Hydrophobic Ion Barrier‐Enabled Ultradurable Zn (002) Plane Orientation towards Long‐Life Anode‐Less Zn Batteries

Abstract Gradual disability of Zn anode and high negative/positive electrode (N/P) ratio usually depreciate calendar life and energy density of aqueous Zn batteries (AZBs). Herein, within original Zn 2+ ‐free hydrated electrolytes, a steric hindrance/electric field shielding‐driven “hydrophobic ion barrier” is engineered towards ultradurable (002) plane‐exposed Zn stripping/plating to solve this issue. Guided by theoretical simulations, hydrophobic adiponitrile (ADN) is employed as a steric hindrance agent to ally with inert electric field shielding additive (Mn 2+ ) for plane adsorption priority manipulation, thereby constructing the “hydrophobic ion barrier”. This design robustly suppresses the (002) plane/dendrite growth, enabling ultradurable (002) plane‐exposed dendrite‐free Zn stripping/plating. Even being cycled in Zn‖Zn symmetric cell over 2150 h at 0.5 mA cm −2 , the efficacy remains well‐kept. Additionally, Zn‖Zn symmetric cells can be also stably cycled over 918 h at 1 mA cm −2 , verifying uncompromised Zn stripping/plating kinetics. As‐assembled anode‐less Zn‖VOPO 4 ⋅ 2H 2 O full cells with a low N/P ratio (2 : 1) show a high energy density of 75.2 Wh kg −1 full electrode after 842 cycles at 1 A g −1 , far surpassing counterparts with thick Zn anode and low cathode loading mass, featuring excellent practicality. This study opens a new avenue by robust “hydrophobic ion barrier” design to develop long‐life anode‐less Zn batteries.