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As the byproduct of TiO_2 industrial production, impure FeSO_4·7H_2O was used for the synthesis of LiFePO_4. With the purified solution of FeSO_4·7H_2O, FePO_4·xH_2O was prepared by a normal titration method and a controlled crystallization method, respectively. Then LiFePO_4 materials were synthesized by calcining the mixture of FePO_4·xH_2O, Li_2CO_3, and glucose at 700℃ for 10 h in flowing Ar. The results indi-cate that the elimination of FeSO_4·7H_2O impurities reached over 95%, and using FePO_4·xH_2O prepared by the controlled crystallization method, the obtained LiFePO_4 material has free and sphere-like particles. The material delivers a higher initial discharge specific capacity of 149 mAh·g~(-1)1 at a current density of 0.1C rate (1C=170 mA·g~(-1)); the discharge specific capacity also maintains above 120 mAh·g~(-1)after 100 cycles even at 2C rate. Thus, the employed processing is promising for easy control, low cost of raw material, and high electrochemical per-formance of the prepared material.