LiF-rich SEI generated by in-situ gel polymer electrolyte process for lithium metal rechargeable batteries

A gel electrolyte was prepared by using lithium hexafluorophosphate (LiPF6) as the polymerization initiator of tetrahydrofuran, and at the same time as a fluorine source, a LiF-rich solid electrolyte interface (SEI) was constructed in-situ on the surface of the lithium metal anode to suppress the growth of lithium dendrites and side reactions between metallic lithium/electrolyte. The as-prepared gel polymer electrolyte presents an ionic conductivity of 1.33 mS·cm−1 at room temperature and shows a high electrochemical stability up to 4.5 V. Compared with linear sweep voltammetry in 335C electrolyte, lower reduction current is observed at the range of 0-1.5 V (vs Li/Li+) in the cell with gel polymer electrolyte, which indicates that gel polymer electrolyte can mitigate the side reaction of metallic lithium with electrolyte. The lithium metal anode in the symmetric-cell with in-situ polymerization gel polymer electrolyte exhibits no obvious lithium dendrite and damaged morphology. X-Ray photoelectron spectroscopy results further reveal that the lithium metal anode in gel polymer electrolyte is formed a stable SEI with LiF-rich compound, which is much enhanced than that of in 335C electrolyte. Consequently, the Li|LiFePO4 cells with gel polymer electrolyte exhibits a long-term cycling stability, which can release a reversible capacity 118.7 mAh·g−1 after 400 cycles at a current density of 1 C, as well as coulombic efficiency of 99.5%. Benefit from the ring opening polymerization process of tetrahydrofuran, PF5 participates the formation reaction of intermediate product [(THF)+(PF5)−], which caused the equilibrium of the decomposition reaction shift to the right and therefore increase the formation of LiF on the surface of lithium metal anode. This process results in a great enhancement of the cyclability due to LiF-rich formed in the SEI. Therefore, the growth of lithium dendrite can be prevented by the stable SEI, as well as the side reaction between lithium metal and electrolyte. © 2022 Chemical Industry Press. All rights reserved.