Modulating solvated structure of Zn2+ and inducing surface crystallography by a simple organic molecule with abundant polar functional groups to synergistically stabilize zinc metal anodes for long-life aqueous zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs) have attracted significant attention owing to their inherent security, low cost, abundant zinc (Zn) resources and high energy density. Nevertheless, the growth of zinc dendrites and side reactions on the surface of Zn anodes during repeatedly plating/stripping shorten the cycle life of AZIBs. Herein, a simple organic molecule with abundant polar functional groups, 2,2,2-trifluoroether formate (TF), has been proposed as a high-efficient additive in the ZnSO₄ electrolyte to suppress the growth of Zn dendrites and side reaction during cycling. It is found that TF molecules can infiltrate the solvated sheath layer of the hydrated Zn²⁺ to reduce the number of highly chemically active H₂O molecules owing to their strong binding energy with Zn²⁺. Simultaneously, TF molecules can preferentially adsorb onto the Zn surface, guiding the uniform deposition of Zn²⁺ along the crystalline surface of Zn(002). This dual action significantly inhibits the formation of Zn dendrites and side reactions, thus greatly extending the cycling life of the batteries. Accordingly, the Zn//Cu asymmetric cell with 2 % TF exhibits stable cycling for more than 3,800 cycles, achieving an excellent average Columbic efficiency (CE) of 99.81 % at 2 mA cm^-2/1 mAh cm^-2. Meanwhile, the Zn||Zn symmetric cell with 2 % TF demonstrates a superlong cycle life exceeding 3,800 h and 2,400 h at 2 mA cm^-2/1 mAh cm^-2 and 5 mA cm^-2/2.5 mAh cm^-2, respectively. Simultaneously, the Zn//VO₂ full cell with 2 % TF possesses high initial capacity (276.8 mAh/g) and capacity retention (72.5 %) at 5 A/g after 500 cycles. This investigation provides new insights into stabilizing Zn metal anodes for AZIBs through the co-regulation of Zn²⁺ solvated structure and surface crystallography.