Free‐Standing Hierarchically Porous Covalent Organic Polymer With Closed‐F Edges Directly for Advanced Flexible Zinc‐Air Batteries

ABSTRACT Enhancing the intrinsic activity of the catalyst and the apparent activity of the catalytic layer in the air electrode is crucial for improving the power density and cycling durability of zinc‐air batteries (ZABs). However, challenges persist in the precise construction of active centers, exposure of active sites, and effective mitigation of mass transfer resistance at the membrane electrode interface. This study employs a pyrolysis‐free strategy to design fluorine‐functionalized covalent organic polymers (COPs) with well‐defined Fe‐N 4 active centers. Leveraging the inherent solubility of COPs, we fabricate a free‐standing hierarchically porous nanofiber electrode (COP@F/GO‐NFs) via electrospinning. Fluorine atoms exert a remote electron‐withdrawing effect on Fe‐N 4 sites through the conjugated backbone, modulating electron density and the d‐band center to optimize oxygen intermediate adsorption and lower the ORR energy barrier. Moreover, the three‐dimensional hierarchically porous nanofiber network constructed via electrospinning maximizes the exposure of active sites and facilitates mass transfer across the gas‐liquid‐solid triphase interface. The resulting catalyst achieves a peak power density of 200 mW cm −2 in ZABs, representing approximately 16% enhancement over powder counterparts. Flexible devices achieve 82.92 mW cm −2 with excellent mechanical flexibility and cycling stability. This work establishes a scalable material platform for high‐performance ZABs via a pyrolysis‐free molecular design strategy.