Multi‐N‐Heterocycle Donor‐Acceptor Conjugated Amphoteric Organic Superstructures for Superior Zinc Batteries

Abstract Multiple redox‐active amphoteric organics with more n‐p fused electron transfer is an ongoing pursuit for superior zinc–organic batteries (ZOBs). Here we report multi‐heterocycle‐site donor‐acceptor conjugated amphoteric organic superstructures (AOSs) by integrating three‐electron‐accepting n‐type triazine motifs and dual‐electron‐donating p‐type piperazine units via H‐bonding and π–π stacking. AOSs expose flower‐shaped N‐heteromacrocyclic electron delocalization topologies to promise full accessibility of built‐in n‐p redox‐active motifs with an ultralow activation energy, thus liberating superior capacity (465 mAh g −1 ) for Zn||AOSs battery. More importantly, the extended multiple donor‐acceptor‐fused conjugated AOSs feature satisfied discharge voltage and anti‐dissolution in electrolytes, pushing both the energy density and cycle life of the ZOBs to a new level (412 Wh kg −1 and 70,000 cycles@10 A g −1 ). An anion–cation hybrid 18 e − charge storage mechanism is rationalized for heteromacrocyclic modules of AOSs cathode, entailing six tert‐N motifs coupling with CF 3 SO 3 − ions at high potential and twelve imine sites coordinating with Zn 2+ ions at low potential. These findings constitute a major advance of amphoteric multielectron organic materials and stand for a good starting point for advanced ZOBs.