Revealing the Correlations between Morphological Evolution and Surface Reactivity of Catalytic Cathodes in...

Lithium-oxygen batteries suffer from the degradation of the catalytic cathode during long-term operation, which limits their practical use. Understanding the direct correlations between the surface morphological evolution of catalytic cathodes at nanoscale and their catalytic activity during cycling has proved challenging. Here, using in situ electrochemical atomic force microscopy, the dynamic evolution of the Pt nanoparticles electrode in a working Li-O₂ battery and its effects on the Li-O₂ interfacial reactions are visualized. In situ views show that repeated oxidation-reduction cycles (ORCs) trigger the increase in the size of Pt nanoparticles, eventually causing the Pt nanoparticles to fall off the electrode. In 0-80 ORCs, the grown Pt nanoparticles promote the conversion of the Li-O₂ reaction route from the surface-mediated pathway to the solution-mediated pathway during discharging and significantly increase the discharge capacity. After 250 ORCs, accompanied by the part of the Pt nanoparticles detaching from the electrode, the nucleation potential of reaction product decreases, and the reaction dynamic slows down, which cause the performance to degrade. Modification of a proper amount of Au nanoparticle on the Pt nanoparticles electrode could improve its stability and maintain the high catalytic activity. These results provide a direct evidence for clarifying the correlations between morphological evolution and surface reactivity of catalytic cathodes during cycling, which is critical for developing high-performance catalysts.