Co–Ni Alloy Encapsulated by N-doped Graphene as a Cathode Catalyst for Rechargeable Hybrid Li–Air Batteries

A hybrid Li–air battery uses a protected lithium anode and a porous air cathode in an aqueous electrolyte, based on a 4-e oxygen reduction reaction/oxygen evolution reaction (ORR/OER). It avoids the insoluble and insulating Li2O2 product in a typical nonaqueous Li–air battery, and it owns unique advantages. A bifunctional cathode catalyst is crucial to battery performance. Here, we synthesize an ultrathin N-doped graphene-encapsulated nanosphere Co–Ni alloy (Co–Ni@NG). It has hierarchical architecture consisting of a uniform Co–Ni nanoalloy coated with a thin layer of N-doped graphene, showing high activity, high stability, and lower overpotential between the ORR and OER (0.55 V between onset potentials). It exhibited a discharge/charge voltage gap of 0.55 V at a current density of 1.4 mA cm–2, which is much smaller than the commercial Pt/C catalyst. It delivered an energy density of 3158 Wh kg–1 and a power density as high as 134.2 W m–2 at a current density of 7 mA cm–2. The graphene shells protect the alloy catalyst and improve the durability of the catalyst. One hundred cycles were demonstrated without significant deterioration. It was testified as a promising energy storage system with high energy density, efficiency, reliability, and durability.