The purpose of this thesis was to carry out the experimental study of direct ammonia fuel cells. The use of hydrogen in fuel cells poses a lot of problems. There is a lot of safety, technical and economic issues to be overcome to make its use as a fuel widespread. Ammonia is being considered as a very promising source of hydrogen for fuel cells. However, until now its use in fuel cells has received very little attention. Ammonia presents many advantages over hydrogen and other potential sources of hydrogen such as an easy storage and a world-wide distribution network. Ammonia is a suitable hydrogen carrier and can be easily cracked at high temperatures such as those used in solid oxide fuel cells. The present study was conducting using ammonia as fuel and argon as carrier gas in different solid oxide fuel cell systems: an annular design, a planar design and a micro laminated reactor. The electrolyte materials were calcia stabilized zirconia and yttria stabilized zirconia. As far as the electrodes are concerned, silver, platinum and nickel cermet were used as anode/materials and silver was employed as cathode material. The cell yoltage was measured as function of reactor configuration, space time, ammonia flow rate and ammonia concentration. The results demonstrate the high potential of ammonia over hydrogen when nickel is used as anode material. Solid proton conducting fuel cells operating on ammonia fuel were also studied. The electrolyte materials were fabricated from neodymium and gadolinium doped barium and strontium cerates. The dopant fraction ranged from 1 to 20 wt%. Silver was employed as cathode and anode material and was spray deposited. The application of proton conducting electrolytes results in higher current densities for a given voltage than the using typical oxide ion conductors such as 8mol % yttria stabilized zirconia. The potential of the proton conducting materials for application in ammonia synthesis at atmospheric pressure was also studied. They demonstrated promising results and could prove to be an alternative to the common ammonia synthesis processes.

Dans ce travail, différentes solutions aqueuses de PEDOT: polyelectrolyte ont été synthétisées à partir de polymères anioniques de types polysaccharides et polystyrènes substitués par des groupements bis(sulfonylimide). Leurs morphologies, dopages,comportements rhéologiques ainsi que leurs propriétés opto-électroniques ont notammen tété caractérisés. Une étude systématique a révélé que les polyélectrolytes de masse molaire élevée portant un groupement fortement acide et ayant un squelette rigide permettent d'obtenir un dopage élevé, une dispersion efficace du PEDOT et donc des complexes PEDOT : polyelectrolyte plus conducteurs. L'utilisation du polyelectrolyte PSTFSI en tant qu'agent de complexation pour le PEDOT donne une dispersion stable montrant les caractéristiques d'un gel, ce qui facilite la fabrication de films minces par 'spin coating' ou doctor blade. Les films de PEDOT : PSTFSI ainsi obtenus montrent une transparence élevée et une conductivité de 330S.cm-1. Ces propriétés ont permis de les intégrer avec succès comme matériaux d'électrodes dans des dispositifs OLED, OPV et OECT. / In this work different aqueous dispersions of conducting poly(3,4-ethylenedioxythiophene) :polyelectrolyte (PEDOT:polyelectrolyte) complexes,made from anionic polysaccharides and from synthetic bis(sulfonylimide) substituted polystyrenes, have been synthesized and characterized regarding their doping, morphology, rheological behavior and opto-electronic properties. A systematic study revealed, that high molar mass polyelectrolytes with strongly acidic groups and a rigid backbone structure were favorable for a high doping and an efficient dispersion of PEDOT and allowed the development of highly conducting PEDOT:polyelectrolyte complexes. The use of the polyelectrolyte poly(4-styrenetrifluoromethane(bissulfonylimide)) (PSTFSI) as complexing agent for PEDOT resultedin stable dispersions with gel character, which allowed easy processing by spin coating and doctor blading. The obtained PEDOT:PSTFSI films were highly transparent,displayed a conductivity of up to 330S.cm-1 and were successfully integrated as electrodes in OLED, OPV and OECT devices.

This study investigated the relationship between selected measures of self concept as perceived by a group of choral conductors, their eye dependency on score, and the measures of expressive voice. The problems were (1) to determine the degree of perceived self concept of a selected group of choral music teachers through measures of (a) total self, (b) physical self, (c) moral-ethical self, (d) personal self, (e) family self, and (f) social self? (2) to assess eye dependency on score of the same teachers; (3) to assess the aspect of expressive voice through measures of (a) pitch levels of modulation, (b) speech flow, and (c) voice energy level; and (4) to examine the relationship between the measures of self concept, eye dependency on score and expressive voice.

The role of the choir leader is a complex one. When working with a choir, choir leaders often use several aspects of their professional role. The aim of this qualitative study is to describe, verbalise and make visible the mediating tools that choir directors working with children and youth choirs use. In a longitude study, four choir leaders were observed closely while working with their choirs. They also took part in semi-structured interviews. The empirical data material consists of observation notes, reflective writing, individualinterviews, focus conversations and videotapes. Analysed from a sociocultural perspective, the result points to eight groups of mediating tools: a) a listening attitude towards the choir, with the music in focus; b) a variation in ways of working with the choir, where a variety of physical tools are used; c) the use of musical routines; d) the choir director acting as a role model in shaping musicalexpression with the group; e) a concentrated cooperation with the choir through short and expressive instructions; f) reflection in practice by planning and self-evaluation; g) storytelling, which results in memory training, stimulation of the imagination and the sharing of common experience, and h) the use of target images expressed as visions, small/big goals or jointly stated, communicated targets. The choir directors who participated in the study use a variety of approaches and ways of working as a strategy for communicating and working with child and youth choirs.

Supercapacitors have emerged in recent years as a promising energy storage technology. The main mechanism of energy storage is based on electrostatic separation of charges in a region at the electrode-electrolyte interface called double layer. Various electrode materials including carbon and conducting polymers have been used in supercapacitors. Also, supercapacitors offer high life cycle and high power density among electrochemical energy storage devices. Despite their interesting features, supercapacitors present some disadvantages that limit their competitivity with other storage devices in some applications. One of those drawbacks is high self-discharge or leakage. The leakage occurs when electrons cross the double layer to be involved in electrochemical reactions in the supercapacitor’s electrolyte. In this work, the first research project demonstrates that the addition of a very thin blocking layer to a supercapacitor electrode, can improve the energy storage capability of the device by reducing the leakage. However, the downside of adding a blocking layer is the reduction of the capacitance. A second project developed a mathematical model to study how the thickness of the blocking layer affects the capacitance and the energy density. The model combines electrochemical and quantum mechanical effects on the electrons transfer responsible of the leakage. Based on the model, a computational code is developed to simulate and study the self-discharge and the energy loss in hypothetical devices with different thicknesses of the blocking layer. The third research project identified the optimal amount of a surfactant (Triton-X 100) that had a significant effect on the double layer capacitance and conductivity of a spin-coated PEDOT:PSS (poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate)) electrode. The effect of the concentration of the surfactant was investigated by measuring the electrochemical properties and the conductivity of different electrodes. The electrodes were fabricated with different concentrations of the surfactant. Scanning electron microscopy characterizations confirmed the structural change in the PEDOT:PSS that contributed to the capacitance and conductivity enhancement. A final research project proposed an approach on how to utilize the modified PEDOT:PSS added to different photoactive dyes to design a photoactive supercapacitor. The new approach showed the possibility of using a supercapacitor device as an energy harvesting as well as a storage device.

De nombreux dispositifs pour l’électronique organique et la bioélectronique reposent sur le transport mixte (électronique et ionique).Le transport électronique dans les matériaux organique est relativement bien compris, mais une compréhension fondamentale du transport des ions est manquante. J'ai développé un modèle analytique qui décrit le transport d'ions dans une jonction planaire entre un électrolyte et un film de polymère conducteur.Le modèle permet des prédictions de l'évolution temporelle du courant et du drift length des ions.Ces prédictions sont validées par des simulations numériques et en utilisant des paramètres réalistes, je montre que le modèle analytique peut être utilisé pour obtenir la mobilité des ions dans le film. De plus, j'ai développé une méthode expérimentale qui permet l'application du modèle analytique et conduit à une estimation de la mobilité des ions dans les polymères conducteurs. Le PEDOT:PSS offre un transport efficace pour les ions, qui peut être mis en relation avec le gonflement important du film dans l'eau. Je montre que la réticulation du film diminue son gonflement ainsi que la mobilité des ions. Comprendre la forte corrélation entre l'hydratation et la conductivité ionique nous permet de développer des matériaux à mobilité ionique définie et importante. A titre d'exemple, le réglage de la mobilité ionique du PEDOT:TOS est présenté en ajustant le rapport relatif de la phase hygroscopique. Pour finir, j'ai effectué des mesures de spectroscopie d'impédance électrochimique au cours d'une expérience de moving front, afin de proposer une interprétation physique des spectres d'impédance mesurés à une jonction polymère conducteur/électrolyte / Many organic electronic and bioelectronics devices rely on mixed (electronic and ionic) transport within a single organic layer. Although electronic transport in these materials is relatively well understood, a fundamental understanding of ion transport is missing. I developed a simple analytical model that describes ion transport in a planar junction between an electrolyte and a conducting polymer film. The model leads to predictions of the temporal evolution of drift length of ions and current. These predictions are validated by numerical simulations and by using realistic parameters, I show that the analytical model can be used to obtain the ion mobility in the film. Furthermore, I developed an experimental method which allows the application of the analytical model and leads to a straightforward estimation of the ion drift mobilities in conducting polymers. PEDOT:PSS was found to support efficient transport of common ions, consistent with extensive swelling of the film in water. Crosslinking the film decreased its swelling and the ion mobility. Understanding the high correlation of hydration and ionic conductivity enables us to engineer materials with high and defined ion mobilities. As an example tuning of ion mobility by adjusting the relative ratio of the hydroscopic phase to PEDOT:TOS is presented. Finally I performed electrochemical impedance spectroscopy during a moving front experiment, in order to give a physical interpretation of the impedance spectra at a conducting polymer/electrolyte junction.

Lors de ce travail de thèse nous nous sommes intéressés à deux thèmes principaux dans le but de fabriquer des matériaux conducteurs chiraux : la synthèse de TTF-hélicènes présentant une chiralité hélicoïdale moléculaire, ainsi que l’obtention de molécules de symétrie 3 à base de TTF ayant la capacité à former des auto-assemblages supramoléculaires hélicoïdaux. Dans la partie TTF-hélicène, plusieurs tailles d’hélicènes ont été envisagées avec pour objectif d’obtenir des énantiomères stables et séparables. Ils ont été caractérisés par diffraction de rayons X, de même que les sels obtenus par électrocristallisation. De plus, une étude théorique de la réaction de photocyclisation des stilbènes en hélicènes a été menée pour comprendre sa régiosélectivité. Les molécules de symétrie 3 sont composées d’un coeur BTA-DABP sur lequel sont fixés des TTF avec leurs substituants chiraux. L’assemblage colonnaire des molécules est étudié par CD et les fibres formées sont observées par microscopie ce qui permet de déterminer leur hélicité. On varie le cœur ainsi que les groupements fixés dessus. / In this work, we have been interested in two different topics to make chiral conducting materials: the synthesis of TTF-helicenes, with molecular helical chirality, as well as the formation of three-fold symmetry molecules based on TTF units able to self-assemble into supramolecular helical aggregates. For the TTF-helicenes, several lengths of helicenes are considered in order to form stable and separable enantiomers. They are characterized by X-ray diffraction just as the salts that are obtained by electrocrystallization. Moreover, a theoretical study of the photocyclisation reaction of stilbenes into helicenes was performed to understand its regioselectivity. The three-fold symmetry molecules are composed of a BTA-DABP core on which TTF with chiral substituents are fixed. The assembly into columnar aggregates is followed by CD and the fibers formed are observed by microscopy in order to determine their helicity. Variation of the core and the substituents are made.

Philosophiae Doctor - PhD / Supercapacitors are charge-storage devices. Compared to batteries, they have higher power density, more excellent reversibility and longer cycle life. Therefore, supercapacitors have played an increasingly important role in the fields of power source especially in automotive applications, such as electric and hybrid electric vehicles. The higher power density of supercapacitors offers improved vehicle acceleration and the ability to recover more energy from regenerative breaking, since they can be charged and discharged at high current. Generally, the key for supercapacitors to achieve high specific power depends on the inherent properties and the surface areas of their electrode materials. Therefore, current research in the field of supercapacitors has been carried out with increased emphasis on the development of new electrode materials. Optimal novel synthesis of electrode materials for supercapacitor application in hybrid vehicles was accomplished with polypyrrole nanowires, manganese oxide and its carbon composites, ruthenium oxide and its carbon composites being the products. A set of structural and chemical parameters influencing the performance of synthesized electrode materials were identified. Parameters included crystallinity, particle size, particle size distribution, surface area, electrochemical activity. A large range of analytical tools were employed in characterizing the electrode materials of interest. High accuracy and precision in the quantitative and qualitative structural characterization of electrode materials collected by x-ray diffractometry, transmission electron microscopy, scanning electron microscopy and Fourier transform infra-red spectroscopy was demonstrated. N₂-physisorption produced surface area and pore size distribution data of high quality. Cyclic voltammetry, charge and discharge cycling, electron impedance spectroscopy were employed in the electrochemical characterization of the synthesized electrode materials and both qualitative and quantitative information obtained. The techniques were able to discriminate between various synthesized electrode materials and identify the highly electroactive materials. Preparation variables could be critically evaluated for the synthesis of electrode materials. The techniques were deemed to be applicable in discriminating high and low activity electrode materials based on their structural and chemical properties.

La bioélectronique est un domaine émergent qui vise à combiner les mondes de la biologie et de l'électronique. Les matériaux organiques présentent un ensemble de caractéristiques uniques qui les rendent candidats idéaux pour répondre aux contraintes spécifiques de ce domaine. Leur flexibilité leur donne une meilleure stabilité mécanique, tandis que leur nature de conducteurs ioniques et électroniques leur permet d’interférer parfaitement entre un tissu vivant et un dispositif électronique. En outre, ils présentent des interfaces non oxydées pour des interactions biologiques plus efficaces. Il est également possible de modifier chimiquement ces matériaux afin de les fonctionnaliser. Ces idées, ainsi que les différentes approches de fabrication des dispositifs organiques sont présentées au chapitre 1.L’électrode est le principal outil expérimental pour l’électrophysiologie in vitro. Les principes physiques du fonctionnement de l’électrode sont donc tout d’abord présentés au chapitre 2. Dans les chapitres 3 et 4, les connaissances acquises à partir de la modélisation de l’électrode sont mises en applications sur des mesures biologiques réelles. Le chapitre 3 présente des enregistrements d'activité de cellules hippocampiques de culture et le chapitre 4 de cellules pancréatiques.Le chapitre 5 introduit un autre dispositif, le transistor électrochimique organique (OECT) et présent une carte électronique de conversion qui pourrait faciliter l’usage d’OECT dans futures applications d’électrophysiologie. Le chapitre 6 clôture cette thèse en décrivant des mesures effectuées sur des astrocytes à l’aide d’OECT. / Bioelectronics is an emerging field that is aiming to combine the worlds of biology and electronics. Among all the other materials, organics present a unique set of features that renders them ideal candidates for this new field. Their soft nature gives better mechanical stability, while the fact that they can conduct both electrically and ionically makes them ideal candidates to bridge the gap between electronic devices and living tissue. In addition they provide oxide free interfaces that could interact more efficiently with biology and allow chemically modification that increase biological functionality. These ideas, together with the organic devices fabrication approaches are presented in Chapter 1.Electrodes are the main experimental tool for electrophysiology and this is why Chapter 2 presents the main physics principle behind them. Chapters 3 and 4 implement the knowledge obtained from the electrode modeling to real biological measurements. Chapter 3 presents activity recordings from Hippocampal cell cultures and Chapter 4 form pancreatic cells. Chapter 5 introduces us to a different device as it presents the Organic electrochemical transistor (OECT) and presents a read out circuit board that could facilitate OECT electrophysiological recordings. Chapter 6 closes this thesis with an application of OECT on astrocyte recordings.

No description available.