Defect‐Enriched Nitrogen Doped–Graphene Quantum Dots Engineered NiCo2S4 Nanoarray as High‐Efficiency Bifunctional Catalyst for Flexible Zn‐Air Battery

Abstract Flexible Zn‐air batteries have recently emerged as one of the key energy storage systems of wearable/portable electronic devices, drawing enormous attention due to the high theoretical energy density, flat working voltage, low cost, and excellent safety. However, the majority of the previously reported flexible Zn‐air batteries encounter problems such as sluggish oxygen reaction kinetics, inferior long‐term durability, and poor flexibility induced by the rigid nature of the air cathode, all of which severely hinder their practical applications. Herein, a defect‐enriched nitrogen doped–graphene quantum dots (N‐GQDs) engineered 3D NiCo 2 S 4 nanoarray is developed by a facile chemical sulfuration and subsequent electrophoretic deposition process. The as‐fabricated N‐GQDs/NiCo 2 S 4 nanoarray grown on carbon cloth as a flexible air cathode exhibits superior electrocatalytic activities toward both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), outstanding cycle stability (200 h at 20 mA cm −2 ), and excellent mechanical flexibility (without observable decay under various bending angles). These impressive enhancements in electrocatalytic performance are mainly attributed to bifunctional active sites within the N‐GQDs/NiCo 2 S 4 catalyst and synergistic coupling effects between N‐GQDs and NiCo 2 S 4 . Density functional theory analysis further reveals that stronger OOH* dissociation adsorption at the interface between N‐GQDs and NiCo 2 S 4 lowers the overpotential of both ORR and OER.