Pr₆O₁₁: Temperature-Dependent Oxygen Vacancy Regulation and Catalytic Performance for Lithium-Oxygen Batteries

Many challenges still exist in lithium-oxygen batteries (LOBs), particularly exploring an efficient catalyst to optimize the reaction pathway and regulate the Li₂O₂ nucleation. Pr₆O₁₁ has a unique 4f electronic structure and the highest oxygen ion mobility among rare earth oxides, exhibiting superior electronic, optical, and chemical properties. These unique properties might endow it with advanced catalytic activities for LOBs. This work reports two crystal forms of Pr₆O₁₁ as novel catalysts and regulates the oxygen vacancy (V_o) concentrations by feasible calcination. Thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) confirm the conversion from commercial Pr₆O₁₁ to cubic fluorite Pr₆O₁₁ and V_o-rich Pr₆O₁₁. Photographs, high-resolution transmission electron microscopy, selected area electron diffraction, XPS, and electron paramagnetic resonance robustly demonstrate the temperature-dependent evolution of V_o. Ex situ XPS, scanning electron microscopy, and electrochemical techniques are used to study the catalytic mechanism and electrochemical reversibility. It is found that an appropriate V_o concentration can boost O₂ adsorption/desorption, accelerate electron transport, and reduce the reaction energy barrier. V_o-rich Pr₆O₁₁ optimizes the reaction pathway by offering an intermediate Li_2-O₂ (with metalloid conductivity) and adjusting Li₂O₂ into vertically staggered nanoflakes, effectively avoiding the suffocation of the catalytic surface and presenting excellent capacity, cycling stability, and rate performance.