锰铁合金制备磷酸锰铁溶液

Preparation of manganese iron phosphate solution from ferromanganese alloy

  • 摘要: 针对锰铁合金资源化利用问题,提出磷酸浸出法制备锂电正极材料前驱体(磷酸铁锰溶液)。经单因素-正交实验优化,在酸过量系数为1.2、液固比为11∶1(单位为g/L,下同)、温度为70 ℃、时间为1 h的条件下,Mn与Fe浸出率分别为97.47%、92.81%。净化后溶液中的杂质含量符合企业标准。通过热力学分析确定反应的自发进行,其ΔG<-40 kJ/mol;构建了Mn-Fe-H3PO4E-pH图,揭示了pH<2.20时Mn²⁺稳定存在、pH>0.56时Fe3+沉淀的临界条件。动力学研究表明:浸出过程符合未反应核模型,Mn与Fe的浸出活化能分别为44.47 kJ/mol和48.08 kJ/mol,属化学反应控制机制。本文为低成本制备磷酸锰铁锂提供新途径。

     

    Abstract: For the resource utilization of ferromanganese alloy, a phosphoric acid leaching method was proposed to prepare the precursor solution (manganese-iron phosphate solution) for lithium battery cathode materials. Through single-factor and orthogonal experiments, the optimal conditions were determined as follows: an acid excess coefficient of 1.2, a liquid-to-solid ratio of 11∶1, a temperature of 70 ℃, and a time of 1 h. Under these conditions, the leaching rates of Mn and Fe reached 97.42% and 92.81%, respectively. The impurity content in the purified solution met industrial standards. Thermodynamic analysis confirmed the spontaneous reaction characteristics (ΔG < -40 kJ/mol), and the E-pH diagram of the Mn-Fe-H3PO4 system was constructed. It revealed the critical conditions for the stable existence of Mn2+ at pH < 2.20 and for the precipitation of Fe3+ at pH > 0.56. Kinetic studies indicated that the leaching process followed the unreacted core model, with activation energies of 44.47 kJ/mol for Mn and 48.08 kJ/mol for Fe, suggesting a chemical reaction-controlled mechanism. This work provided a new low-cost approach for the preparation of lithium manganese iron phosphate (LMFP).

     

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