Chirality‐Engineered Supramolecular Gel Networks: Manipulating Interfacial Chemistry for Ultrastable Zinc Metal Batteries

ABSTRACT While gel polymer electrolytes buffer interfacial stress in aqueous zinc metal batteries (AZMBs), traditional designs rely on isotropic chemical affinities, lacking the spatial precision to actively regulate complex interfacial electrochemistry. To transcend passive physical scaffolds, we embed pure R‐configured enantiomers into an achiral polymer host, translating molecular chirality into configuration‐dependent supramolecular assembly. Unlike S‐enantiomeric and racemic counterparts, the R‐enantiomer develops more favorable configuration‐dependent associations with the polymer backbone via multiplexed non‐covalent interactions, yielding a more integrated and mechanically reinforced supramolecular network. This configuration‐dependent network organization facilitates Zn 2+ transport by establishing more continuous ion‐conduction pathways, successfully circumventing the racemic self‐quenching effect and mitigating the steric penalties of the S‐enantiomer. Thermodynamically, the network strictly confines highly reactive free water to eradicate parasitic reactions and block cathode dissolution. Kinetically, it reshapes the Zn 2+ solvation sheath and constructs sub‐nanoscale channels guiding homogeneous zinc deposition. Consequently, the optimized R‐gel symmetric cells achieve a prolonged lifespan of 5800 h. Assembled Zn||VO 2 full cells deliver an outstanding 91.2% capacity retention after 8000 cycles at 1 A g −1 , alongside robust durability (81.0% retention after 3000 cycles) at 5 A g −1 . This work elevates stereochemical configuration into an active structural parameter, establishing a molecularly precise design paradigm for durable AZMBs.