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In this thesis, the focus is on studying BaZrO3-BaCeO3 based proton conductors due to that they represent very promising proton conductors to be used for Intermediate Temperature Solid Oxide Fuel Cells (ITSOFCs). Here, dense BaZr0.5Ce0.3Y0.2O3-δ (BZCY532) ceramics were selected as the major studied materials. These ceramics were prepared by different sintering methods and doping strategies. Based on achieved results, the thesis work can simply be divided into the following parts: 1) An improved synthesis method, which included a water-based milling procedure followed by a freeze-drying post-processing, was presented. A lowered calcination and sintering temperature for a Hf0.7Y0.3O2-δ (YSH) compound was achieved. The value of the relative density in this work was higher than previously reported data. It is also concluded that this improved method can be used for mass-production of ceramics. 2) As the solid-state reactive sintering (SSRS) represent a cost-effective sintering method, the sintering behaviors of proton conductors BaZrxCe0.8-xLn0.2O3-δ (x = 0.8, 0.5, 0.1; Ln = Y, Sm, Gd, Dy) during the SSRS process were investigated. According to the obtained results, it was found that the sintering temperature will decrease, when the Ce content increases from 0 (BZCLn802) to 0.3 (BZCLn532) and 0.7 (BZCLn172). Moreover, the radii of the dopant ions similar to the radii of Zr4+ or Ce4+ ions show a better sinterability. This means that it is possible to obtain dense ceramics at a lower temperature. Moreover, the conductivities of dense BZCLn532 ceramics were determined. The conductivity data indicate that dense BZCY532 ceramics are good candidates as either oxygen ion conductors or proton conductors used for ITSOFCs. 3) The effect of NiO on the sintering behaviors, morphologies and conductivities of BZCY532 based electrolytes were systematically investigated. According to the achieved results, it can be concluded that the dense BZCY532B ceramics (NiO was added during ball-milling before a powder mixture calcination) show an enhanced oxygen and proton conductivity. Also, that BZCY532A (NiO was added after a powder mixture calcination) and BZCY532N (No NiO was added in the whole preparation procedures) showed lower values. In addition, dense BZCY532B and BZCY532N ceramics showed only small electronic conductivities, when the testing temperature was lower than 800 ℃. However, the BZCY532A ceramics revealed an obvious electronic conduction, when they were tested in the range of 600 ℃ to 800 ℃. Therefore, it is preferable to add the NiO powder during the BZCY532 powder preparation, which can lower the sintering temperature and also increase the conductivity. 4) Dense BZCY532 ceramics were successfully prepared by using the Spark Plasma Sintering (SPS) method at a temperature of 1350 ℃ with a holding time of 5 min. It was found that a lower sintering temperature (&lt; 1400 ℃) and a very fast cooling rate (&gt; 200 ℃/min) are two key parameters to prepare dense BZCY532 ceramics. These results confirm that the SPS technique represents a feasible and cost-effective sintering method to prepare dense Ce-containing BaZrO3-BaCeO3 based proton conductors. 5) Finally, a preliminary study for preparation of Ce0.8Sm0.2O2-δ (SDC) and BZCY532 basedcomposite electrolytes was carried out. The novel SDC-BZCY532 based composite electrolytes were prepared by using the powder mixing and co-sintering method. The sintering behaviors, morphologies and ionic conductivities of the composite electrolytes were investigated. The obtained results show that the composite electrolyte with a composition of 60SDC-40BZCY532 has the highest conductivity. In contrast, the composite electrolyte with a composition of 40SDC-60BZCY532 shows the lowest conductivity. In summary, the results show that BaZrO3-BaCeO3 based proton-conducting ceramic materials represent very promising materials for future ITSOFCs electrolyte applications. / <p>QC 20150423</p>

Ce travail de thèse est consacré à l’étude des nickelates La2-xPrxNiO4+δ, comme nouveaux matériauxde cathodes pour piles à combustible haute température, SOFC, et en particulier à la caractérisationde leur stabilité chimique et leur comportement en fonctionnement. En effet, du fait de leurpropriété de conduction mixte ionique et électronique, MIEC, les nickelates de structure typeK2NiF4, Ln2NiO4+δ (Ln = La, Pr, Nd), correspondant au terme n = 1 de la série de Ruddlesden-Popper (An+1MnO(3n+1)), sont des matériaux prometteurs pour des fonctionnements à températureintermédiaire, IT-SOFC (T < 800 °C). Compromis entre la stabilité chimique de La2NiO4+δ et lestrès bonnes performances électrochimiques de Pr2NiO4+δ, les phases La2-xPrxNiO4+δ, ont étésynthétisées et leurs propriétés physico-chimiques, de transport et électrochimiques ont étédéterminées. L’étude approfondie des caractéristiques des électrodes par spectroscopied’impédance en cellules symétriques a été réalisée à courant nul et sous polarisation anodique etcathodique sur des périodes d’un mois. De façon surprenante, même après la dissociation complètede Pr2NiO4+δ en PrNiO3-δ, Pr4Ni3O10+δ et Pr6O11, la résistance de polarisation ne montre pas dechangement significatif. L’étude de PrNiO3-δ et Pr4Ni3O10+δ, comme matériau de cathode pour pilesà combustible, démontre l’excellent comportement de la phase Pr4Ni3O10+δ et ceci en cellulesymétrique (Rp (Pr4Ni3O10+δ) = Rp (Pr2NiO4+δ) = 0.15 Ω.cm² à 600 ° C) et cellule complète (1.6W.cm-2 at 800 °C). / This PhD work is dedicated to stability and ageing studies of Praseodymium based nickelates ascathodes for Solid Oxide Fuel Cells (SOFCs). With this respect Ln2NiO4+δ (Ln=La, Pr or Nd)compounds with the K2NiF4 type structure act as alternative cathode materials for IT-SOFC due totheir mixed ionic and electronic conductivity (i.e. MIEC properties). Pr2NiO4+δ shows excellentelectrochemical properties at intermediate temperature (i.e. low polarization resistance Rp value, Rp= 0.03 Ω.cm² at 700 °C), while La2NiO4+δ exhibits higher chemical stability. So, the properties ofLa2-xPrxNiO4+δ nickelates were investigated with the aim to find best compromise between chemicalstability and electrochemical performances. After synthesis, the physical and chemical properties aswell as their transport and electrochemical properties have been determined. Measurements of thepolarization resistance of symmetrical half-cells have been carried out by impedance spectroscopy.Then, the chemical stability and the electrochemical performance of the materials have been studiedfor duration up to one month. As an interesting point, even after complete dissociation of Pr2NiO4+δinto PrNiO3-δ,Pr4Ni3O10+δ and Pr6O11, the polarization resistance does not show significant change.So finally, two new materials PrNiO3-δ and Pr4Ni3O10+δ were investigated as SOFCs cathodeshowing very promising results for Pr4Ni3O10+δ in symmetrical cell (Rp (Pr4Ni3O10+δ) = Rp(Pr2NiO4+δ) = 0.15 Ω.cm² à 600 ° C) and complete cell (1.6 W.cm-2 at 800 °C).

This study mainly explores the development of alternative cathode materials for the electrochemical reduction of CO₂ by high temperature solid oxide electrolysis cells (HTSOECs), which operate in the reverse manner of solid oxide fuel cells (SOFCs). The conventional Ni-yttria stabilized zirconia (YSZ) cermets cathode suffered from coke formation, whereas the perovskite-type (La, Sr)(Cr, Mn)O₃ (LSCM) oxide material displayed excellent carbon resistance. Initial CO₂ electrolysis performance tests from different cathode materials prepared by screen-printing showed that LSCM based cathode performed poorer than Ni-YSZ cermets, due to non-optimized microstructure. Efforts were made on microstructure modification of LSCM based cathodes by means of various fabrication methods. Among the LSCM/YSZ graded cathode, extra catalyst (including Pd, Ni, CeO₂, and Pt) aided LSCM/GDC (Gd₀.₁Ce₀.₉O₁.₉₅) cathode, LSCM impregnated YSZ cathode, and GDC impregnated LSCM cathode, the GDC impregnated LSCM cathode, with porous LSCM as backbone for finely dispersed GDC nanoparticles, was found to possess the desired microstructure for CO₂ splitting reaction via SOEC. Incorporating of 0.5wt% Pd into GDC impregnated LSCM cathode gave rise to an Rp of 0.24 Ω cm² at open circuit voltage (OCV) at 900°C in CO₂-CO 70-30 mixture, comparable with the Ni/YSZ cermet cathode operated in the identical conditions. Meanwhile, the cathode kinetics and possible mechanisms of the electrochemical reduction of CO₂ were studied, and factors including CO₂/CO composition, operation temperature and potential were taken into account. The current-to-chemical efficiency of CO₂ electrolysis was evaluated with gas chromatography (GC). The high performance Pd and GDC co-impregnated LSCM cathode was also applied for CO₂ electrolysis without protective CO gas in feed. This cathode also displayed superb performance towards CO₂ electrochemical reduction under SOEC operation condition in CO₂/N₂ mixtures, though it had OCV as low as 0.12V at 900°C. The LSCM/GDC set of SOEC cathode materials were investigated in the application of steam electrolysis and H₂O-CO₂ co-electrolysis as well. For the former, adequate supply of steam was essential to avoid the appearance of S-shaped I-V curves and limited steam transport. The 0.5wt% Pd and GDC co-infiltrated LSCM material has been found to be a versatile cathode with high performance and good durability in SOEC operations.

Cette étude est consacrée au développement d’une pile à combustible à oxyde solide (SOFC) de type monochambre. Contrairement à une pile SOFC conventionnelle, le système monochambre fonctionne dans un mélange de gaz hydrocarbure/air ce qui permet de s’affranchir des contraintes d’étanchéités. Le principe de fonctionnement est basé sur la différence d’activité catalytique entre l’anode et la cathode : l’anode doit être sélective à l’oxydation des hydrocarbures et la cathode à la réduction de l’oxygène. La configuration monochambre implique cependant de nouvelles contraintes concernant notamment la stabilité des matériaux sous mélange hydrocarbure/air à haute température.L’objectif de cette thèse est d’optimiser les performances d’une pile monochambre fonctionnant sous mélange méthane/oxygène et d’améliorer la compréhension de ce système.Les différents éléments d’une pile (électrolyte, cathode, anode) ont été caractérisés sous mélange méthane/oxygène. Quatre matériaux de cathodes (LSM, BSCF, SSC, LSCF) ont été comparés au niveau de leur activité catalytique, stabilité, conductivité électrique et résistance de polarisation. Une étude catalytique de l’anode a été réalisée afin d’identifier les réactions chimiques qui se produisent. Une étude de pile complète en géométrie électrolyte support a permis de sélectionner le matériau de cathode LSCF. Cette étude a également mis en évidence la nécessité de diminuer l’épaisseur de l’électrolyte, la géométrie anode support a donc été étudiée. La première pile anode support a présentée une anode inhomogène et un électrolyte poreux. Des travaux ont été menés afin d’homogénéiser l’anode et de diminuer la porosité de l’électrolyte. En optimisant les conditions de fonctionnement (température et rapport CH4/O2), une densité de puissance maximale de 160 mW.cm-2 a été obtenue. / This study is devoted to the development of a single-chamber solid oxide fuel cell. Contrary to a conventional solid oxide fuel cell, a single chamber fuel cell works under a hydrocarbon/air mixture with no more sealing needed. The working principle of this device is based on the difference of catalytic activity between the anode and the cathode: the anode must be selective to hydrocarbon oxidation and the cathode to oxygen reduction. With single-chamber geometry, chemical stability of materials has to be taken into account under hydrocarbon/air mixture at high temperature.The goal of this work is to optimize the performances of a single-chamber cell working under methane/oxygen mixture and to improve this device comprehension.Each part of the cell (electrolyte, anode, cathode) was characterized under methane/oxygen mixture. Four cathode materials (LSM, BSCF, SSC, LSCF) were compared regarding their catalytic activity, stability, electrical conductivity and polarization resistance. The catalytic activity of the anode was studied in order to identify the chemical reactions happening. A study of electrolyte supported cells showed that LSCF material is the most suitable cathode. Furthermore, this study showed that the electrolyte was too thick; the anode supported configuration was studied. The first anode supported cell showed an inhomogeneous anode and a porous electrolyte. From that, a study of the homogeneity of the anode and the densification of the electrolyte was performed. A maximum power density of 160mW.cm-2 was obtained by optimizing the working conditions of the cells (temperature and CH4/O2 ratio).