COORDINATION AND FLUORINE-CONTROLLED REGULATOR Zn2+ FOR STABLE AQUEOUS ZINC-ION BATTERIES
DOI:
https://doi.org/10.65164/wjwgvd14Keywords:
aqueous zinc-ion batteries, electrolyte additive, solid electrolyte interphase, solvation structure, zinc dendritesAbstract
Electrolyte additives that simultaneously regulate Zn2+ solvation and induce the formation of a
solid electrolyte interphase (SEI) offer an effective way to suppress dendrite growth, hydrogen
evolution, and side reactions in aqueous zinc-ion batteries (AZIBs). Here, fluorinated acetylacetone
derivatives are used to achieve these dual functions at low concentrations. Progressive fluorination
enhances electron delocalization and lowers the lowest unoccupied molecular orbital (LUMO), which
allows preferential accumulation on the Zn surface. In particular, hexafluoroacetylacetone (HFAT)
forms stable [Zn(H2O)5HFAT]2+ solvation shells, which reduce the interfacial water activity and
promote Zn2+ desolvation. The lower LUMO value of HFAT further enhances its preferential
electrochemical reduction, leading to the formation of a gradient cement-brick-like ZnF2-rich SEI
that stabilizes Zn deposition and enhances Zn2+ transport. As a result, Zn||Zn symmetric cells exhibit
a lifetime of over 4300 h at 1 mA cm−2 /1 mAh cm−2, Zn||Cu cells achieve an average Coulomb
efficiency of 99.62% over 1500 cycles, and Zn||I2 full cells retain 125.8 mAh g−1 after 10,000 cycles.
This study highlights the potential of fluorine-guided electrolyte design to synergistically optimize
solvation structure and interface stability for high-performance AZIBs.
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