Ce travail de thèse s'inscrit dans le cadre du développement des piles à combustible à céramique conductrice protonique (PCFC) anode support, opérant dans le domaine de température 400 – 600 °C. Une attention particulière a été portée sur la diminution des températures d'élaboration des composants constituants les piles. Les stratégies mises en œuvre pour l'élaboration des anodes et des couches minces électrolytiques à basse température ont été la nano-structuration et l'ajout d'additifs aidant au frittage. La réalisation de couche mince électrolytique a fait l'objet d‘un développement par pulvérisation de suspensions. Le choix des matériaux et leur optimisation ont permis de minimiser les résistances spécifiques surfaciques (ASR). Les tests en pile de cellules élémentaires PCFC ont montré des résultats prometteurs concurrentiels aux autres types de pile à combustible de l'ordre de 400mW/cm². / The aim of present work was to develop PCFC materials and fuel cells working in 400-600°C. The work deals with the optimization of materials and elaboration processes with the aim of decreasing the sintering temperature. In order to achieve high performances, nanostructured and architecture electrodes and optimized electrolytes have been investigated. Efficient anode support PCFCs were fabricated using wet powder spraying whiten simply method easily suitable on order to scaling-up. The maximum power densities obtained in this work are among, one of the best reported for PCFC

Conventional oxygen anion conducting yttria-stabilized zirconia (YSZ) based solid oxide fuel cells (SOFCs) operate at high temperatures (800oC-1000oC). SOFCs based on proton conducting ceramics, however, can operate at intermediate temperatures (450oC-750oC) due to low activation energy for protonic defect transport when compared to oxygen vacancy transport. Fuel cells that operate at intermediate temperatures ease the critical materials requirements of cell components and reduce system costs, which is necessary for large scale commercialization. BaCeO3-based perovskite materials are candidates for use as ion conductors in intermediate temperature SOFCs (IT-SOFCs) when doped with trivalent cations in the B-site. B-site doping forms oxygen vacancies which greatly increases the electrical conductivity of the material. The oxygen vacancies are consumed during the creation of protonic defects or electronic defects, depending on the atmosphere and temperature range. High performance IT-SOFCs based on the Y3+ and Yb3+ doped BaCeO3-based system, BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb) have been recently reported. High conductivity in O2/H2O atmosphere was reported, however, a more basic understanding of the BZCYYb structure, electrical conductivity, and the portion of the charge carried by each charge carrier under fuel cell conditions is lacking. In this work, the BZCYYb material is fabricated by the solid state reaction method and the crystal structure at intermediate temperatures is studied using HT-XRD. The total conductivity of BZCYYb in H2/H2O, O2/H2O, and air atmospheres in the IT-SOFC temperature range is reported. The activation energy for transport at these conditions is determined from the conductivity data and the transference numbers of protonic defects, oxygen anion defects and electronic defects in the BZCYYb material are determined by the concentration cell - OCV method. BZCYYb is a mixed proton, oxygen anion, and electronic conductor at IT-SOFC temperature ranges (450oC - 750oC), in H2, O2, and H2O containing atmospheres. Ni-BZCYYb/BZCYYb/BZCYYb-LSCF fuel cells were constructed and peak power densities of ~1.2 W/cm2 were reported at 750oC after optimization of the Ni-BZCYYb anode porosity. Decreasing the Ni-BZCYYb anode porosity did not significantly affect the electrical conductivity of the anode, however the peak power densities of the IT-SOFCs based on the anode with less porosity, calculated from I-V curve data, showed dramatic improvement. The fuel cell with the lowest anode porosity demonstrated the highest performance. This finding is in stark contrast to the optimal anode porosity needed for high performance in YSZ-based, oxygen anion conducting SOFCs. Because of significant proton conduction in the BZCYYb material, fuel cell reaction products (water) form at the cathode side and less porosity is required on the anode side. The improvement in performance in the BZCYYb based IT-SOFC is attributed to the unique microstructure formed in the Ni-BZCYYb anode when no pore forming additives are used which may contribute to high electrocatalytic behavior for anode reactions. This work provides a basic understanding of the electrical properties of BZCYYb and clarifies the feasibility of using BZCYYb in each component of the IT-SOFC system as well as in other electrochemical devices. The high performance of the Ni-BZCYYb/BZCYYb/BZCYYb-LSCF IT-SOFC, due to low anode porosity, provides a new understanding for the rational development of high performance IT-SOFCs based on electrolytes with significant protonic conduction.