Interweaved Nanofiber Anode Coating Based on Covalent Organic Frameworks for High‐Performance Lithium‐Metal Batteries

High‐rate lithium‐metal batteries call for unique interfacial structures of anode with interfacial compatibility, facilitated lithium insertion/extraction and dendrite suppression properties to meet the growing high‐rate demand. Here, we develop an interweaved porous coating based on a kind of covalent organic framework (ODH‐Cu3‐COF) based helical nanofibers through the assembly of non‐linear oxalyldihydrazide unit and rigid Cu3 unit. The interweaved helical nanofibers network with well‐arranged polar groups (i.e. C=N, ‐CO‐NH‐ and pyrazole groups) could serve as nuclei sites to achieve fast Li+ insertion/extraction and dendrite suppression in high‐rate conditions. Benefiting from the advantages of interface design, the resultant ODH‐Cu3‐COF modified anode improves the Coulombic efficiency (97.5%, 120 cycles at 5 mA cm‐2) and showcases a stable lifespan (1000 h at 2 mA cm‐2 and 2 mAh cm‐2) in symmetric cell. Moreover, the high‐rate property of ODH‐Cu3‐COF@Li||LFP full cell presents an excellent cycling stability (900 cycles at 5 C) in commercial carbonate electrolyte. Theoretical calculations reveal that lithiophilic ODH‐Cu3‐COF has high Li affinity to reduce the nucleation barrier and achieve fast desolvation process in interface to promote the lifespan of high‐rate lithium‐metal batteries.