Plasma‐Assisted Formation of Oxygen Defective NiCoO/NiCoN Heterostructure with Improved ORR/OER Activities for Highly Durable All‐Solid‐State Zinc‐Air Batteries

Abstract A plasma approach is reported to synthesize carbon cloth supported carbon fiber and oxygen defect‐rich NiCoO/NiCoN hetero‐nanowire co‐integrated hybrid catalyst (P‐NCO/NCN‐CF@CC), which includes the advanced features of carbon integration, cation doping, defect/vacancy introduction, and heterostructuring. The P‐NCO/NCN shows a fascinating structure with the periphery composed of NCO and the interior co‐composed of NCO and NCN. Its formation mainly depends on the high reactivity of energetic species of NH, H a , and H b formed during the plasma discharge. The P‐NCO/NCN‐CF@CC exhibits the oxygen reduction reaction (ORR) activity comparable to the Pt/C and the oxygen evolution reaction (OER) activity higher than RuO 2 . When used in the all‐solid‐state zinc‐air batteries, it gives a high maximum power density of 109.8 mW cm −2 with no performance drop observed for >300 cycles. The DFT calculations indicate that the NCO/NCN heterostructuring and oxygen defects in NCO play the important roles in the high ORR/OER activities of the catalyst. They can modulate the electronic structure of the catalyst, lowering the energy barriers of rate determining steps.