Unraveling the Interphasial Chemistry for Highly Reversible Aqueous Zn Ion Batteries

A robust solid electrolyte interface (SEI) is crucial to widen the electrochemical stability window of the electrolyte and enable sustainably stable electrode reactions in aqueous Zn ion batteries. Different from the SEI in nonaqueous electrolytes, it is of great importance to form a functional and stable SEI due to parasitic reactions with water in aqueous Zn ion batteries. However, the concrete SEI formation in aqueous electrolytes has been elusive so far. Here, we regulate and unravel the decomposition mechanisms of organic Zn salts at the Zn anode–electrolyte interface in the widely studied zinc triflate-based aqueous electrolytes. By introducing a buffering adsorption layer with an optimal concentration of acetate anions, the uncontrollable decomposition of organic zinc triflate salt is greatly inhibited on Zn anodes, resulting in a stable interface. The average Coulombic efficiency of the Zn anode thus can reach as high as 99.95% and stable cycling for 4200 h. With the cooperation of buffering adsorption layers, the tetraethyl ammonium trifluoromethanesulfonate additive as the decomposition promoter could further regulate the decomposition of triflate anions for the formation of robust SEI layers for Zn anodes in electrolytes with a dilute salt concentration. Zn–polyaniline (PANI) full cells demonstrate stable cycling with controlled N/P ratios in such electrolytes. This work proposes an insightful perspective on rational regulation of the decomposition pathway of electrolyte components by forming a stable electrode–electrolyte interface for improved electrochemical performance of aqueous Zn ion batteries.