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Jinglong Liang, Dongbin Wang, Le Wang, Hui Li, Weigang Cao, and Hongyan Yan, Electrochemical process for recovery of metallic Mn from waste LiMn2O4-based Li-ion batteries in NaCl−CaCl2 melts, Int. J. Miner. Metall. Mater., 29(2022), No. 3, pp. 473-478. https://doi.org/10.1007/s12613-020-2144-7
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李慧 E-mail: lh@ncst.edu.cn
750°C条件下NaCl−CaCl2熔融盐中直接电解还原LiMn2O4回收金属锰为废旧锂离子电池的回收提供了新的思路。采用电化学手段研究LiMn2O4在涂覆电极表面的还原过程，结果显示，锰酸锂的还原过程是分步进行的，还原过程为Mn(IV) → Mn(III) → Mn(II) → Mn；在电脱氧12 h条件下，0.5−3 V的产物为CaMn2O4、MnO、(MnO)x(CaO)1−x、Mn，电解电压达到电压在2.6 V时单质锰出现，增加电压可促进锰的脱氧进程。电脱氧随着三相界面的推进由外向芯部逐渐进行，当电压较大时会加快还原反应的动力学过程，并产生两个阶段的三相界面。
A new method is proposed for the recovery of Mn via the direct electrochemical reduction of LiMn2O4 from the waste of lithium-ion batteries in NaCl−CaCl2 melts at 750°C. The results show that the LiMn2O4 reduction process by the electrochemical method on the coated electrode surface occurs in three steps: Mn(IV) → Mn(III) → Mn(II) → Mn. The products of this electro-deoxidation are CaMn2O4, MnO, (MnO)x(CaO)1−x, and Mn. Metal Mn appears when the electrolytic voltage increases to 2.6 V, which indicates that increasing the voltage may promote the deoxidation reaction process. With the advancement of the three-phase interline (3PI), electric deoxygenation gradually proceeds from the outer area of the crucible to the core. At high voltage, the kinetic process of the reduction reaction is accelerated, which generates double 3PIs at different stages.
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