Interessante Optionen in der dezentralen Energieversorgung ergeben sich mit dem Einsatz von erdgasbetriebenen Gas-Otto-Motor-, Mikrogasturbinen-, Stirlingmotor- und PEMFC-Modulen. In dem Zusammenhang ist zu beachten, dass die Nutzungsmöglichkeiten dieser KWK-Systeme auch durch die elektrischen und thermischen Bedarfswerte und -strukturen der zu versorgenden Objekte bestimmt werden. Der Schwerpunkt dieser Arbeit ist, neben einer experimentellen und theoretischen Untersuchung ausgewählter KWK-Module, die vergleichende Bewertung von KWK-Anwendungen in der Hausenergieversorgung. Am Beispiel der Energieversorgung von Modell-Siedlungen nach VDI 2067-7 wird der stationäre Betrieb der untersuchten KWK-Module im bi- und polyvalenten Einsatz nachgebildet und bilanziert. Zur Bewertung der KWK-Konzepte erfolgt ein Vergleich zu einer konventionellen Energieversorgungsstrategie mit getrennter Bereitstellung elektrischer und thermischer Energie. Als Indikatoren zur Beurteilung der dezentralen Energieversorgungsvarianten dienen definierte energetische, ökologische und ökonomische Faktoren. Im Rahmen von Simulationsanalysen wird die Bedeutung der Integrations- und Einsatzweise der KWK-Module untersucht. Ein Variantenvergleich der Energieversorgungsstrategien verdeutlicht, welche Einsatzmöglichkeiten der KWK-Module für die untersuchte Struktur der Hausenergieversorgung beim gegenwärtigen Stand der Technik zweckmäßig sind.

No description available.

Climate change has propelled the development of alternative power sources that minimize the emission of greenhouse effect gases. Widespread commercialization of polymer electrolyte membrane fuel cell (PEM-FC) technology for transportation and stationary applications requires cost-competitiveness with improved durability and performance. Advantages compared to battery electric vehicles include fast refueling and long distance range. One way to improve performance and minimize costs of PEM-FC involves the optimization of the nanostructure of the catalyst layer. The rate limiting oxygen reduction reaction occurs at a triple-phase interface in the cathode catalyst layer (CL) between the proton conductor perfluorosulfonic acid, PFSA, the Pt catalyst particles decorating the electron conductor carbon support and gaseous O2 available through the porous framework of the carbon support. Visualization and quantitation of the distribution of components in the CL requires microscopy techniques. Electron and X-ray microscopy have been used to characterize the distribution of the PFSA relative to the carbon support and porosity in CLs. Understanding and limiting the analytical impact of radiation damage, which occurs due to the ionizing nature of electrons and X-rays, is needed to improve quantitation, particularly of PFSA. This thesis developed scanning transmission X-ray microscopy (STXM) methods for quantitation of damage due to electron and soft X-ray irradiation in PFSA materials. Chemical damage to PFSA when irradiated by photons and electrons is dominated by fluorine loss and CF2-CF2 amorphization. The quantitative results are used to set maximum dose limits to help optimize characterization and quantitation of PFSA in fuel cell cathode catalyst layers using: analytical electron microscopy, X-ray microscopy, spectromicroscopy, spectrotomography, spectroptychography and spectro-ptycho-tomography. / Thesis / Doctor of Philosophy (PhD) / Polymer electrolyte membrane fuel cells are an alternative, environmentally friendly power source for transportation and stationary applications. Major challenges for mass production include cost competitiveness, improved durability and performance. A key component to enhance the performance and lower costs involves understanding and improving the spatial distribution of the perfluorosulfonic acid (PFSA) polymer in the catalyst layer. The ionizing nature of electrons and X-rays used in microscopy characterization tools challenges PFSA characterization since this material is radiation sensitive. This thesis developed measurement protocols and methods for quantitative studies of radiation damage to PFSA and other polymers using scanning transmission X-ray microscopy. The chemical changes to PFSA films irradiated with photons, electrons and ultraviolet (UV) photons were studied. The quantitative results identify limits to analytical electron and soft X-ray microscopy characterization of PFSA. The results are used to optimize methods for soft X-ray microscopy characterization of PFSA in fuel cell applications.

Constitutive relationships are developed to describe the water transport characteristics of the gas diffusion layer (GDL) of proton exchange membrane fuel cells (PEMFCs). Additionally, experimental fixtures and procedures for the determination of the constitutive relationships are presented. The water transport relationships are incorporated into analytical models that assess the impact of the water transport relations and that make PEMFC performance predictions. The predicted performance is then compared to experimental results. The new constitutive relationships are significantly different than the currently popular relationships used in PEMFC modeling because they are derived from experiments on actual PEMFC gas diffusion layer materials. In prior work, properties of the GDL materials such as absolute permeability, liquid water relative permeability, porosity, and capillary behavior are often assumed or used as adjustment parameters in PEMFC models to simplify the model or to achieve good fits with polarization data. In this work, the constitutive relations are not assumed but are determined via newly developed experimental techniques. The experimental fixtures and procedures were used to characterize common GDL materials including carbon papers and carbon cloths, and to investigate common treatments applied to these materials such as the bulk application of a hydrophobic polymer within the porous structure. A one-dimensional model is developed to contrast results based on the new constitutive relations with results based on commonly used relationships from the PEMFC literature. The comparison reveals that water transport relationships can have a substantial impact on predicted GDL saturation, and consequently a significant impact on cell performance. The discrepancy in saturation between cases can be nearly an order of magnitude. A two-dimensional model is also presented that includes the impact of the compressed GDL region under the shoulder of a bipolar plate. Results show that the compression due to the bipolar plate shoulder causes a significant increase in liquid saturation, and a significant reduction in oxygen concentration and current density for the paper GDL. In contrast, compression under the shoulder has a minimal impact on the cloth GDL. Experimental inputs to the 2-D model include: absolute permeability, liquid water relative permeability, the slope of the capillary pressure function with saturation, total porosity, GDL thickness, high frequency resistance, and appropriate Tafel parameters. Computational polarization curve results are compared to experimental polarization behavior and good agreement is achieved. / Ph. D.

Bakalauro baigiamąjį darbą „ Vandenilio kuro elementų tyrimas srovės trūkio metodu“ sudaro 5 skyriai: įvadas, teorinė dalis, tyrimų dalis, išvados, literatūra ir priedai. Darbo apimtį sudaro 73 puslapiai, 69 paveikslėliai, 3 lentelės ir 4 priedai. Darbe aprašomos įvairių tipų kuro elementai, jų veikimas. Nagrinėjama PEM kuro elemento veikimo principai. Pateikti PEM kuro elemento savybių eksperimentinio tyrimo rezultatai. / The final work for bachelors degree „Investigation of Fuel Cells by Current Interrupt Technique“ consists of 5 parts: introduction, theoretical part, research part, conclusions, literature and accessories. The work consists of 73 pages, 69 pictures, 3 tables and 4 accessories. This work describes various types of fuel cells, how it works. Operation principles of PEM fuel cell element are analysed. The results of experimental examination of PEM fuell cell element are give.

Ces travaux de thèse s'inscrivent dans le contexte des efforts de recherches menés pour proposer des matériaux susceptibles de lever les verrous technologiques au développement des piles à combustible à membrane. L'un de ces enjeux est l'augmentation de la température de fonctionnement (150 - 250 °C) afin d'améliorer les cinétiques réactionnelles permettant une diminution de la quantité de catalyseur ainsi qu'une simplification de la gestion de l'eau, une réduction du système de refroidissement et une meilleure résistance à l'empoisonnement au monoxyde de carbone du platine. La motivation de cette étude a été de substituer au carbone un matériau support de catalyseur avec une plus grande résistance électrochimique.Notre choix s'est porté sur le carbure de tungstène qui, en plus d'une conductivité électronique élevée, présente une activité catalytique pour l'oxydation de l'hydrogène et la réduction de l'oxygène en milieu acide. La mise au point d'une méthode de synthèse innovante par voie hydrothermale a permis l'élaboration de microsphères de carbure de tungstène (MCT) de surface spécifique élevée (68 m2.g-1 avec 4 % de carbone résiduel) et d'architecture inusuelle. Des nanoparticules de platine de taille contrôlée ont été préparées par méthode polyol afin d'être déposées en surface des MCT. Après caractérisations électrochimiques ex-situ couplées à des analyses de surface (XPS) de ces catalyseurs Pt/WC, la mise en forme d'électrodes par enduction et transfert sur la membrane a permis la réalisation d'assemblages membrane - électrode et leurs caractérisations en pile à combustible. Des membranes polybenzimidazole dopé acide phosphorique (PBI-H3PO4) ont été utilisées pour remplacer les membranes Nafion afin d'augmenter la température de fonctionnement. / The objective of this work was to develop alternative suitable materials to increase operating temperature of a Proton Exchange Membrane Fuel Cell. The increase of the operating temperature (150 - 250 °C) is attractive for cost reduction and reliability in terms of reaction kinetics, catalyst tolerance, heat rejection and water management. Our work was focused on tungsten carbide which has an high electrical conductivity and exhibits a significant catalytic activity for hydrogen oxidation and oxygen reduction in acidic environment. We have reported a novel approach to produce tungsten carbide microspheres (TCM) with an high surface area (68 m2.g-1 including only 4 % of residual carbon) and an unusual architecture. Platinum nanoparticles were prepared by polyol method and were then deposited on TCM. Physical, chemical as well as electrochemical characterisations of WC supported platinum nanoparticles Pt/WC are described and discussed in comparison with a platinum electrocatalyst on a commercial carbon support (Vulcan XC-72R). Membrane Electrode Assembly was then prepared by coating - decal process, and characterised by single cell test and compared to conventional Pt/C assembly. Phosphoric acid doped polybenzimidazole PBI(H3PO4) was used as electrolyte to replace Nafion membrane in order to carry out fuel cell testing at higher temperature.

The gas diffusion layer (GDL) is one of the key components in a polymer electrolyte membrane (PEM) fuel cell. It performs several functions including the transport of reactant gases and product water to and from the catalyst layer, conduction of both electrons and heat produced in the catalyst layer, as well as mechanical support for the membrane. The overarching goal of this work is to thoroughly examine the GDL structure and properties for use in PEM fuel cells, and more specifically, to determine how to characterize the GDL experimentally ex-situ, to understand its performance in-situ, and to relate theory to performance through controlled experimentation. Thus, the impact of readily measured effective water vapor diffusivity on the performance of the GDL is investigated and shown to correlate to the wet limiting current density, as a surrogate of the oxygen diffusivity to which it is more directly related. The influence of microporous layer (MPL) design and construction on the fuel cell performance is studied and recommendations are made for optimal MPL designs for different operating conditions. A method for modifying the PTFE (Teflon) distribution within the GDL is proposed and the impact of distribution of PTFE in the GDL on fuel cell performance is studied. A method for characterizing the surface roughness of the GDL is developed and the impact of surface roughness on various ex-situ GDL properties is investigated. Finally, a detailed analysis of the physical structure and permeability of the GDL is provided and a theoretical model is proposed to predict both dry and wet gas flow within a GDL based on mercury intrusion porosimetry and porometry data. It is hoped that this work will contribute to an improved understanding of the functioning and structure of the GDL and hence advance PEM fuel cell technology.

3-Diazonium- 4-(trifluorovinyloxy) - perfluorobutanesulfonyl benzenesulfonimide zwitterionic monomer (see figure 1) is proposed to be polymerized and further act as a new electrolyte for Polymer exchange membrane fuel cells (PEMFCs). One reason is that, the aromatic trifluorovinyl aryl ether (TFVE) group can easily be homopolymerized to aromatic perfluorocyclobutane (PFCB) polymer. Furthermore, the diazonium moiety in the monomer is expected to covalently attach the electrolyte to the carbon electrodes support. The perfluoroalkyl(aryl) sulfonimide (PFSI) pendant provides good chemical and mechanical stability as well as better proton conductivity. Several multi-step synthetic schemes are designed to obtain such monomer from perfluoroalkyl(aryl) sulfonimide (PFSI). Among them, the purified coupling product 4-OCF2CF2Br-3-NO2-PhSO2(M) SO2C4F9 from the first approach was successfully completed. The next stages of the work will involve dehalogenation, reduction, and diazotization to achieve the targeting monomer. All the intermediates were characterized by 1H and 19F NMR and FT-IR spectroscopy.

Le fonctionnement de la pile à combustible (PAC) de type PEM (à membrane polymère) est encore soumis à de nombreuses incertitudes, aux natures différentes, qui affectent ses performances électriques, sa fiabilité et sa durée de vie. L'objectif général de cette thèse est de proposer une méthode d'aide à l'évaluation de la fiabilité des PAC par la simulation ; la fiabilité étant vue ici comme la garantie d’accéder à un niveau de performance électrique donné dans les différentes conditions d’usage envisagées pour la PAC. La démarche proposée s’appuie sur un couplage physico-fiabiliste où la complexité des phénomènes physiques présents dans la pile est prise en compte par une modélisation de connaissance, dynamique, symbolique et acausale, développée dans l’environnement Modelica - Dymola. La modélisation retenue, monodimensionnelle, non isotherme inclut une représentation diphasique des écoulements fluidiques pour mieux retranscrire la complexité des échanges d’eau dans le coeur de la pile PEM. La modélisation permet aussi d’intégrer des incertitudes sur certains de ses paramètres physiques et semi-empiriques (classés en trois catégories : opératoires, intrinsèques et semi-empiriques) puis d’entreprendre, par des tirages de Monte-Carlo, la modélisation probabiliste des conséquences des incertitudes injectées sur la performance d’une PAC. Il est ainsi possible, par la suite, d’estimer la fiabilité d’une PAC par le calcul de la probabilité que la performance électrique reste supérieure à un seuil minimal à définir en fonction de l’application. Une analyse physico-fiabiliste détaillée a été menée en introduisant à titre d’exemple une incertitude sur la valeur de la porosité de la couche de diffusion cathodique d’une PAC de type PEM (coefficients de variation retenus : 1%, 5% et 10%). L’étude des conséquences de cette incertitude sur la tension et l’impédance d’une PAC a été menée en réalisant un plan d’expériences numériques et en mettant en oeuvre différents outils d’analyse statistique : graphes des effets, analyses de la variance, graphes des coefficients de variation des distributions en entrée et sortie du modèle déterministe. Dans cet exemple d’analyse et dans les conditions d’usages considérées, le taux de fiabilité prévisionnel (probabilité pour que la cellule de pile fournisse un minimum de tension de 0.68V) a été estimé à 91% avec un coefficient de variation d’entrée à 10%. / The Proton Exchange Membrane Fuel Cell (PEMFC) operation is subject to inherent uncertainty in various material, design and control parameters, which leads to performance variability and impacts the cell reliability. Some inaccuracies in the building process of the fuel cell (in the realization of the cell components and also during the assembly of the complete fuel cell stack), some fluctuations in the controls of the operating parameters (e.g. cell and gas temperatures, gas pressures, flows and relative humidity rates) affect the electrical performance of the cell (i.e. cell voltage) as well as its reliability and durability. For a given application, the selections of the different materials used in the various components of the electrochemical cell, the choices in the cell design (geometrical characteristics / sizes of the cell components) correspond to tradeoffs between maximal electrical performances, minimal fuel consumption, high lifespan and reliability targets, and minimal costs.In this PhD thesis, a novel method is proposed to help evaluating the reliability of a PEMFC stack. The aim is to guarantee a target level of electrical performance that can be considered as sufficient to meet any application requirements. The approach is based on the close coupling between physical modeling and statistical analysis of reliability. The complexity of the physical phenomena involved in the fuel cell is taken into account through the development of a dynamical, symbolic, acausal modeling tool including physical and semi-empirical parameters as well. The proposed knowledge PEMFC model is one-dimensional, non-isothermal and it includes a two-phase fluidic flow representation (each reactant is considered as a mix of gases and liquid water) in order to better take into account the complexity of the water management in the cell. The modeling is implemented using the MODELICA language and the DYMOLA software; one of the advantages of this simulation tool is that it allows an effective connection between multi-physical modeling and statistical treatments. In this perspective, the modeling is done with the aim of having as much relevant physical parameters as possible (classified in our work as operating, intrinsic, and semi-empirical parameters). The different effects of these parameters on the PEMFC electrical behavior can be observed and the performance sensitivity can be determined by considering some statistical distributions of input parameters, which is a step towards reliability analysis.A detailed physical and reliability analysis is conducted by introducing (as an example) an uncertainty rate in the porosity value of the cathodic Gas Diffusion Layer (coefficients of variance equal to 1%, 5% and 10%). The study of the uncertainty consequences on the cell voltage and electrical impedance is done through a design of numerical experiments and with the use of various statistical analysis tools, namely: graphs of the average effects, statistical sensitivity analyses (ANOVAs), graphs displaying the coefficients of variances linked with the statistical distributions observed in the inputs and outputs of the deterministic model. In this example of analysis and in the considered cell operating conditions, the provisional reliability rate (probability that the cell voltage is higher than 0.68V) is estimated to 91% with an input coefficient of variance equal to 10%.

Les liquides ioniques pourront remplacer l'eau dans les électrolytes des PEMFCs opérant à 130°C. Les liquides ioniques résultant de la neutralisation des amines aliphatiques par l'acide trifluoromethanesulfonique montrent que les points de fusion dépendent de plusieurs critères, nature de l'anion, nature des substitutions sur l'amine. D'autre part, la majorité de ces sels sont thermiquement stables jusqu'à 400°C. L'étude par la voltamétrie cyclique a prouvé que les amines et les sels (HNR3+, A) s'oxydent à des potentiels très élevés (> 1,9 V/ESH), compatible avec leur utilisation dans les piles à combustible. D'autre part, les meilleures conductivités sont obtenues par les sels résultant de l'association acide trifluoromethanesulfonique et amines dissymétriques. Les conductivités à 130°C sont entre 5 mS.cm-1 et 45 mS.cm-1. L'incorporation de ces composés dans le Nafion a donné une bonne compatibilité LIP/Nafion. Cependant, l'effet plastifiant du LIP sur le polymère diminue les propriétés mécaniques du Nafion. Les conductivités sont aussi nettement réduites d'un facteur de 5 dans les meilleurs cas.