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用于高性能锌有机电池的多电子氧化还原双极四硝基卟啉大环阴极

Multielectron Redox-Bipolar Tetranitroporphyrin Macrocycle Cathode for High-Performance Zinc-Organic Batteries.

作者信息

Song Ziyang, Miao Ling, Duan Hui, Lv Yaokang, Gan Lihua, Liu Mingxian

机构信息

Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, 200092 Shanghai, P. R. China.

College of Chemical Engineering, Zhejiang University of Technology, 310014, Hangzhou, P. R. China.

出版信息

Angew Chem Int Ed Engl. 2024 Apr 15;63(16):e202401049. doi: 10.1002/anie.202401049. Epub 2024 Mar 6.

Abstract

Bipolar organics fuse the merits of n/p-type redox reactions for better Zn-organic batteries (ZOBs), but face the capacity plafond due to low density of active units and single-electron reactions. Here we report multielectron redox-bipolar tetranitroporphyrin (TNP) with quadruple two-electron-accepting n-type nitro motifs and dual-electron-donating p-type amine moieties towards high-capacity-voltage ZOBs. TNP cathode initiates high-kinetics, hybrid anion-cation 10e charge storage involving four nitro sites coordinating with Zn ions at low potential and two amine species coupling with SO ions at high potential. Consequently, Zn||TNP battery harvests high capacity (338 mAh g), boosted average voltage (1.08 V), and outstanding energy density (365 Wh kg ). Moreover, the extended π-conjugated TNP macrocycle achieves anti-dissolution in electrolytes, prolonging the battery life to 50,000 cycles at 10 A g with 71.6 % capacity retention. This work expands the chemical landscape of multielectron redox-bipolar organics for state-of-the-art ZOBs.

摘要

双极有机物融合了n/p型氧化还原反应的优点,可用于性能更优的锌有机电池(ZOBs),但由于活性单元密度低和单电子反应,面临容量上限问题。在此,我们报道了具有四重双电子接受n型硝基基团和双电子供体p型胺基的多电子氧化还原双极四硝基卟啉(TNP),用于高容量-电压的ZOBs。TNP阴极引发了高动力学、混合阴离子-阳离子10e电荷存储,包括四个硝基位点在低电位与锌离子配位,以及两个胺物种在高电位与硫酸根离子耦合。因此,锌||TNP电池实现了高容量(338 mAh g)、提高的平均电压(1.08 V)和出色的能量密度(365 Wh kg)。此外,扩展的π共轭TNP大环在电解质中实现了抗溶解,使电池在10 A g下循环寿命延长至50,000次,容量保持率为71.6%。这项工作扩展了用于先进ZOBs的多电子氧化还原双极有机物的化学领域。

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