Superior Anodic Lithium Storage in Core–Shell Heterostructures Composed of Carbon Nanotubes and Schiff‐Base Covalent Organic Frameworks

Covalent organic frameworks (COFs) after undergoing the superlithiation process promise high‐capacity anodes while suffering from sluggish reaction kinetics and low electrochemical utilization of redox‐active sites. Herein, integrating carbon nanotubes (CNTs) with imine‐linked covalent organic frameworks (COFs) was rationally executed by in‐situ Schiff‐base condensation between 1,1′‐biphenyl]‐3,3′,5,5′‐tetracarbaldehyde and 1,4‐diaminobenzene in the presence of CNTs to produce core–shell heterostructured composites (CNT@COF). Accordingly, the redox‐active shell of COF nanoparticles around one‐dimensional conductive CNTs synergistically creates robust three‐dimensional hybrid architectures with high specific surface area, thus promoting electron transport and affording abundant active functional groups accessible for electrochemical utilization throughout the whole electrode. Remarkably, upon the full activation with a superlithiation process, the as‐fabricated CNT@COF anode achieves a specific capacity of 2324 mAh g−1, which is the highest specific capacity among organic electrode materials reported so far. Meanwhile, the superior rate capability and excellent cycling stability are also obtained. The redox reaction mechanisms for the COF moiety were further revealed by Fourier‐transform infrared spectroscopy in conjunction with X‐ray photoelectron spectroscopy, involving the reversible redox reactions between lithium ions and C=N groups and gradual electrochemical activation of the unsaturated C=C bonds within COFs. Coupling conductive carbon nanotubes with redox‐active imine‐linked covalent organic frameworks generates core–shell heterostructures capable of building 3D hierarchical architectures with fully exposed active sites for boosting anodic lithium storage.