Multi-Heteroatom-Doping and Defect Co-Engineered Hollow Carbon Nanocages for Ultralong-Cycle Zinc–Air Batteries

Abstract

Developing cost-effective oxygen reduction reaction (ORR) electrocatalysts with simultaneously enhanced activity and durability remains a critical challenge for zinc-air batteries (ZABs). Herein, a multi-heteroatom-doping and defect co-engineering strategy is proposed to construct nitrogen, phosphorus, and sulfur tridoped hollow carbon nanocages (NPS-HCs) through a facile template-induced pyrolysis of a ZIF-8@PZS precursor. The synergistic effect of multi-heteroatom doping and introducing defects creates abundant active species, while the hollow architecture facilitates mass/electron transport during the ORR process. As a result, the optimized NPS-HC-900 catalyst demonstrates exceptional ORR performance with a high half-wave potential (<i>E</i>_1/2 = 0.87 V vs RHE). Impressively, the NPS-HC-900 + IrO₂-assembled rechargeable ZABs achieve an ultralong cycling stability over 1000 h. <i>In situ</i> spectroscopy and theoretical calculations verify that this synergistic effect promotes the conversion of key intermediate *OOH to *O, thereby significantly facilitating the ORR o. This work provides a paradigm-shifting platform for designing high-performance multi-heteroatom-doped carbon electrocatalysts via synergistic defect engineering.