Phase control of Mn-based spinel films via pulsed laser deposition

Phase transformations in battery cathode materials during electrochemical-insertion reactions lead to capacity fading and low cycle life. One solution is to keep the same phase of cathode materials during cation insertion-extraction processes. Here, we demonstrate a novel strategy to control the phase and composition of Mn-based spinel oxides for magnesium-ion battery applications through the growth of thin films on lattice-matched substrates using pulsed laser deposition. Materials at two extreme conditions are considered: fully discharged cathode MgMn2O4 and fully charged cathode Mn2O4. The tetragonal MgMn2O4 (MMO) phase is obtained on MgAl2O4 substrates, while the cubic MMO phase is obtained on MgO substrates. Similarly, growth of the empty Mn2O4 spinel in the cubic phase is obtained on an MgO substrate. These results demonstrate the ability to control separately the phase of spinel thin films (e.g., tetragonal vs. cubic MMO) at nominally fixed composition, and to maintain a fixed (cubic) phase while varying its composition (MgxMn2O4, for x = 0, 1). This capability provides a novel route to gain insights into the operation of battery electrodes for energy storage applications.