Regulating Electrolyte Solvation Structures via Diluent‐Solvent Interactions for Safe High‐Voltage Lithium Metal Batteries

Abstract Local high concentration electrolytes (LHCEs) have been proved to be one of the most promising systems to stabilize both high voltage cathodes and Li metal anode for next‐generation batteries. However, the solvation structures and interactions among different species in LHCEs are still convoluted, which bottlenecks the further breakthrough on electrolyte development. Here, it is demonstrated that the hydrogen bonding interaction between diluent and solvent is crucial for the construction of LHCEs and corresponding interphase chemistries. The 2,2,2‐trifluoroethyl trifluoromethane sulfonate (TFSF) is selected as diluent with the solvent dimethoxy‐ethane (DME) to prepare a non‐flammable LHCE for high voltage LMBs. This is first find that the hydrogen bonding interaction between TFSF and DME solvent tailors the electrolyte solvation structures by weakening the coordination of DME molecules to Li+ cations and allows more participation of anions in the first solvation shell, leading to the formation of aggregates (AGGs) clusters which are conducive to generating inorganic solid/cathodic electrolyte interphases (SEI/CEIs). The proposed TFSF based LHCE enables the Li||NCM811 (LiNi0.8Mn0.1O2) batteries to realize >80% capacity retention with a high average Coulombic efficiency of 99.8% for 230 cycles under aggressive conditions (NCM811 cathode: 3.4 mAh cm−2, cut‐off voltage: 4.4 V, and 20 µm Li foil).