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We have successfully developed both advanced primary and rechargeable Zn-air batteries with cathodes catalyzed by MnO2 nanotubes-supported Co3O4(Co3O4/MnO2)and its carbon nanotubes(CNTs)-hybridized catalyst(Co3O4/MnO2-CNTs).These catalysts are synthesized through a facile two-pot precipitation reaction and hydrothermal process,which exhibit the superior bi-functional catalytic activity for both ORR and OER.The high performance is believed to be induced by the hybrid effect among MnO2 nanotubes,Co3O4 and CNTs,which can produce a synergetic enhancement.When used for integrated into the practical primary and electrochemically rechargeable Zn-air battery,such a hybrid catalyst can give a discharge peak power density in exceeding of 450 mW cm-2.At 1.0 V of cell voltage,a current density of 324 mA cm-2 is achieved.This performance is superior to all reported non-precious metal catalysts in literature for zinc–air batteries and significantly outperforms the state-of-the-art platinum-based catalyst.Particularly,the rechargeable Zn-air battery can be fabricated into all-solid-state one through a simple solid-state approach,which exhibits excellent peak power density of 62 mW cm-2,and the charge and discharge potentials remain virtually unchanged during the overall cycles as to the one with liquid electrolyte.