Advanced Zinc–Air Batteries with Free-Standing Hierarchical Nanostructures of the Air Cathode for Portable Applications

It is today advanced that the development of a free-standing (binderless) air cathode via direct growth of nonprecious metal electrocatalysts onto the surface of the conductive collector would be a cutting-edge strategy to reduce the interfacial resistance, improve the mechanical stability, and reduce the final weight and the cost of manufacturing. Here, for Zn-air batteries (ZABs), we propose an innovative binderless noble-metal-free hierarchical nanostructured bifunctional air cathode in which high-density MnOx nanorods (NRs) are directly grown on carbon nanotubes (CNTs) themselves synthesized on a microfibrous carbon paper (CP) substrate. All carbon/MnOx air cathodes achieved specific capacities very close to the theoretical value of 820 mAh gZn-1. A very stable voltage gap between the charge and discharge processes along hundred cycles was obtained, demonstrating the stability and good bifunctional electrocatalytic activities of these cathodes toward the oxygen reduction reaction/oxygen evolution reaction in a real ZAB device. As a proof-of-concept for handheld electronic applications, a ZAB assembled with CP/MnOx NRs as the air electrode and a Zn plate anode operated a timer for 14 days successfully, whereas two ZAB-based CNTs/MnOx cathodes connected in series powered a 2 V light-emitting diode (LED) bulb and a 3 V multimeter. The proposed strategy and results may pave the way for the rational design of hierarchical free-standing bifunctional electrocatalysts for ZABs, other metal-air batteries, and fuel cells.