Preparation of lithium manganese iron phosphate cathode material from vanadium tailings
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摘要: 以钒渣提钒过程中产生的富含铁锰的浸出液为原料，通过共沉淀法制备了二水草酸铁锰Mn0.5Fe0.5C2O4∙2H2O，以此为前驱体，通过高温固相法成功合成了磷酸锰铁锂LiFe0.5Mn0.5PO4正极材料，实现了钒渣浸出液中铁锰资源的综合利用。结果表明，在初始pH值为3.5，温度25 ℃，反应时间90 min，草酸铵加料量为理论值的1.1倍，加料方式为正加的条件下，铁和锰的沉淀率分别为99.5%和99.4%，与其他杂质实现深度分离，Mn0.5Fe0.5C2O4·2H2O的纯度达99.97%，且粒径较小，分散性良好。可将其作为合成磷酸锰铁锂正极材料的前驱体，为磷酸锰铁锂的工业化生产提供了思路。Abstract: Using the iron-manganese-rich leaching solution generated during vanadium extraction from vanadium slag was used as the raw material, and ferromanganese oxalate dihydrate Mn0.5Fe0.5C2O4∙2H2O was prepared by co-precipitation, and lithium ferromanganese iron phosphate LiFe0.5Mn0.5PO4 anode material was successfully synthesized by the high-temperature solid-phase method using this precursor, which achieved the comprehensive utilization of the iron-manganese resources in the vanadium slag leaching solution. The results showed that under the conditions of initial pH 3.5, temperature 25 ℃, reaction time 90 min, ammonium oxalate addition 1.1 times of the theoretical value, and the addition mode of positive addition, the precipitation efficiency of Fe and Mn were 99.5% and 99.4%, respectively. The depth separation from other impurities was achieved, and the purity of Mn0.5Fe0.5C2O4·2H2O reached 99.97% with small particle sizes and good dispersion. It can be used as a precursor for synthesizing lithium manganese iron phosphate cathode materials, which provides the idea for the industrial production of lithium iron manganese phosphate.
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图 1 （a）不同pH值对铁、锰、钒、铬沉淀率的影响；不同pH值（b）3.0；（c）3.5；（d）4.0；（e）4.5的SEM形貌
Figure 1. (a) Effect of reaction pH on the precipitation efficiency of Fe, Mn, V and Cr; SEM images of co-precipitation products at different pH (b) 3.0, (c) 3.5, (d) 4.0, (e) 4.5
图 2 （a）不同温度对铁、锰、钒、铬沉淀率的影响；不同温度（b）25 ℃；（c）35 ℃；（d）45 ℃；（e）55 ℃的SEM形貌
Figure 2. (a) Effect of temperature on the precipitation efficiency of Fe, Mn, V and Cr; SEM images of different temperatures (b) 25 ℃, (c) 35 ℃, (d) 45 ℃, and (e) 55 ℃
图 3 （a）反应时间对铁、锰、钒、铬沉淀率的影响；不同反应时间（b）0.5 h；（c）1 h；（d）1.5 h；（e）2 h的SEM形貌
Figure 3. (a) Effect of reaction time on the precipitation efficiency of Fe, Mn, V and Cr; SEM images of different reaction times (b) 0.5 h, (c) 1 h, (d) 1.5 h, (e) 2 h
图 4 草酸铵加料量对铁、锰、钒、铬沉淀率的影响
Figure 4. Effect of (NH4)2C2O4 addition on the precipitation efficiency of Fe, Mn, V and Cr
图 5 （a）加料方式对铁、锰、钒、铬沉淀率的影响；不同加料方式： （b）正加；（c）并加；（d）反加产物的SEM形貌
Figure 5. (a) Effect of addition methods on the precipitation efficiency of Fe, Mn, V, Cr; SEM images of different addition modes (b) forward addition, (c) parallel addition, (d) reverse addition
图 6 加料方式对共沉淀产物粒度的影响
Figure 6. Effect of addition method on the particle sizes of co-precipitation products
图 7 最佳条件共沉淀产物的XRD谱
Figure 7. XRD pattern of co-precipitation products under optimum conditions
图 8 最佳条件共沉淀产物的SEM-EDS谱
（a）SEM形貌；（b）图8（a）中A区的EDS元素含量；（c）沉淀产物中元素Fe, Mn, V和Cr的分布
Figure 8. SEM-EDS profiles of co-precipitated products under optimum conditions
图 9 （a）LiMn0.5Fe0.5PO4的XRD谱；（b）LiMn0.5Fe0.5PO4的SEM形貌；（c）LiMn0.5Fe0.5PO4的倍率性能；（d）LiMn0.5Fe0.5PO4在0.1C倍率下的循环性能
Figure 9. (a) XRD patterns of LiMn0.5Fe0.5PO4, (b) SEM images of LiMn0.5Fe0.5PO4, (c) Rate performance of the LiMn0.5Fe0.5PO4, (d) Cycle performance of the LiMn0.5Fe0.5PO4 at 0.1C
表 1 溶液中主要元素及其含量
Table 1. Major elemental contents in the solution
g·L−1 Fe Mn V Cr 25.21 5.13 0.26 0.24 
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表 2 不同加料方式共沉淀产物的粒度
Table 2. Particle sizes of co-precipitation products with different addition methods
加料方式 D10/μm D50/μm D90/μm 正加 2.89 7.57 17.32 并加 10.57 26.66 46.31 反加 12.14 41.87 62.46
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表 3 沉淀产物的组成
Table 3. Compositions of the precipitation product
% Fe Mn V Cr 49.94 50.03 0.03 <0.01
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