Integrated Hollow Microfibers of Covalent Organic Framework on Cu Foil as a Gradient Zn Metal Anode Host for Bottom‐Up Deposition

Rechargeable aqueous Zn metal batteries are promising choices for future grid-scale energy storage because of cost-effectiveness, high-rate performance and safety. Nonetheless, the sluggish desolvation of hydrated Zn²⁺ ions usually leads to uncontrolled Zn dendrite growth and detrimental side reactions on Zn metal anodes (ZMAs). Herein, we report the formation of integrated hollow microfibers of covalent organic frameworks on Cu foil (denoted as HMCOF-Cu) as a ZMA host with gradient design. Of note, interactions between carbonyl groups of HMCOF and H₂O in [Zn(H₂O)₆]²⁺ promote rapid desolvation of hydrated Zn²⁺. Besides, 3D HMCOF network can accelerate Zn²⁺ diffusion and accommodate the volumetric deformation during the deposition/stripping cycles. Moreover, the gradient design can induce bottom-up deposition for dendrite-free ZMA. As a result, the HMCOF-Cu host enables stable Zn plating/stripping processes over 2500 h at 10 mA cm^-2. Moreover, the full cell based on HMCOF-Cu@Zn anode presents a long-term stability over 7000 cycles at 10 A g^-1.