Song Ziyang, Huang Qi, Lv Yaokang, Gan Lihua, Liu Mingxian
Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Shanghai, 200092, P. R. China.
Institute for Electric Light Sources, School of Information Science and Technology, Fudan University, Shanghai, 200438, P. R. China.
Angew Chem Int Ed Engl. 2025 Feb 3;64(6):e202418237. doi: 10.1002/anie.202418237. Epub 2024 Nov 16.
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) 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 and 70,000 cycles@10 A g). An anion-cation hybrid 18 e charge storage mechanism is rationalized for heteromacrocyclic modules of AOSs cathode, entailing six tert-N motifs coupling with CFSO ions at high potential and twelve imine sites coordinating with Zn 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.
具有更多n-p稠合电子转移的多种氧化还原活性两性有机物是高性能锌有机电池（ZOBs）的一个持续追求目标。在此，我们通过氢键和π-π堆积整合三电子接受型n型三嗪基序和双电子供体型p型哌嗪单元，报道了多杂环位点供体-受体共轭两性有机超结构（AOSs）。AOSs呈现出花状N-杂大环电子离域拓扑结构，有望以超低活化能完全利用内置的n-p氧化还原活性基序，从而为Zn||AOSs电池释放出优异的容量（465 mAh g）。更重要的是，扩展的多供体-受体稠合共轭AOSs具有令人满意的放电电压和在电解质中的抗溶解性能，将ZOBs的能量密度和循环寿命都提升到了一个新水平（412 Wh kg和在10 A g下70000次循环）。一种阴离子-阳离子混合18e电荷存储机制被合理化用于AOSs阴极的杂大环模块，即在高电位下六个叔氮基序与CFSO离子耦合，在低电位下十二个亚胺位点与锌离子配位。这些发现构成了两性多电子有机材料的一项重大进展，并代表了先进ZOBs的一个良好起点。
