The high temperature oxidation of ferritic stainless steel interconnects results in chromium poisoning of the solid oxide fuel cell (SOFC) electrodes, which is a limiting factor for their utilisation as SOFC interconnects. Chromium-rich spinel materials were studied as electrode supports that would be situated at the interface between interconnect and electrode, in order to reduce the effect of chromium poisoning of the electrodes. The main goal of this thesis was to find chromium-rich spinel materials with good electrical conductivity (σ ≥ 0.1 S∙cm⁻¹) in air and reducing atmosphere, chemically and mechanically stable in SOFC testing conditions. The structure and properties of newly formulated chromium-rich spinels, such as Mn₁₊ₓCr₂₋ₓO₄ (x = 0, 0.5), MnFeₓCr₂₋ₓO₄ (x = 0.1, 1), MgMnCrO₄, MnLiₓCr₂₋ₓO₄ (x = 0.1) and MgMₓCr₂₋ₓO₄, (M = Li, Mg, Ti, Fe, Cu, Ga) were studied aiming at their application as electrode support material for solid oxide fuel cells. Cation distributions were determined by Rietveld refinement from X-ray diffraction (XRD), within the limits of XRD precision and correlated with electrical properties determined experimentally. The chemical stability in reducing conditions was studied and the reduction effects upon materials were evaluated by XRD phase analysis and microstructure analysis. It was found that MnMₓCr₂₋ₓO₄ materials have a limited stability to reduction, only MnCr₂O₄ proved to have good stability when reduced, with negative influence for its p-type semiconductor conductivity. Even though MnFeCrO₄ had limited stability to reduction, in reducing conditions the conductivity changed from p-type to n-type semiconductor. A similar behaviour to reduction was observed for MgFeCrO₄. Also the mechanical and chemical compatibility of some spinels with YSZ was studied in terms of thermal expansion coefficient (TEC/K⁻¹), sintering step and possible chemical reactions. Lithium titanate spinels, starting with LiCrTiO₄, were investigated in terms of structure, properties and spinel - ramsdellite phase transition temperature also with the purpose of new material development. For these materials positive results were obtained in conductivity and chemical stability in reducing conditions. The performance of MnFeCrO₄ and MgFeCrO₄ as electrode support materials was investigated when used alone or impregnated with (La₀.₇₅Sr₀.₂₅)₀.₉₇Cr₀.₅Mn₀.₅O₃, La₀.₈Sr₀.₂FeO₃, Ce₀.₉Gd₀.₁O₂, CeO₂ or Pd. Composite anodes for SOFC were prepared by aqueous infiltration of nitrate salts into porous MnFeCrO₄ and MgFeCrO₄ scaffolds and studied by electrochemical impedance spectroscopy (EIS) in symmetrical cell configuration. The performance of the composite anodes was evaluated in humidified 5%H₂/Ar in order to understand their stability and performance at 850 °C or lower temperature with respect to the porous substrates. It was found that all the impregnated phases adhere very well to the spinel and considerably enhance performance and stability to a level required for SOFC applications. An interesting next step in this work would be to apply such spinel materials on steel interconnects, integrate them into testing SOFC devices and evaluate their effect upon chromium poisoning of the electrodes.

Le but de cette thèse a été le développement de capteurs électrochimiques en flux, basés sur l'utilisation du feutre de graphite comme électrode de travail pour l'analyse pharmaceutique et environnementale du cuivre (II) et du zinc (II), deux métaux lourds essentiels pour l'homéostasie de l'organisme humain, mais toxiques en excès. Pour la détection des ions zinciques (II), une cellule d'analyse en flux, bien adaptée pour l'utilisation du feutre de graphite utilisé comme électrode de travail a été élaborée. Les conditions analytiques ont été optimisées et ont conduit à la détection du zinc (II) avec de bonnes sensibilités. Ces résultats montrent l'intérêt de réaliser en flux l'étape de pré-concentration pour augmenter la cinétique d'électrodéposition. Nous avons réalisé une étude complète sur une électrode en feutre de graphite modifiée par réduction d'un sel de diazonium, conduisant à la formation d'un film organique ayant une forte affinité pour les ions cuivriques. L'électrode modifiée combinée avec une étape de pré-concentration en flux permet la réalisation d'un capteur d'ions Cu2+ avec une grande sensibilité et une bonne sélectivité. Nous avons développé, aussi, un capteur électrochimique en flux pour l'analyse des traces d'ions cuivriques à l'aide d'une électrode en feutre de graphite modifiée avec un récepteur capable de complexer de façon sélective les ions de cuivre (II) dans des solutions aqueuses. Enfin, nous avons testé la détection électrochimique du cuivre (II) à l'aide d'électrodes modifiées bidimensionnelles, CPE et SPE. Les résultats préliminaires montrent une bonne capacité de ces électrodes pour la complexation et la détection des ions cuivriques (II). / The scope of this thesis was the development of flow electrochemical sensors, based on the use of graphite felt as a working electrode for the pharmaceutical and environmental analysis of zinc (II) and copper (II) ions, two heavy metals essential for the homeostasis of the human organism, but toxic if found in excess. For the detection of zinc (II) ions, a custom made flow cell was developed, well suited for the use of a graphite felt as working electrode in anodic stripping voltammetry analyses. The analytical conditions were optimized, leading to the detection of zinc with good sensitivities. These results prove the capacity of the preconcentration in flow to increase the kinetics of electrodeposition. A complet study on a graphite felt electrode modified by reduction of a diazonium salt, resulting in the formation of an organic film with high affinity for copper (II) ions was performed. The modified electrode combined with a flow preconcentration step allowed the achievement of a Cu2+ sensor with high sensitivity and good selectivity. We developed, also, a flow electrochemical sensor, allowing the analysis of traces of copper (II) ions, using a graphite felt electrode modified with a ligand proved to be able to selectively complex the copper (II) in aqueous solutions. Finally, we tested the electrochemical detection of zinc (II) and copper (II) ions by using modified bi-dimensional electrodes, CPE and SPE. Preliminary results show a good capacity of these modified electrodes for the complexation and detection of the copper (II) ions.

Dans la lutte contre le cancer, la médecine personnalisée est une stratégie nécessaire et très prometteuse. En effet, il est primordial de pouvoir tester l'innocuité et l'efficacité de médicaments anticancéreux sur des échantillons provenant du patient lui-même, du fait de la diversité des réponses entre patients. Le but est d'améliorer la performance des soins et d'éviter des traitements inutiles et même parfois nocifs pour le patient. Ainsi, l'exemple de la chimiothérapie illustre parfaitement cette stratégie. Le cout élevé des molécules thérapeutiques, la nocivité de ces molécules et les réponses variées des patients face à une même molécule implique le recours aux tests de ces molécules sur un échantillon provenant du patient lui-même. Il en résulte un intérêt croissant dans le développement de tests simples, robustes et peu couteux permettant l'évaluation de la chimio sensibilité de cellules biologiques issues d'une biopsie. Les problématiques liées à la mise en place de tels tests sont la quantité de cellules disponibles dans une biopsie, la diversité des molécules thérapeutiques à tester et également le choix d'une technique de détection permettant de suivre la cinétique d'action des molécules sur les cellules biologiques. L'une des réponses à la faible quantité de cellules est le développement de tests dans des environnements microfluidiques qui nécessitent donc l'intégration et la miniaturisation d'une technique de détection. La stratégie qui sera étudiée dans cette thèse est l'utilisation de l'impedancemetrie par le biais d'électrodes inter digitées d'Oxyde d'Etain et d'Indium (ITO) pour l'analyse quantitative de l'état de cellules de cancer du sein pour des applications de criblage de médicaments anticancéreux. Ce matériau présente l'avantage d'être transparent permettant ainsi des mesures d'impédance qui pourrait être couplées à des mesures optiques dans un environnement microfluidique. Dans une première partie, nous avons caractérisé et étudié des électrodes inter digitées d'or et d'ITO pour des mesures d'impédance avec des cellules cancéreuses. Cette caractérisation par spectroscopie d'impédance réalisée dans des solutions de milieu de culture en présence et absence de cellules, ont permis de démontrer que la différence de sensibilité entre ces deux matériaux provenait à la fois d'une différence de comportement résistif mais également d'une différence d'impédance interfaciale, dans les deux cas à la défaveur de l'ITO. Après ce constat, nous avons donc poursuivi l'étude afin d'évaluer les capacités de l'ITO pour des mesures de chimio sensibilité de la molécule 5-fluorouracil et également proposé une stratégie pour améliorer la sensibilité de l'ITO tout en conservant sa transparence. La stratégie développée consiste en la modification de la surface de d'électrodes d'ITO avec de l'oxyde d'iridium pour améliorer la sensibilité de l'ITO, tout en gardant sa transparence. Cette approche est intéressante pour pouvoir concevoir un dispositif transparent et facile à coupler avec un système d'observation microscopique dans un environnement microfluidique / In the fight against cancer, personalized medicine is a necessary and very promising strategy. In fact, it is essential to be able to test the safety and effectiveness of anticancer drugs on samples from the patient, due to the diversity of responses between patients. The aim is to improve the performance of health care and avoid unnecessary and sometimes harmful treatments. Thus, chemotherapy perfectly illustrates this strategy. The high cost of therapeutic molecules, the harmfulness of these molecules and the varied responses of patients involve the use of tests with chemotherapeutic molecules on samples coming from cancer patients. This results in a growing interest in the development of simple, robust and inexpensive tests for assessing the chemo sensitivity of biological cells from a biopsy. The problems related to carrying out such tests are the quantity of cells available in a biopsy, the diversity of the therapeutic molecules to be tested and also the choice of a detection technique, able to monitor the kinetics of action of the molecules on the biological cells. One solution to the small amount of cells is to carry out the tests in microfluidic environments which therefore require the integration and miniaturization of a detection technique. The strategy that will be studied in this thesis is the use of electrical impedance with interdigitated electrodes of indium tin oxide (ITO) for the quantitative analysis of the state of breast cancer cells for screening applications of anticancer drugs. This material has the advantage of being transparent allowing impedance measurements that could be coupled to optical measurements in a microfluidic environment. In the first part, we characterized and studied interdigitated electrodes of gold and ITO for impedance measurements with cancer cells. This impedance spectroscopy characterization carried out in culture medium solutions, in the presence and absence of cells, demonstrated that the difference in sensitivity between these two materials comes from a difference in resistive behavior and also from a difference in interfacial impedance, in both cases to the disadvantage of ITO. After this, we continued the study to evaluate the capabilities of ITO for chemosensitivity measurements using the molecule 5 fluorouracil and we suggested a strategy to improve the sensitivity of ITO while maintaining its transparency. The strategy developed consists of modifying the surface of ITO electrodes with iridium oxide to improve the sensitivity of the ITO, while keeping its transparency. This approach is interesting for developing a transparent device and easy to couple with a microscopic observation system in a microfluidic environment

This dissertation has focused on i) optimizing charge transfer rates at indium-tinoxide (ITO) electrodes, and ii) characterization of the supramolecular structure and properties of ultra thin surface modifier films on modified electrodes for various device applications. Commercial ITO surfaces were modified using conducting polymer thin film architectures with and without various chemical activation procedures. Ferrocene derivatives were used as redox probes, which showed dramatic changes in electron transfer rate as the SA-PANI/PAA layers were added to the ITO surface. Highest rates of electron transfer were observed for DMFc, whose oxidation potential coincides with the potential region where these SA-PANI/PAA films reach their optimal electroactivity. Apparent heterogeneous electron transfer rate constants, kS, measured voltammetrically, were ca.10 x higher for SA-PANI/PAA films on ITO, versus clean ITO substrates. These films also showed linear potentiometric responses with retention of the ITO transparency with the capability to create smoothest films using an aqueous deposition protocol, which proved important in other applications. ITO electrodes were also modified via chemisorption of carboxy functionalized EDOTCA and electropolymerization of PEDOTCA/PEDOT copolymers, when properly optimized for thickness and structure, enhance voltammetrically determined electron transfer rates (kS) to solution probe molecules, such as dimethylferrocene (DMFc). Values of kS ≥ 0.4 cm•sec⁻¹, were determined, approaching rates seen on clean gold surfaces. ITO activation combined with formation of these co-polymer films has the effect of enhancing the electroactive fraction of electrode surface, versus a non-activated, unmodified ITO electrode, which acts as a “blocked” electrode. The electroactivity and spectroelectrochemistry of these films helped to resolve the electron transfer rate mechanism and enabled the construction of models in combination with AFM, XPS, UPS and RAIRS studies. The surface topography, structure, composition, work function and contact angle, also revealed other desirable properties for molecular electronic devices. The carboxylic functionality of the EDOTCA molecule adds more desirable properties compared to normal PEDOT films, such as favoring the deposition of smooth films, increasing the optical contrast, participating in hydrogen-bonding, chemisorption to oxide surface, self-doping and providing a linker for incorporation of different functional groups, new molecules, or nanoparticles. Periodic sub-micron electrode arrays can be created using micro-contact printing and electropolymerization. The sinusoidal modulation of the refractive index of such confined conducting polymer nanostructures or nanoparticle stripes allows efficient visible light diffraction. The modulation of the diffraction efficiency at PANI and PEDOT gratings in the presence of an analytical stimulus such as pH or potential demonstrate the sensing capability at these surfaces. The template stripped gold surfaces that are being developed in our lab demonstrate several advantages over commercially available evaporated gold films especially for nanoscale surface modification.

The topic of this thesis is the development of devices for telecom applications based on poled optical fibers. The focus is on a specific function, optical switching/modulation. Some of the most important results are summarized below. Optical switching at telecom wavelengths (1.55 μm) is demonstrated in an all-fiber switch based on a fiber with internal electrodes. The fiber is made electro-optically active with a thermal poling process in which a strong electric field is recorded in the glass at a temperature of 255 °C. After poling, the fiber is put in one arm of a Mach-Zehnder interferometer and by applying a voltage across the two electrodes the refractive index is modulated and the optical signal switched from one output port to the other. A switching voltage of 190 V at 1550 nm was achieved, which to the best of our knowledge is the lowest value reported. By carefully matching the lengths of the fibers in the two arms of the interferometer the optical bandwidth could be made as large as 20 nm. The extinction ratio, determined by the power ratio in the two arms, was 30 dB and the highest modulation frequency was 30 MHz. Poled fibers were packaged to increase the thermal and mechanical stability and to make handling easier. 40 Gb/s transmission test through the device showed no bit-error-rate performance degradation. Protection switching of a 10 Gb/s signal is also demonstrated. The depletion region in a poled fiber was found to be wedge-shaped and very wide, 13 μm and completely overlapped with the core. In a time-resolved poling experiment the recorded electric field was measured. The sign of the field changed after ~20 min, when the depletion region passed through the core, which led to the conclusion that an electric field is present also outside of the depletion region. A ring laser was constructed with an erbium doped fiber as the gain medium. A fiber modulator was placed inside the cavity and when a small RF signal, with a frequency matched to the cavity ground frequency, was applied to the modulator the laser was modelocked. The output pulse train contained pulses of sub ns duration and is the first demonstration of mode-locking using poled fibers. A sampled grating with 16 channels spaced by 50 GHz was inserted into the cavity. The fiber modulator had optical bandwidth of 7 nm with center wavelength that depends on the applied voltage. By applying of 10 – 210 V to the modulator it was possible to tune the laser to 11 of the 16 channels for a total tuning range of over 4 nm. A scheme to deposit 1 μm thin silver electrodes inside the holes of an optical fiber is demonstrated together with a new method of creating periodic electrodes by periodically ablating the silver film electrodes. The periodic electrodes are used to create a quasi-phase matched (QPM) nonlinearity in a fibers which is showed in a proof of principle experiment. / QC 20101015

Les électrodes transparentes sont les composants indispensables de nombreux dispositifsoptoélectroniques commerciaux (cellules solaires, écrans plats, écrans tactiles ou encorediodes électroluminescentes). Elles sont constituées le plus souvent d’oxyde d’indium etd'étain (ITO). Les électrodes à base d'ITO sont produites par un procédé relativementcoûteux et sont très fragiles à la contrainte mécanique, ce qui limite leur utilisation au seinde dispositifs optoélectroniques flexibles. Des matériaux alternatifs, sans indium, à base deréseaux de nano-fils d’argent, font actuellement l'objet d'un grand nombre de recherches.Ces réseaux à base de nanostructures métalliques ont des propriétés opto-électroniquescomparables voire supérieures à celles de l’ITO. Ils sont adaptables à des substrats flexibleset sont compatibles avec les procédés de dépôt « roll to roll ». L'objectif de cette thèse estd'explorer de nouvelles voies de synthèse et de modification de surface de nanofils d'argentpour développer des électrodes transparentes plus performantes. De nouvelles nanostructuresmétalliques, différentes de celles commercialisées, ont été élaborées : (i) des fils d’argentultra-longs (ii) des fils d’argent présentant une architecture inhabituelle i.e avec desramifications. Des paramètres clés du procédé polyol ont été modifiés pour élaborer les filsà facteur de forme très élevé. Ils ont permis d'accroître les performancesrésistance/transparence des dispositifs conventionnels. Des nano-fils d’argent de forme « Y» ou « V » ont également été synthétisés en soumettant le milieu de croissance à des ultrasons.Ces nanostructures devraient permettre de limiter les problèmes de conduction quiapparaissent, à l'heure actuelle, au niveau des contacts entre les fils dans les dispositifsnanostructurés. Par ailleurs, des réseaux de fils d'argent modifiés en surface avec de l'acide11-mercaptoundecanoïque (MuA) ont été élaborés. Ils constituent une solution trèsintéressante pour améliorer la stabilité chimique des réseaux métalliques. Le MuA limite l'oxydation de surface du métal et permet aux électrodes de conserver leurs transparence etconductivité initiales. / Transparent electrodes are a necessary component in a number of devices such as solar cells,flat panel displays, touch screens and light emitting diodes. The most commonly usedtransparent conductor, indium tin oxide (ITO), is expensive and brittle, the latter propertymaking it inappropriate for up-and-coming flexible devices. Films consisting of randomnetworks of solution-synthesized silver nanowires have emerged as a promising alternative toITO. They have transparency and conductivity values better than competing new technologies(e.g. carbon nanotubes films, graphene, conductive polymers, etc.) and comparable to ITO.Furthermore, these silver nanowire films are cheap, flexible, and compatible with roll-to-rolldeposition techniques. The main objectives of this PhD work are to improve the properties ofsilver nanowire electrodes and to study and solve issues that are currently hindering their usein commercial devices. Specifically, I studied the important areas of electrode conductivity andstability. To increase the conductivity of nanowire electrodes, two silver nanostructuresdifferent from what is commercially available were synthesized i) ultra-long nanowires and (ii)branched nanowires. Regarding (i), by using 1.2-propanediol as the medium rather than thetypical ethylene glycol in the polyol synthesis process, as well as the molecular weight of PVP,the temperature of the process, or the concentration of silver nitrate, we obtained silvernanowires with an aspect ratio between their lengths and diameters of 1050. Among all theultra-long silver nanowires elaborated in polyol process reported in the literature, they have themaximum length. The synthesis developed is also cheap and the reaction time takes less than2h. Moreover, they have a high yield of 2 mg/ml. Electrodes with a sheet resistance of 5 Ω/Sqfor a transparency of 94% were obtained (with post thermal treatment applied). However, thispost-deposition anneal is shown to have a small influence on the decrease of the sheetresistance. It is thus not required to elaborate electrodes with good performance, which is veryadvantageous for the elaboration of electrodes on plastic substrates. Regarding (ii), “V-like shape” or “Y-like branched” nanowires were elaborated thanks to the input of ultrasonicirradiation during the polyol process. Unfortunately, their length being short (6 μm), theirinterest is limited to enhance the performance of transparent electrodes. In addition, structuralanalyses of both branched and unbranched nanowires revealed the nanostructures notmonocrystalline. Concerning the stabilities issues, the thermal stability of silver nanowireelectrodes coated with graphene was investigated. This coating allows a better homogeneity ofthe heat through the network, decreasing the number of hot spots and thus increasing thelifetime of the electrodes. The corrosion of silver nanowire and the resulting electrode resistanceincrease over time is a severe problem hindering their use in commercial devices. 11-mercaptoundecanoic acid (MuA) was identified as a promising passivation agent of silvernanowires. Lifetime testing showed that the electrode resistance increased more slowly (12%)than any other passivated electrodes reported in the literature. Furthermore, unlike many otherpassivation methods, the MuA molecule itself does not negatively affect the conductivity ortransparency of the electrode and is very inexpensive, all contributing to the commercialviability of the passivation method.

Parmi les défis que le Monde devra affronter dans les prochaines décennies, le plus difficile est l’utilisation d’énergie durable. Dans un scénario où les sociétés occidentales sont fortement dépendantes des combustibles fossiles pour garder leur niveau de bien-être (chauffage domestique, transport et production d’électricité), complété par les pays en voie de développement qui ont besoin d’alimenter leurs économies croissantes, il est nécessaire de souligner l’impact négatif sur l’environnement causé par l’utilisation de ces ressources fossiles mais aussi les problèmes géopolitiques pour les pays « non producteurs ». La collecte d’énergie provenant des sources renouvelables peut limiter la dépendance des combustibles fossiles, pourtant cette dernière ne peut remplacer les centrales électriques classiques à cause de son caractère intermittent.Les batteries sont des dispositifs qui peuvent résoudre définitivement cette limitation, puisqu’elles sont capables d’accumuler l’excès d’énergie produit afin de le délivrer au moment souhaité. De plus elles ont été envisagées comme les dispositifs principaux pour toutes les applications portables (téléphones et ordinateurs portables mais aussi véhicules). Grâces à ses excellentes performances et sa technologie bien développée, les batteries lithium-ion ont un rôle déterminant dans le support de cette nouvelle révolution énergétique. Pourtant leur usage répandu a été récemment remis en question à cause de la faible disponibilité de lithium, qui est un élément rare et concentré seulement dans certaines zones du monde. L’emploie du lithium pourrait donc engendrer les mêmes problèmes que les combustibles fossiles. De plus, cette technologie semble avoir atteint son niveau de développement maximal et ne pourrait plus être suffisante pour satisfaire des applications de plus en plus énergivores. Il est donc nécessaire d’envisager des alternatives au lithium en axant les recherches sur des ressources plus abondantes que lithium et à moindre coût mais aussi sur des systèmes plus performantes.Les batteries post-lithium, qui sont basées sur d’autres porteur de charges que le Li+, pourrait représenter des alternatives plus sécurisées, respectueuse de l'environnement et aussi plus attractifs en termes de capacité stockée. Le magnésium est un candidat prometteur pouvant remplacer le lithium dans les systèmes électrochimiques de stockage d’énergie, grâce à son abondance, son faible coût et sa capacité volumique qui est doublée par rapport à cette du lithium. Cependant, l’obstacle le plus important au développement des batteries rechargeable au magnésium est la mauvaise compatibilité entre les électrolytes classiques et le magnésium métal. Dans cette optique il est encore nécessaire d’utiliser des mélanges de sel/solvant extrêmement dangereux dans les prototypes proposés. En revanche, la recherche de possible alternatives au magnésium métal, c.-à-d. des matériaux capable de réagir à bas potentiel avec le Mg, permettrait de réaliser une véritable batterie aux ions de magnésium (MIB), compatible avec des formulations d’électrolyte classiques.Cette thèse est dédiée à l’investigation des comportements électrochimiques de plusieurs éléments du bloc p (In, Sn, Sb, Bi) qui peuvent s’allier réversiblement avec le Mg à bas potentiel. Des possibles synergies entre ces éléments ont été aussi explorées (composite Sn-Bi, phases intermétalliques BixSb1-x et InBi) qui puissent être employés comme électrodes négatives pour MIBs. Des poudres micrométriques ont été obtenues par broyage/alliage mécanique, technique de synthèse simple à mettre en œuvre. Une attention particulière a été portée à l’étude des mécanismes électrochimiques d’alliage et/ou conversion avec la diffraction des rayons X en mode operando. L’évaluation des performances électrochimiques a permis de sélectionner le meilleur candidat pour être testé comme électrode négative dans un prototype de batterie magnésium-ion. / One of the most challenging hurdles that the World has to face in the next decades is the sustainable use of energy. In a scenario where western societies are largely dependent of the fossil fuels for maintaining their wellness, i.e. for heating, automotive transportation and electricity production, and developing countries need to feed their growing economies, it is worth underlying both the major impact on the environment due to the indiscriminate use of such combustibles but also the geopolitical issues for the non-producing countries. Energy harvesting by renewable sources can help limiting the dependence on fossil fuel exploitation but cannot perfectly replace conventional power plant due to its intrinsic intermittency.Batteries are the devices that can draw a line under this situation, since they can stock the energy surplus when the plant is operating and then can squeeze it in the power grid when there is a lack of production. Moreover, they are also targeted to fulfil the even growing demand of energy for portable applications (mobile phones and computers, and nowadays cars and trucks). The excellent performance and the well-established technology of Lithium-ion batteries (LIBs) put them in a crucial position for supporting this new energy revolution. However their ubiquitous role has been recently questioned for two main reasons: i) of the low availability of Li, which is a rare and not-uniformly spread element that may lead to the similar problems caused by fossil fuels. And ii) the effective capacity to satisfy the highly energy-demanding applications, since Li-ion technology seems reaching is upper limit in terms of overall performance. Therefore cheaper and more powerful alternative to Li-based systems are needed.Post-Lithium-based batteries, based on other charge carriers than Li+ can be offer safer, more sustainable and performing alternative to LIBs. Mg is a promising candidate that can replace Li in electrochemical systems due to its abundance, low cost and a theoretical volume capacity twice higher than that of Li. Although the efforts devoted to the realization of a rechargeable Mg battery were made in the last 15 years, the major hurdle represented by the low compatibility between metallic Mg and conventional electrolytes still obliges the use of hazardous salt/solvent mixtures in research prototypes. Searching alternative negative electrodes to the Mg metal, i.e. compounds able to reversibly react with Mg at low potential, will pave the way for a veritable Magnesium-ion battery (MIB), allowing the use of conventional electrolytes.The present thesis is devoted to investigate the electrochemical behaviour of several p-block elements that can reversibly alloy with Mg at low potential (In, Sn, Sb, Bi). Possible synergies between these elements are also explored, realizing composite materials (Sn-Bi), or intermetallic phases (BixSb1-x and InBi) that could be employed as negative electrodes in MIBs. The chosen synthetic route for obtaining micrometric-sized particles is the mechanical milling/alloying, since it is simple, cost-effective and upscalable. Particular attention is put on the study of electrochemical mechanisms through the operando X-ray diffraction. Electrochemical performance evaluation allows selecting the best candidate for an effective test as negative electrode in MIB prototype.

Submitted by Mery Piedad Zamudio Igami (mery@ipen.br) on 2017-03-10T15:20:01Z No. of bitstreams: 1 22060.pdf: 3959215 bytes, checksum: 0a58b276270c30e02d2f6935bafba229 (MD5) / Made available in DSpace on 2017-03-10T15:20:01Z (GMT). No. of bitstreams: 1 22060.pdf: 3959215 bytes, checksum: 0a58b276270c30e02d2f6935bafba229 (MD5) / Neste trabalho avaliou-se a ação positiva da substituição de lantânio por praseodímio e de lantânio por magnésio na performance eletroquímica de eletrodos de ligas de armazenamento de hidrogênio em estado bruto de fusão e com tratamento térmico. O La foi substituído por Mg nas ligas La0,7-xMgxPr0,3Al0,3Mn0,4Co0,5Ni3,8 (x=0,0-0,7) e por Pr nas ligas La0,7-yPryMg0,3Al0,3Mn0,4Co0,5Ni3,8 (y=0,0-0,7). Os parâmetros eletroquímicos analisados foram ativação, capacidade de descarga, retenção da capacidade de descarga, autodescarga e alta taxa de descarga. As ligas apresentaram comportamento passivo em relação à corrosão. As análises por MEV/EDS e por DRX com refinamento por Rietveld revelaram a presença majoritária de fases similares às fases LaNi5, PrNi5, LaMg2Ni9 e PrMg2Ni9 em função das composições das ligas estudadas. Os parâmetros de rede e os volumes da célula unitária das fases diminuíram com a substituição crescente de La por Mg e de La por Pr. As capacidades de descarga máxima decresceram com a substituição crescente de La por Mg e de La por Pr, acompanhando o decréscimo da abundância da fase similar à fase LaNi5 e o aumento da abundância da fase similar à fase LaMg2Ni9. Comparativamente, menores taxas de autodescarga e maior estabilidade cíclica foram observadas para o eletrodo da liga na condição x=0,1, ao passo que o eletrodo da liga na condição y=0,0 apresentou maiores valores de alta taxa de descarga, indicando melhor performance cinética. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

La pile à combustible Solid Oxide Fuel Cell (PAC-SOFC) est un système de production d’énergie « propre » qui permet de convertir de l’hydrogène en énergie électrique en ne rejetant que de l’eau. Une nouvelle configuration appelée « monochambre » semble être particulièrement attrayante compte tenu de ces nombreux avantages sur la configuration bi-chambre classique : simplification de fabrication, baisse de la température de fonctionnement, utilisation d’hydrocarbures comme combustible… La mise en place d’un tel système implique le développement de nouveaux matériaux d’électrodes satisfaisants à de nouveaux critères. L’évaluation en condition réaliste de 7 matériaux de cathode potentiels par diverses caractérisations structurale, texturale et catalytique à mis en évidence la difficulté de développer un matériau possédant toutes les caractéristiques requises. Ainsi, un matériau présentant le meilleur compromis est proposé. Une bibliothèque de 15 catalyseurs supportés (3 métaux et 5 supports différents) a ensuite été développée. Ces catalyseurs, ayant pour but d’être intégrés dans l’anode de la pile pour réaliser le reformage d’hydrocarbures, ont été évalués selon une approche combinatoire en condition réaliste (présence d’hydrocarbure, d’eau, de dioxyde de carbone), ce qui a permis de sélectionner les catalyseurs imprégnés de platine, plus robuste notamment en présence d’eau. Finalement, le couplage de la spectroscopie d’impédance avec la chromatographie en phase gaz a permis d’évaluer le comportement électrochimique d’une nouvelle architecture anodique comportant un catalyseur issu de la bibliothèque. Les tests ont montré que l’ajout d’un catalyseur est bénéfique pour la diminution des résistances de polarisation anodiques par production localisée d’hydrogène à partir d’hydrocarbure. / Solid Oxide Fuel Cell is a device for “clean” electricity production from chemical energy. The new configuration called “single-chamber” seems to be very attractive with several advantages over bi-chamber conventional configuration: easier manufacturing, lowering of working temperature, possible use of hydrocarbons as fuel… Such configuration involves the development of new electrode materials satisfying new requirements. The evaluation of 7 potential cathode materials through several characterizations has shown that a compromise has to be found since one material does not exhibit all the requested features. A library of 15 supported catalysts (3 metals and 5 supports) was developed. These catalysts, aimed at be located inside the anodic cermet, were evaluated through a combinatorial approach in realistic condition (presence of hydrocarbon, water, carbon dioxide). Platinum-based catalysts are found the most robust, especially in presence of water. Finally, innovative coupling of electrochemical impedance spectroscopy with gas chromatography measurements was carried out to characterise a new anodic architecture with an enclosed Pt-based catalyst previously evaluated. Tests revealed the beneficial effect of the catalyst insertion over anodic polarisation resistance by hydrogen production from hydrocarbon.

The Orbitrap is a mass analyzer that employs an electrostatic field to confine ions. The mass of an ion is determined from the frequency of its axial oscillations in the Orbitrap. The Orbitrap has high resolving power and accuracy. However, the electrodes of the Orbitrap have complicated curved shapes. As a consequence the Orbitrap is not easy to miniaturize. In this thesis we have proposed a class of easily machinable cylindrical-electrode structures to mimic the behavior of an Orbitrap. The proposed structure consists of a single cylinder and many coaxial equally spaced thick rings. A detailed numerical simulation of the cylindrical-electrode structure reveals that axial ion oscillations in it have many spurious frequency components in addition to the dominant frequency component. We have carried out a systematic shape optimization that adjusts the dimensions of the structure to minimize the amplitudes of the spurious frequency components of ion motion in the axial direction. The performance of the optimized structure was found to rival that of a practical Orbitrap.