Si-Wen Ke, Wei Li, Lei Gao, Jian Su, Rengan Luo, Shuai Yuan, Ping He, Jing-Lin Zuo
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引用次数: 0
摘要
合理设计具有高导电性和可逆氧化还原活性的多孔共价有机框架(COF)是提高其在钠离子电池(SIB)中性能的关键。在此,我们报告了一系列基于有机硫连接体 ((三氧代环己烷-三亚甲基)三(二硫代-二亚甲基))六苯甲醛 (FPDC) 的 COFs(FPDC-TPA-COF、FPDC-TPB-COF 和 FPDC-TPT-COF)。这些 COF 具有二维结晶结构、高孔隙率、良好的导电性和密集的氧化还原活性位点,因此适合用于储能设备。其中,FPDC-TPT-COF 作为 SIB 的阳极,具有 420 mAh g-1 (0.2 A g-1)的显著高比容量、出色的循环稳定性(3000 次循环后约 87% 的容量保持率,1.0 A g-1)和高速率性能(2.0 A g-1 时 339 mAh g-1),超过了大多数已报道的基于 COF 的电极。这种优异的性能归功于二硫代分子增强了导电性,以及氧化还原活性羰基、亚胺和三嗪位点的存在促进了 Na 的储存。此外,还通过原位实验和密度泛函理论(DFT)计算阐明了钠化机理。这项工作凸显了将多个官能团整合到氧化还原活性 COF 中以合理设计高效稳定的 SIB 的优势。
Integrating Multiple Redox-Active Units into Conductive Covalent Organic Frameworks for High-Performance Sodium-Ion Batteries
The rational design of porous covalent organic frameworks (COFs) with high conductivity and reversible redox activity is the key to improving their performance in sodium-ion batteries (SIBs). Herein, we report a series of COFs (FPDC-TPA-COF, FPDC-TPB-COF, and FPDC-TPT-COF) based on an organosulfur linker, (trioxocyclohexane-triylidene)tris(dithiole-diylylidene))hexabenzaldehyde (FPDC). These COFs feature two-dimensional crystalline structures, high porosity, good conductivity, and densely packed redox-active sites, making them suitable for energy storage devices. Among them, FPDC-TPT-COF demonstrates a remarkably high specific capacity of 420 mAh g−1 (0.2 A g−1), excellent cycling stability (~87% capacity retention after 3000 cycles, 1.0 A g−1) and high rate performance (339 mAh g−1 at 2.0 A g−1) as an anode for SIBs, surpassing most reported COF-based electrodes. The superior performance is attributed to the dithiole moieties enhancing the conductivity and the presence of redox-active carbonyl, imine, and triazine sites facilitating Na storage. Furthermore, the sodiation mechanism was elucidated through in-situ experiments and density functional theory (DFT) calculations. This work highlights the advantages of integrating multiple functional groups into redox-active COFs for the rational design of efficient and stable SIBs.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.