Free-Standing Air Cathodes Based on 3D Hierarchically Porous Carbon Membranes: Kinetic Overpotential of Continuous Macropores in Li-O2 Batteries.

Free-standing macroporous air electrodes with enhanced interfacial contact, rapid mass transport, and tailored deposition space for large amounts of Li2 O2 are essential for improving the rate performance of Li-O2 batteries. An ordered mesoporous carbon membrane with continuous macroporous channels was prepared by inversely topological transformation from ZnO nanorod array. Utilized as a free-standing air cathode for Li-O2 battery, the hierarchically porous carbon membrane shows superior rate performance. However, the increased cross-sectional area of the continuous macropores on the cathode surface leads to a kinetic overpotential with large voltage hysteresis and linear voltage variation against Butler-Volmer behavior. The kinetics were investigated based on the rate-determining step of second electron transfer accompanied by migration of Li+ in solid or quasi-solid intermediates. These discoveries shed light on the design of the air cathode for Li-O2 batteries with high-rate performance.