Gd- and Pr-based double perovskite cobaltites as oxygen electrodes for proton ceramic fuel cells and electrolyser cells

• Novel oxygen electrode for Proton Ceramic Fuel Cells
• Hydration of mixed conducting perovskite
• Modelling of electrode reactions for protons and oxide ions at the oxygen electrode
• Correcting for partial electronic conductivity under characterization conditions
• Polarisation resistance of 0.05 and 10 Ω cm2 at 650 and 350 °C, respectively

Double perovskite oxides BaGd0.8La0.2Co2O6−δ (BGLC), BaGdCo1.8Fe0.2O6−δ (BGCF), BaPrCo2O6−δ (BPC) and BaPrCo1.4Fe0.6O6−δ (BPCF) were investigated as oxygen electrodes on mixed conducting BaZr0.7Ce0.2Y0.1O3 (BZCY72) electrolyte using impedance spectroscopy vs temperature, pO2, and pH2O. We propose and have applied a novel approach to extract and parameterise the charge transfer and diffusion impedances of the electrode reactions in a system comprising charge transport of protons, oxide ions, and electrons. Given by the properties of the BZCY72, transport of protons dominates at lower temperatures and high pH2O, oxide ions at higher temperatures, and electron holes increasingly at high temperatures and high pO2. The electrodes showed good performance, with the lowest total apparent polarisation resistance for BGLC/BZCY72 being 0.05 and 10 Ωcm2 at 650 and 350 °C, respectively. The low temperature rate limiting reaction step is a surface related process, involving protonic species, with an activation energy of approximately 50 kJ mol−1 for BGLC/BZCY72. The oxide ion transport taking over at higher temperatures exhibits a higher activation energy typical of SOFC cathodes. Thermogravimetric studies revealed that BGLC exhibits considerable protonation at 300–400 °C, which may be interpreted as hydration with an enthalpy of approximately –50 kJ mol−1. The resulting mixed proton electron conduction may explain its good performance as electrode on BZCY72.