A Durable and High-Voltage Mn-Graphite Dual-Ion Battery Using Mn-Based Hybrid Electrolytes

Rechargeable Mn-metal batteries (MMBs) can attract considerable attention because Mn has the intrinsic merits including high energy density (976 mAh g(-1)), high air stability, and low toxicity. However, the application of Mn in rechargeable batteries is limited by the lack of proper cathodes for reversible Mn2+ 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 LiPF6-Mn(TFSI)(2) hybrid electrolyte, which shows a high discharge voltage of 2.34 V and long-term stability of up to 1000 cycles. Mn(TFSI)(2) can reduce the plating/stripping overpotential of Mn ions, while LiPF6 can efficiently improve the conductivity of the electrolyte. Electrochemical in-situ characterization implies the dual-anions intercalation/de-intercalation at the cathode and Mn2+ 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.