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 electr...

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