Switching Electric Double Layer Potential by Phase Structure Control for Advanced Oxygen Reduction Reaction of Cobalt@Nitrogen Doped Carbon Core–Shell

Abstract

The key to design an advanced oxygen reduction reaction (ORR) electrocatalyst is a well‐balance between the adsorption and desorption of oxygen intermediates. This study systematically evaluated the ORR activity of HCP and FCC cobalt core–shell cobalt/N‐doped carbon (Cobalt@NC) catalyst via theoretical and experimental studies. The electronic structure calculations using density functional theory (DFT) calculations revealed that the ORR activity of carbon layer can be improved by 1) switching the electrostatic potential in the electrical double layer due to the polarization induced at the carbon–cobalt interface and 2) modulating the electron population in the bonding orbital in the C–O bonds in an ORR. The results revealed that an O atom is bounded stronger to the outer NC shell with FCC Cobalt than HCP Cobalt, which hindered the desorption steps of OH*. Experimentally, plasma‐engineered HCP Cobalt@NC also showed remarkably advanced performance toward ORR compared to that FCC Cobalt@NC. The kinetic current density of HCP Cobalt@NC at 0.85 V versus RHE is calculated as 6.24 mA cm−2, which is six folds higher than FCC Cobalt@NC and even outperform 20 wt.% Pt/C. In a practical Aluminium‐air battery, HCP Cobalt@NC also exhibited slightly higher peak power density (110.57 mW cm−2) compared to 20 wt.% Pt/C.