Gel polymer electrolyte (GPE) is a promising candidate for lithium-ion batteries due to its adhesion property (like a solid), diffusion property (like a liquid), and inhibition of the growth of lithium dendrite. In this paper, 2-(2-ethoxyethoxy)ethyl acrylate (EOEOEA) and LiBF
4 electrolyte were
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Gel polymer electrolyte (GPE) is a promising candidate for lithium-ion batteries due to its adhesion property (like a solid), diffusion property (like a liquid), and inhibition of the growth of lithium dendrite. In this paper, 2-(2-ethoxyethoxy)ethyl acrylate (EOEOEA) and LiBF
4 electrolyte were mixed as precursors of gel polymer electrolytes. Through thermal curing, a thermally stable GPE with high ionic conductivity (5.60 × 10
−4 s/cm at 30 °C) and wide room temperature electrochemical window (4.65 V) was prepared, and the properties of the GPE were measured by linear sweep voltammetry (LSV), AC impedance spectroscopy, Thermogravimetric analysis (TG), and X-ray diffraction (XRD) techniques. On the basis of the in-situ deep polymerization on a LiFePO
4 electrode and cellulose membrane in a battery case, EOEOEA-based GPE could be derived on both LiFePO
4 electrode and cellulose membrane. Meanwhile, the contact between GPE, LiFePO
4 electrode, and lithium electrode was promoted. The capacity retention rate of the as-prepared LiBF
4-EOEOEA 30% gel lithium battery reached 100% under the condition of 0.1 °C after 50 cycles, and the Coulombic efficiency was over 99%. Meanwhile, the growth of lithium dendrite could be effectively inhibited. GPE can be applied in high-performance lithium batteries.
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