Asymmetric Anion Zinc Salt Derived Solid Electrolyte Interphase Enabled Long-Lifespan Aqueous Zinc Bromine Batteries

Organic additives with high-reduction potentials are generally applied in aqueous electrolytes to stabilize the Zn anode, while compromise safety and environmental compatibility. Highly concentrated water-in-salt electrolytes have been proposed to realize the high reversibility of Zn plating/stripping; however, their high cost and viscosity hinder their practical applications. Therefore, exploring low-concentration Zn salts, that can be used directly to stabilize Zn anodes, is of primary importance. Herein, we developed an asymmetric anion group, bi(difluoromethanesulfonyl)(trifluoromethanesulfonyl)imide (DFTFSI^-)-based novel zinc salt, Zn(DFTFSI)₂, to obtain a high ionic conductivity and a highly stable dendrite-free Zn anode. Experimental tests and theoretical calculations verified that DFTFSI⁻ in the Zn²⁺ solvation sheath and inner Helmholtz plane would be preferentially reduced to construct layer-structured SEI films, inhibiting hydrogen evolution and side reactions. Consequently, the Zn (Formula presented.) Zn symmetric cell with 1M Zn(DFTFSI)₂ aqueous electrolyte delivers an ultralong cycle life for >2500 h outperforming many other conventional Zn salt electrolytes. The Zn (Formula presented.) Br₂ battery also exhibits a long lifespan over 1200 cycles at ~99.8 % Coulombic efficiency with a high capacity retention of 92.5 %. Furthermore, this outstanding performance translates well to a high-areal-capacity Zn (Formula presented.) Br₂ battery (~5.6 mAh ⋅ cm^-2), cycling over 320 cycles with 95.3 % initial capacity retained. © 2024 Wiley-VCH GmbH.