Direct Visualization of the Reversible O2−/O− Redox Process in Li‐Rich Cathode Materials

Conventional cathodes of Li-ion batteries mainly operate through an insertion-extraction process involving transition metal redox. These cathodes will not be able to meet the increasing requirements until lithium-rich layered oxides emerge with beyond-capacity performance. Nevertheless, in-depth understanding of the evolution of crystal and excess capacity delivered by Li-rich layered oxides is insufficient. Herein, various in situ technologies such as X-ray diffraction and Raman spectroscopy are employed for a typical material Li_1.2 Ni_0.2 Mn_0.6 O₂ , directly visualizing O^- O^- (peroxo oxygen dimers) bonding mostly along the c-axis and demonstrating the reversible O^2- /O^- redox process. Additionally, the formation of the peroxo OO bond is calculated via density functional theory, and the corresponding OO bond length of ≈1.3 Å matches well with the in situ Raman results. These findings enrich the oxygen chemistry in layered oxides and open opportunities to design high-performance positive electrodes for lithium-ion batteries.