Directional Regulation of Zinc Deposition Through Constructing Hierarchical Janus Carbon Matrix with Organic‐Decorated Multi‐Channels

ABSTRACT The development of rechargeable aqueous zinc‐ion battery (AZIB) has been hampered by parasitic reactions, despite the low cost, high safety, and environmental friendliness. Here, we design an artificial interfacial layer using a hierarchical Janus carbon matrix on Zn anodes to direct Zn deposition behavior. By covalently anchoring zincophilic organic sulfonic groups within the inner pores of the hierarchical multi‐channel structure of CMK‐5 (CMK‐5/PS), we establish a charge gradient between the grafted inner and unmodified outer surfaces that promotes Zn 2+ diffusion and deposition. The negatively charged inner surface facilitates fast Zn 2+ adsorption and uniform nucleation, while the interconnected porous structure facilitates fast Zn 2+ transport. The confinement effect localizes Zn deposition exclusively within the tubular pores and reduces direct contact with electrolytes, thereby suppressing parasitic reactions and improving the plating/stripping efficiency. As a result, CMK‐5/PS@Zn anode achieves a high Coulombic efficiency of 99.2% and stability over 8000 h. When paired with an NH 4 V 4 O 10 cathode, the CMK‐5/PS@Zn delivers a high reversible capacity of 213.8 mAh g −1 after 1000 cycles at 1 A g −1 . This work provides a new paradigm for interfacial engineering of Zn metal anodes through carbon‐organic composite architectures, advancing the design of durable and high‐performance AZIB technologies.