Supramolecular Self‐Assembled Multi‐Electron‐Acceptor Organic Molecule as High‐Performance Cathode Material for Li‐Ion Batteries

Abstract Organic electrode materials possess many advantages such as low toxicity, sustainability, and chemical/structural tunability toward high energy density. However, to compete with inorganic‐based compounds, crucial aspects such as redox potential, capacity, cycling stability, and electronic conductivity need to be improved. Herein, a comprehensive strategy on the molecular design of small organic electron‐acceptor‐molecule—hexaazatrianthranylene (HATA) embedded quinone (HATAQ) is reported. By introducing conjugated quinone moieties into the electron‐deficient hexaazatriphenylene‐derivative core, HATAQ with highly extended π‐conjugation can yield extra‐high capacity for lithium storage, delivering a capacity of 426 mAh g −1 at 200 mA g −1 (0.4C). At an extremely high rate of 10 A g −1 (19C), a reversible capacity of 209 mAh g −1 corresponding to nearly 85% retention is obtained after 1000 cycles. A unique network of unconventional lock‐and‐key hydrogen bonds in the solid‐state facilitates favorable supramolecular 2D layered arrangement, enhancing cycling stability. To the best of the authors’ knowledge, the capacity and rate capability of HATAQ are found to be the best ever reported for organic small‐molecule‐based cathodes. These results together with density functional theory studies provide proof‐of‐concept that the design strategy is promising for the development of organic electrodes with exceptionally high energy density, rate capability, and cycling stability.