Descriptor‐Inspired Oligomer Additives Enabling Long‐Life Zinc Metal Batteries

Abstract Interfacial dendrite growth and parasitic reactions pose major challenges to the stability and efficiency of zinc metal batteries, prompting the exploration of electrolyte additives for interface stabilization. Here, we reveal that the interfacial adsorption of organic additives cannot be captured by the simplified Langmuir model, but is concurrently governed by vertical anodic affinity and intermolecular constraints. Building on this insight, we propose a dual‐descriptor design strategy and introduce the tailored oligomers as brand‐new type of electrolyte additives, aiming to balance the adsorption intensity and interfacial order at interface, thereby preventing steric agglomeration. The representative oligochitosan (OCS) synergistically optimizes the consecutive desolvation‐diffusion process, facilitating vertically stacking of larger zinc grains and inhibiting hydrogen evolution, demonstrates exceptional high Coulombic efficiency (over 99.5% for Zn||Cu cells) and ultralong stability (>4,400 h at 1 mAh cm −2 and >880 h at 10 mAh cm −2 ), significantly outperforming conventional analogues. Moreover, Zn||V 6 O 13 full cells retain 130.8 mAh g −1 after 5,000 cycles at 5 A g −1 , and 0.2 Ah pouch cells maintain 91% capacity over 100 cycles. This work establishes a universal framework that connects molecular architecture with adsorption modes and interfacial dynamics, providing new insights for advanced electrolyte additives design.