Porous materials are more popular in electrochemical applications. In this study, MgMn2O4 microspheres with graded porous structure were prepared at lower temperature using a convenient template method, and MnCO3 microspheres were used as self-sacrificial templates. MgMn2O4 spinel microspheres were also prepared by template free method for comparison. The MgMn2O4 graded porous microspheres obtained by template method were assembled from nanoparticles with size of 20–50 nm, and have larger specific surface area (twice that of MgMn2O4 prepared by template free method). XPS studies show that both materials have mixed spinel structure with Mn present in multivalent states, and the material prepared by template method exhibits lower inversion degree. The electrochemical test results indicate that MgMn2O4 graded porous microspheres prepared by template method exhibit more excellent cycling and rate performance compared to materials prepared by template free method. The initial discharge capacity is up to 1429.5 mAh g−1 at a current density of 100 mA g−1, and discharge capacity remains 778.0 mAh g−1 after 150 cycles. Even at high rates (1000 mA g−1), it can stably output a cycling capacity of 295.5 mAh g−1. The MgMn2O4/LiCoO2 full cell delivers an initial discharge capacity of 83.4 mAh g−1 at a current of 100 mA g−1. The excellent electrochemical performance of MgMn2O4 microspheres prepared by template method may be related to their graded porous structure and low inversion degree. This study indicates that the electrochemical performance of MgMn2O4 materials can be greatly improved by adjusting the microstructural morphology.
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