Sequential oxygen evolution and decoupled water splitting via electrochemical redox reaction of nickel hydroxides

Alkaline water electrolysis is a promising low-cost strategy for clean and sustainable hydrogen production but is largely limited by the sluggish anodic oxygen evolution reaction and the challenges in maintaining adequate separation between H₂ and O₂. Here, we reveal an anodic-cathodic sequential oxygen evolution process via electrochemical oxidation and subsequent reduction of Ni hydroxides, enabling much lower overpotentials than conventional anodic oxygen evolution. By using (isotope-labeled) differential electrochemical mass spectrometry and in situ Raman spectroscopy combined with density functional theory calculations, we evidence that the sequential oxygen evolution originates from the electrochemical oxidation of Ni hydroxides to NiOO^- active species while undergoing a different, reductive step of NiOO^- for the final release of O₂ due to weakened Ni-O covalency. Based on this sequential process, we propose and demonstrate a hybrid water electrolysis and energy storage device, which enables time-decoupled hydrogen and oxygen evolution and electrochemical energy storage in the Ni hydroxides.