Molecular Tailoring of Interfacial Chemistry via Aromatic‐Based Functions Toward Stable Zinc Metal Anodes

ABSTRACT The accelerated failure in aqueous zinc‐ion batteries primarily stems from the unpredictable evolution of zinc anode‐electrolyte interface. Aromatic molecule renders a promising application as electrolyte additives to mediate interfacial chemistry due to the steady spatial configuration and tunable functional groups, especially under high current densities. Herein, we report a comparative study by exploring three different non‐polar carbon backbones to elucidate the mechanism correlations between aromatic molecular structure and interfacial environment. Findings reveal that, compared with carbocyclic sodium benzenesulfonate (SBS) and hexane‐chain sodium 1‐hexanesulfonate (SHS), the sodium 3‐pyridinesulfonate (3‐PSA) with an electronegative pyridine‐nitrogen group could promote the morphological dominance of Zn(002) texture, ameliorating the water‐related side reactions and homogenizing zinc deposition/stripping. Meanwhile, with synergy of pyridine‐N π‐electron delocalization and sulfonate group, 3‐PSA adsorbs on Zn anode, induces a gradient solid electrolyte interphase, alters the solvation structure and hydrogen bond networks. Consequently, even under a harsh condition of 50 mA cm ⁻² , 5 mAh cm ⁻² , the Zn//Zn cells deliver a long‐term cycling life of over 3450 cycles. In addition, Zn//V ₂ O ₅ pouch cells with 3‐PSA electrolytes exhibit a superior stability over 1000 cycles, establishing a foundation for practical Zn‐based energy storage systems at molecule‐mediated level.