Topological Frustration of Ångström‐Confined Water for Stable Aqueous Zinc‐Ion Batteries

ABSTRACT Despite extensive efforts to regulate water activity in hydrogel electrolytes for aqueous zinc‐ion batteries (AZIBs), current strategies are insufficient to impose spatial constraints on water molecules and prevent the self‐assembly of bulk water networks. Herein, we report a quasi‐solid hybrid electrolyte (HM) by integrating polyacrylamide with a rigid inorganic montmorillonite (MMT) framework that imposes strong ångström confinement on interlayer water molecules. Such spatial confinement restricts the volume required to assemble a bulk three‐dimensional tetrahedral hydrogen‐bond network. Concurrently, polar Si‐O bonds on the MMT surface chemically anchor water molecules in a one‐hydrogen‐down configuration, inducing symmetry breaking and topological frustration. Consequently, Grotthuss‐type proton transport and water autoionization are suppressed. This molecular‐level regulation mitigates water‐induced parasitic reactions and byproduct accumulation, ensuring a reversible Zn/electrolyte interface. As a result, the assembled Zn||NH 4 V 4 O 10 full cell achieves stable cycling for over 800 cycles at 1 A g −1 . By shifting the electrolyte design toward ångström topological engineering, this work establishes a promising paradigm for suppressing water‐induced parasitic reactions in high‐performance AZIBs.