Besides Li＋ and Mg2＋, the electrochemical behavior of Na^＋ and K＋ in LiFePO4/FePO4 structures was studied since they naturally coexist with Li＋ and Mg2＋ in brine. The cyclic voltammogram （CV） results indicated...Besides Li＋ and Mg2＋, the electrochemical behavior of Na^＋ and K＋ in LiFePO4/FePO4 structures was studied since they naturally coexist with Li＋ and Mg2＋ in brine. The cyclic voltammogram （CV） results indicated that Na＋ exhibits some reversibility in LiFePO4/FePO4 structures. Its reduction peak appears at -0.511 V, more negative than that of Li＋ （-0.197 V）, meaning that a relatively positive potential is beneficial for decreasing Na＋ insertion. The reduction peak of K＋ could not be found clearly, indicating that K＋ is difficult to insert into the FePO4 structure. Furthermore, technical experiments using real brine with a super high Mg/Li ratio （493） at a cell voltage of 0.7V showed that the final extracted capacity of Li＋, Mg2＋ and Na＋ that can be attained in 1 g LiFePO4 is 24.1 mg, 7.32 mg and 4.61 mg, respectively. The Mg/Li ratio can be reduced to 0.30 from 493, and the Na/Li ratio to 0.19 from 16.7, which proves that, even in super high Mg/Li ratio brine, if a cell voltage is appropriately controlled, it is possible to separate Li^＋ and other impurities effectively.展开更多
The thermodynamic equilibrium diagrams of Mg2＋- 3-4PO - ＋4NH -H2O system at 298 K were established based on the thermodynamic calculation. From the diagram, the thermodynamic conditions for removing phosphorus from ...The thermodynamic equilibrium diagrams of Mg2＋- 3-4PO - ＋4NH -H2O system at 298 K were established based on the thermodynamic calculation. From the diagram, the thermodynamic conditions for removing phosphorus from the tungstate solution by magnesium salt precipitation were obtained. The results show that when the concentration of total magnesium increases from 0.01 mol/L to 1.0 mol/L, the optimal pH for the phosphorus removal by magnesium phosphate decreases from 9.8 to 8.8. The residual concentration of total phosphorus almost keeps the level of 4.0×10-6 mol/L in the system. MgHPO4, Mg3（PO4）2 and the mixture of Mg3（PO4）2 and Mg（OH）2 are stabilized in these system, respectively. However, increasing the total concentration of magnesium has little effect on phosphorus removal by magnesium ammonium phosphate, while it is helpful for phosphorus removal by increasing the total ammonia concentration. The calculated results demonstrate that the residual concentration of total phosphorus can decrease to 5.0×10-7 mol/L as the total concentration of ammonia reaches 5.0 mol/L and the optimal pH value is 9-10. Finally, verification experiments were conducted with home-made ammonium tungstate solution containing 50 g/L WO3 and 13 g/L P. The results show that when the dosage of MgCl2 is 1.1 times of the theoretical amount, the optimum pH for removing phosphorus is 9.5, which matches with the results of the theoretical calculation exactly.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 52174340, 51704338)the Basic Science Center of the National Natural Science Foundation of China (No. 72088101)the National Key Research and Development Project of China (No. 2022YFC2904505)。
基金Project(K1205034-11) supported by Technology Program of Changsha,China
文摘Besides Li＋ and Mg2＋, the electrochemical behavior of Na^＋ and K＋ in LiFePO4/FePO4 structures was studied since they naturally coexist with Li＋ and Mg2＋ in brine. The cyclic voltammogram （CV） results indicated that Na＋ exhibits some reversibility in LiFePO4/FePO4 structures. Its reduction peak appears at -0.511 V, more negative than that of Li＋ （-0.197 V）, meaning that a relatively positive potential is beneficial for decreasing Na＋ insertion. The reduction peak of K＋ could not be found clearly, indicating that K＋ is difficult to insert into the FePO4 structure. Furthermore, technical experiments using real brine with a super high Mg/Li ratio （493） at a cell voltage of 0.7V showed that the final extracted capacity of Li＋, Mg2＋ and Na＋ that can be attained in 1 g LiFePO4 is 24.1 mg, 7.32 mg and 4.61 mg, respectively. The Mg/Li ratio can be reduced to 0.30 from 493, and the Na/Li ratio to 0.19 from 16.7, which proves that, even in super high Mg/Li ratio brine, if a cell voltage is appropriately controlled, it is possible to separate Li^＋ and other impurities effectively.
基金Project(2012BAB10B04)supported by the National Key Technologies R&D Program of China
文摘The thermodynamic equilibrium diagrams of Mg2＋- 3-4PO - ＋4NH -H2O system at 298 K were established based on the thermodynamic calculation. From the diagram, the thermodynamic conditions for removing phosphorus from the tungstate solution by magnesium salt precipitation were obtained. The results show that when the concentration of total magnesium increases from 0.01 mol/L to 1.0 mol/L, the optimal pH for the phosphorus removal by magnesium phosphate decreases from 9.8 to 8.8. The residual concentration of total phosphorus almost keeps the level of 4.0×10-6 mol/L in the system. MgHPO4, Mg3（PO4）2 and the mixture of Mg3（PO4）2 and Mg（OH）2 are stabilized in these system, respectively. However, increasing the total concentration of magnesium has little effect on phosphorus removal by magnesium ammonium phosphate, while it is helpful for phosphorus removal by increasing the total ammonia concentration. The calculated results demonstrate that the residual concentration of total phosphorus can decrease to 5.0×10-7 mol/L as the total concentration of ammonia reaches 5.0 mol/L and the optimal pH value is 9-10. Finally, verification experiments were conducted with home-made ammonium tungstate solution containing 50 g/L WO3 and 13 g/L P. The results show that when the dosage of MgCl2 is 1.1 times of the theoretical amount, the optimum pH for removing phosphorus is 9.5, which matches with the results of the theoretical calculation exactly.
