Electrochemically Induced Structural Transformation in a γ-MnO2 Cathode of a High Capacity Zinc-Ion Battery System

In the present study, an in-depth investigation on the structural transformation in a mesoporous γ-MnO2 cathode during electrochemical reaction in a zinc-ion battery (ZIB) has been undertaken. A combination of in situ Synchrotron XANES and XRD studies reveal that the tunnel-type parent γ-MnO2 undergoes a structural transformation to spinel-type Mn(III) phase (ZnMn2O4) and two new intermediary Mn(II) phases, namely, tunnel-type γ-ZnxMnO2 and layered-type L-ZnyMnO2, and that these phases with multioxidation states coexist after complete electrochemical Zn-insertion. On successive Zn-deinsertion/extraction, a majority of these phases with multioxidation states is observed to revert back to the parent γ-MnO2 phase. The mesoporous γ-MnO2 cathode, prepared by a simple ambient temperature strategy followed by low-temperature annealing at 200 °C, delivers an initial discharge capacity of 285 mAh g–1 at 0.05 mA cm–2 with a defined plateau at around 1.25 V vs Zn/Zn2+. Ex situ HR-TEM studies of the discharged electrode aided to identify the lattice fringe widths corresponding to the Mn(III) and Mn(II) phases, and the stoichiometric composition estimated by ICP analysis appears to be concordant with the in situ findings. Ex situ XRD studies also confirmed that the same electrochemical reaction occurred on repeated discharge/charge cycling. Moreover, the present synthetic strategy offers solutions for developing cost-effective and environmentally safe nanostructured porous electrodes for cheap and eco-friendly batteries.