High capacity surface route discharge at the potassium-O₂ electrode

Discharge by a surface route at the cathode of an aprotic metal-O₂ battery typically results in surface passivation by the non-conducting oxide product. This leads to low capacity and early cell death. Here we investigate the cathode discharge reaction in the potassium-O₂ battery and demonstrate that discharge by a surface route is not limited to growth of thin (<10 nm) metal oxide layers. Electrochemical analysis and in situ Raman spectroscopy confirmed that the product of the cathode reaction is a combination of KO₂ and K₂O₂, depending on the applied potential. Use of the low donor number solvent, acetonitrile, allows us to directly probe the surface route. Rotating ring-disk electrode, electrochemical quartz crystal microbalance and scanning electron microscope characterisations clearly demonstrate the formation of a thick >1 μm product layer, far in excess of that possible in the related lithium-O₂ battery. These results demonstrate a high-capacity surface route in a metal-O₂ battery for the first time and the insights revealed here have significant implications for the design of the K-O₂ battery.