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.

Intermediate band materials for more efficient solar energy use: quantum modelling and experimental realizations

The intermediate band (IB) solar cell (Fig. 1) has been proposed [1] to increase photovoltaic efficiency by a factor above 1.5, based on the absorption of two sub-bandgap photons to promote an electron across the bandgap. To realize this principle, that can be applied also to obtain efficient photocatalysis with sunlight, we proposed in recent years several materials where a metal or heavy element, substituting for an electropositive atom in a known semiconductor that has an appropriate band gap width (around 2 eV), forms inside the gap the partially filled levels needed for this aim

Analysis of metallic nanoantennas for solar energy conversion

Recently thermo-electrical nanoantennas, also known as Seebeck nanoantennas, have been proposed as an alternative for solar energy harvesting applications. In this work we present the optical and thermal analysis of metallic nanoantennas operating at infrared wavelengths, this study is performed by numerical simulations using COMSOL Multiphysics. Several different nanoantenna designs were analyzed including dipoles, bowties and square spiral antennas. Results show that metallic nanoantennas can be tuned to absorb electromagnetic energy at infrared wavelengths, and that numerical simulation can be useful in optimizing the performance of these types of nanoantennas at optical and infrared wavelengths.

TILTED COLUMNAR THIN FILM COATINGS WITH ANISOTROPIC LIGHT SCATTERING PROPERTIES FOR SOLAR ENERGY APPLICATIONS

The main goal of this thesis is to show the versatility of glancing angle deposition (GLAD) thin films in applications. This research is first focused on studying the effect of select deposition variables in GLAD thin films and secondly, to demonstrate the flexibility of GLAD films to be incorporated in two different applications: (1) as a reflective coating in low-level concentration photovoltaic systems, and (2) as an anode structure in dye-sensitized solar cells (DSSC). A particular type of microstructure composed of tilted micro-columns of titanium is fabricated by GLAD. The microstructures form elongated and fan-like tilted micro-columns that demonstrate anisotropic scattering. The thin films texture changes from fiber texture to tilted fiber texture by increasing the vapor incidence angle. At very large deposition angles, biaxial texture forms. The morphology of the thin films deposited under extreme shadowing condition and at high temperature (below recrystallization zone) shows a porous and inclined micro-columnar morphology, resulting from the dominance of shadowing over adatom surface diffusion. The anisotropic scattering behavior of the tilted Ti thin film coatings is quantified by bidirectional reflectance distribution function (BRDF) measurements and is found to be consistent with reflectance from the microstructure acting as an array of inclined micro-mirrors that redirect the incident light in a non-specular reflection. A silver-coating of the surface of the tilted-Ti micro-columns is performed to enhance the total reflectance of the Ti-thin films while keeping the anisotropic scattering behavior. By using such coating is as a booster reflector in a laboratory-scale low-level concentration photovoltaic system, the short-circuit current of the reference silicon solar cell by 25%. Finally, based on the scattering properties of the tilted microcolumnar microstructure, its scattering effect is studied as a part of titanium dioxide microstructure for the anode in DSSCs. GLAD-fabricated TiO2 microstructures for the anode in a DSSC, consisting of vertical micro-columns, and combined vertical topped with tilted micro-columns are compared. The solar cell with the two-part microstructure shows the highest monochromatic incident photon to current efficiency with 20% improvement compared to the vertical microstructure, and the efficiency of the cell increases from 1.5% to 2% due to employing the scattering layer.

Adsorption Calorimetry for Energy Conversion Technologies: Applications in Organic Photovoltaics, Catalysis, and Atomic Layer Deposition

Thesis (Ph.D.)--University of Washington, 2016-07

Modelling of a Stirling engine with parabolic dish for thermal to electric conversion of solar energy

Stirling engines with parabolic dish for thermal to electric conversion of solar energy is one of the most promising solutions of renewable energy technologies in order to reduce the dependency from fossil fuels in electricity generation. This paper addresses the modelling and simulation of a solar powered Stirling engine system with parabolic dish and electric generator aiming to determine its energy production and efficiency. The model includes the solar radiation concentration system, the heat transfer in the ther- mal receiver, the thermal cycle and the mechanical and electric energy conversion. The thermodynamic and energy transfer processes in the engine are modelled in detail, including all the main processes occur- ring in the compression, expansion and regenerator spaces. Starting from a particular configuration, an optimization of the concentration factor is also carried out and the results for both the transient and steady state regimes are presented. It was found that using a directly illuminated thermal receiver with- out cavity the engine efficiency is close to 23.8% corresponding to a global efficiency of 10.4%. The com- ponents to be optimized are identified in order to increase the global efficiency of the system and the trade-off between system complexity and efficiency is discussed.

Solar and thermal radiative effects during the 2011 extreme desert dust episode over Portugal

This paper analyses the influence of the extreme Saharan desert dust (DD) event on shortwave (SW) and longwave (LW) radiation at the EARLINET/AERONET Évora station (Southern Portugal) from 4 up to 7 April 2011. There was also some cloud occurrence in the period. In this context, it is essential to quantify the effect of cloud presence on aerosol radiative forcing. A radiative transfer model was initialized with aerosol optical properties, cloud vertical properties and meteorological atmospheric vertical profiles. The intercomparison between the instantaneous TOA shortwave and longwave fluxes derived using CERES and those calculated using SBDART, which was fed with aerosol extinction coefficients derived from the CALIPSO and lidar-PAOLI observations, varying OPAC dataset parameters, was reasonably acceptable within the standard deviations. The dust aerosol type that yields the best fit was found to be the mineral accumulation mode. Therefore, SBDART model constrained with the CERES observations can be used to reliably determine aerosol radiative forcing and heating rates. Aerosol radiative forcings and heating rates were derived in the SW (ARFSw, AHRSw) and LW (ARFLw, AHRLw) spectral ranges, considering a cloud-aerosol free reference atmosphere. We found that AOD at 440 nm increased by a factor of 5 on 6 April with respect to the lower dust load on 4 April. It was responsible by a strong cooling radiative effect pointed out by the ARFSw value (−99 W/m2 for a solar zenith angle of 60°) offset by a warming radiative effect according to ARFLw value (+21.9 W/m2) at the surface. Overall, about 24% and 12% of the dust solar radiative cooling effect is compensated by its longwave warming effect at the surface and at the top of the atmosphere, respectively. Hence, larger aerosol loads could enhance the response between the absorption and re-emission processes increasing the ARFLw with respect to those associated with moderate and low aerosol loads. The unprecedented results derived from this work complement the findings in other regions on the modifications of radiative energy budget by the dust aerosols, which could have relevant influences on the regional climate and will be topics for future investigations.

Non-equilibrium energy and momentum accommodation coefficients of Ar atoms scattered from Ni(001) in the thermal regime: A molecular dynamics study

Molecular dynamics simulations are used to study energy and momentum transfer of low-energy Ar atoms scattered from the Ni(001) surface. The investigation concentrates on the dependence of these processes on incident energy, angles of incidence and surface temperature. Energy transfer exhibits a strong dependence on the surface temperature, at incident energies below 500 meV, and incident angles close to specular incidence. Above 500 meV, the surface temperature dependence vanishes, and a limiting value in the amount of energy transferred to the surface is attained. Momentum exchange is investigated in terms of tangential and normal components. Both components exhibit a weak surface temperature dependence, but they have opposite behaviours at all incidence angles. In each component, momentum can be lost or gained following the interaction with the surface. (C) 1997 Elsevier Science B.V.

Self-Scheduling for energy and spinning reserve of wind/CSP plants by a MILP approach

This paper is on the self-scheduling for a power producer taking part in day-ahead joint energy and spinning reserve markets and aiming at a short-term coordination of wind power plants with concentrated solar power plants having thermal energy storage. The short-term coordination is formulated as a mixed-integer linear programming problem given as the maximization of profit subjected to technical operation constraints, including the ones related to a transmission line. Probability density functions are used to model the variability of the hourly wind speed and the solar irradiation in regard to a negative correlation. Case studies based on an Iberian Peninsula wind and concentrated solar power plants are presented, providing the optimal energy and spinning reserve for the short-term self-scheduling in order to unveil the coordination benefits and synergies between wind and solar resources. Results and sensitivity analysis are in favour of the coordination, showing an increase on profit, allowing for spinning reserve, reducing the need for curtailment, increasing the transmission line capacity factor. (C) 2014 Elsevier Ltd. All rights reserved.

The Endocannabinoid System as Pharmacological Target Derived from Its CNS Role in Energy Homeostasis and Reward. Applications in Eating Disorders and Addiction

The endocannabinoid system (ECS) has been implicated in many physiological functions, including the regulation of appetite, food intake and energy balance, a crucial involvement in brain reward systems and a role in psychophysiological homeostasis (anxiety and stress responses). We first introduce this important regulatory system and chronicle what is known concerning the signal transduction pathways activated upon the binding of endogenous cannabinoid ligands to the Gi/0-coupled CB1 cannabinoid receptor, as well as its interactions with other hormones and neuromodulators which can modify endocannabinoid signaling in the brain. Anorexia nervosa (AN) and bulimia nervosa (BN) are severe and disabling psychiatric disorders, characterized by profound eating and weight alterations and body image disturbances. Since endocannabinoids modulate eating behavior, it is plausible that endocannabinoid genes may contribute to the biological vulnerability to these diseases. We present and discuss data suggesting an impaired endocannabinoid signaling in these eating disorders, including association of endocannabinoid components gene polymorphisms and altered CB1-receptor expression in AN and BN. Then we discuss recent findings that may provide new avenues for the identification of therapeutic strategies based on the endocannabinod system. In relation with its implications as a reward-related system, the endocannabinoid system is not only a target for cannabis but it also shows interactions with other drugs of abuse. On the other hand, there may be also a possibility to point to the ECS as a potential target for treatment of drug-abuse and addiction. Within this framework we will focus on enzymatic machinery involved in endocannabinoid inactivation (notably fatty acid amide hydrolase or FAAH) as a particularly interesting potential target. Since a deregulated endocannabinoid system may be also related to depression, anxiety and pain symptomatology accompanying drug-withdrawal states, this is an area of relevance to also explore adjuvant treatments for improving these adverse emotional reactions.

On the use of spatially discrete data to compute energy and mass balance

In many practical applications the state of field soils is monitored by recording the evolution of temperature and soil moisture at discrete depths. We theoretically investigate the systematic errors that arise when mass and energy balances are computed directly from these measurements. We show that, even with no measurement or model errors, large residuals might result when finite difference approximations are used to compute fluxes and storage term. To calculate the limits set by the use of spatially discrete measurements on the accuracy of balance closure, we derive an analytical solution to estimate the residual on the basis of the two key parameters: the penetration depth and the distance between the measurements. When the thickness of the control layer for which the balance is computed is comparable to the penetration depth of the forcing (which depends on the thermal diffusivity and on the forcing period) large residuals arise. The residual is also very sensitive to the distance between the measurements, which requires accurately controlling the position of the sensors in field experiments. We also demonstrate that, for the same experimental setup, mass residuals are sensitively larger than the energy residuals due to the nonlinearity of the moisture transport equation. Our analysis suggests that a careful assessment of the systematic mass error introduced by the use of spatially discrete data is required before using fluxes and residuals computed directly from field measurements.

Soil diffuse degassing and thermal energy fluxes from the southern Lakki plain, Nisyros (Greece)

Two diffuse soil CO2 flux surveys from the southern Lakki plain show that CO2 is mainly released from the hydrothermal explosion craters. The correspondence between high CO2 fluxes and elevated soil temperatures suggests that a flux of hot hydrothermal fluids ascends towards the surface. Steam mostly condenses near the surface and the heat given off is conductively transferred to the atmosphere through the soil, accompanied by a large CO2 flux. Tt was calculated, that 68 t d(-1) of hydrothermal CO2 are released through the total surveyed area of similar to1.3 km(2) Admitting that a steam flux of 2200 t d(-1) accompanies this CO2 flux, the thermal energy released through steam condensation amounts to 58 MW.

Calculation analysis of energy saving tools for fan and pump applications

This thesis analyses the calculation of FanSave and PumpSave energy saving tools calculation. With these programs energy consumption of variable speed drive control for fans and pumps can be compared to other control methods. With FanSave centrifugal and axial fans can be examined and PumpSave deals with centrifugal pumps. By means of these programs also suitable frequency converter can be chosen from the ABB collection. Programs need as initial values information about the appliances like amount of flow and efficiencies. Operation time is important factor when calculating the annual energy consumption and information about it are the length and profile. Basic theory related to fans and pumps is introduced without more precise instructions for dimensioning. FanSave and PumpSave contain various methods for flow control. These control methods are introduced in the thesis based on their operational principles and suitability. Also squirrel cage motor and frequency converter are introduced because of their close involvement to fans and pumps. Second part of the thesis contains comparison between results of FanSave’s and PumpSave’s calculation and performance curve based calculation. Also laboratory tests were made with centrifugal and axial fan and also with centrifugal pump. With the results from this thesis the calculation of these programs can be adjusted to be more accurate and also some new features can be added.

Energy and Dynamics of the solar agricultural robot "SolarSprayer"

The main objective of the present study was to design an agricultural robot, which work is based on the generation of the electricity by the solar panel. To achieve the proper operation of the robot according to the assumed working cycle the detailed design of the main equipment was made. By analysing the possible areas of implementation together with developments, the economic forecast was held. As a result a decision about possibility of such device working in agricultural sector was made and the probable topics of the further study were found out.