SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS FOR DYE-SENSITIZED SOLAR CELLS

Graphene, which is a two-dimensional carbon material, exhibits unique properties that promise its potential applications in photovoltaic devices. Dye-sensitized solar cell (DSSC) is a representative of the third generation photovoltaic devices. Therefore, it is important to synthesize graphene with special structures, which possess excellent properties for dye-sensitized solar cells. This dissertation research was focused on (1) the effect of oxygen content on the structure of graphite oxide, (2) the stability of graphene oxide solution, (3) the application of graphene precipitate from graphene oxide solution as counter electrode for DSSCs, (4) the development of a novel synthesis method for the three-dimensional graphene with honeycomb-like structure, and (5) the exploration of honeycomb structured graphene (HSG) as counter electrodes for DSSCs. Graphite oxide is a crucial precursor to synthesize graphene sheets via chemical exfoliation method. The relationship between the oxygen content and the structures of graphite oxides was still not explored. In this research, the oxygen content of graphite oxide is tuned by changing the oxidation time and the effect of oxygen content on the structure of graphite oxide was evaluated. It has been found that the saturated ratio of oxygen to carbon is 0.47. The types of functional groups in graphite oxides, which are epoxy, hydroxyl, and carboxylgroups, are independent of oxygen content. However, the interplanar space and BET surface area of graphite oxide linearly increases with increasing O/C ratio. Graphene oxide (GO) can easily dissolve in water to form a stable homogeneous solution, which can be used to fabricate graphene films and graphene based composites. This work is the first research to evaluate the stability of graphene oxide solution. It has been found that the introduction of strong electrolytes (HCl, LiOH, LiCl) into GO solution can cause GO precipitation. This indicates that the electrostatic repulsion plays a critical role in stabilizing aqueous GO solution. Furthermore, the HCl-induced GO precipitation is a feasible approach to deposit GO sheets on a substrate as a Pt-free counter electrode for a dye-sensitized solar cell (DSSC), which exhibited 1.65% of power conversion efficiency. To explore broad and practical applications, large-scale synthesis with controllable integration of individual graphene sheets is essential. A novel strategy for the synthesis of graphene sheets with three-dimensional (3D) Honeycomb-like structure has been invented in this project based on a simple and novel chemical reaction (Li2O and CO to graphene and Li2CO3). The simultaneous formation of Li2CO3 with graphene not only can isolate graphene sheets from each other to prevent graphite formation during the process, but also determine the locally curved shape of graphene sheets. After removing Li2CO3, 3D graphene sheets with a honeycomb-like structure were obtained. This would be the first approach to synthesize 3D graphene sheets with a controllable shape. Furthermore, it has been demonstrated that the 3D Honeycomb-Structured Graphene (HSG) possesses excellent electrical conductivity and high catalytic activity. As a result, DSSCs with HSG counter electrodes exhibit energy conversion efficiency as high as 7.8%, which is comparable to that of an expensive noble Pt electrode.

Benzo1,2-b:4,5-b 'difuran-based sensitizers for dye-sensitized solar cells

Two BDF-based organic sensitizers, as first examples for their use in dye-sensitized solar cells, are prepared and characterized. They yield promising power conversion efficiencies of up to 5.5 and high open circuit voltages up to 0.82 V. This work demonstrates that the BDF chromophore acts as an effective donor in organic sensitizers.

A quinoxaline-fused tetrathiafulvalene-based sensitizer for efficient dye-sensitized solar cells

A new quinoxaline-fused tetrathiafulvalene-based sensitizer has been prepared and characterized. The resulting power conversion efficiency of 6.47% represents the best performance to date for tetrathiafulvalene-sensitized solar cells.

Electronic tuning effects via π-linkers in tetrathiafulvalene-based dyes

Four new tetrathiafulvalene (TTF)-based dyes featured with a donor–bridge–acceptor (D–π–A) structure were synthesized and characterized. All of them undergo two reversible oxidations to form stable radical cation and dication species. The electronic interactions between the TTF donor and the cyanoacrylic acid acceptor through the different π-linkers have been demonstrated by the presence of a photo-induced intramolecular charge-transfer (ICT) absorption band in the visible region. A red shift of the ICT state can be finely tuned by the degree of aromaticity and extended conjugation of π-bridges. To some extent, the oxidation potentials of these dyes are affected by the nature of π-bridges. They have been applied in organic dye-sensitized solar cells, showing relatively low power conversion efficiencies of up to 0.87% due to substantial charge recombination losses.

Characterization of HFO2 Capacitors

Hafnium oxide (HfOn) is a promising dielectric for future microelectronic applications. Hf02 thin films (10-75nm) were deposited on Pt/Si02/Si substrates by pulsed DC magnetron reactive sputtering. Top electrodes of Pt were formed by e-beam evapo- ration through an aperture mask on the samples to create MIM (Metal-Insulator-Metal) capacitors. Various processing conditions (Arloz ratio, DC power and deposition rate) and post-deposition annealing conditions (time and temperature) were investigated. The structure of the Hf02 films was characterized by X-ray diffraction (XRD) and the roughness was measured by a profilometer. The electrical properties were characterized in terms of their relative permittivity (E,(T) and ~,.(f)) and leakage behavior (I-V, I-T and I- time). The electrical measurements were performed over a temperature range from -5 to 200°C. For the samples with best experimental results, the relative permittivity of HfOa was found to be -- 27 after anneal and increased by 0.027%/"C with increasing temperature over the measured temperature range. At 25"C, leakage current density was below lop8 ~ l c m ' at 1 volt. The leakage current increased with temperature above a specific threshold temperature below which the leakage current didn't change much. The leakage current increased with voltage. At voltages below lvolt, it's ohmic; at higher voltages, it follows Schottky model. The breakdown field is - 1 . 8 2 ~ lo6 Vlcm. The optical bandgap was measured with samples deposited on quartz substrates to be 5.4eV after anneal.

PWM Control of a Buck Converter with an Amorphous Core Coil

Pulse-width modulation is widely used to control electronic converters. One of the most topologies used for high DC voltage/low DC voltage conversion is the Buck converter. It is obtained as a second order system with a LC filter between the switching subsystem and the load. The use of a coil with an amorphous magnetic material core instead of air core lets design converters with smaller size. If high switching frequencies are used for obtaining high quality voltage output, the value of the auto inductance L is reduced throughout the time. Then, robust controllers are needed if the accuracy of the converter response must not be affected by auto inductance and load variations. This paper presents a robust controller for a Buck converter based on a state space feedback control system combined with an additional virtual space variable which minimizes the effects of the inductance and load variations when a not-toohigh switching frequency is applied. The system exhibits a null steady-state average error response for the entire range of parameter variations. Simulation results are presented.

Survey of architectures and optimizations for wide bandwidth envelope amplifier

In the last years, RF power amplifiers are taking advantage of the switched dc-dc converters to use them in several architectures that may improve the efficiency of the amplifier, keeping a good linearity. The use of linearization techniques such as Envelope Elimination and Restoration(EER) and Envelope Tracking (ET) requires a very fast dc-dc power converter to provide variable voltage supply to the power amplifier but theoretically the efficiency can be much higher than using the classical amplifiers belonging to classes A, B or AB. The purpose of this paper is to analyze the state of the art of the power converters used as envelope amplifiers in this application. The power topologies will be explored and several important parameters such as efficiency, bandwidth will be discussed.

Space-state robust control of a Buck converter with amorphous core coil and variable load

Pulse-width modulation is widely used to control electronic converters. One of the most frequently used topologies for high DC voltage/low DC voltage conversion is the Buck converter. These converters are described by a second order system with an LC filter between the switching subsystem and the load. The use of a coil with an amorphous magnetic material core rather than an air core permits the design of smaller converters. If high switching frequencies are used to obtain high quality voltage output, then the value of the auto inductance L is reduced over time. Robust controllers are thus needed if the accuracy of the converter response must be preserved under auto inductance and payload variations. This paper presents a robust controller for a Buck converter based on a state space feedback control system combined with an additional virtual space variable which minimizes the effects of the inductance and load variations when a switching frequency that is not too high is applied. The system exhibits a null steady-state average error response for the entire range of parameter variations. Simulation results and a comparison with a standard PID controller are also presented.

A bankable method for the field testingor a CPV plant

The bankability of CPV projects is an important issue to pave the way toward a swift and sustained growth in this technology. The bankability of a PV plant is generally addressed through the modeling of its energy yield under a b aseline loss scenario, followed by an on-site measurement campaign aimed at verifying its energetic behavior. The main difference between PV and CPV resides in the proper CPV modules, in particular in the inclusion of optical lements and III-V multijunction cells that are much more sensitive to spectral variations than xSi cells, while the rest of the system behaves in a way that possesses many common points with xSi technology. The modeling of the DC power output of a CPV system thus requires several impo rtant second order parameters to be considered, mainly related to optics, spectral direct solar radiation, wind speed, tracker accuracy and heat dissipation of cells.

Influencia de las restricciones medioambientales en el sector eléctrico

El objetivo de esta tesis es la caracterización de la generación térmica representativa de la existente en la realidad, para posteriormente proceder a su modelización y simulación integrándolas en una red eléctrica tipo y llevar a cabo estudios de optimización multiobjetivo económico medioambiental. Para ello, en primera instancia se analiza el contexto energético y eléctrico actual, y más concretamente el peninsular, en el que habiendo desaparecido las centrales de fuelóleo, sólo quedan ciclos combinados y centrales de carbón de distinto rango. Seguidamente se lleva a cabo un análisis de los principales impactos medioambientales de las centrales eléctricas basadas en combustión, representados sobre todo por sus emisiones de CO2, SO2 y NOx, de las medidas de control y mitigación de las mismas y de la normativa que les aplica. A continuación, a partir de las características de los combustibles y de la información de los consumos específicos, se caracterizan los grupos térmicos frente a las funciones relevantes que definen su comportamiento energético, económico y medioambiental, en términos de funciones de salida horarias dependiendo de la carga. Se tiene en cuenta la posibilidad de desnitrificación y desulfuración. Dado que las funciones objetivo son múltiples, y que están en conflicto unas con otras, se ha optado por usar métodos multiobjetivo que son capaces de identificar el contorno de puntos óptimos o frente de Pareto, en los que tomando una solución no existe otra que lo mejore en alguna de las funciones objetivo sin empeorarlo en otra. Se analizaron varios métodos de optimización multiobjetivo y se seleccionó el de las ε constraint, capaz de encontrar frentes no convexos y cuya optimalidad estricta se puede comprobar. Se integró una representación equilibrada de centrales de antracita, hulla nacional e importada, lignito y ciclos combinados en la red tipo IEEE-57, en la que se puede trabajar con siete centrales sin distorsionar demasiado las potencias nominales reales de los grupos, y se programó en Matlab la resolución de flujos óptimos de carga en alterna con el método multiobjetivo integrado. Se identifican los frentes de Pareto de las combinaciones de coste y cada uno de los tres tipos de emisión, y también el de los cuatro objetivos juntos, obteniendo los resultados de costes óptimos del sistema para todo el rango de emisiones. Se valora cuánto le cuesta al sistema reducir una tonelada adicional de cualquier tipo de emisión a base de desplazarse a combinaciones de generación más limpias. Los puntos encontrados aseguran que bajo unas determinadas emisiones no pueden ser mejorados económicamente, o que atendiendo a ese coste no se puede reducir más allá el sistema en lo relativo a emisiones. También se indica cómo usar los frentes de Pareto para trazar estrategias óptimas de producción ante cambios horarios de carga. ABSTRACT The aim of this thesis is the characterization of electrical generation based on combustion processes representative of the actual power plants, for the latter modelling and simulation of an electrical grid and the development of economic- environmental multiobjective optimization studies. In this line, the first step taken is the analysis of the current energetic and electrical framework, focused on the peninsular one, where the fuel power plants have been shut down, and the only ones remaining are coal units of different types and combined cycle. Then it is carried out an analysis of the main environmental impacts of the thermal power plants, represented basically by the emissions of CO2, SO2 y NOx, their control and reduction measures and the applicable regulations. Next, based on the combustibles properties and the information about the units heat rates, the different power plants are characterized in relation to the outstanding functions that define their energy, economic and environmental behaviour, in terms of hourly output functions depending on their load. Optional denitrification and desulfurization is considered. Given that there are multiple objectives, and that they go in conflictive directions, it has been decided the use of multiobjective techniques, that have the ability of identifying the optimal points set, which is called the Pareto front, where taken a solution there will be no other point that can beat the former in an objective without worsening it in another objective. Several multiobjective optimization methods were analysed and pondered, selecting the ε constraint technique, which is able to find no convex fronts and it is opened to be tested to prove the strict Pareto optimality of the obtained solutions. A balanced representation of the thermal power plants, formed by anthracite, lignite, bituminous national and imported coals and combined cycle, was integrated in the IEEE-57 network case. This system was selected because it deals with a total power that will admit seven units without distorting significantly the actual size of the power plants. Next, an AC optimal power flow with the multiobjective method implemented in the routines was programmed. The Pareto fronts of the combination of operative costs with each of the three emissions functions were found, and also the front of all of them together. The optimal production costs of the system for all the emissions range were obtained. It is also evaluated the cost of reducing an additional emission ton of any of the emissions when the optimal production mix is displaced towards cleaner points. The obtained solutions assure that under a determined level of emissions they cannot be improved economically or, in the other way, at a determined cost it cannot be found points of lesser emissions. The Pareto fronts are also applied for the search of optimal strategic paths to follow the hourly load changes.

Analysis and Design Considerations of an Electric Vehicle Powertrain regarding Energy Efficiency and Magnetic Field Exposure

En esta tesis se analiza el sistema de tracción de un vehículo eléctrico de batería desde el punto de vista de la eficiencia energética y de la exposición a campos magnéticos por parte de los pasajeros (radiación electromagnética). Este estudio incluye tanto el sistema de almacenamiento de energía como la máquina eléctrica, junto con la electrónica de potencia y los sistemas de control asociados a ambos. Los análisis y los resultados presentados en este texto están basados en modelos matemáticos, simulaciones por ordenador y ensayos experimentales a escala de laboratorio. La investigación llevada a cabo durante esta tesis tuvo siempre un marcado enfoque industrial, a pesar de estar desarrollada en un entorno de considerable carácter universitario. Las líneas de investigación acometidas tuvieron como destinatario final al diseñador y al fabricante del vehículo, a pesar de lo cual algunos de los resultados obtenidos son preliminares y/o excesivamente académicos para resultar de interés industrial. En el ámbito de la eficiencia energética, esta tesis estudia sistemas híbridos de almacenamiento de energía basados en una combinación de baterías de litio y supercondensadores. Este tipo de sistemas son analizados desde el punto de vista de la eficiencia mediante modelos matemáticos y simulaciones, cuantificando el impacto de ésta en otros parámetros tales como el envejecimiento de las baterías. Respecto a la máquina eléctrica, el estudio se ha centrado en máquinas síncronas de imanes permanentes. El análisis de la eficiencia considera tanto el diseño de la máquina como la estrategia de control, dejando parcialmente de lado el inversor y la técnica de modulación (que son incluidos en el estudio como fuentes adicionales de pérdidas, pero no como potenciales fuentes de optimización de la eficiencia). En este sentido, tanto la topología del inversor (trifásico, basado en IGBTs) como la técnica de modulación (control de corriente en banda de histéresis) se establecen desde el principio. El segundo aspecto estudiado en esta tesis es la exposición a campos magnéticos por parte de los pasajeros. Este tema se enfoca desde un punto de vista predictivo, y no desde un punto de vista de diagnóstico, puesto que se ha desarrollado una metodología para estimar el campo magnético generado por los dispositivos de potencia de un vehículo eléctrico. Esta metodología ha sido validada mediante ensayos de laboratorio. Otros aspectos importantes de esta contribución, además de la metodología en sí misma, son las consecuencias que se derivan de ella (por ejemplo, recomendaciones de diseño) y la comprensión del problema proporcionada por esta. Las principales contribuciones de esta tesis se listan a continuación: una recopilación de modelos de pérdidas correspondientes a la mayoría de dispositivos de potencia presentes en un vehículo eléctrico de batería, una metodología para analizar el funcionamiento de un sistema híbrido de almacenamiento de energía para aplicaciones de tracción, una explicación de cómo ponderar energéticamente los puntos de operación par-velocidad de un vehículo eléctrico (de utilidad para evaluar el rendimiento de una máquina eléctrica, por ejemplo), una propuesta de incluir un convertidor DC-DC en el sistema de tracción para minimizar las pérdidas globales del accionamiento (a pesar de las nuevas pérdidas introducidas por el propio DC-DC), una breve comparación entre dos tipos distintos de algoritmos de minimización de pérdidas para máquinas síncronas de imanes permanentes, una metodología predictiva para estimar la exposición a campos magnéticos por parte de los pasajeros de un vehículo eléctrico (debida a los equipos de potencia), y finalmente algunas conclusiones y recomendaciones de diseño respecto a dicha exposición a campos magnéticos. ABSTRACT This dissertation analyzes the powertrain of a battery electric vehicle, focusing on energy efficiency and passenger exposure to electromagnetic fields (electromagnetic radiation). This study comprises the energy storage system as well as the electric machine, along with their associated power electronics and control systems. The analysis and conclusions presented in this dissertation are based on mathematical models, computer simulations and laboratory scale tests. The research performed during this thesis was intended to be of industrial nature, despite being developed in a university. In this sense, the work described in this document was carried out thinking of both the designer and the manufacturer of the vehicle. However, some of the results obtained lack industrial readiness, and therefore they remain utterly academic. Regarding energy efficiency, hybrid energy storage systems consisting in lithium batteries, supercapacitors and up to two DC-DC power converters are considered. These kind of systems are analyzed by means of mathematical models and simulations from the energy efficiency point of view, quantifying its impact on other relevant aspects such as battery aging. Concerning the electric machine, permanent magnet synchronous machines are studied in this work. The energy efficiency analysis comprises the machine design and the control strategy, while the inverter and its modulation technique are taken into account but only as sources of further power losses, and not as potential sources for further efficiency optimization. In this sense, both the inverter topology (3-phase IGBT-based inverter) and the switching technique (hysteresis current control) are fixed from the beginning. The second aspect studied in this work is passenger exposure to magnetic fields. This topic is approached from the prediction point of view, rather than from the diagnosis point of view. In other words, a methodology to estimate the magnetic field generated by the power devices of an electric vehicle is proposed and analyzed in this dissertation. This methodology has been validated by laboratory tests. The most important aspects of this contribution, apart from the methodology itself, are the consequences (for instance, design guidelines) and the understanding of the magnetic radiation issue provided by it. The main contributions of this dissertation are listed next: a compilation of loss models for most of the power devices found in a battery electric vehicle powertrain, a simulation-based methodology to analyze hybrid energy storage performance in traction applications, an explanation of how to assign energy-based weights to different operating points in traction drives (useful when assessing electrical machine performance, for instance), a proposal to include one DC-DC converter in electric powertrains to minimize overall power losses in the system (despite the new losses added by the DC-DC), a brief comparison between two kinds of loss-minimization algorithms for permanent magnet synchronous machines in terms of adaptability and energy efficiency, a predictive methodology to estimate passenger magnetic field exposure due to power devices in an electric vehicle, and finally some useful conclusions and design guidelines concerning magnetic field exposure.

Quantum Dot-Sensitized Solar Cells Based on Directly Adsorbed Zinc Copper Indium Sulfide Colloids

Heavy metal-based quantum dots (QDs) have demonstrated to behave as efficient sensitizers in QD-sensitized solar cells (QDSSCs), as attested by the countless works and encouraging efficiencies reported so far. However, their intrinsic toxicity has arisen as a major issue for the prospects of commercialization. Here, we examine the potential of environmentally friendly zinc copper indium sulfide (ZCIS) QDs for the fabrication of liquid-junction QDSSCs by means of photoelectrochemical measurements. A straightforward approach to directly adsorb ZCIS QDs on TiO2 from a colloidal dispersion is presented. Incident photon-to-current efficiency (IPCE) spectra of sensitized photoanodes show a marked dependence on the adsorption time, with longer times leading to poorer performances. Cyclic voltammograms point to a blockage of the channels of the mesoporous TiO2 film by the agglomeration of QDs as the main reason for the decrease in efficiency. Photoanodes were also submitted to the ZnS treatment. Its effects on electron recombination with the electrolyte are analyzed through electrochemical impedance spectroscopy and photopotential measurements. The corresponding results bring out the role of the ZnS coating as a barrier layer preventing electron leakage toward the electrolyte, as argued in other QD-sensitized systems. The beneficial effect of the ZnS coating is ultimately reflected on the power conversion efficiency of complete devices, reaching values of 2 %. In a more general vein, through these findings, we aim to call the attention to the potentiality of this quaternary alloy, virtually unexplored as a light harvester for sensitized devices.

Lead sulfide nanocrystal: conducting polymer solar cells

In this paper, we report photovoltaic devices fabricated from lead sulfide nanocrystals and the conducting polymer poly(2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylene vinylene). This composite material was produced via a new single-pot synthesis which solves many of the issues associated with existing methods. Our devices have white light power conversion efficiencies under AM 1.5 illumination of 0.7% and single wavelength conversion efficiencies of 1.1%. Additionally, they exhibit remarkably good ideality factors (n = 1.15). Our measurements show that these composites have significant potential as soft optoelectronic materials.

Single-phase active rectifier selection for fault tolerant machine

A fault tolerant, 5-phase PM generator has been developed for use on the low pressure (LP) shaft of an aircraft gas turbine engine. The machine operates at variable speed and therefore has a variable voltage, variable frequency electrical output (VVVF). The generator is to be used to provide a 350V DC bus for distribution throughout the aircraft, and a study has been carried out that identifies the most suitable AC-DC converter topology for this machine in terms of losses, electrical component ratings, filtering requirements and circuit complexity.

Estudo de um sistema de frenagem eletromagnética empregando correntes parasitas

This work deals with the analytical, computational and experimental study of phenomena related to the Eddy current induction in low permeability means for embedded electromagnetic braking systems applications. The phenomena of forces generation in opposing to the variation of stationary magnetic flux produced by DC power supplies, set in motion by the application of an external propulsive force are addressed. The study is motivated by search for solving the problem of speed control of PIGs used to verifying and maintaining pipelines, and is led based on the analytical models synthesis, validated by means of computer simulations in Finite Elements environment, provided by engineering support software; and with experimental tests conducted under controlled laboratory conditions. Finally, a damping systems design methodology based on analyzes results conducted throughout the study is presented