RESUMEN
We herein report a simple two-step procedure for fabricating tetragonal CoMn2O4 spinel nanocrystals on carbon fibers. The battery-type behavior of these composite fibers arises from the redox activity of CoMn2O4 in an alkaline aqueous solution, which, in combination with the carbon fibers, endows good electrochemical performance and long-term stability. The C@CoMn2O4 electrode exhibited high specific capacity, up to 62 mA h g-1 at 1 A g-1 with a capacity retention of around 90% after 4000 cycles. A symmetrical coin-cell device assembled with the composite electrodes delivered a high energy density of 7.3 W h kg-1 at a power density of 0.1 kW kg-1, which is around 13 times higher than that of bare carbon electrodes. The coin cell was cycled for 5000 cycles with 96.3% capacitance retention, at a voltage of up to 0.8 V, demonstrating excellent cycling stability.
RESUMEN
Aprotic alkali metal-O2 batteries face two major obstacles to their chemistry occurring efficiently, the insulating nature of the formed alkali superoxides/peroxides and parasitic reactions that are caused by the highly reactive singlet oxygen (1O2). Redox mediators are recognized to be key for improving rechargeability. However, it is unclear how they affect 1O2 formation, which hinders strategies for their improvement. Here we clarify the mechanism of mediated peroxide and superoxide oxidation and thus explain how redox mediators either enhance or suppress 1O2 formation. We show that charging commences with peroxide oxidation to a superoxide intermediate and that redox potentials above ~3.5 V versus Li/Li+ drive 1O2 evolution from superoxide oxidation, while disproportionation always generates some 1O2. We find that 1O2 suppression requires oxidation to be faster than the generation of 1O2 from disproportionation. Oxidation rates decrease with growing driving force following Marcus inverted-region behaviour, establishing a region of maximum rate.