Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
School of Physical Science & Technology, ShanghaiTech University, 100 Haike Road, Shanghai, 201210, P. R. China.
Angew Chem Int Ed Engl. 2023 Jun 12;62(24):e202302754. doi: 10.1002/anie.202302754. Epub 2023 May 3.
Metal-free organic electrode materials have attracted vast research attention owing to their designable structures and tunable electrochemical properties. Although n-type cathode materials could be used in various metal-ion batteries, p-type ones with high potential can deliver high energy density. Herein, we report a new p-type polymeric cathode material, poly(2-vinyl-5,10-dimethyl-dihydrophenazine) (PVDMP), with a theoretical capacity of 227 mAh g . PVDMP featuring two-step redox reaction will be doped by two anions to maintain electroneutrality during oxidation, which resulted in an anion-dependent electrochemical behavior of PVDMP-based cathode. The suitable dopant anion for PVDMP was selected and the doping mechanism was confirmed. Under the optimized condition, PVDMP cathode can deliver a high initial capacity of 220 mAh g at 5 C and even remains 150 mAh g after 3900 cycles. This work not only provides a new kind of p-type organic cathode materials but also deepens the understanding of its anion-dependent redox chemistry.
由于其可设计的结构和可调谐的电化学性能，无金属有机电极材料引起了广泛的研究关注。虽然 n 型阴极材料可用于各种金属离子电池，但具有高电势的 p 型材料可提供高能量密度。在此，我们报告了一种新的 p 型聚合物阴极材料，聚（2-乙烯基-5,10-二甲基-二氢吩嗪）（PVDMP），其理论容量为 227 mAh g-1。PVDMP 具有两步氧化还原反应，在氧化过程中通过两个阴离子掺杂以保持电中性，这导致了基于 PVDMP 的阴极的阴离子依赖性电化学行为。选择了适合 PVDMP 的掺杂阴离子，并证实了掺杂机制。在优化条件下，PVDMP 阴极在 5 C 时可提供 220 mAh g-1 的高初始容量，甚至在 3900 次循环后仍保持 150 mAh g-1。这项工作不仅提供了一种新型的 p 型有机阴极材料，还加深了对其阴离子依赖性氧化还原化学的理解。
