Simultaneous Stabilization of the Solid/Cathode Electrolyte Interface in Lithium Metal Batteries by a New Weakly Solvating Electrolyte

So far, the practical application of Li metal batteries has been hindered by the undesirable formation of Li dendrites and low Coulombic efficiencies (CEs). Herein, 1,2‐diethoxyethane (DEE) is proposed as a new electrolytic solvent for lithium metal batteries (LMBs), and the performances of 1.0 m LiFSI in DEE are evaluated. Because of the low dielectric constant and dipole moment of DEE, the majority of the FSI− exists in associated states like contact ion pairs and aggregates, which is similar to the highly concentrated electrolytes. These associated complexes are involved in the reduction reaction on the Li metal anode, forming sound solid electrolyte interphase layers. Furthermore, free FSI− ions in DEE are observed to participate in the formation of cathode electrolyte interphase layers. These passivation layers not only suppress dendrite growth on the Li anode but also prevent unwanted side‐reactions on the LiFePO4 cathode. The average CE of the Li||Cu cells in LiFSI–DEE is observed to be 98.0%. Moreover, LiFSI–DEE also plays an important role in enhancing the cycling stability of the Li||LiFP cell with a capacity retention of 93.5% after 200 cycles. These results demonstrate the benefits of LiFSI–DEE, which creates new possibilities for high‐energy‐density rechargeable LMBs. A consisting mixture of LiFSI and 1,2‐diethoxyethane (DEE)at 1.0 m is chosen as the novel electrolyte for lithium metal batteries. The LiFSI–DEE electrolyte is observed to be mostly dominated by CIPs and AGGs, which supports the simultaneous formation of sound SEI/CEI layers with inorganic conductive components. Consequently, cells with LiFSI–DEE not only exhibit high Coulombic efficiencies but also suppress Li dendrites.