Electrochemical phase transformation accompanied with Mg extraction and insertion in a spinel MgMn₂O₄ cathode material

One of the key challenges when developing magnesium rechargeable batteries (MRB) is to develop Mg-intercalation cathodes exhibiting higher redox potentials with larger specific capacities. Although Mg-transition-metal spinel oxides have been shown to be excellent candidates as MRB cathode materials by utilizing the valence change from trivalent to divalent of transition metals starting from Mg insertion, there is no clear evidence to date that Mg can be indeed extracted from the initial spinel hosts by utilizing the change from trivalent to quadrivalent. In this work, we clearly present various experimental evidences of the electrochemical extraction of Mg from spinel MgMn₂O₄. The present electrochemical charge, i.e., extraction treatment of Mg, was performed in an ionic liquid at 150 °C to ensure Mg hopping in the spinel host. Our analyses show that Mg can be extracted from Mg_1-xMn₂O₄ up to x = 0.4 and, afterwards, successively be inserted into the Mg-extracted (demagnesiated) host via a two-phase reaction between tetragonal and cubic spinels. Finally, we also discuss the difference in electrochemical features between LiMn₂O₄ and MgMn₂O₄