Electronic‐State Polarization Engineering‐Regulated Fluorinated Covalent Organic Framework Nanocables for Fast Lithium‐Ion Storage

ABSTRACT Covalent organic frameworks (COFs) are promising anode materials for lithium‐ion batteries (LIBs) owing to their tunable porous structures and abundant redox‐active sites; however, insufficient electronic‐structure regulation and sluggish kinetics severely limit their rate capability and cycling stability. Herein, an electronic‐state polarization engineering strategy is proposed by in situ constructing fluorinated COF nanocables enriched with multipolar C─F units on conductive carbon nanotube scaffolds to form a high‐performance anode (F‐COF@CNT). The strong polarity of C─F bonds induces localized electronic polarization within the COF framework, enhancing electrostatic attraction toward Li + and accelerating ion transport. Combined GITT analysis and density functional theory calculations reveal a reduced Li + diffusion barrier and a sustained diffusion coefficient on the order of 10 −11 cm 2 s −1 . Meanwhile, the interconnected CNTs network provides continuous electron‐transport pathways, effectively mitigating interfacial polarization and structural degradation. As a result, the F‐COF@CNT anode delivers 496.32 mAh g −1 at 0.1 A g −1 and maintains 281.21 mAh g −1 after 2000 cycles at 2.0 A g −1 . An NCM811||F‐COF@CNT full cell retains 105.94 mAh g −1 after 500 cycles, demonstrating excellent practical stability. This work establishes electronic‐state polarization engineering as a general strategy to overcome kinetic limitations in organic framework anodes.