Bifunctional electrode performance for zinc-air flow cells with pulse charging

Bifunctional air electrodes with tuned composition consisting of two precious metal-free oxide catalysts are manufactured for application in rechargeable zinc-air flow batteries and electrochemically tested via long-term pulse charge and discharge cycling experiments at 50 mA cm(-2) (mean). NiCo2O4 spinel, synthesized via direct impregnation on carbon nanofibers or nickel powder and characterized by energy dispersive X-ray spectroscopy and X-ray diffraction experiments, shows high activity toward oxygen evolution reaction with low charge potentials of < 2.0 V vs. Zn/Zn2+. La0.6Sr0.4Co0.2Fe0.8O3 perovskite exhibits bifunctional activity and outperforms the NiCo2O4 spinel in long-term stability tenfold. By combining the catalysts in one bi-catalyzed bifunctional air electrode, stable performances of more than 1000 h and 450 cycles are achieved when supplied with oxygen and over 650 h and 300 cycles when supplied with synthetic air. In addition, the pulse charging method, which is beneficial for compact zinc deposition, is successfully tested on air electrodes during long-term operation. The oxygen evolution potentials during pulse, i.e. at tripled charge current density of 150 mA cm(-2), are only 0.06-0.08 V higher compared to constant charging current densities. Scanning electron microscopy confirms that mechanical degradation caused by bubble formation during oxygen evolution results in slowly decreasing discharge potentials. (C) 2017 Elsevier Ltd. All rights reserved.