Cette thèse concerne les phénomènes locaux qui se produisent dans une pile à combustible à membrane (PEMFC) fonctionnant en mode bouché. Ce mode de fonctionnement consiste à alimenter l’anode en hydrogène sec tout en maintenant sa sortie fermée ce qui favorise l’accumulation d’eau et d’azote (issus du compartiment cathodique) près de la sortie anodique. Certaines régions sont donc convenablement alimentées en gaz tandis que d’autres ne le sont plus. Ces déséquilibres s’accompagnent de hausses localisées de potentiel (à l'anode et à la cathode) qui accélèrent la dégradation du catalyseur et de son support carboné à la cathode. Afin d’étudier ces dégradations à une échelle locale, une cellule segmentée novatrice permettant la mesure simultanée des densités de courant et des potentiels locaux a été développée. Des protocoles de vieillissement accélérés reposant sur un fonctionnement prolongé en mode bouché montrent que les pics de potentiel ont pour conséquence, après quelques heures, une distribution non-uniforme de la surface active (ECSA) à la cathode et des courants le long de la cellule : les dommages sont plus prononcés dans les zones les plus touchées par le déficit en hydrogène. Des études paramétriques et un modèle numérique permettent de comprendre que le déficit en hydrogène résulte principalement de l’accumulation d’eau liquide dans les canaux de l’anode, bien que l'azote joue également un rôle. Par conséquent, la gestion de l’eau impacte fortement les variations de potentiel à la cathode et donc leurs conséquences en termes de dégradation ; basées sur ces constatations, des solutions sont proposées pour améliorer les durée de vie des piles / This work investigates the local transient phenomena occurring in proton exchange membrane fuel cells (PEMFC) operated with a dead-ended anode. The dead-end mode consists in closing the anode outlet, which leads eventually to local hydrogen starvation due to the excessive accumulation of liquid water and nitrogen (because of membrane crossover) in the anode compartment. Such fuel-starvation events may remain undetected but can entail a significant rise of the anode (and thus cathode) potentials and accelerate carbon corrosion and catalyst degradation. To access local information, we developed an innovative segmented linear cell with reference electrodes along the gas channels. By simultaneously monitoring the local potentials and current densities during operation, we assessed the impact of fuel starvation and observed strong local cathode potential excursions close to the anode outlet. Aging protocols based on fuel cell operation with a dead-ended anode (longer than in real use condition) showed non-uniform cathode ElectroChemical Surface Area (ECSA) losses and performance degradation along the cell area: the damage was more severe in the regions suffering the longest from fuel starvation. Parametric studies completed by numerical simulations showed that the fuel starvation is mainly governed by liquid water accumulation in the anode channels, as well as nitrogen crossover through the membrane. As a consequence, water management impacts significantly the cathode potential variations and thus the resulting electrode degradation. Starting from this founding, we propose strategies to improve fuel cell lifetime

In dieser Arbeit werden drei voneinander unabhängige Verfahren zur Diagnose von Alterungsvorgängen an automobilen Polymer-Elektrolyt-Membran-Brennstoffzellen-Stapeln und -Aggregaten entwickelt. Gemeinsam ermöglichen diese Methoden ein tieferes Verständnis für die elektrochemischen Schadensmechanismen und stellen Mittel zu deren Reduktion zur Verfügung. Die erste Methode behebt die an Stapeln auftretenden Probleme konventioneller Zyklovoltammetrie mittels gezielter Modifikation der Spannungstransienten. Dieses Vorgehen ermöglicht die exakte und sehr zuverlässig reproduzierbare Bestimmung von Wasserstoff- Crossoverstrom, Doppelschichtkapazität und aktiver Katalysator-Oberfläche im Stapel und stellt damit eine neue Art der Alterungsdiagnose an Stapeln dar. Der Zweck der zweiten Methode ist es, die systematische Entwicklung einer schonenden Betriebsstrategie für Luft-/Luft-Starts auf Aggregate-Ebene zu ermöglichen. Hierfür wird eine Reihe von Referenzelektroden in ein Fahrzeug-Aggregat eingebracht, um die im Stapel während des Starts ablaufenden elektrochemischen Vorgänge örtlich und zeitlich aufgelöst beobachten zu können. Auf diese Weise werden zwei Startprozeduren analysiert und bzgl. ihrer Eignung verglichen. Beim dritten Verfahren handelt es sich um eine Parameterschätzung, die die modellbasierte Diagnose und Regelung von schwer zu messenden Zustandsgrößen zum Ziel hat. Der echtzeitfähige Algorithmus schätzt die aktive Katalysator-Oberfläche, die Gaszusam- mensetzungen auf Anode und Kathode sowie den rezirkulierten Volumenstrom mittels verschiedener Modelle für Stapel und Systemkomponenten.:(1) Einleitung (2) Aufbau und elektrochemische Limitierungen von PEM-Brennstoffzellen (3) Aufbau von automobilen PEM-Brennstoffzellenaggregaten (4) Eine Übersicht bekannter Diagnosemethoden für PEM-Brennstoffzellen (5) In-situ-Charakterisierung von PEM-Brennstoffzellenstapeln (6) Bewertungsmethode für Startprozeduren von PEM-Brennstoffzellenaggregaten (7) Online-Diagnose mittels gekoppelter Echtzeit-Parameterschätzung (8) Zusammenfassung und Ausblick / This thesis presents three newly developed methods for the diagnosis of deterioration in automotive polymer electrolyte membrane fuel cell stacks and systems. The combination of these methods allows for a more comprehensive understanding of electrochemical degradation processes and provides means for their mitigation. The first technique aims at the elimination of problems associated with the application of conventional cyclic voltammetry on fuel cell stacks. This is achieved by specific modification of the voltage transients. The procedure enables the precise and highly reproducible measurement of the hydrogen crossover current, double layer capacity and the electrochemically active surface area within the stack and thus represents a completely new kind of stack diagnosis method. The intention of the second method is to facilitate the purposeful development of damage mitigating air-/air-startup operating strategies on system level. To that intent, a number of dynamic hydrogen reference electrodes are positioned within the stack of a vehicle system, which allows for locally and temporally resolved observation of the electrochemical processes. Using this method, two startup procedures are analysed and compared with regard to their suitability. The third technique is an online parameter estimation aiming at the model based diagnosis and control of quantities, which can only be measured with difficulty. The algorithm estimates the electrochemically active surface area, the gas compositions on anode and cathode and the recirculated volumetric flow using various models for stack and system components. With these three methods, all relevant parameters for the intrinsical quantification of the degradation of each single cell within the stack can be precisely quantified. The methods thus enable a direct observation of the deterioration of the fuel cell and contribute to a further increase in durability as well as faster and more efficient development processes.:(1) Einleitung (2) Aufbau und elektrochemische Limitierungen von PEM-Brennstoffzellen (3) Aufbau von automobilen PEM-Brennstoffzellenaggregaten (4) Eine Übersicht bekannter Diagnosemethoden für PEM-Brennstoffzellen (5) In-situ-Charakterisierung von PEM-Brennstoffzellenstapeln (6) Bewertungsmethode für Startprozeduren von PEM-Brennstoffzellenaggregaten (7) Online-Diagnose mittels gekoppelter Echtzeit-Parameterschätzung (8) Zusammenfassung und Ausblick

The chemistry of actinides in solution is a very important aspect of the nuclear fuel cycle, especially as the energy needs of the world continue to increase. However, the radio-active nature of the actinides makes experimentation very difficult and dedicated expensive instruments are required. In addition, the disposal of radio-active waste materials requires a proper understanding of their chemistry at a molecular level. To tackle the problem, and to underpin the experimental studies, in this thesis we have studied the redox chemistry and disproportionation mechanism of actinyl complexes in solution using state-of-the art computational methods. Reduction potentials of actinyl complexes in solution have been estimated in solution using density functional theory (DFT) approaches. Solvation effects were included in the quantum chemistry calculations with the conductor like polarisable continuum model (CPCM) solvation method. First of all, we have validated our computational method by studying a variety of solute cavity definitions within the CPCM solvation model and assessed the performance of a range of DFT functionals to suitable to accurately describe the actinide chemistry in solution. Penta-valent uranyl(V) ions are unstable and readily disproportionate; in this study we have explored outer-sphere electron transfer and disproportionation mechanisms to determine the stability of these ions in solution. We have found that the process of outer-sphere disproportionation is unlikely to occur in non-aqueous solutions, such as DMSO, DMF, DCM, acetonitrile and pyridine, when the uranyl(V) ion is bound with a multi-dentate organic ligand. However, our computational results hypothesise that the presence of a trace of water in the experimental conditions can promote a disproportionation reaction by protonating the uranyl(V) ‘yl’ oxygen atoms and then the electron transfer process would proceed through either inner or outer sphere mechanism. In addition, the effect of alkali metal cations on the outer-sphere disproportionation mechanisms was also studied. Overall it has been shown that DFT can be used to accurately predict the redox properties of actinyl complexes in solution and thus contributing for an effective and efficient design of nuclear material separations, proper as well as safer radioactive waste disposal.