Machine-Learning-Guided Screening of Advantageous Solvents for Solid Polymer Electrolytes in Lithium Metal Batteries

Trace residual solvents in solid polymer electrolytes (SPEs) significantly affect electrolyte and interface properties, where optimal selection enhances the ionic conductivity and transference numbers. However, the solvent complexity hinders general screening methods. We establish a universal criterion linking electronic (highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO)) and macroscopic properties (dielectric constant, dipole moment, polarizability) via machine learning on an ∼10 000-solvent dataset from high-throughput density functional theory (DFT). Two solvents, <i>N</i>-methoxy-<i>N</i>-methyl-2,2,2-trifluoroacetamide and 2,2,2-trifluoro-<i>N</i>,<i>N</i>-dimethylacetamide were identified. Experimental incorporation of trace <i>N</i>-methoxy-<i>N</i>-methyl-2,2,2-trifluoroacetamide into a poly(vinylidene fluoride-co-hexafluoropropylene) matrix achieves a 4.5 V window, conductivity of 5.5 × 10^-4 S cm^-1 (30 °C), and Li⁺ transference number of 0.78. The cell retains 86.7% capacity over 500 cycles (LiFePO₄) and 98.7% after 200 cycles at 2C (LiNi_0.9Co_0.05Mn_0.05O₂), outperforming 2,2,2-trifluoro-<i>N</i>,<i>N</i>-dimethylacetamide, dimethylformamide, <i>N</i>-methyl-2-pyrrolidone, and dimethyl sulfoxide. This synergy enables balanced ion transport, wide stability, and cycling durability, advancing safer high-energy lithium metal batteries. Our integrated approach establishes a solvent screening paradigm for rational SPE design, accelerating next-generation battery development.