Thesis (Ph. D.)--University of Texas at Austin, 2004. / Supervisor: Arumugam Manthiram. Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2006. / Vita. Includes bibliographical references.

Li-ion batteries have become the more dominant battery type used in portable electronic devices such as cell phones, computers and more recently their application in full electric vehicles (EV). Li-ion batteries have many advantages over the traditional rechargeable systems (Pb-acid and Ni-MH) such as their higher energy density, low self-discharge, long capacity cycle life and relatively maintenance free. Due to their commercial advantages, a lot of research is done in developing new novel Li-ion electrode materials, improving existing ones and to reduce manufacturing costs in order to make them more cost effective in their applications. This study looked at the cathode material chemistry that has a typical spinel manganese oxide (LiMn2O4) type structure. For comparison the study also considered the influence of doping the phase with various metals such as Al, Mg, Co and Ni that were made as precursors using various carboxylic acids (Citric, Ascorbic, Succinic and Poly-acrylic acid) from a sol-gel process. Traditional batch methods of synthesizing the electrode material is costly and do not necessarily provide optimized electrochemical performance. Alternative continuous less energy intensive methods would help reduce the costs of the preparation of the electrode materials. This study investigated the influence of two synthesis techniques on the materials physical and electrochemical characteristics. These synthesis methods included the use of a typical batch sol-gel method and the continuous spray-drying technique. The spinel materials were prepared and characterized by Powder X-Ray Diffraction (PXRD) to confirm the formation of various phases during the synthesis process. In addition, in-situ PXRD techniques were used to track the phase changes that occurred in the typical batch synthesis process from a sol-gel mixture to the final crystalline spinel oxide. The materials were also characterized by thermal gravimetric analysis (TGA), whereby the materials decomposition mechanisms were observed as the precursor was gradually heated to the final oxide. These synthesized materials prepared under various conditions were then used to build suitable Li-ion coin type of cells, whereby their electrochemical properties were tested by simple capacity tests and electrochemical impedance spectroscopy (EIS). EIS measurements were done on the built cells with the various materials at various charge voltages. TG analysis showed that the materials underwent multiple decomposition steps upon heating for the doped lithium manganese oxides, whereas the undoped oxide showed only a single decomposition step. The results showed that all the materials achieved their weight loss below 400 °C, and that the final spinel oxide had already formed. The in-situ PXRD analysis showed the progression of the phase transitions where certain of the materials changed from a crystalline precursor to an amorphous intermediate phase and then finally to the spinel cathode oxide (Li1.03Mg0.2Mn1.77O4, and LiCo1.09Mn0.91O4). For other materials, the precursor would start as an amorphous phase, and then upon heating, convert into an impure intermediate phase (Mn2O3) before forming the final spinel oxide (Li1.03Mn1.97O4 and LiNi0.5Mn1.5O4). The in-situ study also showed the increases in the materials respective lattice parameters of the crystalline unit cells upon heating and the significant increases in their crystallite sizes when heated above 600 °C. Hence the results implied that a type of sintering of the particles would occur at temperatures above 600 °C, thereby increasing the respective crystallite size. The study showed that the cathode active materials made by the sol-gel spray-drying method would give a material that had a significantly larger surface area and a smaller crystallite size when compared to the materials made by the batch process. The electrochemical analysis showed that there was only a slight increase in the discharge capacities of the cells made with the spray-drying technique when compared to the cells made with the materials from the batch sol-gel technique. Whereas, the EIS study showed that there were distinct differences in the charging behavior of the cells made with the various materials using different synthesis techniques. The EIS results showed that there was a general decrease in the cells charge transfer resistance (Rct) as the charge potential increased regardless of the synthesis method used for the various materials. The results also showed that the lithium-ion diffusion coefficient (DLi) obtained from EIS measurements were in most of the samples higher for the cathode materials that had a larger surface area. This implied that the Li-ion could diffuse at a faster rate through the bulk material. The study concluded that by optimizing the synthesis process in terms of the careful control of the thermal parameters, the Li-ion batteries‟ cathode active material of the manganese spinel type could be optimized and be manufactured by using a continuous flow micro spray process.

Mémoire (M.Sc.A.)-- Université du Québec à Chicoutimi, 1988. / Document électronique également accessible en format PDF. CaQCU

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

Solid oxide fuel cells (SOFCs) are power generation devices that offer many great advantages compared to lower temperature fuel cells; for example, they are able to operate at high efficiencies without the use of expensive precious metal catalysts, and are also able to directly utilize hydrocarbon fuels without the need of an external reformer. Unfortunately, the conventional high operating temperature of these devices (T ≈ 1000 °C) requires the use of expensive, specialized materials that can withstand these high temperatures. This issue has generated considerable interest in reducing the operating temperature of these devices to the intermediate-temperature (600 – 800 °C) to allow for the use of less-expensive materials, such as stainless steel. However, the conventionally utilized SOFC cathode materials exhibit poor electrochemical performance at these reduced temperatures. Currently considered alternative intermediate temperature cathodes, such as Ba₀.₅Sr₀.₅Co₀.₈Fe₀.₂O₃₋δ (BSCF), offer improved performance, but have a large thermal expansion coefficient (TEC), leading to cell failure. In light of these issues, this dissertation focuses on the development of low TEC cathodes for intermediate temperature SOFCS (IT-SOFCs). The primary focus of this dissertation is on the swedenborgite-type RBaCo₃MO₇₊δ (R = Y, In, and Ca; M = Zn and Fe) series of cathodes. Due to their tetrahedrally-coordinated M site, the cobalt ions in these materials do not undergo a spin-state transition, and have TECs similar to conventional SOFC electrolyte materials. The long-term phase stability of these materials was addressed, and it was discovered that a slight In substitution significantly promoted phase stability. In the Y₁₋[subscript x] In [subscript x] BaCo₃ZnO₇₊δ series, it was observed that x = 0.1 successfully stabilized the phase without observable degradation of performance. Similarly, a high-Ca content material (Y₀.₅In₀.₁Ca₀.₄BaCo₃ZnO₇₊δ) was successfully stabilized, though Ca is known to destabilize the phase; furthermore, this compound showed improved performance compared to YBaCo₃ZnO₇₊δ. Lastly, the replacement of the performance-inhibiting Zn with Fe was investigated, and the Y₀.₉In₀.₁BaCo₃Zn₀.₆Fe₀.₄O₇₊δ sample showed low temperature performance rivaling BSCF. Other work in this dissertation focuses on the application of functional silver materials for use in SOFCs, with good performance; these materials were easily manufactured, and they showed performance drastically greater than the conventionally utilized platinum. / text

Lithium ion batteries have revolutionized the portable electronics market since their commercialization first by Sony Corporation in 1990. They are also being intensively pursued for electric and hybrid electric vehicle applications. Commercial lithium ion cells are currently made largely with the layered LiCoO₂ cathode. However, only 50% of the theoretical capacity of LiCoO₂ can be utilized in practical cells due to the chemical and structural instabilities at deep charge as well as safety concerns. These drawbacks together with the high cost and toxicity of Co have created enormous interest in alternative cathodes. In this regard, spinel LiMn₂O₄ has been investigated widely as Mn is inexpensive and environmentally benign. However, LiMn₂O₄ exhibits severe capacity fade on cycling, particularly at elevated temperatures. With an aim to overcome the capacity fading problems, several cationic substitutions to give LiMn[subscript 2-y]M[subscript y]O₄ (M = Cr, Fe, Co, Ni, and Cu) have been pursued in the literature. Among the cation-substituted systems, LiMn[subscript 1.5]Ni[subscript 0.5]O₄ has become attractive as it shows a high capacity of ~ 130 mAh/g (theoretical capacity: 147 mAh/g) at around 4.7 V. With an aim to improve the electrochemical performance of the 5 V LiMn[subscript 1.5]Ni[subscript 0.5]O₄ spinel oxide, various cation-substituted LiMn[subscript 1.5-y]Ni[subscript 0.5-z]M[subscript y+z]O₄ (M = Li, Mg, Fe, Co, and Zn) spinel oxides have been investigated by chemical lithium extraction. The cation-substituted LiMn[subscript 1.5-y]Ni[subscript 0.5-z]M[subscript y+z]O₄ spinel oxides exhibit better cyclability and rate capability in the 5 V region compared to the unsubstituted LiMn[subscript 1.5]Ni[subscript 0.5]O₄ cathodes although the degree of manganese dissolution does not vary significantly. The better electrochemical properties of LiMn[subscript 1.5-y]Ni]subscript 0.5-z]M[subscript y+z]O₄ are found to be due to a smaller lattice parameter difference among the three cubic phases formed during the chargedischarge process. In addition, while the spinel Li[subscript 1-x]Mn[subscript 1.58]Ni[subscript 0.42]O₄ was chemically stable, the spinel Li[subscript 1-x]Co₂O₄ was found to exhibit both proton insertion and oxygen loss at deep lithium extraction due to the chemical instability arising from a overlap of the Co[superscript 3+/4+]:3d band on the top of the O[superscript 2-]:2p band. The irreversible oxygen loss during the first charge and the consequent reversible capacities of the solid solutions between Li[Li[subscript 1/3]Mn[subscript 2/3]]O₂ and Li[Co[subscript 1-y]Ni[subscript y]]O₂ has been found to be determined by the amount of lithium in the transition metal layer of the O3 type layered structure. The lithium content in the transition metal layer is, however, sensitively influenced by the tendency of Ni[superscript 3+] to get reduced to Ni[superscript 2+] and the consequent volatilization of lithium during synthesis. Moreover, high Mn4+ content causes a decrease in oxygen mobility and loss. In addition, the chemically delithiated samples were found to adopt either the parent O3 type structure or the new P3 or O1 type structures depending upon the composition and synthesis temperature of the parent samples and the proton content inserted into the delithiated sample. In essence, the chemical and structural stabilities and the electrochemical performance factors of the layered (1-z) Li[Li[subscript 1/3]Mn[subscript 2/3]]O₂ · (z) Li[Co[subscript 1-y]Ni[subscript y]]O₂ solid solution cathodes are found to be maximized by optimizing the contents of the various ions. / text