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

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, Ha, and Hb 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 RuO2. 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. [ABSTRACT FROM AUTHOR]