Solid oxide fuel cells (SOFCs) can be fueled with various gases, including carbon-containing compounds. High operating temperatures, exceeding 600 °C, and the presence of a porous, nickel-based SOFC anode, might lead to the formation of solid carbon particles from fuels such as carbon monoxide and other gases with hydrocarbon-based compounds. Carbon deposition on fuel electrode surfaces can cause irreversible damage to the cell, eventually destroying the electrode. Soot formation mechanisms are strictly related to electrochemical, kinetic, and thermodynamic conditions. In the current study, the effects of carbon deposition on the lifetime and performance of SOFCs were analyzed in-operando, both in single-cell and stack conditions. It was observed that anodic gas velocity has an impact on soot formation and deposition, thus it was also studied in depth. Single-anode-supported solid oxide fuel cells were fueled with gases delivered in such a way that the initial velocities in the anodic compartment ranged from 0.1 to 0.7 m/s. Both cell operation and post-mortem observations proved that the carbon deposition process accelerates at higher anodic gas velocity. Furthermore, single-cell results were verified in an SOFC stack operated in carbon-deposition regime by dry-coupling with a downdraft 150 kWth biomass gasifier.

Manganese-substituted 5 mol.% yttria-stabilized zirconia (5YSZ) was explored as a prospective material for protective interlayers between electrolyte and oxygen electrodes in reversible solid oxide fuel/electrolysis cells. [(ZrO₂)_0.95(Y₂O₃)_0.05]_1−x[MnO_y]_x (x = 0.05, 0.10 and 0.15) ceramics with cubic fluorite structure were sintered in air at 1600 °C. The characterization included X-ray diffraction (XRD), scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), thermogravimetry and dilatometry in controlled atmospheres, electrical conductivity measurements, and determination of oxygen-ion transference numbers by the electromotive force (EMF) technique. Mn-substituted 5YSZ solid solutions exhibit variable oxygen nonstoichiometry with manganese cations in a mixed 2+/3+ oxidation state under oxidizing conditions. Substitution by manganese gradually increases the extent of oxygen content variation on thermal/redox cycling, chemical contribution to thermal expansion and dimensional changes on reduction. It also deteriorates oxygen-ionic conductivity and improves p-type electronic conductivity under oxidizing conditions, leading to a gradual transformation from predominantly ionic to prevailing electronic transport with increasing x. Mn^2+/3+→Mn²⁺ transformation under reducing atmospheres is accompanied by the suppression of electronic transport and an increase in ionic conductivity. All Mn-substituted 5YSZ ceramics are solid electrolytes under reducing conditions. Prolonged treatments in reducing atmospheres, however, promote microstructural changes at the surface of bulk ceramics and Mn exsolution. Mn-substituted 5YSZ with 0.05 ≤ x < 0.10 is considered the most suitable for the interlayer application, due to the best combination of relevant factors, including oxygen content variations, levels of ionic/electronic conductivity and thermochemical expansion.

Ceramics samples with the nominal composition [(ZrO₂)_0.95(Y₂O₃)_0.05]_1-x[PrO_y]_x and praseodymia contents of x = 0.05–0.15 were prepared by the direct firing of compacted 5YSZ + PrO_y mixtures at 1450–1550 °C for 1–9 h and characterized for prospective applicability in reversible solid oxide cells. XRD and SEM/EDS analysis revealed that the dissolution of praseodymium oxide in 5YSZ occurs via the formation of pyrochlore-type Pr₂Zr₂O₇ intermediate. Increasing PrO_y additions results in a larger fraction of low-conducting pyrochlore phase and larger porosity, which limit the total electrical conductivity to 2.0–4.6 S/m at 900 °C and 0.28–0.68 S/m at 700 °C in air. A longer time and higher temperature of firing promotes the phase and microstructural homogenization of the ceramics but with comparatively low effect on density and conductivity. High-temperature processing leads to the prevailing 3+ oxidation state of praseodymium cations in fluorite and pyrochlore structures. The fraction of Pr⁴⁺ at 600–1000 °C in air is ≤2% and is nearly independent of temperature. 5YSZ ceramics with praseodymia additions remain predominantly oxygen ionic conductors, with p-type electronic contribution increasing with Pr content but not exceeding 2% for x = 0.15 at 700–900 °C. The average thermal expansion coefficients of prepared ceramics are in the range of 10.4–10.7 ppm/K.

This study focuses on the preparation and characterization of composite gaskets designed for the sealing of the solid oxide cell stacks operating below 700 °C. The seals were fabricated with the addition of various amounts (10–90 wt.%) of 3 mol.% yttria partially stabilized zirconia to a BaO-Al₂O₃-CaO-SiO₂ glass matrix. The sample gaskets in the form of thin frames were shaped by tape casting. The quality of the junctions between the composites and Crofer 22APU steel commonly used as an SOC interconnect was evaluated after thermal treatment of heating to 710 °C, then cooling to the working temperature of around 620 °C and then leaving them for 10h in an air atmosphere, before cooling to room temperature. The samples were also studied after 3, 5, and 10 thermal cycles to determine the changes in microstructure and to evaluate the porosity and possible crystallization of the glass phase. The compression of the seals was calculated on the basis of differences in thickness before and after thermal treatment. The influence of zirconia additions on the mechanical properties of the seals was studied. The experimental results confirmed that glass–ceramic composites are promising materials for gaskets in SOC stacks. The most beneficial properties were obtained for a composite containing 40 wt.% of YSZ.