Unveiling the Role of Cationic Pyridine Sites in Covalent Triazine Framework for Boosting Zinc-Iodine Batteries Performance.

Rechargeable Zinc-iodine batteries (ZIBs) are gaining attention as energy storage devices due to their high energy density, low-cost, and inherent safety. However, the poor cycling performance of these batteries always arises from the severe leakage and shuttle effect of polyiodides (I 3 - and I 5 - ). Herein, a novel cationic pyridine-rich covalent triazine framework (CCTF-TPMB) is developed to capture and confine iodine (I 2 ) species via strong electrostatic interaction, making it an attractive host for I 2 in ZIBs. The as-fabricated ZIBs with I 2 loaded CCTF-TPMB (I 2 @CCTF-TPMB) cathode achieve a large specific capacity of 243 mAh g -1 at 0.2 A g -1 and an exceptionally stable cyclic performance, retaining 93.9% of its capacity over 30 000 cycles at 5 A g -1 . The excellent electrochemical performance of the ZIBs can be attributed to the pyridine-rich cationic sites of CCTF-TPMB, which effectively suppress the leakage and shuttle of polyiodides, while also accelerating the conversion reaction of I 2 species. Combined in situ Raman and UV-vis analysis, along with theoretical calculations, clearly reveal the critical role played by pyridine-rich cationic sites in boosting the ZIBs performances. This work opens up a promising pathway for designing advanced I 2 cathode materials toward next-generation ZIBs and beyond.