Molecular Engineering‐Enabled Self‐Adaptive Topological Adsorption Interface: Synergistic Hydrophobic Nanoconfinement and Electrostatic Shielding for Highly Stable Zn Anode

The Zn metal anodes suffer from severe side reactions and uncontrolled dendrite growth, limiting their practical application. To stabilize the Zn anode, a novel dynamic self‐adaptive dual‐ion stabilization mechanism is developed via in‐situ self‐assembly of multifunctional Oktakis (tetramethylammonium)‐T 8 ‐silsesquioxane (TMA‐POSS) topological molecular additives. In the electrolyte, TMA‐POSS dissociates into tetramethyl quaternary ammonium (TMA + ) cations and polyhedral oligomeric silsesquioxane [T 8 (Si‐O) 8 8− ] anions. TMA + preferentially adsorbs on the Zn surface, forming an inner self‐healing electrostatic shielding layer that ensures uniform Zn nucleation and deposition. Concurrently, T 8 (Si‐O) 8 8− self‐organizes into a hydrophobic nanoconfined buffer layer, which synergistically regulates Zn 2+ /SO 4 2− migration, promotes [Zn(H 2 O) 6 ] 2+ desolvation, and restricts H 2 O penetration, thereby suppressing space charge layer‐introduced dendrite growth and side reactions. More notably, this self‐assembled dual‐ion layer dynamically adapts to interfacial changes without degradation, exhibiting high stability and non‐sacrificial nature. Consequently, the Zn anode delivers exceptional reversibility 4700 h, and 99.6% Coulombic efficiency over 2110 cycles. Zn//MnO 2 and Zn//V 2 O 5 full cells deliver outstanding capacity retentions of 81.2% (1700 cycles at 1 A g −1 ) and 80.1% (2500 cycles at 10 A g −1 ), respectively. This work pioneers a novel multifunctional dual‐ion interface based on topological molecular engineering, providing a feasible strategy to advance the practical application of aqueous zinc‐ion batteries.