The electrochemical reduction mechanism of Mn in LiMn2O4 in molten salt was studied. The results show that in the NaCl-CaCl2 molten salt, the process of reducing from Mn (IV) to manganese is: Mn (IV)→Mn (III)→Mn (II)→Mn. LiMn2O4 reacts with molten salt to form CaMn2O4 after being placed in molten salt for 1 h. The reaction of reducing CaMn2O4 to Mn is divided into two steps: Mn (III)→Mn (II)→Mn. The results of constant voltage deoxidation experiments under different conditions show that the intermediate products of LiMn2O4 reduction to Mn are CaMn2O4, MnO, and (MnO)x(CaO)(1−x). As the reaction progresses, x gradually decreases, and finally the Mn element is completely reduced under the conditions of 3 V for 9 h. The CaO in the product can be removed by washing the sample with deionized water at 0 °C.
