Sulfur and Wavy‐Stacking Boosted Superior Lithium Storage in 2D Covalent Organic Frameworks

2D conjugated covalent organic frameworks (c-COFs) provide an attractive foundation as organic electrodes in energy storage devices, but their storage capability is long hindered by limited ion accessibility within densely π-π stacked interlayers. Herein, two kinds of 2D c-COFs based on dioxin and dithiine linkages are reported, which exhibit distinct in-plane configurations-fully planar and undulated layers. X-ray diffraction analysis reveals wavy square-planar networks in dithiine-bridged COF (COF-S), attributed to curved C─S─C bonds in the dithiine linkage, whereas dioxin-bridged COF (COF-O) features densely packed fully planar layers. Theoretical and experimental results elucidate that the undulated stacking within COF-S possesses an expanded layer distance of 3.8 Å and facilitates effective and rapid Li⁺ storage, yielding a superior specific capacity of 1305 mAh g^-1 at 0.5 A g^-1, surpassing that of COF-O (1180 mAh g^-1 at 0.5 A g^-1). COF-S also demonstrates an admirable cycle life with 80.4% capacity retention after 5000 cycles. As determined, self-expanded wavy-stacking geometry, S-enriched dithiine in COF-S enhances the accessibility and redox activity of Li storage, allowing each phthalocyanine core to store 12 Li⁺ compared to 8 Li⁺ in COF-O. These findings underscore the elements and stacking modes of 2D c-COFs, enabling tunable layer distance and modulation of accessible ions.