Lewis Pair Interaction Self‐Assembly of Carbon Superstructures Harvesting High‐Energy and Ultralong‐Life Zinc‐Ion Storage

Abstract Tailor‐made nanoarchitecturing of highly zincophilic and stable carbon scaffolds is critical but still challenging for Zn‐ion storage with double‐high supercapacitive activity and durability. Herein, a Lewis pair interaction‐guided self‐assembly strategy is reported to design carbon superstructures for activating Zn‐storage sites. The Lewis acid (ferric chloride) and base ( p ‐phenylenedimethanol) can interact to form organic nanoparticle modules that self‐assemble into well‐defined superstructures constructed from nanotentacle‐building blocks via hydrogen‐bonding and π−π stacking. As‐designed carbon superstructures as aqueous Zn‐ion capacitor cathodes empower the high accessibility of the build‐in zincophilic sites and efficient ion migration with low‐energy hurdles. A charge‐storage mechanism, i.e., opposite charge‐carrier uptake coupled with multielectron redox response, is proposed, which entails the alternate binding of Zn 2+ /CF 3 SO 3 − at active sites and the robust interactions between Zn 2+ and electronegative carbonyl/pyridine motifs to form O−Zn−N bonds. This unique electrochemistry contributes to high‐rate survivability (100 A g −1 ), high‐energy density (161.2 Wh kg −1 cathode ), and ultralong lifespan (400 000 cycles), superior to state‐of‐the‐art Zn‐ion devices in comprehensive performances. This study sheds light on structural engineering for carbon‐based materials toward advanced energy storage.