High Li⁺ Transference Number Electrolyte Enabled by Fluoride Acceptor for Low-Temperature Li-Ion Batteries

To enable wide-temperature operation of lithium-ion batteries (LIBs), new electrolyte formulations have been developed to enhance the performance, particularly at low temperatures. A key challenge lies in achieving both high ionic conductivity and a high lithium-ion transference number due to their inherent trade-off. In this study, we designed an electrolyte system comprising tris(pentafluorophenyl)borane (TPFPB), a fluoride acceptor, and LiF salt in ethylene carbonate (EC)-free solvents. TPFPB, with its electron-deficient boron center, facilitates fluoride transfer reactions that promote the dissociation of otherwise insoluble LiF. When methyl acetate (MA) was used as the solvent, the electrolyte exhibited a high transference number ( t Li + = 0.85) and ionic conductivity (σ = 5.0 × 10 –3 S cm –1 ). The optimized electrolyte demonstrated excellent performance at −20 °C, with no evidence of lithium plating. This work presents a new strategy for electrolyte design by leveraging cation desolvation to achieve high-performance LIBs for low-temperature and high-power applications.