Plasma‐Engineering of Oxygen Vacancies on NiCo2O4 Nanowires with Enhanced Bifunctional Electrocatalytic Performance for Rechargeable Zinc‐air Battery

Abstract Designing an efficient, durable, and inexpensive bifunctional electrocatalyst toward oxygen evolution reactions (OER) and oxygen reduction reactions (ORR) remains a significant challenge for the development of rechargeable zinc‐air batteries (ZABs). The generation of oxygen vacancies plays a vital role in modifying the surface properties of transition‐metal‐oxides (TMOs) and thus optimizing their electrocatalytic performances. Herein, a H 2 /Ar plasma is employed to generate abundant oxygen vacancies at the surfaces of NiCo 2 O 4 nanowires. Compared with the Ar plasma, the H 2 /Ar plasma generated more oxygen vacancies at the catalyst surface owing to the synergic effect of the Ar‐related ions and H‐radicals in the plasma. As a result, the NiCo 2 O 4 catalyst treated for 7.5 min in H 2 /Ar plasma exhibited the best bifunctional electrocatalytic activities and its gap potential between E j = 10 for OER and E 1/2 for ORR is even smaller than that of the noble‐metal‐based catalyst. In situ electrochemical experiments are also conducted to reveal the proposed mechanisms for the enhanced electrocatalytic performance. The rechargeable ZABs, when equipped with cathodes utilizing the aforementioned catalyst, achieved an outstanding charge–discharge gap, as well as superior cycling stability, outperforming batteries employing noble‐metal catalyst counterparts.