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

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//V₂O₅ 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.