Boosting Aluminum Storage in Highly Stable Covalent Organic Frameworks with Abundant Accessible Carbonyl Groups

Abstract Aluminum batteries employing organic electrode materials present an appealing avenue for sustainable and large‐scale energy storage. Nevertheless, conventional organic materials encounter limitations due to their restricted active sites, known instability, and sluggish redox kinetics. In this study, a redox‐active covalent organic framework supported by CNT is reported, enriched with substantial C═O groups, as an advanced cathode material for Al‐organic batteries. Theoretical simulation and ex situ analysis unveil the pivotal roles of C═O groups in effectively storing AlCl 2+ . As a result, Al batteries with the organic cathode exhibit a specific capacity of 290 mAh g −1 at 0.2 A g −1 and outstanding rate performance. Furthermore, it retains a reversible capacity of 170 mAh g −1 even after 32 000 cycles at 10 A g −1 and attains an energy density of 389 Wh kg −1 . The remarkable performance stems not only from the abundant C═O and C─N groups enabling the storage of multiple AlCl 2+ by the favorable pseudocapacitive process, but also from the synergistic interplay between the robust COF network and the conductive CNT channels that significantly enhances structural stability and accelerates ion/electron diffusion. This work stands to inspire further research in the pursuit of stable organic cathodes, fostering designs with plentiful accessible redox‐active sites to boost energy storage capabilities.