Dilute Electrolytes with Fluorine‐Free Ether Solvents for 4.5 V Lithium Metal Batteries

The limited oxidation stability of ether solvents has posed significant challenges for their applications in high-voltage lithium metal batteries (LMBs). To tackle this issue, the prevailing strategy either adopts a high concentration of fluorinated salts or relies on highly fluorinated solvents, which will significantly increase the manufacturing cost and create severe environmental hazards. Herein, an alternative and sustainable salt engineering approach is proposed to enable the utilization of dilute electrolytes consisting of fluorine (F)-free ethers in high-voltage LMBs. The proposed 0.8 M electrolyte supports stable lithium plating-stripping with a high Coulombic efficiency of 99.47 % and effectively mitigates the metal dissolution, phase transition, and gas release issues of the LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathode upon charging to high voltages. Consequently, the 4.5 V high-loading Li||NCM 811 cell shows a capacity retention of 75.2 % after 300 cycles. Multimodal experimental characterizations coupled with theoretical investigations demonstrate that the boron-containing salt plays a pivotal role in forming the passivation layers on both anode and cathode. The present simple and cost-effective electrolyte design strategy offers a promising and alternative avenue for using commercially mature, environmentally benign, and low-cost F-free ethers in high-voltage LMBs.