Using hydrofluoropolyether (E10H) as raw material and fluorinating with a mixture of fluorine and nitrogen, a double-terminated hydroxyl perfluoropolyether (F-E10H-AL) was prepared. Three fluorination processes were explored, including normal temperature fluorination, low temperature fluorination, and first low temperature and then normal temperature fluorination. Then it is combined with lithium bistrifluoromethanesulfonate (LiTFSI) to prepare a lithium-ion electrolyte. The structure of the fluorinated product was analyzed by infrared spectroscopy, hydrogen nuclear magnetic spectroscopy and fluorine spectroscopy. The impedance and chronoamperometry(CA) were tested by electrochemical workstation. The results show that the low-temperature fluorination process has high fluorination efficiency. After direct fluorination of E10H at -10°C for 12 hours, 21.0% of H atoms in the molecular chain is replaced by F atoms, but more CF3O- are produced. When the hydroxyl group on E10H was protected by hexafluoropropylene oxide dimer, the fluorination process of low temperature followed by normal temperature was adopted, and 48.3% of H atoms in the molecular chain were replaced by F atoms. Finally, the fluorinated product is reduced to obtain F-E10H-AL with a CF3O- content of 0.7% at the end of the molecular chain. Combining the impedance and CA datas, lithium-ion transference number of F-E10H-AL/LiTFSI is calculated to be 0.32, which is higher than that of PFPE-OH/LiTFSI (0.07).