Clarifying the Controversial Catalytic Performance of Co(OH)2 and Co3O4 for Oxygen Reduction/Evolution Reactions toward Efficient Zn–Air Batteries

Cobalt-based nanomaterials have been widely studied as catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) due to their remarkable bifunctional catalytic activity, low cost, and easy availability. However, controversial results concerning OER/ORR performance exist between different types of cobalt-based catalysts, especially for Co(OH)₂ and Co₃O₄. To address this issue, we develop a facile electrochemical deposition method to grow Co(OH)₂ directly on the skeleton of carbon cloth, and further Co₃O₄ was obtained by post thermal treatment. The entire synthesis strategy removes the use of any binders and also avoids the additional preparation process (e.g., transfer and slurry coating) of final electrodes. This leads to a true comparison of the ORR/OER catalytic performance between Co(OH)₂ and Co₃O₄, eliminating uncertainties arising from the electrode preparation procedures. The surface morphologies, microstructures, and electrochemical behaviors of prepared Co(OH)₂ and Co₃O₄ catalysts were systemically investigated by scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and electrochemical characterization methods. The results revealed that the electrochemically deposited Co(OH)₂ was in the form of vertically aligned nanosheets with average thickness of about 4.5 nm. After the thermal treatment in an air atmosphere, Co(OH)₂ nanosheets were converted into mesoporous Co₃O₄ nanosheets with remarkably increased electrochemical active surface area (ECSA). Although the ORR/OER activity normalized by the geometric surface area of mesoporous Co₃O₄ nanosheets is higher than that of Co(OH)₂ nanosheets, the performance normalized by the ECSA of the former is lower than that of the latter. Considering the superior apparent overall activity and durability, the Co₃O₄ catalyst has been further evaluated by integrating it into a Zn-air battery prototype. The Co₃O₄ nanosheets in situ supported on carbon cloth cathode enable the assembled Zn-air cells with large peak power density of 106.6 mW cm^-2, low charge and discharge overpotentials (0.67 V), high discharge rate capability (1.18 V at 20 mA cm^-2), and long cycling stability (400 cycles), which are comparable or even superior to the mixture of state-of-the-art Pt/C and RuO₂ cathode.