Lack of energy storage is a key issue in the development of renewable energy sources. Most renewables, especially solar and wind, when used alone, cannot sustain a reliably constant power output over an extended period of time. These sources generally generate variable amounts of power intermittently, therefore, an efficient electrical energy storage (EES) method is required to better temporally balance power generation to power consumption. One of the more promising methods of electrical energy storage is the unitized regenerative fuel cell (UFRC.) UFRCs are fuel cells that can operate in a charge-discharge cycle, similar to a battery, to store and then to subsequently release power. Power is stored by means of electrolysis while the products of this electrolysis reaction can be recombined as in a normal fuel cell to release the stored power. A major advantage of UFRCs over batteries is that storage capacity can be decoupled from cell power, thus reducing the potential cost and weight of the cell unit. Here we investigate UFRCs based on hydrogen-halogen systems, specifically hydrogen-bromine, which has potential for improved electrode reaction kinetics and hence cheaper catalysts and higher efficiency and energy density. A mathematical model has been developed to analyze this system and determine cell behavior and cycle efficiency under various conditions. The conventional H2-Br2 URFCs, however also so far have utilized Pt catalysts and Nafion membranes. Consequently, a goal of this work was to explore alternate schemes and materials for the H2-Br2 URFC. Thus, three generations of test cells have been created. The first two cells were designed to use a molten bromide salt, ionic liquid or anion exchange membrane as the ion exchange electrolyte with the liquids supported on a porous membrane. This type of system provides the potential to reduce the amount of precious metal catalyst required, or possibly eliminate it altogether. Each cell showed improvement over the previous generation, although the results are preliminary. The final set of results are promising for anion exchange membranes on a cost basis compared Nafion. Another promising energy storage solution involves liquid methanol as an intermediate or as a hydrogen carrier. An alternative to storing high-pressure hydrogen is to produce it on-board/on-site on demand via a methanol electrocatalytic reformer (eCRef), a PEM electrolyzer in which methanol-water coelectrolysis takes place. Methanol handling, storage, and transportation is much easier than that for hydrogen. The hydrogen produced via methanol eCref may then be used in any number of applications, including for energy storage and generation in a standard H2-O2 PEM fuel cell. The mathematical modeling and analysis for an eCref is very similar to that of the HBr URFC. In this work, a comprehensive model for the coelectrolysis of methanol and water into hydrogen is created and compared with experimental data. The performance of the methanol electrolyzer coupled with a H2-O2 fuel cell is then compared for efficiency to that of a direct methanol fuel cell data and was found to be superior. The results suggest that an efficient and small paired eCRef-fuel cell system is potentially be a cheaper and more viable alternative to the standard direct methanol fuel cell. Both the H2-Br2 URFC and the methanol eCref in combination with a H2-O2 fuel cell have significant potential to provide higher energy efficiency and energy density for EES purposes.

Selon le taux de sodium, par exemple de bonnes caractéristiques thermoélectriques pour les phases riches en sodium, ainsi que la supraconductivité pour certaines compositions (x ~ 0.3) hydratées, en font un exemple de choix pour étudier les corrélations entre la structure et les propriétés. La première partie de ce travail utilise l’électrochimie et la technique de batteries au sodium pour explorer en détail et de manière continue le diagramme de phase de ce système (pour x ≥ 0.5), en particulier avec un suivi in situ par diffraction des rayons X de l’intercalation d’ions sodium. Les compositions monophasées sont caractérisées par un potentiel électrochimique propre, et leur stabilité thermique relative est étudiée lors de cyclages à différentes températures.Dérivant de P2-NaxCoO2, le système ordonné OP4-(Li/Na)CoO2 se caractérise également par des propriétés thermoélectriques remarquables. La seconde partie de ce travail approfondit la connaissance de ce système caractérisé par une intercalation alternée des ions lithium et sodium. A partir de cet empilement, par des échanges ioniques topotactiques, trois nouveaux empilements théoriquement simulés sont expérimentalement mis en évidence et caractérisés. Il s’agit des polytypes inédits O4-LiCoO2 et D4-AgCoO2, ainsi que de l’empilement OD4-(Li/Ag)CoO2, premier exemple d’une intercroissance NaCl / delafossite au sein d’une même structure lamellaire. / The P2-NaxCoO system exhibits various outstanding physical phenomena such as promising thermoelectric properties (for x ~ 0.7) and superconductivity for hydrated compositions. The first part of the present study uses electrochemistry through sodium batteries to deeply explore the P2-NaxCoO2 phase diagram (for x ≥ 0.5) in a continuous way, with especially an in situ XRD experiment that follows sodium ions intercalation. Peculiar single-phase compositions are characterized by a specific electrochemical voltage, and their relative thermal stability is studied through electrochemical cycling at various temperatures.The second part of this project deals with the ordered OP4-(Li/Na)CoO2 system which also exhibits promising thermoelectric features. Its structure is characterized by an alternate intercalation of lithium and sodium ions. Using this system, topotactic ionic exchanges enable to obtain three new stackings, O4-LiCoO2, D4-AgCoO2, and the OD4-(Li/Ag)CoO2 which are first simulated, experimentally evidenced and then characterized. The OD4 stacking is thefirst example of a NaCl / delafossite intergrowth in the same layered structure.

Les préoccupations actuelles concernant l'exploitation sécuritaire des centrales nucléaires existantes et la conception d’architectures spéciales envisagées pour la quatrième génération de réacteurs nucléaires se combinent avec l’intérêt plus prononcé pour l'efficacité et la fiabilité de l'équipement d'un système énergétique. Cela fait que dans un souci de meilleure compréhension et optimisation basée sur des moyens modernes de conception assistée par l’ordinateur, l'étude de différentes parties de ces systèmes fait de plus en plus l’objet de recherches approfondies. . Parmi les types proposés pour la quatrième génération de réacteurs nucléaires font partie ceux ayant comme agent de refroidissement les sels fondus, respectivement le sodium fondu. En raison de leurs propriétés physiques, les sels fondus et le sodium liquide ont le potentiel d'être déplacés par les pompes électromagnétiques. Cet ouvrage est à la fois une étude approfondie des phénomènes qui se produisent en raison de l'écoulement du fluide dans le champ électromagnétique d’une pompe électromagnétique - interaction magnétohydrodynamique - et un rapport sur les capacités et les avantages des outils informatiques modernes pour faciliter la conception et l'optimisation des pompes électromagnétiques. Afin d’atteindre l'objectif principal de la thèse, notamment une meilleure compréhension des phénomènes interdépendants spécifique à l’opération des pompes électromagnétiques, deux objectifs secondaires ont été considérés. Le premier objectif concerne la pleine exploitation des modèles électromagnétiques numériques en éléments finis afin d'obtenir autant d'informations que possible sur le comportement des pompes électromagnétiques, dans l’hypothèse où on ne tient pas compte de l'écoulement des fluides. Le deuxième objectif était la construction des modèles numériques qui réunissent l’électromagnétisme et la dynamique des fluides, respectivement des modèles numériques qui regroupent les deux phénomènes caractérisant l’écoulement magnétohydrodynamique dans les canaux des pompes électromagnétiques. Dans l'étude dédiée au pompage électromagnétique de sels fondus, la thèse met en évidence des problèmes spécifiques liés à la génération de forces électromagnétiques dans les fluides faibles conducteurs d'électricité et fournit des résultats sur les applications où le pompage électromagnétique de sels fondus peut être efficace. À l’aide des modèles électromagnétiques nous avons obtenu des informations importantes sur l'influence du nombre de pôles électromagnétiques et de la fréquence d’alimentation sur la caractéristique Pression - Vitesse des pompes annulaires à induction. Ils ont été analysés le phénomène de blindage créé par les parois métalliques - avec des répercussions négatives sur les performances de la pompe, les effets de freinage exercés à l'entrée et à la sortie du canal de la pompe et la relation entre la capacité de surcharge hydrodynamique et la caractéristique Pression - Vitesse des pompes à induction. Une section spéciale a été consacrée à l'analyse de la dépendance de la force électromagnétique du temps et de l’espace et à l’étude de non-uniformitées des quantités de nature électromagnétique en direction azimutale dans les pompes annulaires à induction.Dans le chapitre qui traite de l'interaction magnétohydrodynamique à base de modèles couplés, ils sont proposés deux modèles qui couplent l'électromagnétisme et l’écoulement. Ils sont présentés les avantages des modèles couplés, en matière de la précision des résultats, par rapport aux modèles électromagnétiques. Il est également présenté l'évolution des profils de vitesse, de densité de force et de courant sous l'influence du champ électromagnétique et de l’écoulement de sodium à vitesses différentes. Les contributions de la thèse sont complétées par des observations importantes sur les méthodes de travail et les logiciels utilisés tout au long de l'étude. / The actual concerns with respect to safe operation of existing nuclear plants and to designing special architectures envisaged for the fourth generation of nuclear reactors, corroborated with the increasing interest for efficiency and reliability of any equipment belonging to an energetic system, make that more and more research endeavors to be devoted to the study of various parts of these systems for a better understanding and optimization based on modern techniques of computer aided design. Among the types proposed for the fourth generation of nuclear reactors belong those that have as cooling agent molten salts, respectively liquid sodium. Many reactors of previous generations use mechanical pumps of special design for driving the coolants. Molten salts and liquid sodium, thanks to their physical properties, have the potential to be driven using electromagnetic pumps. Although the technology of electromagnetic pumping of electroconductive fluids was developed since the first half of the last century, currently it undergoes a revival due to the reconsideration of its multiple technological and security advantages. This work is both an intimate study of the phenomena that occur as a result of the electroconductive fluids flow in the electromagnetic field of an electromagnetic pump – magnetohydrodynamic interaction - and a report on the capabilities and advantages of modern computational tools to facilitate design and optimization of electromagnetic pumps.To achieve the principal goal of deeper understanding of the interdependent phenomena specific to electromagnetic pumps operation, two auxiliary objectives were considered. The first is related to the full exploitation of electromagnetic finite element models in order to retrieve as much information as possible about electromagnetic pumps behavior in a simplifying hypothesis that does not take into account the fluid dynamics. The second auxiliary objective is to build numerical models that couple the electromagnetism and the fluid dynamics, namely the two interdependent physics that govern the magnetohydrodynamic flow through channels of electromagnetic pumps.In the section dealing with the study of electromagnetic pumping of molten salts, the thesis highlights specific problems related the generation of electromagnetic forces in fluids with low electrical conductivity and provides results with respect to applications where electromagnetic pumping of molten salts can be effective. With the electromagnetic numerical models were obtained important data about the influence of the number of electromagnetic poles and supply frequency on the Pressure – Velocity characteristic of annular linear induction pumps. Were analyzed the shielding effect generated by the metallic walls - with negative repercussions on pumps performances, braking effects exerted at pump inlet and pump outlet and the connection between the overload capacity and Pressure – Velocity characteristic of induction pumps. A special portion was devoted to the analysis of the time and space dependence of the electromagnetic force and to the study of the non-uniformities of electromagnetic quantities in azimuth direction of annular linear induction pumps.In the chapter devoted to the magnetohydrodynamic interaction through coupled models, the thesis proposes two models that couple the electromagnetism and the fluid flow, one realized using multiphysic software and the second by coupling two different softwares. There are presented the advantages of the coupled models with respect to the results accuracy in comparison with electromagnetic models. It is presented the evolution of velocity, force and current densities profiles under the influence of the electromagnetic field and of different sodium mean velocities.The contributions of the thesis are completed with significant observations related to the study methods and software tools used along the study process. / Preocupările actuale în legătură cu exploatarea în siguranță a centralelor nucleare existente și în legătură cu proiectarea arhitecturilor speciale de reactoare nucleare pentru generația a patra,coroborate cu interesul tot mai pronunțat pentru eficiența și fiabilitatea oricărui echipament dintr-un sistem energetic, fac ca tot mai multe demersuri de cercetare să se îndrepte spre studiul diverselor subansamble ale acestor sisteme pentru o mai buna înțelegere și optimizare pe baza mijloacelor moderne de proiectare asistată de calculator. Din rândul tipurilor propuse pentru generația a patra de reactoare nucleare fac parte și cele care au ca agent de răcire săruri topite, respectiv sodiu topit. Multe reactoare nucleare de generație anterioară folosesc ca mijloc de antrenare a fluidelor de răcire pompe mecanice de construcție specială. Sărurile topite ăi sodiul lichid, datorită proprietăților fizice,au potențialul de a fi recirculate cu ajutorul pompelor electromagnetice. Deși tehnologia pompării electromagnetice a fluidelor electroconductoare a fost dezvoltată încă din prima parte a secolului trecut, în prezent cunoaște o renaștere datorită reconsiderării multiplelor avantaje tehnologice și de securitate în exploatare. Lucrarea de față este atât un studiu al fenomenelor intime ce au loc ca urmare a curgerii fluidelor electroconductoare în câmpul electromagnetic al pompelor electromagnetice – interacțiune magnetohidrodinamică - cât și un raport despre capabilitățile și avantajele uneltelor moderne de calcul de a înlesni proiectarea și optimizarea pompelor electromagnetice. Pentru a atinge scopul principal al tezei, și anume o înțelegere mai adâncă a fenomenelor interdependente specifice funcționării pompelor electromagnetice, au fost considerate două obiective secundare. Primul obiectiv se referă la exploatarea la maximum a modelelor electromagnetice numerice în element finit cu scopul de a obține cât mai multe informații cu putință despre comportamentul pompelor electromagnetice în ipoteza care nu ia în considerare curgerea fluidelor. Al doilea obiectiv a fost construirea unor modele numerice care cuplează electromagnetismul și curgerea, respectiv, cuplează modelele numerice ale celor două fenomene ce caracterizează curgerea magnetohidrodinamică din canalele pompelor electromagnetice. În partea dedicată studiului pompării electromagnetice a sărurilor topite, teza evidențiază problemele specifice legate de generarea forțelor electromagnetice în fluide slab conductoare electric și oferă rezultate cu privire la aplicațiile unde pomparea electromagnetică a sărurilor topite poate fi eficientă. Cu ajutorul modelelor electromagnetice s-au obținut date importante despre influența numărului de poli electromagnetici și frecvența de alimentare asupra caracteristicii Presiune – Viteză a pompelor electromagnetice inelare de inducție. Au fost analizate fenomenul de ecranare creat de peretii metalici – cu repercursiuni negative asupra performanțelor pompelor, efectele de frânare exercitate la intrarea și la ieșirea din canalul de pompare și legătura dintre capacitatea de suprasarcină hidrodinamică și caracteristica Presiune – Viteză a pompelor de inducție. O secțiune specială a fost consacrată analizei dependenței de timp și a variației de la punct la punct a forței electromagnetice, precum și studiului neuniformităților mărimilor de natură electromagnetic în direcție azimutală în pompele inelare de inducție. În capitolul despre interacțiunea magnetohidrodinamică pe baza modelelor cuplate, se propun două modele ce cuplează electromagnetismul și curgerea fluidelor, unul realizat cu ajutorul unui singur software și al doilea realizat prin cuplarea a două software-uri diferite. Sunt prezentate avantajele modelelor cuplate din punctul de vedere al acurateței rezultatelor în comparație cu modelele electromagnetice …