Transforming Detrimental Crystalline Zinc Hydroxide Sulfate to Homogeneous Fluorinated Amorphous Solid-Electrolyte Interphase on Zinc Anode

ACS Nano. 2025 Jan 13. doi: 10.1021/acsnano.4c04795. Online ahead of print.

Abstract

The formation of non-ion conducting byproducts on zinc anode is notoriously detrimental to aqueous zinc-ion batteries (AZIBs). Herein, we successfully transform a representative detrimental byproduct, crystalline zinc hydroxide sulfate (ZHS) to fast-ion conducting solid-electrolyte interphase (SEI) via amorphization and fluorination induced by suspending CaF2 nanoparticles in dilute sulfate electrolytes. Distinct from widely reported nonhomogeneous organic-inorganic hybrid SEIs that exhibit structural and chemical instability, the designed single-phase SEI is homogeneous, mechanically robust, and chemically stable. These characteristics of the SEI facilitate the prevention of zinc dendrite growth and reduction of capacity loss during long-term cycling. Importantly, AZIB full cells based on this SEI-forming electrolyte exhibit exceptional stability over 20,000 cycles at 3 A/g with a charging voltage of 2.2 V without short circuits and electrolyte dry-out. This work suggests avenues for designing SEIs on a metal anode and provides insights into associated SEI chemistry.

Keywords: Amorphization; Electrolyte; Fluorination; Solid-electrolyte interphase; Zinc anode; Zinc hydroxide sulfate.