Turning Zn(PO3)2-Enriched Inorganic/Organic Hybrid Interfacial Chemistry with Chelating Ligands toward Robust Aqueous Zn Anodes

Due to the inherent redox potential of the zinc metal anode (ZMA), it is susceptible to corrosion and dendrite formation in aqueous electrolytes. These issues compromise the electroplating-stripping process at the electrolyte–electrode interface, adversely affecting the reversibility of aqueous zinc-ion batteries (AZIBs). Here, we propose a chelating-ligand additive (i.e., DS) strategy to construct in situ an inorganic/organic hybrid bilayer interface. The organic molecule enriched in -PO3 groups is calculated to preferentially adsorb onto the surface of ZMA. During subsequent reactions, these adsorbed molecules decompose preferentially due to their low lowest unoccupied molecular orbital energy level (0.34 eV), forming a Zn(PO3)2-enriched inorganic solid electrolyte interphase (SEI) layer. Simultaneously, the intermediate carbon skeleton cross-links, creating an organic layer atop the SEI, thereby forming an inorganic/organic hybrid SEI bilayer interface. This bilayer SEI interface effectively inhibits corrosion and hydrogen evolution reactions (HERs) while regulating the Zn2+ ion flux at the interface, inducing uniform Zn depositions. Consequently, the Zn||Zn symmetric battery demonstrates a long-term cycling lifespan exceeding 1700 h at 5 mA cm–2. The Zn||I2 pouch battery yielded a capacity retention of 71.3% after 1100 cycles. This synergistic modulation strategy offers insights into the development of ZMA stabilizer additives, potentially advancing the performance and durability of AZIBs.