An Organic Small Molecule Electrode with Intermolecular Intercalation and Synergistic Effects for High‐Rate Alkali Metal‐Ion Batteries

Abstract Designable molecular structures, unique ion‐coordination charge storage mechanisms, and resource sustainability enable organic electrode materials to become potential candidates for alkali metal‐ion batteries (AMIBs). Herein, integrating the excellent π–π stacking ability of Hexaazatriphenylene units and strong electron‐withdrawing properties of cyano (C≡N) groups into one moleuce, a π‐conjugated organic compound 1,4,5,8,9,11‐Hexaazatriphenylenehexacarbonitrile (HAT‐CN) is synthesized and systematically investigated as electrodes in Li/Na/K‐ion batteries. Explored by mechanism characterizations and density functional theory calculations, HAT‐CN can provide nine redox‐active sites for Na/K‐ions to intercalate/de‐intercalate, among which six Na/K‐ions are distributed evenly to both sides of conjugated skeletons through intermolecular intercalation and three Na/K‐ions are stored with the synergistic effect of C≡N groups. Employing HAT‐CN as electrodes, AMIBs are found to exhibit high reversible capacities, excellent rate capabilities, and stable cycle performances. After 100 cycles at the current density of 100 mA g −1 , Na‐ion batteries present 415.6 mAh g −1 with a capacity fading rate of 1.2% per cycle. Meanwhile, K‐ion batteries maintain 345 mAh g −1 with a coulombic efficiency ≈100%. Li‐ion batteries display superlithiation performances with ultra‐high reversible capacity. This work emphasizes the necessity of comprehensively studying the electrochemical performance of organic electrodes in different secondary battery systems and is conducive to maximizing electrode functionality.