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

Abstract

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.