Phenylphosphonate surface functionalisation of MgMn2O4 with 3D open-channel nanostructures for composite slurry-coated cathodes of rechargeable magnesium batteries operated at room temperature

Abstract

Spinel-type MgMn₂O₄, prepared by a propylene-oxide-driven sol–gel method, has a high surface area and structured bimodal macro- and mesopores, and exhibits good electrochemical properties as a cathode active material for rechargeable magnesium batteries. However, because of its hydrophilicity and significant water adsorption properties, macroscopic aggregates are formed in composite slurry-coated cathodes when 1-methyl-2-pyrrolidone (NMP) is used as a non-aqueous solvent. Functionalising the surface with phenylphosphonate groups was found to be an easy and effective technique to render the structured MgMn₂O₄ hydrophobic and suppress aggregate formation in NMP-based slurries. This surface functionalisation also reduced side reactions during charging, while maintaining the discharge capacity, and significantly improved the coulombic efficiency. Uniform slurry-coated cathodes with active material fractions as high as 93 wt% can be produced on Al foils by this technique employing carbon nanotubes as an electrically conductive support. A coin-type full cell consisting of this slurry-coated cathode and a magnesium alloy anode delivered an initial discharge capacity of ∼100 mA h g⁻¹ at 25 °C.