Ultrafast Conversion of Water and Oxygen Molecules With Dissociation of Hydrogen Bonding Effect to Achieve Extra‐High Energy Efficiency of Secondary Metal‐Air Batteries

Metal‐air secondary batteries with ultrahigh specific energies have received vast attention and are considered new promising energy storage. The slow redox reactions between oxygen‐water molecules lead to low energy efficiency (55–71%) and limited applications. Herein, it is proposed that the MIL‐68(In)‐derived porous carbon nanotube supports the CoNiFeP heteroconjugated alloy catalyst with an overboiling point electrolyte to achieve the ultrahigh oxidation rate of water molecules. Structural characterization and density functional theory calculations reveal that the new catalyst greatly reduces the free energy of the process, and the overboiling point further accelerates the dissociation of O─H and hydrogen bonds, and the release of O₂ molecules, achieving an extra‐low overpotential of 110 mV@10 mA cm⁻² far lower than commercial Ir/C catalysts of 192 mV at 125 °C and state‐of‐the‐art. Furthermore, the energy efficiency of assembled rechargeable zinc‐air batteries begins to break through at 85 °C, jumps at 100 °C, and reaches ultrahigh energy efficiency of 88.1% at 125 °C with an ultralow decay rate of 0.0068% after 150 cycles far superior to those of reported metal‐air batteries. This work provides a new catalyst and electrolyte joint‐design strategy and reexamines the battery operating temperature to construct higher energy efficiency for secondary fuel cells.