The integration of Solid Oxide Fuel Cells (SOFCs) in hybrid power generation systems offers the opportunity to achieve higher electric efficiencies. In the SOS-CO₂ cycle [1], a newly developed cycle for blue power production (i.e., power generated starting from natural gas while capturing CO₂), the SOFC cathode is supplied with mixtures of CO₂ and O₂, up to 79% CO₂ molar fraction, while the anode is supplied with a reformate feed, containing H₂, CH₄, CO, CO₂, and water vapour. Aim of this work is to experimentally evaluate the performance and the durability of industrial 5x5 cm² Ni-YSZ anode-supported SOFCs under the SOS-CO₂ cycle conditions, focusing on the effects of the CO₂-rich cathodic atmosphere. The cells mounted a LSCF-based (La_0.6Sr_0.4Co_0.2Fe_0.8O₃) single phase cathode, coated by a current collection layer of LSC (La_0.6Sr_0.4CoO₃). Laboratory tests were performed at 700°C, acquiring polarization (I/V) curves and EIS spectra by means of a Horiba – FuelCon C50 Evaluator test station. Initial investigations with 7% humidified H₂ and 21/79 O₂/CO₂ cathodic mixture revealed 25% power loss compared to the base case with cathodic air. The test showed not only that the loss of performance was stable in time, but also that the power reduction was reversible since the initial performance in air was recovered. The EIS spectra showed an increase of the polarization resistance and of the ohmic resistance upon feeding CO₂. This latter observation suggested a reduction of the electronic conductivity of the cathode, compatible with the formation of Sr carbonates on the perovskite surface [2–4]. To assess the performance of the SOFC under the operating conditions of the SOS-CO₂ cycle, the anode was supplied with reformate. Compared to the base case with humidified hydrogen and air, the current density at 0.7 V decreased by 37% (490 mA/cm²). When supplying the 21/79 O₂/CO₂ mixture at the cathode, the current density stabilized at 420 mA/cm² (Figure 1). Durability tests (over 300 h) at 700°C with reformate and 21/79 O₂/CO₂ mixture highlighted a moderate decrease of the current density at 0.7 V. After these tests, the cathode was characterized post-mortem with XRD, SEM and Raman to analyse the consequences of the prolonged exposure to CO₂. To further quantify the effect of CO₂ on the cathode, symmetric button cells were also characterized with EIS, measuring ohmic and polarization resistances. The results suggested that the adsorption of CO₂ is reversible and indicated a better suitability of LSCF- compared to LSC-based cathodes for operations with CO₂-rich mixtures. Experiments performed between 550 and 700°C at varying CO₂ and O₂ partial pressures allowed to describe the kinetics of the oxygen reduction reaction and extract its activation energy. Overall, the results provided key elements for the integration of SOFCs in the SOS-CO₂ blue power technology. References [1] R. Scaccabarozzi, M. Gatti, S. Campanari, and E. Martelli, “Solid oxide semi-closed CO₂ cycle: A hybrid power cycle with 75% net efficiency and zero emissions,” Appl. Energy, vol. 290, no. February, p. 116711, 2021. [2] Y. Chen et al., “A highly active, CO₂-tolerant electrode for the oxygen reduction reaction,” Energy Environ. Sci., vol. 11, no. 9, pp. 2458–2466, Sep. 2018. [3] Y. Yu et al., “Chemical characterization of surface precipitates in La_0.7Sr_0.3Co_0.2Fe_0.8O_3-δ as cathode material for solid oxide fuel cells,” J. Power Sources, vol. 333, pp. 247–253, Nov. 2016. [4] J. Hwang et al., “CO₂ Reactivity on Cobalt-Based Perovskites,” J. Phys. Chem. C, vol. 122, no. 35, pp. 20391–20401, 2018. Figure 1 - Polarization curves of 5x5 cm² industrial SOFC supplied with 1.0 Nl/min of 7% humidified hydrogen and 2.5 Nl/min of air (black); 0.5 Nl/min of reformate mixture and 1.2 Nl/min of air (red); 0.5 Nl/min of reformate mixture and 1.2 Nl/min of cathodic 21% O₂ / 79% CO₂ mixture (green). Figure 1