Synthesis of metal-doped todorokite-type MnO2 and its cathode characteristics for rechargeable lithium batteries

Todorokite-type MnO2-doped with Co and Fe has been synthesized by hydrothermal treatment of layered metal-doped manganese oxide, buserite, in water at 120–200 °C. The prepared todorokite products have been characterized by XRD and energy dispersive X-ray spectroscopic (EDX) measurements, TEM observation and thermogravimetric analysis. These measurements showed that the hydrothermal products are the metal-doped todorokite phase having large (3 × 3) tunnel structure, and the chemical compositions are shown to be MgxMyMn1−yO2·zH2O, where x = 0.08–0.10, y = 0.23–0.29, z = 0.35–0.54 in M = Co and x = 0.13–0.14, y = 0.03–0.16, z = 0.19–0.28 in M = Fe. The preliminary electrochemical characteristics including charge–discharge cyclings of the metal-doped-todorokite electrodes were examined as lithium insertion hosts for cathodes in rechargeable lithium batteries. The metal-doped todorokite exhibited S-shaped discharge behavior and the Co-doped one with x = 0.10, y = 0.29 showed a high discharge capacity of ca. 132 mAh g−1-oxide and cycling capacity of 90–100 mAh g−1.