Chelation‐Driven Electrolyte Design for Enhanced Interface and Electrochemical Window in Aqueous Aluminum Batteries

Aqueous aluminum‐ion batteries have garnered significant attention owing to the abundance of aluminum resources, high theoretical specific capacity, and excellent safety. However, challenges such as electrolyte‐induced water decomposition, aluminum anode corrosion, and electrode material compatibility continue to constrain their performance. In this study, we restructured the solvation environment using the chelating reagent Bis(2‐methoxyethyl)amine (BMEA), achieving an expanded electrochemical window of 2.2 V and mitigating hydrogen evolution side reactions. Advanced atom probe tomography analysis confirmed that BMEA actively participates in the formation of the solid‐electrolyte interphase (SEI), effectively preventing aluminum surface corrosion and extending the cycle life of the aluminum anode. Employed as a BMEA‐containing electrolyte in aluminum‐organic batteries, the resulting Al||Tetrachloro‐1,4‐benzoquinone (TCB) battery delivered a high capacity of 218.0 mAh g−1 and demonstrated stable cycling over 300 cycles. This study highlights the potential of surface chelating agents in advancing high‐performance aluminum batteries.