High-Concentrated Binary-Salt Ether Electrolytes for High-Voltage Lithium Metal Batteries with Ni-Rich Cathode

The incompatibility of ether electrolytes with a cathode dramatically limits its application in high-voltage Li metal batteries. Herein, we report a new highly concentrated binary salt ether-based electrolyte (HCBE, 1.25 M LiTFSI + 2.5 M LiFSI in DME) that enables stable cycling of high-voltage lithium metal batteries with the Ni-rich (NCM83, LiNi_0.83Co_0.12Mn_0.05O₂) cathode. Experimental characterizations and density functional theory (DFT) calculations reveal the special solvation structure in HCBE. A solvation structure rich in aggregates (AGGs) can effectively broaden the electrochemical window of the ether electrolyte. The anions in HCBE preferentially decompose under high voltage, forming a CEI film rich in inorganic components to protect the electrolyte from degradation. Thus, the high-energy-density Li||NCM83 cell has a capacity retention of ≈95% after 150 cycles. Significantly, the cells in HCBE have a high and stable average Coulombic efficiency of over 99.9%, much larger than that of 1 M LiPF₆ + EC + EMC + DMC (99%). The result emphasizes that the anionic-driven formation of a cathode electrolyte interface (CEI) can reduce the number of interface side reactions and effectively protect the cathode. Furthermore, the Coulombic efficiency of Li||Cu using the HCBE is 98.5%, underscoring the advantages of using ether-based electrolytes. This work offers novel insights and approaches for the design of high-performance electrolytes for lithium metal batteries.