Characterization and Control of Irreversible Reaction in Li-Rich Cathode during the Initial Charge Process

Li-rich layered oxide has been known to possess high specific capacity beyond the theoretical value from both charge compensation in transition metal and oxygen in the redox reaction. Although it could achieve higher reversible capacity due to the oxygen anion participating in electrochemical reaction, however, its use in energy storage systems has been limited. The reason is the irreversible oxygen reaction that occurs during the initial charge cycle, resulting in structural instability due to oxygen evolution and phase transition. To suppress the initial irreversible oxygen reaction, we introduced the surface-modified Li[Li_0.2Ni_0.16Mn_0.56Co_0.08]O₂ prepared by carbon coating (carbonization process), which was verified to have reduced oxygen reaction during the initial charge cycle. The electrochemical performance is improved by the synergic effects of the oxygen-deficient layer and carbon coating layer formed on the surface of particles. The sample with suitable carbon coating exhibited the highest structural stability, resulting in reduced capacity fading and voltage decay, which are attributed to the mitigated layered-to-spinel-like phase transition during prolonged cycling. The control over the oxygen reaction of Li₂MnO₃ by surface modification affects the activation reaction above 4.4 V in the initial charge cycle and structure changes during prolonged cycling. X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy analyses as well as electrochemical performance measurement were used to identify the correlation between reduced oxygen activity and structural changes.