Design and Application of Hydrogen‐Bonded Organic Frameworks with Tetrathiafulvalene‐Tetrabenzoate for Cathode Active Materials in Lithium‐ and Sodium‐Ion Batteries

Hydrogen‐bonded organic frameworks (HOFs) have been increasingly applied in industrial fields owing to their low weight and high pore volume. In particular, HOFs incorporating redox‐active units have emerged as promising electrode materials for energy storage devices alongside other porous organic polymers. This study explores the application of HOFs incorporating tetrathiafulvalene (TTF) derivatives that are well‐known as molecular conductors with multielectron redox properties for rechargeable batteries. Specifically, the battery performance of HOFs‐based TTF‐tetrabenzoate (H 4 TTFTB) as a cathode active material in lithium‐ion (LIBs) and sodium‐ion batteries (SIBs) is evaluated. H 4 TTFTB‐based HOFs demonstrate enhanced cycling stability, with a particularly large enhancement achieved in SIB systems, due to the inherent structural stability of HOFs. Additionally, driven by the synergistic redox activity of TTF and bipyridine units, TTF‐hybrid‐HOFs combining H 4 TTFTB with redox‐active bipyridine units exhibit improved battery capacities. These findings underscore the potential of H 4 TTFTB‐based HOFs, which combine excellent redox activity and mechanical stability, as promising candidates for high‐performance energy storage devices, highlighting the advantages of integrating rigid heterocyclic compounds with redox‐active functionalities into HOF structures for future battery applications.