Zhang Yehui, 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 Apr 7;64(15):e202423936. doi: 10.1002/anie.202423936. Epub 2025 Feb 7.
Protons (H) with the smallest size and fastest redox kinetics are regarded as competitive charge carriers in the booming Zn-organic batteries (ZOBs). Developing new H-storage organic cathode materials with multiple ultralow-energy-barrier protophilic sites and super electron delocalization routes to propel superior ZOBs is crucial but still challenging. Here we design multiple protophilic redox-active reticular organic skeletons (ROSs) for activating better proton storage, triggered by intermolecular H-bonding and π-π stacking interactions between 2,6-diaminoanthraquinone and 2,4,6-triformylphloroglucinol nanofibrous polymer. ROSs expose reticular electron delocalization geometries to fully access build-in protophilic carbonyl sites and promote ultrarapid H migration with an ultralow activation energy (0.13 vs. 0.29 eV of Zn ions), thus delivering high capacity (359 mAh g) and large-current survivability (100 A g). Moreover, the extended interconnected reticular structures strengthen the anti-dissolution of ROSs in aqueous electrolytes, affording long-lasting proton-storage activity in ZOBs to a superior level (60,000 cycles at 20 A g). Systematic studies identify the source of excellent charge storage as high-kinetics H-coupled five-electron redox process of carbonyl motifs in superstable ROSs. These findings can be of importance for evoking superior proton activity in multiple redox organics to build advanced Zn-organic batteries.
质子（H）尺寸最小且氧化还原动力学最快，被视为蓬勃发展的锌有机电池（ZOBs）中具有竞争力的电荷载体。开发具有多个超低能垒亲质子位点和超电子离域途径的新型储氢有机正极材料以推动高性能ZOBs的发展至关重要，但仍具有挑战性。在此，我们设计了多个亲质子氧化还原活性网状有机骨架（ROSs），通过2,6 - 二氨基蒽醌与2,4,6 - 三(甲酰基)间苯三酚纳米纤维聚合物之间的分子间氢键和π - π堆积相互作用来激活更好的质子存储。ROSs展现出网状电子离域几何结构，以充分利用内置的亲质子羰基位点，并促进具有超低活化能（0.13 eV，而锌离子为0.29 eV）的超快氢迁移，从而实现高容量（359 mAh g）和大电流耐受性（100 A g）。此外，扩展的互连网状结构增强了ROSs在水性电解质中的抗溶解能力，使ZOBs中的持久质子存储活性达到卓越水平（在20 A g下循环60,000次）。系统研究确定了优异电荷存储的来源是超稳定ROSs中羰基基序的高动力学氢耦合五电子氧化还原过程。这些发现对于激发多种氧化还原有机物中的卓越质子活性以构建先进的锌有机电池具有重要意义。
