Plasma Surface Engineering of NiCo₂S₄@rGO Electrocatalysts Enables High-Performance Li-O₂ Batteries

The sluggish redox reaction kinetics for aprotic Li-O₂ batteries (LOBs) caused by the insulating discharge product of Li₂O₂ could result in the poor round-trip efficiency, low rate capability, and cyclic stability. To address these challenges, we herein fabricated NiCo₂S₄ supported on reduced graphene oxide (NiCo₂S₄@rGO), the surface of which is further modified via a unique low-pressure capacitive-coupled nitrogen plasma (CCPN-NiCo₂S₄@rGO). The high ionization environment of the plasma could etch the surface of NiCo₂S₄@rGO, introducing effective nitrogen doping. The as-prepared CCPN-NiCo₂S₄@rGO has been employed as an efficient catalyst for advanced LOBs. The electrochemical analysis, combined with theoretical calculations, reveals that the N-doping can effectively improve the thermodynamics and kinetics for LiO₂ adsorption, giving rise to a well-knit Li₂O₂ formation on CCPN-NiCo₂S₄@rGO. The LOBs based on the CCPN-NiCo₂S₄@rGO oxygen electrode deliver a low overpotential of 0.75 V, a high discharge capacity of 10,490 mA h g^-1, and an improved cyclic stability (more than 110 cycles). This contribution may pave a promising avenue for facile surface engineering of the electrocatalyst in LOBs and other energy storage systems.