MOF-derived CoNi,CoO,NiO@N–C bifunctional oxygen electrocatalysts for liquid and all-solid-state Zn–air batteries

Abstract

Metal–organic framework (MOF)-derived carbon composites with embedded metal alloy/metal oxides have attracted much attention due to their low-cost and excellent electrochemical reactivity. However, the drawback of this concept is the severe carbon evaporation during their synthesis, resulting in a reduction of active sites and catalytic durability. To solve this problem, this study proposes the possibility of using Ketjen black (KB) to replenish the carbon content. Impressively, MOF-derived bimetal and oxide N-doped porous carbon (CoNi-CoO-NiO@NC-800) exhibits extremely high catalytic activity with an oxygen reduction reaction (half-wave potential: 0.83 V) and oxygen evolution reaction (overpotential: 352 mV @ 10 mA cm⁻²) potential gap of 0.75 V due to the virtue of the hierarchically porous structure and sufficient active sites. By combining theoretical studies, a strong synergetic coupling of the CoNi dual metal is proposed in decreasing the overall reaction barriers and promoting the reversible oxygen reactions. Moreover, the assembled liquid- and all-solid-state Zn–air batteries (ZABs) with the bifunctional catalyst as the air cathode demonstrate superior discharging (223 mW cm⁻² at 310 mA cm⁻²) and charging–discharging performance and long lifetime (450 cycles, 75 h). This work will provide guidance for the rational design of metal/carbon hybrid catalysts and cut-price reproducible energy systems.