dc ionic conductivity and EIS were measured using a Novocontrol broadband dielectric/impedance spectrometer. Field-emission SEM (FESEM) images of MnO2 cathode and Al anode were obtained using a Leo 1550 Keck FESEM, in which EDX analysis was also carried out with a Bruker EDX detector. The XRD pattern of α-MnO2 cathodes during electrochemical reaction was taken with a Rigaku x-ray diffractometer. ATR-FTIR spectra of different electrolytes were obtained using a Bruker Hyperion FTIR spectrometer. XPS SSX-100 was applied to study the chemistry information of SEI on the Al surface and MnO2 cathodes. Galvanostatic measurements of Al batteries were performed using Neware battery testers at room temperature. CV diagram was performed on an electrochemical workstation of CH 600E. TEM images were obtained from the FEI Titan Themis CryoS/TEM, in which EELS spectra were obtained using a Gatan GIF Tridiem energy filter.

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