Cobalt nanoclusters Deposit on Nitrogen-Doped graphene Sheets as bifunctional electrocatalysts for high performance lithium – Oxygen batteries

Abstract

Rechargeable lithium-oxygen (Li-O₂) batteries are being considered as the next-generation energy storage systems due to their higher theoretical energy density. However, the practical application of Li-O₂ batteries is hindered by slow kinetics and the formation of side products during the oxygen reduction and evolution reactions on the cathode. These reactions lead to high overpotentials during charging and discharging. To address these challenges, we propose a simple ultrasonic method for synthesizing cobalt nanoclusters embedded in nitrogen-doped graphene nanosheets (GrZnCo) derived from metal-organic frameworks (MOFs). The resulting material, due to the retention of metallic cobalt structure, exhibits better electronic conductivity. Additionally, the GrZnCo catalyst shows vigorous catalytic activity, which can improve reaction kinetics and suppress side reactions, thus lowering the charging overpotential. We have investigated the impact of different catalyst compositions (GrZnCo_x; x  = 1, 3, 5) by varying the amounts of cobalt and zinc. The optimum catalyst, GrZnCo₃, contains high cobalt-N active components, graphitic-N, pyridinic-N, pyrrolic-N, and abundant defect structures, which enhance the electrochemical performance. The defect-rich GrZnCo₃ catalyst enables Li-O₂ batteries to achieve a high discharge capacity of 13500 mAh·g⁻¹ at 50 mA·g⁻¹ and a remarkable long-term cycling performance of over 400 cycles at 100 mA·g⁻¹ with a limited capacity of 500 mAh·g⁻¹. This work demonstrates an effective approach to fabricate cost-effective electrocatalysts for various energy storage systems.