Reservoir-type dispenser hollow cathodes are currently being developed for use on NASAs Prometheus 1 mission. In these cathodes, the reaction between a barium source material and tungsten powder contained in a cavity surrounding a porous tungsten emitter produces barium vapor which is crucial to operation of the cathode. The primary objective of this research was to investigate the reactions between tungsten and a commercial barium source material in a simulated reservoir hollow cath-ode environment. Mixtures of tungsten and a barium calcium aluminate material were sealed inside molybdenum capsules with porous tungsten closures and heated to 1000?1200?and 1300?or 100, 200, and 400 hours. Based on the reaction products, which were identified to be BaAl2O4 and Ba2CaWO6, a reaction was proposed for the barium calcium aluminate material with tungsten. The bottom pellets in the capsules were found to have reacted to a much further extent than the top pellets in all of the samples, possibly due to a temperature gradient or excessive moisture in the base of the capsules. Quantita-tive and semi-quantitative x-ray analysis results did not show a clear trend as to how the concentrations of BaAl2O4 and Ba2CaWO6 vary with time. Most of the barium source materials are hygroscopic, and hydration of the materi-als would substantially reduce the performance of the cathode. Therefore, the environ-mental stability of several barium compounds, 3BaO??2O3 (B3A), 6BaO????2O3 (612), 4BaO????O3 (411), Ba2.9Ca1.1Al2O7 (B4ASSL), and Ba3Sc4O9, were investi-gated in order to evaluate their suitability for use as barium source materials. A micro-balance was used to measure weight gain of the materials as they were exposed to dew points of ??C and 11?t room temperature. The results showed that B3A hydrated more extensively than any of the other materials tested in the low- and intermediate-humidity environments, while the 612, 411, and B4ASSL materials were all reasonably stable in the low-humidity environment. The Ba3Sc4O9 was extremely stable compared to the barium aluminates in the intermediate-humidity conditions.

In this study, we have developed a dense La0.85Sr0.15MnO3-δ (LSM) Ce0.9Gd0.1O1.95 (GDC) composite electrode system for studying the surface modification of cathodes. The LSM and GDC grains in the composite were well defined and distinguished using energy dispersive x-ray (EDX) analysis. The specific three-phase boundary (TPB) length per unit electrode surface area was systematically controlled by adjusting the LSM to GDC volume ratio of the composite from 40% up to 70%. The TPB length for each tested sample was determined through stereological techniques and used to correlate the cell performance and degradation with the specific TPB length per unit surface area. An overlapping spheres percolation model was developed to estimate the activity of the TPB lines on the surface of the dense composite electrodes developed. The model suggested that the majority of the TPB lines would be active and the length of those lines maximized if the volume percent of the electrolyte material was kept in the range of 47 57%. Additionally, other insights into the processing conditions to maximize the amount of active TPB length were garnered from both the stereology calculations and the percolation simulations. Steady-state current voltage measurements as well as electrochemical impedance measurements on numerous samples under various environmental conditions were completed. The apparent activation energy for the reduction reaction was found to lie somewhere between 31 kJ/mol and 41 kJ/mol depending upon the experimental conditions. The exchange current density was found to vary with the partial pressure of oxygen differently over two separate regions. At relatively low partial pressures, i0 had an approximately dependence and at relatively high partial pressures, i0 had an approximately dependence. This led to the conclusion that a change in the rate limiting step occurs over this range. A method for deriving the electrochemical properties from proposed reaction mechanisms was also presented. State-space modeling was used as it is a robust approach to addressing these particular types of problems due to its relative ease of implementation and ability to efficiently handle large systems of differential algebraic equations. This method combined theoretical development with experimental results obtained previously to predict the electrochemical performance data. The simulations agreed well the experimental data and allowed for testing of operating conditions not easily reproducible in the lab (e.g. precise control and differentiation of low oxygen partial pressures).

The rechargeable lithium ion batteries (LIB) are playing increasingly important roles in powering portal commercial electronic devices. They are also the potential power sources of electric mobile vehicles. The first kind of the cathode materials, LiXCoO2, was commercialized by Sony Company in 1980s, and it is still widely used today in LIB. However, the high cost of cobalt source, its environmental unfriendliness and the safety issue of LiXCoO2 have hindered its widespread usage today. Searching for alternative cathode materials with low cost of the precursors, being environmentally benign and more stable in usage has become a hot topic in LIB research and development. In the first part of this study, lithium nickel manganese cobalt oxide (LiNi0.6Mn0.35Co0.05O2) is studied as the electrode. The materials are synthesized at high temperatures by solid state reaction method. The effect of synthesis temperature on the electrochemical performance is investigated, where characterizations by, for example, X-ray diffraction (XRD) and scanning electron microscopy (SEM), for particle size distribution, specific surface area, and charge-discharge property, are done over samples prepared at different conditions for comparison. The electrochemical tests of the rechargeable Li ion batteries using LiNi0.6Mn0.35Co0.05 cathode prepared at optimum conditions are carried out in various voltage ranges, at different discharge rates and at high temperature. In another set of experiments, the material is adopted as anode with lithium foil as the cathode, and its capacitance is tested. In the second part of this study, the iron based cathode material is investigated. Lithium iron orthosilicate with carbon coating is synthesized at 700℃ by solid state reaction, which is assisted by high energy ball milling. Characterizations are done for discharge capacities of the samples with different carbon weight ratio coatings. / published_or_final_version / Physics / Master / Master of Philosophy

The current technological age is embodied by a constant push for increased performance and efficiency of electronic devices. This push is particularly observable for technologies that comprise free electron sources, which are used in various technologies including electronic displays, x-ray sources, telecommunication equipment, and spacecraft propulsion. Performance of these systems can be increased by reducing weight and power consumption, but is often limited by a bulky electron source with a high energy demand. Carbon nanotubes (CNTs) show favorable properties for field electron emission (FE) and performance as electron sources. This dissertation details the developments of a uniquely designed Spindt type CNT field emission array (CFEA), from initial concept to working prototype, to specifically prevent electrical shorting of the gate. The CFEA is patent pending in the United States. Process development enabled fabrication of a CFEA with a yield of up to 82%. Furthermore, a novel oxygen plasma etch process was developed to reverse shorting after CNT synthesis. CFEA testing demonstrates FE with a current density of up to 293 μA/cm² at the anode and 1.68 mA/cm² at the gate, with lifetimes in excess of 100 hours. A detailed analysis of eighty tested CFEAs revealed three distinct types of damage. Surprisingly, about half of the damaged chips are not electrically shorted, indicating that the CFEAs are very robust. Potential applications of this technology as cathodes for spacecraft electric propulsion were explored. Exposure to an operating electric propulsion thruster showed no significant effect or damage to the CFEAs, marking the first experimental study of CNT field emitters in an electric propulsion environment. A second effort in spacecraft propulsion is a collaboration with the Air Force Institute of Technology (AFIT). CFEAs are the payload on an AFIT developed Cube Satellite, called ALICE, to test electron emission in the space environment. ALICE has passed flight tests and is awaiting launch scheduled for 5 December 2013.

Titanium dioxide, TiO₂, materials have received much attention in recent years due to their potential use as intercalation negative electrodes for rechargeable lithium-ion batteries. The aim of this doctoral work was to synthesise and characterise new titanium dioxide nanomaterials and to investigate their electrochemical behaviour. Three morphologies of TiO₂(B) phase: micro-sized (bulk), nanowires and nanotubes, were synthesised. All three exhibit properties which make them excellent hosts for lithium intercalation. The nanotubes show the best capability of accommodating lithium in the structure, being able to host over one molar equivalent of lithium at low current rates (5 mA g⁻¹). The lithium insertion mechanism in the TiO₂(B) was studied using powder neutron diffraction. In addition, the nature of the irreversible capacity of the nanotubes was studied and ways of reducing it proposed. Nanotubes of another titanium dioxide polymorph, anatase, were synthesised and characterised. Their electrochemical performance was compared with that of commercially available counterparts with different morphologies and particle sizes. The interrelation between particle size/morphology and electrochemical properties has been established. The insertion of lithium which leads to phase variations was studied using in situ Raman microscopy and neutron powder diffraction. It has been demonstrated that doping of the TiO₂(B) nanotubes with vanadium improves their electronic conductivity which is essential for practical applications. Remarkably good electrochemical performance is exhibited by the 6% V-doped TiO₂(B) nanotubes.

abstract: The automotive industry is committed to moving towards sustainable modes of transportation through electrified vehicles to improve the fuel economy with a reduced carbon footprint. In this context, battery-operated hybrid, plug-in hybrid and all-electric vehicles (EVs) are becoming commercially viable throughout the world. Lithium-ion (Li-ion) batteries with various active materials, electrolytes, and separators are currently being used for electric vehicle applications. Specifically, lithium-ion batteries with Lithium Iron Phosphate (LiFePO4 - LFP) and Lithium Nickel Manganese Cobalt Oxide (Li(NiMnCo)O2 - NMC) cathodes are being studied mainly due to higher cycle life and higher energy density values, respectively. In the present work, 26650 Li-ion batteries with LFP and NMC cathodes were evaluated for Plug-in Hybrid Electric Vehicle (PHEV) applications, using the Federal Urban Driving Schedule (FUDS) to discharge the batteries with 20 A current in simulated Arizona, USA weather conditions (50 ⁰C & <10% RH). In addition, 18650 lithium-ion batteries (LFP cathode material) were evaluated under PHEV mode with 30 A current to accelerate the ageing process, and to monitor the capacity values and material degradation. To offset the high initial cost of the batteries used in electric vehicles, second-use of these retired batteries is gaining importance, and the possibility of second-life use of these tested batteries was also examined under constant current charge/discharge cycling at 50 ⁰C. The capacity degradation rate under the PHEV test protocol for batteries with NMC-based cathode (16% over 800 cycles) was twice the degradation compared to batteries with LFP-based cathode (8% over 800 cycles), reiterating the fact that batteries with LFP cathodes have a higher cycle life compared to other lithium battery chemistries. Also, the high frequency resistance measured by electrochemical impedance spectroscopy (EIS) was found to increase significantly with cycling, leading to power fading for both the NMC- as well as LFP-based batteries. The active materials analyzed using X-ray diffraction (XRD) showed no significant phase change in the materials after 800 PHEV cycles. For second-life tests, these batteries were subjected to a constant charge-discharge cycling procedure to analyze the capacity degradation and materials characteristics. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2017

Made available in DSpace on 2014-10-09T12:53:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:56Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:27:23Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:51Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:53:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:56Z (GMT). No. of bitstreams: 0 / O manganito de neodímio dopado com estrôncio (NSM) é um dos materiais catódicos alternativos e que estão sendo estudados e pesquisados para aplicação em células a combustível de óxido sólido de temperatura intermediária (ITSOFCs). O estrôncio (Sr) auxilia consideravelmente na condutividade elétrica e na proximidade do coeficiente de expansão térmica do NSM com os eletrólitos de céria gadolínia (GDC) e céria samária (SDC), e que tornam o material adequado ao uso em temperaturas entre 500 e 800 ºC. Seguindo este contexto, o presente trabalho é uma contribuição ao estudo da síntese de NSM com diferentes concentrações molares de Sr (10, 30 e 50 %), através da técnica de reação no estado sólido. Os materiais foram obtidos e caracterizados visando avaliá-los quanto às características adequadas para emprego na ITSOFC. Após a síntese dos pós e processamento do material sinterizado, avaliou-se principalmente o teor do dopante Sr para a identificação das composições químicas obtidas, estrutura cristalina formada, morfologia dos pós e cerâmicas, além da expansão térmica e condutividade elétrica do material sinterizado. Verificou-se que os valores das concentrações molares dos elementos químicos constituintes para a formação do NSM estão próximos dos valores calculados estequiometricamente antes da etapa de calcinação. A porosidade se mostrou mais adequada para as amostras sinterizadas a 1100 e a 1200 ºC. Comprovou-se que, o teor de dopante não altera significativamente a área de superfície específica e o valor das densidades. Os coeficientes de expansão térmica encontrados estão bastante próximos aos eletrólitos comerciais e verificou-se que com o aumento das concentrações molares de estrôncio, ocorre o acréscimo nos valores de coeficientes de expansão térmica. A condutividade elétrica está adequada para aplicação como material catódico. Os resultados mostram que a síntese por mistura de sólidos apesar de ter as suas desvantagens, quando realizada com cuidados, proporciona pós de NSM, com boas características físicas, químicas e microestruturais. Conclui-se que as características do material com composição de 30 % em mol de Sr é a mais adequada para a preparação de suspensões cerâmicas para posterior deposição no eletrólito sólido de GDC e/ou SDC, embora sejam necessários outros estudos das características deste material como dispositivo eletroquímico para aplicação em ITSOFCs. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:27:23Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:51Z (GMT). No. of bitstreams: 0 / Os filmes cerâmicos de manganito de lantânio dopado com estrôncio (LSM) e de manganito de lantânio dopado com estrôncio/zircônia estabilizada com ítria (LSM/YSZ) são utilizados como catodos das células a combustível de óxido sólido de temperatura alta (CaCOSTA). Estes filmes cerâmicos porosos foram depositados sobre o substrato cerâmico denso de YSZ, utilizado como eletrólito, componente estrutural do módulo, assim conferindo uma configuração de meia-célula denominada auto-suporte. O estudo da meia-célula é fundamental, pois na interface catodo/eletrólito ocorre a reação de redução do oxigênio, conseqüentemente influenciando no desempenho da CaCOSTA. Neste sentido, o presente trabalho contribui para a síntese de pós de LSM e LSM/YSZ e para o processamento de filmes finos, utilizando a técnica de pulverização de pó úmido, adotada para a conformação dos filmes cerâmicos por permitir a obtenção de camadas porosas com espessuras variadas na ordem de micrômetros. Os pós de LSM foram sintetizados pela técnica de citratos e os pós de LSM/YSZ pela técnica de mistura de sólidos. Na etapa de conformação foram preparadas suspensões orgânicas de LSM e LSM/YSZ alimentada por gravidade em um aerógrafo manual. Para a conformação do substrato de YSZ utilizou-se uma prensa uniaxial hidráulica. Foram possíveis a obtenção das meia-células de óxido sólido catodo/eletrólito de estruturas cristalinas hexagonal para a fase LSM e cúbica para a fase YSZ. E as micrografias das meia-células mostram que o substrato YSZ é denso, suficiente para ser utilizado como eletrólito sólido, e os filmes de LSM e LSM/YSZ apresentam-se porosos com espessura de aproximadamente 30 &mu;m e com boa aderência entre os catodos e o eletrólito. A presença do catodo compósito entre o catodo LSM e o substrato YSZ, possibilitou um aumento no desempenho eletroquímico na reação de redução do oxigênio. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP