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

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 CF₃SO₃ ^- ions at high potential and twelve imine sites coordinating with Zn²⁺ 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.