π–π Stacking‐Directed Crystallographic Orientation of Zn Elec‐trodeposition for Ultralong‐Life Anodes

ABSTRACT The practical deployment of aqueous zinc (Zn) metal batteries is hindered by non‐uniform Zn deposition, where rampant dendrite growth and parasitic reactions lead to rapid performance decay. It remains a fundamental barrier to maintain control deposition behavior for reliable operation, especially under demanding practical conditions (e.g., wide currents and capacities). Here, we precisely guide the Zn deposition via the introduction of an aromatic Lewis base (ALB) as a molecular director that reconstructs the Zn 2+ solvation sheath and guides interfacial Zn 2+ self‐assembly via directional π–π stacking. The pre‐ordered configuration steers the crystallization of reduced Zn adatoms into a highly (002)‐textured and compact morphology through a thermodynamically favored pathway. As a result, the π–π stacking‑guided deposition strategy achieves exceptional Zn stability across a wide range of current densities from 2 mA cm −2 (>388 days) to 50 mA cm −2 (>480 h) and sustains stable operation for >600 h with a Zn utilization rate of 93.89%. This ALB‐incorporation strategy demonstrates remarkable universality with extended lifetime across supercapacitors (>50 000 cycles), Zn||PANI full cells (>20 000 cycles at −30°C), Ah‐level pouch cells (>20 cycles at 1A), and Zn‐air batteries (700 h). This work provides a molecular‐level pathway toward long‐lasting and high‐capacity Zn‐based energy storage devices.