Electrochemical cells with aluminum (Al) as the active material offer the benefits of high energy density, low cost, and high safety. Although several research groups have assembled rechargeable Al//MxOy (M = Mn, V, etc) cells with 2 m aqueous Al trifluoromethanesulfonate as an electrolyte and demonstrated the importance of the artificial solid electrolyte interphase (ASEI) on the Al anode for realizing high rechargeable capacity, the reactions of the Al anode in such cells remain underexplored. Herein, we investigate the effects of the ASEI on the charge/discharge cycling stability and activity of Al cells with the abovementioned aqueous electrolyte and reveal that this interphase provides chloride anions to induce the corrosion of Al rather than to support the transportation of Al3+ ions during charge/discharge. Regardless of the ASEI presence/absence, the main reactions at the Al anode during charge/discharge cycling are identified as oxidation and gas evolution, which suggests that the reduction of Al in the employed electrolyte is irreversible. The simple introduction of chloride anions (e.g., 0.15 m NaCl) into the electrolyte is shown to allow the realization of an Al//MnO2 cell with superior performance (discharge working voltage ≈ 1.5 V and specific capacity = 250 mA h/g). Thus, the present work unveils the mechanisms of reactions occurring at the Al anode of aqueous electrolyte Al cells to support their further development.
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