pH‐Regulated Organic–Inorganic Additive Engineering for Dendrite‐Free and Long‐Life Aqueous Zinc‐Ion Batteries

ABSTRACT Aqueous zinc‐ion batteries (AZIBs) are promising candidates for large‐scale energy storage systems due to their inherent high safety, low cost, and environmental friendliness. However, their practical employment is hindered by dendrite growth, hydrogen evolution reaction (HER), and interfacial corrosion, which severely degrade cycling stability. This study proposes a synergistic organic–inorganic d ual additives strategy that simultaneously regulates zinc deposition, suppresses parasitic reactions, and stabilizes electrode interfaces. The organic additive nonafluorobutane‐1‐sulfonic acid (FBSA) tailors the electrolyte solvation structure, while the inorganic additive diammonium phosphate (DAP) enhances ionic conductivity and the zinc ion transference number (t + ). A pH‐regulated optimization enables the formation of a robust hybrid organic–inorganic solid electrolyte interphase (SEI) layer on the zinc anode. Moreover, this combined additive strategy disrupts the water hydrogen‐bonding network, effectively mitigating HER. Benefiting from these synergistic effects, Zn||Zn symmetric cells exhibit ultra‐stable cycling exceeding 2800 h at 5 mA cm −2 . The Zn||MnO 2 full cell maintains a capacity above 100 mAh g −1 after 1000 cycles at 1 A g −1 . This work elucidating the synergistic mechanism of organic–inorganic dual additives provides a new electrolyte design paradigm for high‐performance AZIBs.