Monomer‐Ratio Controlled Pyridinic‐N Enrichment Modulating p‐Band Centers in Carbon Nanospheres for Efficient Zinc‐Air Batteries

Abstract Rational design of high‐performance, low‐cost oxygen reduction reaction (ORR) catalysts is critical for advancing zinc‐air batteries (ZABs). This study proposed a closed‐loop paradigm integrating first‐principles active site identification, precursor‐ratio‐controlled synthesis, and device validation to develop superior metal‐free ORR electrocatalysts. Density functional theory (DFT) calculations identify pyridinic‐N as the optimal doping configuration, exhibiting the lowest energy barrier (0.17 eV) for the rate‐determining step (RDS, *O 2 → *OOH). Further electronic structure analyses revealed that this enhancement originates from pyridinic‐N‐induced upward shifts in the p‐band center of adjacent carbon atoms during the RDS, establishing this shift as a universal activity descriptor. Guided by these insights, aniline(A)/pyrrole(P) co‐polymerization with precise monomer molar ratio control yielded a series of N‐doped carbon materials (A x P y ‐NC). A 0.5 P 0.5 ‐NC achieved the highest pyridinic‐N content (38.91%), demonstrating exceptional ORR activity that surpasses other A x P y ‐NC variants and the benchmark 20 wt.% Pt/C. The optimized catalyst enabled transformative ZAB performance in liquid and flexible configurations, achieving enhanced open‐circuit voltage, superior power densities, high specific capacities, and prolonged durability compared to commercial 20 wt.% Pt/C. This work establishes a catalyst development paradigm bridging mechanistic understanding, controllable synthesis, and practical application for next‐generation energy storage devices.