Engineering Core–Shell Interfaces with Hierarchical Mass Transport for Dendrite‑Free and Highly Reversible Zn Anodes

ABSTRACT Aqueous zinc batteries are plagued by dendrite growth and parasitic reactions, calling for a rational interfacial design. Herein, we construct a core–shell ZIF‐8@SiO 2 architecture on the Zn anode (ZFSI@Zn) via a self‐nucleation route. The hydrophilic SiO 2 shell and anion‐affinitive ZIF‐8 core synergistically facilitate Zn 2+ desolvation and transport, enhancing the 3D diffusion contribution while effectively suppressing interfacial concentration polarization. Consequently, the ZFSI@Zn anode delivers an extended lifespan of 1800 h at 1 mA cm −2 /1 mAh cm −2 and maintains remarkable stability even at an ultrahigh current density of 50 mA cm −2 . Beyond anode protection, strong SO 4 2− adsorption confers a negative surface charge that electrostatically repels I 3 − , thereby eliminating the shuttle effect in Zn‐I 2 batteries. This enables a maximum specific capacity of 202.3 mAh g −1 at 0.2 A g −1 and an outstanding capacity retention of 89.8% over 65 000 cycles at 5 A g −1 , corresponding to an ultralow capacity decay of merely 0.00015% per cycle. The superior performance is further validated under high cathode loadings and in pouch‑cell configurations. Overall, this work establishes core–shell interfacial engineering as a versatile platform for tackling the multiple challenges in zinc‑based energy storage.