Li-Ion Transfer Mechanism of Gel Polymer Electrolyte with Sole Fluoroethylene Carbonate Solvent

Although gel polymer electrolytes (GPEs) represent a promising candidate to address the individual limitations of liquid and solid electrolytes, their extensive development is still hindered due to the veiled Li-ion conduction mechanism. Herein, the related mechanism in GPEs is extensively studied by developing an in situ polymerized GPE comprising fluoroethylene carbonate (FEC) solvent and carbonate ester segments (F-GPE). Practically, although with high dielectric constant, FEC fails to effectively transport Li ions when acting as the sole solvent. By sharp contrast, F-GPE demonstrates superior electrochemical performances, and the related Li-ion transfer mechanism is investigated using molecular dynamics simulations and ⁷Li/⁶Li solid-state nNMR spectroscopy. The polymer segments are extended with the swelling of FEC, then an electron-delocalization interface layer is generated between abundant electron-rich groups of FEC and the polymer ingredients, which works as an electron-rich “Milky Way” and facilitates the rapid transfer of Li ions by lowering the diffusion barrier dramatically, resulting in a high conductivity of 2.47 × 10⁻⁴ S cm⁻¹ and a small polarization of about 20 mV for Li//Li symmetric cell after 8000 h. Remarkably, FEC provides high flame-retardancy and makes F-GPE remains stable under ignition and puncture tests.