Pre‐Established Zincophilic Na ₂ SiO ₃ Decorated Array‐Like Channels to Regulate the Zn ²⁺ Flux and Interfacial Corrosion for Dendrite‐Free Zinc Anode

Aqueous zinc‐ion batteries (AZIBs) have attracted increasing attention in energy storage owing to their high energy density, low redox potential, and cost‐effectiveness. Nevertheless, uncontrolled dendrite accumulation, gas generation, and severe side‐reaction problems hinder the cycling lifespan, which prevents their commercial applications. Herein, array‐like porous channels decorated by Na 2 SiO 3 sites were in situ created on the diatomite layers by etching with NaOH (DH). DFT calculation results demonstrate that in situ formed Na 2 SiO 3 possesses improved Zn 2+ affinity. The negative 3D porous channels combined with zincophilic Na 2 SiO 3 sites provide a fast Zn 2+ transport pathway and facilitate the ion‐pair dissociation of ZnSO 4 , ensuring favorable Zn 2+ transfer kinetics and inhibited side reactions. Moreover, the ordered array‐like structure not only can exert a spatial confinement effect to suppress the 2D diffusion of Zn 2+ but also drive Zn metal preferential deposit toward the rigid microaligned channels and curb the formation of large‐scale zinc dendrites. Additionally, the hydrophobic diatomite protective layer can accelerate desolvation kinetics of Zn(H 2 O) 6 2+ and suppress the hydrogen evolution reactions. As a result, the DH‐modified Zn anode (DH@Zn) achieves a long cycle lifespan of 2500 h at 1 mA cm −2 , much more than that of bare Zn (∼100 h lifespan) in symmetrical cells. Besides, the DH@Zn//NH 4 V 4 O 10 (NVO) full cells demonstrate a high‐capacity retention of 93.3% after 1800 cycles at 5 A g −1 . This work provides a promising strategy and new insights into the design of electrolyte‐anode interfacial protection.