Transforming Zinc‐Ion Batteries with DTPA‐Na: A Synergistic SEI and CEI Engineering Approach for Exceptional Cycling Stability and Self‐Discharge Inhibition

Abstract Aqueous zinc‐ion batteries (ZIBs) hold immense potential for large‐scale energy storage, but their practical implementation faces significant challenges related to the zinc anode, including dendrite formation, corrosion, and hydrogen evolution. This study addresses these challenges by introducing diethylenetriamine pentaacetate sodium salt (DTPA‐Na) as a novel electrolyte additive. DTPA‐Na exhibits a unique dual functionality, enabling the formation of a robust, multi‐layered solid electrolyte interphase (SEI) on the zinc anode and a stable cathode electrolyte interphase (CEI) on the MnOOH cathode. The engineered SEI effectively suppresses interfacial side reactions, facilitates uniform zinc deposition, and mitigates dendrite growth, while the CEI inhibits MnOOH dissolution and detrimental cathode side reactions. This synergistic SEI/CEI engineering approach significantly enhances ZIB performance, achieving remarkable cycling stability and self‐discharge inhibition, as evidenced by the extended lifespan of Zn||Zn symmetrical cells (4400 hours at 0.5 mA/cm 2 ) and the exceptional capacity retention of Zn||MnOOH full cells after prolonged rest (98.61 % after 720 hours).