Advanced Oxygen Electrocatalyst for Air-Breathing Electrode in Zn-Air Batteries

The electrochemical reduction of oxygen to water and the evolution of oxygen from water are two important electrode reactions extensively studied for the development of electrochemical energy conversion and storage technologies based on oxygen electrocatalysis. The development of an inexpensive, highly active, and durable nonprecious-metal-based oxygen electrocatalyst is indispensable for emerging energy technologies, including anion exchange membrane fuel cells, metal-air batteries (MABs), water electrolyzers, etc. The activity of an oxygen electrocatalyst largely decides the overall energy storage performance of these devices. Although the catalytic activities of Pt and Ru/Ir-based catalysts toward an oxygen reduction reaction (ORR) and an oxygen evolution reaction (OER) are known, the high cost and lack of durability limit their extensive use for practical applications. This review article highlights the oxygen electrocatalytic activity of the emerging non-Pt and non-Ru/Ir oxygen electrocatalysts including transition-metal-based random alloys, intermetallics, metal-coordinated nitrogen-doped carbon (M-N-C), and transition metal phosphides, nitrides, etc., for the development of an air-breathing electrode for aqueous primary and secondary zinc-air batteries (ZABs). Rational surface and chemical engineering of these electrocatalysts is required to achieve the desired oxygen electrocatalytic activity. The surface engineering increases the number of active sites, whereas the chemical engineering enhances the intrinsic activity of the catalyst. The encapsulation or integration of the active catalyst with undoped or heteroatom-doped carbon nanostructures affords an enhanced durability to the active catalyst. In many cases, the synergistic effect between the heteroatom-doped carbon matrix and the active catalyst plays an important role in controlling the catalytic activity. The ORR activity of these catalysts is evaluated in terms of onset potential, number of electrons transferred, limiting current density, and durability. The bifunctional oxygen electrocatalytic activity and ZAB performance, on the other hand, are measured in terms of potential gap between the ORR and OER, ΔE = E_j10^OER - E_1/2^ORR, specific capacity, peak power density, open circuit voltage, voltaic efficiency, and charge-discharge cycling stability. The nonprecious metal electrocatalyst-based ZABs are very promising and they deliver high power density, specific capacity, and round-trip efficiency. The active site for oxygen electrocatalysis and challenges associated with carbon support is briefly addressed. Despite the considerable progress made with the emerging electrocatalysts in recent years, several issues are yet to be addressed to achieve the commercial potential of rechargeable ZAB for practical applications.