Abstract
The potentiality of mixed conducting oxides as electrodes in rechargeable oxygen ion batteries is exemplified by impedance measurements and galvanostatic cycling. Porous La0.6Sr0.4CoO3−δ (LSC) thin film electrodes were prepared on yttria-stabilized zirconia electrolytes with a dense ZrO2 blocking layer on top to prevent oxygen exchange with the measurement atmosphere. Half cell measurements performed between 350 and 460°C revealed electrode capacities up to 135mAh/cm3. Measured charge/voltage curves are compared with those reconstructed from chemical capacitance values and with model calculations. Two different storage mechanisms were identified: At low potentials (<0.05V vs. 1bar O2), mainly oxygen vacancies become filled during charging. At higher potentials, however, O2 gas formation (>500bar at potentials >0.1V) in closed pores dominates charge/voltage characteristics, which can be described by calculations based on a real gas model. Moreover, full oxygen ion batteries were investigated, where such a porous LSC electrode served as cathode and a dense La0.9Sr0.1CrO3−δ (LSCr) film was used as anode. Owing to the much lower reducibility of LSCr, a cell voltage of 1.2V was obtained at 460°C with electrode related capacities and energy densities up to 100mAh/cm3 and 53mWh/cm3, respectively.
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