Citation: Ling HUANG, Cheng-Zhi ZHANG, Jun TAN, Sui-Min LI. Recycling FePO4·2H2O from waste LiFePO4 powders and formation mechanisms of the impurities during precipitation process[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(2): 357-366. doi: 10.11862/CJIC.2022.288 shu

Recycling FePO4·2H2O from waste LiFePO4 powders and formation mechanisms of the impurities during precipitation process

  • Corresponding author: Jun TAN, tanjun@jihualab.ac.cn
  • Received Date: 9 September 2022
    Revised Date: 18 November 2022

Figures(4)

  • Applying waste LiFePO4 powders as raw material, the FePO4·2H2O precursor was effectively recycled through chemical precipitation. Thereafter, the formation mechanisms of the impurities were discussed. The potential (φ)-pH diagram of the Fe-P-Li-H2O system was investigated and the result demonstrated that FePO4·2H2O could form at a temperature of 298-363 K under a pH value of 0-5.0 by precipitation. The experiment results indicated that the Fe3PO7 phase started to form through the reaction of Fe(OH)3 and FePO4·2H2O during the sintering process. When the molar ratio of Fe and P (nFenP) was 1∶1, pH=1.5-2.2, some Fe3+ ions will form Fe(OH)3, and the yield coefficient increased with the pH and temperature. This is because the solubility product constant (Ksp) of Fe(OH)3 was much less than the one of FePO4·2H2O, suggesting that the precipitate rate of Fe(OH)3 was faster than FePO4·2H2O. Based on thermodynamic principles, aging may be an effective way to convert Fe(OH)3 into FePO4 ·2H2O according to the φ-pH diagram of the Fe-P-Li-H2O system. Unfortunately, the rate of Fe(OH)3 conversion was slowed, resulting in some Fe(OH)3 in precipitation. Therefore, low pH value and temperature are essential to avoid Fe(OH)3 generation during the co-precipitation process. Also, when nFenP=1∶2, some H3PO4 could react with NaOH to form NaH2PO4, which would further react with FePO4·2H2O to produce NaFeP2O7 during the sintering process. At 333 K, the equimolar ratio of co-precipitation precursor FePO4·2H2O can be obtained by adjusting the pH value at 1.5, matching the molar ratio of 1∶1 of Fe to P. The purity of this as-prepared FePO4·2H2O was 99.97%. Besides, the synthesized LiFePO4 which used this FePO4·2H2O as a precursor exhibited a reversible capacity of 154.1 mAh·g-1 and excellent capacity retention of 96.79% after 100 cycles at 0.2C (1C=180 mA·g-1). FePO4·2H2O obtained from waste LiFePO4 powders can be used as precursor to synthesize LiFePO4 cathode material, which greatly improves the economic effi-ciency of recycling the spent LiFePO4 battery.
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