Determinants of the Surface Film during the Discharging Process in Lithium–Oxygen Batteries

Lithium–oxygen batteries have one of the highest theoretical capacities and specific energies, but several challenges remain. One of them is premature death caused by a passivation layer with poor conductivities (both electronic and ionic) on the electrode surface during the discharge process. Once this thin layer forms on the surface of the catalyst and substrate, the overpotential significantly increases and causes early cell death. Therefore, understanding this thin layer is crucial to achieving high specific energy lithium–oxygen batteries. Herein, we quantitatively compared the ratio of lithium carbonate to lithium peroxide during the discharge process in a flow cell at different potentials. We found that the ratio rapidly increased at low potential and high flow rates. The surface route led to significant byproducts on the Au electrodes, and consequently, a 3 nm thick discharge product film passivates the electrode surface in a flow cell

Electron Localization in Rationally Designed Pt₁Pd Single-Atom Alloy Catalyst Enables High-Performance Li–O₂ Batteries

Li–O2 batteries (LOBs) are considered as one of the most promising energy storage devices due to their ultrahigh theoretical energy density, yet they face the critical issues of sluggish cathode redox kinetics during the discharge and charge processes. Here we report a direct synthetic strategy to fabricate a single-atom alloy catalyst in which single-atom Pt is precisely dispersed in ultrathin Pd hexagonal nanoplates (Pt1Pd). The LOB with the Pt1Pd cathode demonstrates an ultralow overpotential of 0.69 V at 0.5 A g–1 and negligible activity loss over 600 h. Density functional theory calculations show that Pt1Pd can promote the activation of the O2/Li2O2 redox couple due to the electron localization caused by the single Pt atom, thereby lowering the energy barriers for the oxygen reduction and oxygen evolution reactions. Our strategy for designing single-atom alloy cathodic catalysts can address the sluggish oxygen redox kinetics in LOBs and other energy storage/conversion devices