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.

DEVELOPMENT OF THE ECOCAR 3 PROPOSAL AND GUIDELINES FOR MODELING AND DESIGN IN YEAR ONE OF ECOCAR 3

This report summarizes the work done for the Vehicle Powertrain Modeling and Design Problem Proposal portion of the EcoCAR3 proposal as specified in the Request for Proposal from Argonne National Laboratory. The results of the modeling exercises presented in the proposal showed that: An average conventional vehicle powered by a combustion engine could not meet the energy consumption target when the engine was sized to meet the acceleration target, due the relatively low thermal efficiency of the spark ignition engine. A battery electric vehicle could not meet the required range target of 320 km while keeping the vehicle weight below the gross vehicle weight rating of 2000 kg. This was due to the low energy density of the batteries which necessitated a large, and heavy, battery pack to provide enough energy to meet the range target. A series hybrid electric vehicle has the potential to meet the acceleration and energy consumption parameters when the components are optimally sized. A parallel hybrid electric vehicle has less energy conversion losses than a series hybrid electric vehicle which results in greater overall efficiency, lower energy consumption, and less emissions. For EcoCAR3, Michigan Tech proposes to develop a plug-in parallel hybrid vehicle (PPHEV) powered by a small Diesel engine operating on B20 Bio-Diesel fuel. This architecture was chosen over other options due to its compact design, lower cost, and its ability to provide performance levels and energy efficiency that meet or exceed the design targets. While this powertrain configuration requires a more complex control system and strategy than others, the student engineering team at Michigan Tech has significant recent experience with this architecture and has confidence that it will perform well in the events planned for the EcoCAR3 competition.

Electrochemical CO2 Reduction - A Critical View on Fundamentals, Materials and Applications

The electrochemical reduction of CO2 has been extensively studied over the past decades. Nevertheless, this topic has been tackled so far only by using a very fundamental approach and mostly by trying to improve kinetics and selectivities toward specific products in half-cell configurations and liquid-based electrolytes. The main drawback of this approach is that, due to the low solubility of CO2 in water, the maximum CO2 reduction current which could be drawn falls in the range of 0.01–0.02 A cm–2. This is at least an order of magnitude lower current density than the requirement to make CO2-electrolysis a technically and economically feasible option for transformation of CO2 into chemical feedstock or fuel thereby closing the CO2 cycle. This work attempts to give a short overview on the status of electrochemical CO2 reduction with respect to challenges at the electrolysis cell as well as at the catalyst level. We will critically discuss possible pathways to increase both operating current density and conversion efficiency in order to close the gap with established energy conversion technologies.

Microalgal CO2 Sequestering - Modeling Microalgae Production Costs

Microalgae CO2 sequestering facilities might become an industrial reality if microalgae biomass could be produced at cost below $500.00 t-1. We develop a model for estimation of total production costs of microalgae as a function of known production-specific expenses, and incorporate into the model the effects of uncontrollable factors which affect known production-specific expenses. Random fluctuations were intentionally incorporated into the model, consequently into generated cost/technology scenarios, because each and every logically interconnected equipment/operation that is used in design/construction/operation/maintenance of a production process is inevitably subject to random cost/price fluctuations which can neither be eliminated nor a priori controlled. A total of 152 costs/technology scenarios were evaluated to find forty four scenarios in which Predicted Total Production Costs of Microalgae (PTPCM) was in the range $200 to $500 t-1 ha-1 y-1. An additional 24 scenarios were found with PTCPM in the range of $102 to $200 t-1 ha-1 y-1. These findings suggest that microalgae CO2 sequestering and the production of commercial compounds from microalgal biomass can be economically viable venture even today when microalgae production technology is still far from its optimum.

First principles study of Bi dopen CdTe thin film solar cells: electronic and optical properties

Nowadays, efficiency improvement of solar cells is one of the most important issues in photovoltaic systems and CdTe is one of the most promising thin film photovoltaic materials we can found. CdTe reported efficiencies in solar energy conversion have been as good as that found in polycrystalline Si thin film cell [1], besides CdTe can be easily produced at industrial scale.

Current Mode with RMS Voltage and Offset Control Loops for a Single-Phase Aircraft Inverter Suitable for Parallel and 3-Phase Operation Modes

Rms voltage regulation may be an attractive possibility for controlling power inverters. Combined with a Hall Effect sensor for current control, it keeps its parallel operation capability while increasing its noise immunity, which may lead to a reduction of the Total Harmonic Distortion (THD). Besides, as voltage regulation is designed in DC, a simple PI regulator can provide accurate voltage tracking. Nevertheless, this approach does not lack drawbacks. Its narrow voltage bandwidth makes transients last longer and it increases the voltage THD when feeding non-linear loads, such as rectifying stages. On the other hand, the implementation can fall into offset voltage error. Furthermore, the information of the output voltage phase is hidden for the control as well, making the synchronization of a 3-phase setup not trivial. This paper explains the concept, design and implementation of the whole control scheme, in an on board inverter able to run in parallel and within a 3-phase setup. Special attention is paid to solve the problems foreseen at implementation level: a third analog loop accounts for the offset level is added and a digital algorithm guarantees 3-phase voltage synchronization.

Design of envelope amplifier based on interleaved multiphase buck converter with minimum time control for RF application

In this paper, an interleaved multiphase buck converter with minimum time control strategy for envelope amplifiers in high efficiency RF power amplifiers is proposed. The solution for the envelope amplifier is to combine the proposed converter with a linear regulator in series. High efficiency of envelope amplifier can be obtained through modulating the supply voltage of the linear regulator. Instead of tracking the envelope, the buck converter has discrete output voltage that corresponding to particular duty cycles which achieve total ripple cancellation. The transient model for minimum time control is explained, and the calculation of transient times that are pre-calculated and inserted into a lookup table is presented. The filter design trade-off that limits capability of envelope modulation is also discussed. The experimental results verify the fast voltage transient obtained with a 4-phase buck prototype.

Digital Control Implementation to Reduce the Cost and Improve the Performance of the Control Stage of an Industrial Switched-Mode Power Supply

The main objective of this work is the design and implementation of the digital control stage of a 280W AC/DC industrial power supply in a single low-cost microcontroller to replace the analog control stage. The switch-mode power supply (SMPS) consists of a PFC boost converter with fixed frequency operation and a variable frequency LLC series resonant DC/DC converter. Input voltage range is 85VRMS-550VRMS and the output voltage range is 24V-28V. A digital controller is especially suitable for this kind of SMPS to implement its multiple functionalities and to keep the efficiency and the performance high over the wide range of input voltages. Additional advantages of the digital control are reliability and size. The optimized design and implementation of the digital control stage it is presented. Experimental results show the stable operation of the controlled system and an estimation of the cost reduction achieved with the digital control stage.

Optimum Design of an Envelope Tracking Buck Converter for RF PA using GaN HEMTs

In this paper, filter design methodology and application of GaN HEMTs for high efficiency Envelope Amplifier in RF transmitters are proposed. The main objectives of the filter design are generation of the envelope reference with the minimum possible distortion and high efficiency of the amplifier obtained by the optimum trade-off between conduction and switching losses. This optimum point was determined using power losses model for synchronous buck with sinusoidal output voltage and experimental results showed good correspondence with the model and verified the proposed methodology. On the other hand, comparing to Si MOSFETs, GaN HEMTs can provide higher efficiency of the envelope amplifier, due to superior conductivity and switching characteristics. Experimental results verified benefits of GaN devices comparing to the appliance of Si switching devices with very good Figure Of Merit, for this particular application

Serial or Parallel Linear-Assisted Switching Converter as Envelope Amplifier: Optimization and Comparison

This paper presents a theoretical analysis and an optimization method for envelope amplifier. Highly efficient envelope amplifiers based on a switching converter in parallel or series with a linear regulator have been analyzed and optimized. The results of the optimization process have been shown and these two architectures are compared regarding their complexity and efficiency. The optimization method that is proposed is based on the previous knowledge about the transmitted signal type (OFDM, WCDMA...) and it can be applied to any signal type as long as the envelope probability distribution is known. Finally, it is shown that the analyzed architectures have an inherent efficiency limit.

Teaching digital control of switch mode power supplier

This paper explains the methodology followed to teach the subject `Digital control of power converters'. This subject belongs to the research master on `Industrial Electronics' of the Universidad Politécnica de Madrid. The subject is composed of several theoretical lessons plus the development of an actual digital control. For that purpose an ad hoc dc-dc converter has been designed and built. The use of this board together with some software tools seems a very powerful way for the students to learn the concepts from the design to the real world

Potencial del cultivo de la chumbera (Opuntia ficus-indica (L) Miller) para la obtención de biocombustibles

El presente trabajo trata sobre el potencial del cultivo de chumbera (Opuntia ficus-indica (L) Miller) para la obtención de dos biocombustibles: bioetanol y biogás. Para lograr este objetivo se ha estudiado, por una parte, el empleo de procedimientos orientados a la producción de bioetanol no celulósico a partir de cladodios de chumbera, lo que ha dado como resultado rendimientos de entre 156 y 221 litros de etanol por cada tonelada de materia seca de biomasa, y, por otra, la obtención de biogás mediante la digestión anaeróbica de los mismos en régimen mesófilo, donde se han hallado rendimientos en torno a 198 m3 de metano por tonelada de materia seca. Una vez determinado el potencial de la materia prima se han diseñado procesos para una escala industrial que permitan la transformación de los cladodios de chumbera en ambos biocombustibles y se han determinado sus balances energéticos, los cuales han dado como resultado la autosuficiencia de ambos procesos, obteniéndose, además, un excedente térmico de 1.235 kcal L-1 de etanol producido, y en torno a 140 kep de energía total (térmica + eléctrica) por tonelada de materia seca empleada en la digestión anaeróbica. Por último se ha estimado el potencial de producción de ambos combustibles en un área apta para el cultivo de la chumbera. En concreto, este estudio se ha llevado a cabo para la provincia de Almería, elegida por tratarse de una zona con cierta tradición en el manejo de esta planta y presentar un clima semiárido mediterráneo. La superficie apta para el cultivo de la chumbera en esta provincia se ha estimado en 100.616 ha y el rendimiento medio del cultivo en 5 t MS ha-1 año-1. En el caso del bioetanol esto implicaría un potencial de producción en torno a 82.158 m3 año-1 que podrían dar lugar a la creación de dos macrodestilerías (con una producción de 100.000 L diarios) o de 49 microdestilerías (con 5.000 L diarios de producción). Si se optara por la transformación de la biomasa de chumbera en metano, podrían obtenerse 99,4 M de metros cúbicos, lo cual permitiría el establecimiento de 79 plantas de cogeneración de 500 kW cada una. ABSTRACT The present work deals with the potential of prickly pear (Opuntia ficus-indica (L) Mill.) biomass as a feedstock for bioethanol and biogas. In order to reach this objective different procedures aiming at the production of non-cellulosic bioethanol from cladodes were carried out; yields from156 to 221 litres of bioethanol per ton of dry matter were found. Mesophilic anaerobic digestion of cladodes was also studied and yields around 198 m3 of methane per ton of dry matter were reached. From these results, processes on an industrial scale were designed for both pathways of energy conversion of prickly-pear biomass and the respective energy balances were calculated. They resulted to be self-sufficient from an energetic point of view; the bioethanol pathway generated a thermal energy surplus of 1,235 kcal per litre of ethanol, while around 140 kep of total energy (heat + electricity) were obtained from the anaerobic digestion of one ton of dry cladodes. Finally, the potential production of both biofuels from prickly pear biomass was estimated for a specific area. The province of Almeria was chosen because of its climate conditions and the previous existence of prickly pear plantations. The area suitable for prickly pear cultivation in the province was estimated at a maximum of 100.616 ha, with an average yield of about 5 t DM ha-1 year-1. If prickly pear biomass were cropped for bioethanol in Almeria, the potential production of bioethanol could reach 82,158 m3 year-1, in either two macrodistilleries (100,000 L day-1) or 49 microdestilleries (5,000 L day-1). If the biogas pathway were preferred, 99. 4 Mm3 of methane could be reached and this would represent 79 CHP plants (500 kW each one).

Diffuse illuminance availability on horizontal and vertical surfaces at Madrid, Spain

The overall objective of this work is to provide diffuse illuminance availability at Madrid (Spain) through a statistical analysis of illuminance values corresponding to a long-term data series. The illuminance values are obtained from irradiance measurements by means of different empirical models for luminous efficacy. The values of diffuse illuminance on a horizontal and on vertical surfaces facing the four cardinal points are estimated and the different aspects related to daylight availability in an area with specific climatic conditions are analyzed. The experimental data consist of global and diffuse irradiance measurements on a horizontal surface provided by the National Meteorological Agency in Spain (AEMET) for Madrid. These data consist of hourly values measured in the period of 1980–2005. The statistical results derived correspond to a daylight typical year for the five surfaces considered. This information will be useful to building experts to estimate natural illumination availability when daylighting techniques are applied in building design with the main aim of electric energy savings.

Effect of the oxygen isoelectronic substitution in Cu2ZnSnS4 and its photovoltaic application

The optoelectronic properties of Cu2ZnSnS4 and environmental considerations have attracted significant interest for photovoltaics. Using first-principles, we analyze the possible improvement of this material as a photovoltaic absorber via the isoelectronic substitution of S with O atoms. The evolution of the acceptor level is analyzed with respect to the atomic position of the nearest neighbors of the O atom. We estimate the maximum efficiency of this compound when used as a light absorber. The presence of the sub-band gap level below the conduction band could increases the solar-energy conversion with respect to the host.

Nano-imprinted rear-side diffraction gratings for absorption enhancement in solar cells

As wafer-based solar cells become thinner, light-trapping textures for absorption enhancement will gain in importance. In this work, crystalline silicon wafers were textured with wavelength-scale diffraction grating surface textures by nanoimprint lithography using interference lithography as a mastering technology. This technique allows fine-tailored nanostructures to be realized on large areas with high throughput. Solar cell precursors were fabricated, with the surface textures on the rear side, for optical absorption measurements. Large absorption enhancements are observed in the wavelength range in which the silicon wafer absorbs weakly. It is shown experimentally that bi-periodic crossed gratings perform better than uni-periodic linear gratings. Optical simulations have been made of the fabricated structures, allowing the total absorption to be decomposed into useful absorption in the silicon and parasitic absorption in the rear reflector. Using the calculated silicon absorption, promising absorbed photocurrent density enhancements have been calculated for solar cells employing the nano-textures. Finally, first results are presented of a passivation layer deposition technique that planarizes the rear reflector for the purpose of reducing the parasitic absorption.