He Jing, Shi Minjie, Wang Houxiang, Liu He, Yang Jun, Yan Chao, Zhao Jingxin, Yang Jia-Lin, Wu Xing-Long
School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang, 212003, P. R. China.
Nanotechnology Center, School of Fashion and Textiles, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, 999077, P. R. China.
Angew Chem Int Ed Engl. 2024 Oct 24;63(44):e202410568. doi: 10.1002/anie.202410568. Epub 2024 Sep 18.
A ladder-type rigid-coplanar polymer with highly ordered molecular arrangement has been designed via a covalent cycloconjugation conformational strategy. Benefitting from the extended π-electron delocalization in the highly aromatic ladder-type polymeric backbone, the prepared polymer exhibits fast intra-chain charge transport along the polymeric chain, realizing extraordinary proton-storage capability in aqueous proton batteries.Affordable and safe aqueous proton batteries (APBs) with unique "Grotthuss mechanism," are very significant for advancing carbon neutrality initiatives. While organic polymers offer a robust and adaptable framework that is well-suited for APB electrodes, the limited proton-storage redox capacity has constrained their broader application. Herein, a ladder-type polymer (PNMZ) has been designed via a covalent cycloconjugation conformational strategy that exhibits optimized electronic structure and fast intra-chain charge transport within the high-aromaticity polymeric skeleton. As a result, the polymer exhibits exceptional proton-storage redox kinetics, which are evidenced by in-operando monitoring techniques and theoretical calculations. It achieves a remarkable proton-storage capacity of 189 mAh g at 2 A g and excellent long-term cycling stability, with approximately 97.8 % capacity retention over 10,000 cycles. Finally, a high-performance all-polymer APB device has been successfully constructed with a desirable capacity retention of 99.7 % after 6,000 cycles and high energy density of 56.3 Wh kg.
通过共价环共轭构象策略设计了一种具有高度有序分子排列的梯型刚性共平面聚合物。得益于高度芳香族梯型聚合物主链中扩展的π电子离域，所制备的聚合物沿聚合物链表现出快速的链内电荷传输，在水系质子电池中实现了非凡的质子存储能力。具有独特“格罗特斯机制”的经济实惠且安全的水系质子电池（APB）对于推进碳中和倡议具有重要意义。虽然有机聚合物提供了一个坚固且适应性强的框架，非常适合用于APB电极，但有限的质子存储氧化还原容量限制了它们的更广泛应用。在此，通过共价环共轭构象策略设计了一种梯型聚合物（PNMZ），该聚合物在高芳香性聚合物骨架内表现出优化的电子结构和快速的链内电荷传输。结果，该聚合物表现出优异的质子存储氧化还原动力学，这通过原位监测技术和理论计算得到了证实。它在2 A g下实现了189 mAh g的显著质子存储容量和出色的长期循环稳定性，在10000次循环后容量保持率约为97.8%。最后，成功构建了一种高性能全聚合物APB器件，在6000次循环后具有99.7%的理想容量保持率和56.3 Wh kg的高能量密度。
