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Yttrium-doped barium zirconate is a commonly used electrolyte material for Protonic Ceramic Fuel Cells (PCFC) due to its high protonic conductivity and high chemical stability. However, it is also known for its poor sinterability and poor grain boundary conductivity. In this work, in response to these issues, reactive magnetron sputtering was strategically chosen as the electrolyte deposition technique. This method allows the creation of a 4 µm tick electrolyte with a dense columnar microstructure. Notably, this technique is not widely utilized in PCFC fabrication. In this study, a complete cell is elaborated without exceeding a sintering temperature of 1350 °C. Tape casting is used for the anode, and spray coating is used for the cathode. The material of interest is yttrium-doped barium zirconate with the formula BaZr0.8Y0.2O3−δ (BZY). The anode consists of a NiO-BZY cermet, while the cathode is composed of BZY and Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSFC) in a 50:50 weight ratio. The electrochemical impedance spectroscopy analysis reveals a global polarization resistance of 0.3 Ω cm2, indicating highly efficient interfaces between electrolytes and electrodes.

New advanced fuel cell technologies are moving towards high-temperature proton conductors (HTPCs) to meet environmental issues. Their elaboration remains a challenge and micro-computed tomography (µCT) is an innovative way to control their quality. NiO-BZY anodic supports of a protonic ceramic electrochemical cell (PCEC), elaborated by co-tape casting and co-sintered at 1350 °C, were coated with a BZY20 electrolyte layer by DC magnetron sputtering. The µCT allowed to observe defects inside the volume of these PCEC half-cells and to show their evolution after an annealing treatment at 1000 °C and reduction under hydrogen. This technique consists in obtaining a 3D reconstruction of all the cross-sectional images of the whole sample, slice by slice. This allows seeing inside the sample at any desired depth. The resolution of 0.35 µm is perfectly adapted to this type of problem considering the thickness of the different layers of the sample and the size of the defects. Defects were detected, and their interpretation was possible thanks to the 3D view, such as the phenomenon of NiO grain enlargement explaining defects in the electrolyte, the effect of NiO reduction, and finally, some anomalies due to the shaping process. Ways to anticipate these defects were then proposed.

A complete cell consisting of NiO-Ce0.8Sm0.2O3−δ//Ce0.8Sm0.2O3−δ//(La0.6Sr0.4)0.95Co0.2Fe0.8O3−δ elaborated by a co-tape casting and co-sintering process and tested in operating fuel cell conditions exhibited a strong degradation in performance over time. Study of the cathode–electrolyte interface after cell testing showed, on one hand, the diffusion of lanthanum from (La0.6Sr0.4)0.95Co0.2Fe0.8O3−δ into Sm-doped ceria leading to a La- and Sm-doped ceria phase. On the other hand, Ce and Sm diffused into the perovskite phase of the cathode. The grain boundaries appear to be the preferred pathways of the cation diffusion. Furthermore, a strontium enrichment was clearly observed both in the (La0.6Sr0.4)0.95Co0.2Fe0.8O3−δ layer and at the interface with electrolyte. X-ray photoelectron spectroscopy (XPS) indicates that this Sr-rich phase corresponded to SrCO3. These different phenomena led to a chemical degradation of materials and interfaces, explaining the decrease in electrochemical performance.