Fast Microwave-Assisted Hydrothermal Synthesis of Pure Layered δ-MnO₂ for Multivalent Ion Intercalation

This work reports on the synthesis of layered manganese oxides (δ-MnO₂) and their possible application as cathode intercalation materials in Al-ion and Zn-ion batteries. By using a one-pot microwave-assisted synthesis route in 1.6 M KOH (Mn_VII:Mn_II = 0.33), a pure layered δ-MnO₂ birnessite phase without any hausmannite traces was obtained after only a 14 h reaction time period at 110 °C. Attempts to enhance crystallinity level of as-prepared birnessite through increasing of reaction time up to 96 h in 1.6 M KOH failed and led to decreases in crystallinity and the emergence of an additional hausmannite phase. The influence of Mn_II:OH^- ratio (1:2 to 1:10) on phase crystallinity and hausmannite phase formation for 96 h reaction time was investigated as well. By increasing alkalinity of the reaction mixture up to 2.5 M KOH, a slight increase in crystallinity of birnessite phase was achieved, but hausmannite formation couldn't be inhibited as hoped. The as-prepared layered δ-MnO₂ powder material was spray-coated on a carbon paper and tested in laboratory cells with Al or Zn as active materials. The Al-ion tests were carried out in EMIMCl/AlCl₃ while the Zn-Ion experiments were performed in water containing choline acetate (ChAcO) or a ZnSO₄ solution. Best performance in terms of capacity was yielded in the Zn-ion cell (200 mWh g^-1 for 20 cycles) compared to about 3 mAh g^-1 for the Al-ion cell. The poor activity of the latter system was attributed to low dissociation rate of tetrachloroaluminate ions (AlCl₄^-) in the EMIMCl/AlCl₃ mixture into positive Al complexes which are needed for charge compensation of the oxide-based cathode during the discharge step.