Redesigning Solvation Structure toward Passivation-Free Magnesium Metal Batteries

Simple magnesium (Mg) salt solutions are widely considered as promising electrolytes for next-generation rechargeable Mg metal batteries (RMBs) owing to the direct Mg²⁺ storage mechanism. However, the passivation layer formed on Mg metal anodes in these electrolytes is considered the key challenge that limits its applicability. Numerous complex halogenide additives have been introduced to etch away the passivation layer, nevertheless, at the expense of the electrolyte's anodic stability and cathodes' cyclability. To overcome this dilemma, here, we design an electrolyte with a weakly coordinated solvation structure which enables passivation-free Mg deposition while maintaining a high anodic stability and cathodic compatibility. In detail, we successfully introduce a hexa-fluoroisopropyloxy (HFIP^-) anion into the solvation structure of Mg²⁺, the weakly [Mg-HFIP]⁺ contact ion pair facilitates Mg²⁺ transportation across interfaces. As a consequence, our electrolyte shows outstanding compatibility with the RMBs. The Mg||PDI-EDA and Mg||Mo₆S₈ full cells use this electrolyte demonstrating a decent capacity retention of ∼80% over 400 cycles and 500 cycles, respectively. This represents a leap in cyclability over simple electrolytes in RMBs while the rest can barely cycle. This work offers an electrolyte system compatible with RMBs and brings deeper understanding of modifying the solvation structure toward practical electrolytes.