Synergistic Ni/Mn Co-doping in Co₃O₄: A first-principles-based strategy to optimize metal‑oxygen bonds for...

High-energy-density lithium‑oxygen batteries (LOBs) are promising energy storage systems. Nevertheless, their practical application is hindered by critical challenges, including sluggish reaction kinetics and irreversible decomposition of their discharge products. Inspired by the design principles of Ni-Co-Mn (NCM) ternary cathodes, this work develops a Ni, Mn-Co₃O₄ catalyst grown in situ on titanium substrates via electrochemical deposition, forming vertically aligned nanosheet arrays with abundant active sites. Density functional theory (DFT) calculations reveal that Ni/Mn co-doping synergistically optimizes the electronic structure of Co₃O₄ by enhancing CoO bond covalency and inducing charge redistribution. This electronic modulation weakens the adsorption energy of lithium‑oxygen intermediates and stabilizes metal‑oxygen bonds, thereby facilitating reversible decomposition pathways. Distribution of relaxation times (DRT) analysis and electrochemical characterization confirm suppressed side reactions and exceptional reversibility of Li₂O₂ decomposition. Consequently, when utilized as a cathode catalyst for LOBs, it demonstrates an ultra-low charge-discharge overpotential of 0.61 V and an ultra-long cycle stability of 850 cycles. This work provides a paradigm for designing high-efficiency cathodes through synergistic dopant engineering.