Two-dimensional (2D) olefin-linked covalent organic frameworks (COFs) with excellent π-electron communication and high stability are emerging as promising crystalline polymeric materials. However, because of the limited species of COFs, their characteristics, processability and potential applications have not been completely understood and explored. In this work, we prepared two novel olefin-linked 2D COFs through Knoevenagel condensation of 2,4,6-trimethyl-1,3,5-triazine with tritopic triazine-cored aldehydes. The resulting COFs exhibit highly crystalline honeycomb-like structures stacked from hexagonal-latticed polymeric layers and display well-defined nanofibrillar morphologies with the uniform diameters of ca. 80 nm and ultra-lengths up to several micrometers. Such COF nanofibers can be readily composited with carbon nanotubes into high-quality continuous thin films, which are further compacted by a typical hot-pressing process to enhance their densities and mechanical strength without changing their fibrous microstructures. Such film-fabricated interdigital microelectrodes and the ionogel electrolyte are assembled into planar micro-supercapacitors (MSCs), which exhibit an outstanding areal capacitance of 44.3 mF cm⁻², large operating voltage window of 2.5 V, high volumetric energy density of 38.5 mWh cm⁻³ as well as excellent cycling stability.

二维 (2D) 烯烃连接的共价有机框架 (COF) 具有出色的 π 电子通信和高稳定性，正在成为有前途的结晶聚合物材料。然而，由于 COF 的种类有限，其特性、加工性和潜在应用尚未得到完全了解和探索。在这项工作中，我们通过 2,4,6-三甲基-1,3,5-三嗪与三位三嗪核醛的 Knoevenagel 缩合制备了两种新型烯烃连接的二维 COF。由此产生的 COF 显示出由六角晶格聚合物层堆叠而成的高度结晶的蜂窝状结构，并显示出具有 ca 均匀直径的明确定义的纳米原纤维形态。80 nm 和长达几微米的超长。这种 COF 纳米纤维可以很容易地与碳纳米管复合成高质量的连续薄膜，这些薄膜通过典型的热压工艺进一步压实，以提高它们的密度和机械强度，而不改变它们的纤维微观结构。这种薄膜制造的叉指微电极和离子凝胶电解质被组装成平面微型超级电容器 (MSC)，具有 44.3 mF cm 的出色面电容⁻²、2.5 V 的大工作电压窗口、38.5 mWh cm ⁻³的高体积能量密度以及出色的循环稳定性。