Solid Oxide fuel cells (SOFC), is one of the fuel cell types with a greater potential as a commercial electrical power generator. As a high temperature fuel cell type (600-1000ºC), presents one of the biggest opportunity to be integrated in a polygeneration system combining it with existing infrastructure to provide heat and power in a efficient way. Furthermore, unlike other types of fuel cells, SOFC can work using a wide variety of fuels, meaning that with some reformation; most of the commercially available fuels can be utilized, and even some relatively sustainable fuels that are not yet commercial, such as gasified biomass. The main part of this thesis focuses on the design of two gasifier models, one for partial oxidation gasification and other for steam gasification, both models where verified using published experimental results and simulations. Afterwards the models were integrated to work with a SOFC system. Several key parameters where analyzed in other have a complete view of the behavior of the system. The system was studied by changing different parameters like fuel cell operating temperature, fuel cell operating pressure, fuel composition, and moisture content. Finally another part of the thesis is to analyze two different systems, one integrating gasifier and SOFC, and other studying the integration of the gasifier system to a combine cycle system, SOFC-Micro Gas Turbine. The study concludes, as expected, that there is an inverse correlation between the moisture level in the fuel and the efficiencies in all the systems. Also the model shows that increasing the cell operating temperature will reduce the number of cell needed in order to achieve the design power output.

This work represents the integration of a hybrid system based on Micro Gas Turbine system available at the division of Heat and Power Technology at KTH and Solid Oxide Fuel Cell.  The MGT available is an externally fired recuperated and the SOFC is of planar type. Before the integration, these two different candidates of environmentally friendly power generation systems are discussed separately. The advantages and performances of the two separate systems are presented. The operation conditions as pressure and temperature are fixed at different stations based on the previous experiments. Keeping the parameters constant a reduction of fuel to the combustor could be achieved. Finally, layout of the hybrid system diagram is suggested and orientation of a computer designed layout is also presented. An efficiency of 65% from SOFC has been achieved and reductions of the fuel by more than 50% to the MGT are noteworthy.

The island of Malta is highly reliant on fossil fuels for its power (99%), and due to climate mitigation policies implemented by EU the Maltese government is required to have 10% of its power generation from renewables by 2020. To achieve these energy goals, the Maltese government has expressed interest in investing on a Hexicon platform to produce 9% of the Maltese energy demand. The Hexicon platform is a floating structure capable of carrying a wide range of renewable energy generators. The Hexicon platform proposed for Malta is meant to have a rated capacity of 54MW distributed by vertical and horizontal wind energy converters. Nevertheless, due to the irregular nature of wind the Hexicon platform would still use diesel generators on-board as backup power; this inherently defeats the purpose of the Maltese investment, and therefore a Hydrogen backup system was proposed and investigated for its technical and economic viability. A literature study was carried out on renewable hydrogen system in order to familiarise with the type of markets and the best way to apply the technology to the scenario at hand. Four markets were established, small-scale, transportation, stand-alone power systems, and large buffering systems; the large buffering system is the most appropriate for the study, and taking this type of system into account, the most appropriate hydrogen generation and utilisation system were then identified. It was established that the system is composed of three parts, electrolyser, storage tanks and fuel cells stacks. However, an additional water purification system is necessary; this is due to the fact that the Hexicon platform will be located offshore, and salt water is not appropriate for the electrolyser. A literature study was then performed to identify the most appropriate equipment for each stage of the process; it was established that a Reverse Osmosis (RO) system will be used to purify the water, an alkaline electrolyser will be used to generate the Hydrogen, the Hydrogen will then be stored in pressure vessels (at 30bar), thus also requiring compressors, and the recovery of energy will be performed by a proton exchange membrane (PEM) fuel cell (FC) stack. A study was carried out to establish the models to use for each equipment, and based on the hourly demand for Malta, as well as the hourly winds, a first estimate of the size of each equipment was established. The system model was developed in the HOMER software, which unfortunately did not model the desalination plant. The Hexicon (in the design considered in this study) is not able to provide Malta with 9% of the energy demand; this was mainly due to the low wind conditions. In addition to this, it was understood from the literature study that a hydrogen system backup system, i.e. a buffering system, would not be applicable to the scenario initially proposed in this thesis due to the low renewable energy penetration, and also due to the fact that the Hexicon would be connected to the grid, rendering such a system defunct. A micro-grid scenario was assumed and developed. This scenario tried to assess how low the demand would need to be in order to make a hydrogen project feasible. Different percentages were tried and the only one that met the constraints was one with 1.1% of the Maltese demand. The system would consist of a 3MW Fuel Cell, a 4.5MW electrolyser, and hydrogen storage for 10.5tonnes. The NPC of this system would be approx. 130 Million €, with an initial investment of approx. 71 Million €, LCOE of 0.257€.kWh-1, and a Hydrogen cost of approx. 20€.kg-1. While other economic indicators show viability, for example, a short payback time of 3.5 years based on the revenue from the excess electricity, the cost of hydrogen suggests that it is too expensive.

This thesis focuses on developing an appropriate cathode material throughnanotechnology as a key component for a promising alternative of renewable energygenerating systems, Intermediate Temperature Solid Oxide Fuel Cells (IT-SOFC).Aiming at a working cathode material for IT-SOFC, a recently reported capable oxideperovskite material has been synthesized through two different chemical methods.BaxSr1-xCoyFe1-yO3−δ (BSCF) with y =0.8 and x =0.2 was fabricated in nanocrystallineform by a novel chemical alloying approach, co-precipitation- as well as conventionalsol-gel method to produce oxide perovskites. The thermal properties, phase constituents,microstructure and elemental analysis of the samples were characterized by TG-DSC,XRD, SEM and EDS techniques respectively. Thermodynamic modeling has beenperformed using a KTH-developed software (Medusa) and Spark Plasma Sintering (SPS)has been used to obtain pellets of BSCF, preserving the nanostructure and generatingquite dense pellets for electrical conductivity measurements.The results show that the powders synthesized by solution co-precipitation have cubicperovskite-type structure with a high homogeneity and uniform distribution and meanparticle size of 50-90 nm range, while sol-gel powders are not easy to form a pure phaseand mostly the process ends up with large particle containing two or three phases.Finer resultant powder compared to sol-gel technique and earlier research works onBSCF has been achieved in this project using oxalate co-precipitation method. Topreserve nanoscaled features of BSCF powder which possess a significant increase ofelectrical conductivity due to decrease the electrical resistivity of grain boundaries, forthe sample synthesized through co-precipitation, ~92% dense pellet sintered by SPS atV1080 °C and under 50 MPa pressure and its electrical conductivity has been measuredfrom room temperature to 900 °C.Specific conductivity values were precisely measured and the maximum of 63 S.cm-1 at430 °C in air and 25 S.cm-1 at 375°C in N2 correspondingly are two times higher thanconventional BSCF implying a high pledge for nano-BSCF as a strong candidate ascathode material in IT-SOFC.

Manganese compounds have a high potential for treating wastewater, both for utilizing its oxidation, flocculation ability and catalyst ability in anaerobic nitrification. The promising use of manganese compounds (such as permanganate and manganese dioxide) is regarded as an effective method of treating organic compounds in wastewater from municipal and industrial wastewater. Now it is newly realized possibilities to combine manganese compounds with Microbial Fuel Cell technology. Aiming at reusing the biomass in anaerobic digested sludge for degrading organic pollutants and simultaneously recovering electric energy, Single-chamber Microbial Fuel Cell (SMFC) system was developed and investigated during the main experimental part. Considering the electricity generation rate and characteristics of cathode, MnO2 was used as the reactant on the cathode electrode; meanwhile, the substrate types in anode compartment also were investigated and then extra sodium acetate was added to investigate the power generation performance. Two parts of the research were carried out during the whole project. The chemical treatment part was mainly designed to find out the best dosage of KMnO4 in flocculation when concurrent reacted with magnesium and calcium compounds when treating reject wastewater from digester at Hammarby Sjöstadsverk. The other part was studied to see whether it is possible to improve electricity generation by degrading organic pollutants when MnO2 was used as a cathodic reactant in sediment microbial fuel cell which consisted of anaerobic digested sludge from UASB.

Microbial fuel cell (MFC) has become one of the energy-sustainable technologies for wastewater treatment purpose in the recent years. It combines wastewater treatment and electricity generation together so as to achieve energy balance. By inoculating microorganism in the anode chamber and filling catholyte in the cathode chamber, and also with the help of a proton exchange membrane (PEM) between them, the MFC can transfer protons and produce power. Microbial desalination cells (MDC) are based on MFC’s structure and can fulfill desalination function by the addition of a middle chamber and anion exchange membrane (AEM). This study focuses on ammonium removal and electricity generation in MDC system. Mainly two types of liquid were tested, a solution of Hjorthorn Salt and filtrated supernatant. The experiments were performed at Hammarby Sjöstad research station and laboratory of Land and Water Resources department, Stockholm. It consists of a preparation stage, a MFC stage and a MDC stage. Until the end of MFC stage, biofilm in the anode chamber had been formed and matured. After that, solutions of different initial concentrations (1.5, 2.5, 5, 15 g/L) of Hjorthorn Salt and also filtrated supernatant have been tested. Ammonium removal degree can be obtained by measuring the initial concentration and cycle end concentration, while electricity generation ability can be calculated by voltage data which was continuously recorded by a multimeter. Results showed that this MDC system is suitable for ammonium removal in both of Hjorthorn Salt solutions and supernatant. The removal degrees in Hjorthorn Salt solution at desalination chamber were 53.1%, 52.7%, 60.34%, and 27.25% corresponding to initial NH4+ concentration of 340.7, 376, 376 and 2220 mg/L. The ammonium removal degrees in the supernatant were up to 53.4% and 43.7% under 21 and 71 hours operation, respectively. In power production aspect, MDC produced maximum voltage when potassium permanganate was used in the cathode chamber (217 mV). The power density in solutions of Hjorthorn Salt was relative low (46.73 - 86.61 mW/m3), but in the supernatant it showed a good performance, up to 227.7 and 190.8 mW/m3.

Polygeneration systems attract attention recently because of their high efficiency and low emission compare to the conventional power generation technology. Three different polygeneration systems based on low temperature solid oxide fuel cell, atmospheric solid oxide fuel cell/ micro gas turbine, and pressurized solid oxide fuel cell/ micro gas turbine are mathematically modeled in this study using MATLAB (version 7.12.0.635). These systems are designed to provide space heating, cooling and hot domestic water simultaneously. This report provides the design aspects of such systems. Furthermore, the effects of some important operating properties on the polygeneration systems performance are investigated.

In polymer electrolyte fuel cells (PEFC) chemical energy, in for example hydrogen, is converted by an electrochemical process into electrical energy. The PEFC has a working temperature generally below 100 °C. Under these conditions water management and transport of oxygen to the cathode are the parameters limiting the performance of the PEFC. The purpose of this thesis was to better understand the complex processes in different parts of the PEFC. The rate-limiting processes in the cathode were studied using pure oxygen while varying oxygen pressure and humidity. Mass-transport limitations in the gas diffusion layer using oxygen diluted in nitrogen or helium was also studied. A large capacitive loop was seen at 1-10 Hz with 5-20 % oxygen. When nitrogen was changed to helium, which has a higher binary diffusion coefficient, the loop decreased and shifted to a higher frequency. Steady-state and electrochemical impedance spectroscopy (EIS) models have been developed that accounts for water transport in the membrane and the influence of water on the anode. Due to water drag, the membrane resistance changes with current density. This gives rise to a low frequency loop in the complex plane plot. The loop appeared at a frequency of around 0.1 Hz and varied with D/Lm2, where D is the water diffusion coefficient and Lm is the membrane thickness. The EIS model for the hydrogen electrode gave three to four semicircles in the complex plane plot when taking the influence of water concentration on the anode conductivity and kinetics into account. The high-frequency semicircle is attributed to the Volmer reaction, the medium-frequency semicircle to the pseudocapacitance resulting from the adsorbed hydrogen, and the low-frequency semicircles to variations in electrode performance with water concentration. These low-frequency semicircles appear in a frequency range overlapping with the low-frequency semicircles from the water transport in the membrane. The effects of current density and membrane thickness were studied experimentally. An expected shift in frequency, when varying the membrane thickness was seen. This shift confirms the theory that the low-frequency loop is connected to the water transport in the membrane. / <p>QC 20121011</p>

This dissertation is a detailed scientific study concerning a proton exchange membrane fuel cell, which is coupled to a DC-to-DC converter as the power processor, serving as a power source. The novel aspect of the dissertation is the use of a new controller or nonlinear observer to predict parameter estimation of the fuel cell and the DC-to-DC converter as the load potential changes for the automated control system. Nonlinear control algorithms, which include nonlinear observers, were developed for such systems. / acase@tulane.edu

The lack of catalytic efficiency towards the complete ethanol oxidation reaction (EOR) has hindered the development of direct ethanol fuel cells (DEFCs). Ir-based catalysts have recently been shown promise in the complete EOR. However, the reaction mechanism of the complete EOR remains unclear, which impedes the development of better Ir-based catalysts. Herein, we performed extensive density functional theory (DFT) calculations to develop a comprehensive reaction network of EOR on Ir(100). The EOR process consists of four dehydrogenation steps of ethanol leading to the generation of CH2CO species followed by two competitive reaction pathways, i.e., a C-O bond cleavage to poisoning species (e.g., CHC) and the surface diffusion of CH2CO leading to CO2. Furthermore, our studies show that for all CHxCOy (x = 1, 2, or 3 and y = 0 or 1) species, only when the C and O atoms (or two C atoms) bind to two different surface Ir atoms can the C-C/C-O bond cleavage occur. This work highlights the essential roles of adsorption structure and diffusion of CH2CO for the complete EOR and serves as a benchmark for the future investigation of the electronic and solvent effects.Pt-Ir-based alloy electrocatalysts have shown encouraging catalytic performance on the EOR in direct ethanol fuel cells. Nevertheless, designing a suitably qualified EOR electrocatalyst remains challenging because of several convoluted factors (e.g., C1 species poisoning, acetate acid formation, and C-C bond splitting). To understand the relationship between the EOR performance and the type of catalysts, we model three kinds of (100)-exposed Pt-Ir layered catalysts and perform density functional theory (DFT) calculations to explore 58 elementary reactions of the EOR over three catalyst surfaces. According to the calculated activation energies and reaction energies, we mapped out the reaction mechanisms for EOR on different catalysts, indicating corresponding rate-limiting steps (RLSs) of the complete EOR. We demonstrated that the C-O coupling/decoupling ability of the catalyst surface plays a leading role in the overall EOR performance because a perfect complete EOR not only has to avoid some C-O coupling reactions (e.g., CH¬3CO+OH→CH3COOH) but also needs to promote some C-O coupling reactions (e.g., CO+O→CO2). We further illustrated that Pt and Ir exhibit excellent C-O coupling and decoupling abilities, respectively, implying that modifying the compositions and structures of Pt-Ir catalysts is a promising way to achieve the complete EOR. Furthermore, the Ir@Pt(100) surface (Ir monolayer over Pt(100) surface) with a Pt-doped active site possesses the most significant potential on EOR, which could impede the acetate acid formation and facilitate the CO2 formation simultaneously. This work highlights the role of tuning the C-O coupling/decoupling ability of electrocatalyst in EOR activity, providing a new strategy for designing and selecting the EOR electrocatalyst. The solvent effect has always been a non-negligible factor for aqueous reactions. In computational chemistry, researchers have been looking for a compromise between computational efficiency and the rationality of solvent models to mimic the solvent environment. In this work, I investigated the ethanol dehydrogenation and C-C bond cleavages of EOR over Ir(100)using both implicit and explicit solvation models. The implicit model exhibited little impact on the adsorbates without the hydroxyl group, whereas the explicit model can reasonably describe the system’s hydrogen bonding and van der Waals interaction. This solvent effect study showed how different solvent models affected the elementary reactions geometrically and energetically.