Rechargeable Mn-metal batteries (MMBs) can attract considerable attention because Mn has the intrinsic merits including high energy density (976 mAh g), high air stability, and low toxicity. However, the application of Mn in rechargeable batteries is limited by the lack of proper cathodes for reversible Mn intercalation/de-intercalation, thus leading to low working voltage (<1.8 V) and poor cycling stability (≤200 cycles). Herein, a high-voltage and durable MMB with graphite as the cathode is successfully constructed using a LiPF-Mn(TFSI) hybrid electrolyte, which shows a high discharge voltage of 2.34 V and long-term stability of up to 1000 cycles. Mn(TFSI) can reduce the plating/stripping overpotential of Mn ions, while LiPF can efficiently improve the conductivity of the electrolyte. Electrochemical in-situ characterization implies the dual-anions intercalation/de-intercalation at the cathode and Mn plating/stripping reaction at the anode. Theoretical calculations unveil the top site of graphite is the energetically favorable for anions intercalation and TFSI shows the low migration barrier. This work paves an avenue for designing high-performance rechargeable MMBs towards electricity storage.
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