Eggshell-Like Carbon Microspheres with Curvature Scheme: Distorted Energy Band and Atomic Charge Waves-Driven High...

A metal-free nanocarbon with an eggshell structure is synthesized from chitosan (CS) and natural spherical graphite (NSG) as a cathode electrocatalyst for clean zinc-air batteries and fuel cells. It is developed using CS-derived carbons as an eggshell, covering NSG cores. The synthesis involves the in situ growth of CS on NSG, followed by ammonia-assisted pyrolysis for carbonization. The resulting catalyst displays a curved structure and completely coated NSG, showing superior oxygen reduction reaction (ORR) performance. In 1 M NaOH, the ORR half-wave potential reached 0.93 V, surpassing the commercial Pt/C catalyst by 50 mV. Furthermore, a zinc-air battery featuring the catalyst achieves a peak power density of 167 mW cm^-2 with excellent stability, outperforming the Pt/C. The improved performance of the eggshell carbons can be attributed to the distorted energy band of the active sites in the form of N-C moieties. More importantly, the curved thin eggshells induce built-in electric fields that can promote electron redistribution to generate atomic charge waves around the N-C moieties on the carbon shells. As a result, the high positively charged and stable C⁺ sites adjacent to N atoms optimize the adsorption strength of oxygen molecules, thereby facilitating performance.