid instabilities. Therefore, Large Scale Energy Storage (LSES) systems are critical to store excess power when the output exceeds demand in order to supplement output power when it falls short of demand.¹ The Zinc/Bromine Redox Flow Battery (RFB) is a promising technology because of previously reported long cycle-life (CL) capability, high efficiencies, low cost materials, and scalable operating conditions.² The excellent energy storage performance of the Zinc/Bromine system was confirmed by measuring both Faradaic and Coulombic electrochemical cell efficiency dependence on temperature of a bench scale Zinc/Bromine flow cell. At room temperature, near 75% Faradaic efficiency was measured when cycling the system between 20% and 100% State of Charge (SOC), which is in good agreement with published values,³ and was measured to be over 80% efficient when operating at an elevated temperature of 50°C. To elucidate capital and operational costs, key system operation parameters especially focused on degradation mechanisms were investigated. Since deep discharge cycling is perceived as highly damaging to electrochemical systems, a system was cycled between 0% and 5% (SOC) 10,000 times. Performance was quantified by measuring the frequency factor (i[subscript 0]) and relative activation energy (α) for the reactions using Tafel scans. No statistically significant degradation or change to the electrodes was observed during the zero point cycling experiment. However, it was found that under conventional operation damage to the electrodes does accumulate, presumably due to the highly oxidative environment caused by the presence of high concentrations of dissolved bromine or tri-bromide. While the performance of both electrodes shows decreases in frequency factor attributed to the damage process, the bromide oxidation process seems to be more damaging (i.e., at the positive electrode during the charging process). Long term measurements show a degradation of the electrocatalytic parameters at an applied overpotential of 100 mV from ca. 40 mA/cm² to ca. 5 mA/cm² at the positive electrode and from ca. 20 mA/cm² to ca. 10 mA/cm² for the negative electrode. A degradation rate model was proposed to predict the service life expectancy of graphite electrodes in a bromine system based on processes showing a combined second order reaction rate coupled with a negative first order reaction rate. The model can be used to predict the cost of energy when operating any device using graphite electrodes, based on the operating power ratio, defined here as the quotient between operating power and system rated power. This damage could be partially reversed by exposing the electrode surfaces to concentrated potassium hydroxide dissolved in isopropanol, presumably due to exfoliation of the electrocatalytic surface leading to the exposure of a clean surface with electrocatalytic performance close to the original. Further, a chemical pretreatment for the graphite surface imparting enhanced stability in aqueous bromine systems was developed that shows negligible damage when similar amounts of current have passed through the electrode surface. After bromide oxidation equivalent to passing ca. 10 Ah/cm² the treated surface showed a change in steady state current density at an applied overpotential of 100 mV from ca. 50 mA/cm² to ca. 48 mA/cm². / Graduation date: 2013 / Access restricted to the OSU Community at author's request from April 1, 2013 - April 1, 2015