Bifunctional Oxygen Electrodes With Highly Step-Enriched Surface Of Fe-N-X Containing Carbonaceous Thin Film

Carbonaceous air cathodes in zinc-air batteries have attracted attention due to their high electron conductivity and low cost; however, the increment in the catalytic activity for the oxygen reduction and evolution in addition to the durability are demanded. Based on a fundamental study about the substantial effect of a three-dimensional active site at a step on a highly-oriented pyrolytic graphite basal plane on the electrode reactions, we attempted to extend the idea to a graphitic carbon fiber surface as a more applied form for the air electrode. Coating of a carbonaceous thin film derived from iron phthalocyanine on finely-etched graphitic carbon fibers produced a highly step-enriched surface demonstrated by the field-emission scanning electron microscope image and Raman spectra with a developed defect peak. The iron K-edge X-ray absorption fine structure showed a step-oriented iron atom coordinated by two nitrogen atoms and a basal plane oriented iron atom coordinated by 4 nitrogen atoms. The step-enrichment enhanced the oxygen reduction and evolution; in particular, the low overpotential phenomenon observed for the fundamental graphite system was reproduced in the carbon fiber paper, both in a half cell and a full cell of the zinc-air battery, which also showed a favorable cycling performance. (C) 2020 The Electrochemical Society ("ECS"). Published on behalf of ECS by IOP Publishing Limited.