Beyond LiF: Tailoring Li₂O-Dominated Solid Electrolyte Interphase for Stable Lithium Metal Batteries

The components and structures of the solid-electrolyte interphase (SEI) are critical for stable cycling of lithium metal batteries (LMBs). LiF has been widely studied as the dominant component of SEI, but Li₂O, which has a much lower diffusion barrier for Li⁺, has rarely been investigated as the dominant component of SEI. The effect of Li₂O-dominated SEI on electrochemical performance still remains elusive. Herein, an ultrastrong coordinated cosolvation diluent, 2,3-difluoroethoxybenzene (DFEB), is designed to modulate solvation structure and tailor Li₂O-dominated SEI for stable LMBs. In the DFEB-based LHCE (DFEB-LHCE), DFEB intensively participates in the first solvation shell and synergizes with FSI⁻ to tailor an Li₂O-dominated inorganic-rich SEI which is different from the LiF-dominated SEI formed in conventional LHCE. Benefiting from this special SEI architecture, a high Coulombic efficiency (CE) of 99.58% in Li||Cu half cells, stable voltage profiles, and dense and uniform lithium deposition, as well as effective inhibition of Li dendrite formation in the symmetrical cell, are achieved. More importantly, the DFEB-LHCE can be matched with various cathodes such as LFP, NCM811, and S cathodes, and the Li||LFP full cell using DFEB-LHCE possesses 85% capacity retention after 650 stable cycles with 99.9% CE. Especially the 1.5 Ah practical lithium metal pouch cell achieves an excellent capacity retention of 89% after 250 cycles with a superb average CE of 99.93%. This work unravels the superiority of the Li₂O-dominated SEI and the feasibility of tailoring SEI components through modulation of solvation structures.