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

Aqueous zinc‐ion batteries (ZIBs) hold immense promise for large‐scale energy storage, but their practical application is hindered by zinc anode limitations. We introduce diethylenetriamine pentaacetate sodium salt (DTPA‐Na) as a novel electrolyte additive to address these challenges. DTPA‐Na's unique dual functionality enables the formation of robust, multi‐layered solid electrolyte interphases (SEI) on the zinc anode and stable cathode electrolyte interphases (CEI) on the MnOOH cathode. This synergistic SEI/CEI engineering approach effectively suppresses interfacial side reactions, promotes uniform zinc deposition, and inhibits dendrite growth, leading to exceptional cycling stability and self‐discharge inhibition. Asymmetrical cells employing DTPA‐Na achieve an unprecedented 32,000 cycles at a high charging rate of 50 mA/cm2, while symmetric cells demonstrate a lifespan of 160 hours with 95% zinc utilization. Full Zn||MnOOH cells exhibit remarkable stability, maintaining 98.61% capacity retention after 720 hours of self‐discharge and negligible capacity decay over 5000 cycles. Our work highlights the transformative potential of DTPA‐Na as a dual‐functional electrolyte additive, paving the way for high‐performance ZIBs for practical energy storage applications.