Fully sp² Carbon-Conjugated Covalent Organic Frameworks with Multiple Active Sites for Advanced Lithium-Ion Battery...

Covalent organic frameworks (COFs) hold great promise for rechargeable batteries. However, the synthesis of COFs with abundant active sites, excellent stability, and increased conductivity remains a challenge. Here, chemically stable fully sp² carbon-conjugated COFs (sp²c-COFs) with multiple active sites are designed by the polymerization of benzo[1,2-b:3,4-b':5,6-b'']trithiophene-2,5,8-tricarbaldehyde) (BTT) and s-indacene-1,3,5,7(2H,6H)-tetrone (ICTO) (denoted as BTT-ICTO). The morphology and structure of the COF are precisely regulated from "butterfly-shaped" to "cable-like" through an in situ controllable growth strategy, significantly promoting the exposure and utilization of active sites. When the unique "cable-like" BTT-ICTO@CNT is employed as lithium-ion batteries (LIBs) cathode, it exhibits exceptional capacity (396 mAh g^-1 at 0.1 A g^-1 with 97.9 % active sites utilization rate), superb rate capacity (227 mAh g^-1 at 5.0 A g^-1), and excellent cycling performance (184 mAh g^-1 over 8000 cycles at 2.0 A g^-1 with 0.00365 % decay rate per cycle). The lithium storage mechanism of BTT-ICTO is exhaustively revealed by in situ Fourier transform infrared, in situ Raman, and density functional theory calculations. This work provides in-depth insights into fully sp²c-COFs with multiple active sites for high-performance LIBs.