Publication date: 10th April 2024
Proton ceramic electrochemical cells (PCECs) show promise for cost-efficient steam electrolysis, power generation, and membrane reactors. However, the air/steam electrode is a restricting factor in their performance, with the oxygen evolution and reduction reactions being rate limiting. A mechanistic understanding of the reaction steps at the electrodes is therefore required to further develop high-performance electrodes and cell architectures.
Pulsed Isotope Exchange (PIE) is a gas phase analysis method that allows for fast characterisation of the oxygen surface exchange rate of powder samples [1]. The surface exchange of oxygen is measured as a function of oxygen pressure and temperature, as well as the effect of water on the exchange rate. The reaction mechanisms and rate determining steps are investigated further by electrochemical impedance spectroscopy on model electrodes at temperatures from 500 °C down to 200°C in different pO2s and pH2Os.
Various compositions of Ba1-xGd0.8-yLa0.2+x+yCo2O6-δ, which are double perovskite type materials, have been shown to be efficient triple conducting air/steam electrodes for PCECs at intermediate temperatures [2, 3]. BaGd0.3La0.7Co2O6-δ shows an oxygen exchange limited by dissociative adsorption in all measured pO2s with activation energies ranging from 0.8 eV to 1.1 eV in dry atmospheres, which is comparable to other double perovskite cobaltites [4, 5]. While the presence of water does not change the rate limiting step, it lowers the exchange rate and increases the activation energy in high pO2 and increases the exchange rate and lowers the activation energy in low pO2s. Electrochemical impedance measurements show similar activation energies to PIE in the same atmospheres and temperature range.
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