Strong Donor–Acceptor Effect Enables Efficient Polyiodides Confinement and Fast Redox Kinetics Toward Zinc–Iodine Batteries

Aqueous zinc–iodine batteries (ZIBs) based on iodine (I 2 ) redox conversion suffer from severe polyiodides shuttling and sluggish redox kinetics, leading to poor cycling stability. Herein, we propose a donor–acceptor (D–A) synergetic interaction strategy to enable high‐performance ZIBs by employing thiophene‐rich covalent triazine frameworks (SCTF‐DCT) as an advanced I 2 host catalyst. The strong D–A cooperative effect combined with a rich micro‐mesoporous structure not only optimizes the polyiodides adsorption but also enhances the conversion kinetics of I 2 species. Benefiting from the strong D–A effect, the as‐assembled ZIBs with I 2 loaded SCTF‐DCT (I 2 @SCTF‐DCT) cathode demonstrate exceptional cycling life, exceeding 100,000 cycles with a minimal decay rate of only 0.000198% per cycle. In/ex situ characterizations and theoretical calculations reveal the reversible redox mechanism of I 2 species and highlight the significance of the D–A collaborative effect. This work elucidates the mechanisms of adsorption and catalytic conversion of I 2 species via a D–A synergetic interaction strategy, providing a promising approach for designing advanced host catalysts for next‐generation ZIBs and other energy storage systems.