Interfacial Energy‐Level Modulation Enables Electron‐Ion Decoupling for Hydrogen Suppression and Highly Durable Zinc Metal Anodes

ABSTRACT Aqueous zinc‐ion batteries (AZIBs) have attracted increasing attention owing to their high safety and low cost, yet the Zn anode suffers from severe interfacial instability caused by hydrogen evolution reaction (HER) and corrosion coupling. Herein, we propose an electron‐acceptor‐driven interfacial energy‐level regulation mechanism that intrinsically weakens the thermodynamic driving force of HER. The interfacial electronic structure of Zn is reconstructed at the molecular scale, forming a stable electron‐depleted layer and elevating the reduction barrier, as realized by a triazine‐based conjugated polymer (CTP‐BT) incorporating a benzothiadiazole (BT) acceptor unit with a low LUMO energy level. Meanwhile, the N/S coordination sites enhance Zn ²⁺ desolvation and guide preferential Zn deposition along the (002) plane, achieving decoupled electron‐ion transport and optimized deposition kinetics. Theoretical and experimental results confirm that this mechanism significantly increases the Gibbs free energy of hydrogen adsorption and suppresses HER and related byproducts. Consequently, the CTP‐BT@Zn anode delivers over 4000 cycles at 5 mA cm ⁻² with an average Coulombic efficiency of 99.88%, and CTP‐BT@ZN||PANI full cells maintain 89.46% capacity after 10 000 cycles at 5 A g ⁻¹ . This study establishes a molecular‐level strategy for intrinsic HER inhibition and interfacial stabilization.