Tuning Electrochemical Properties of Li-Rich Layered Oxide Cathodes by Adjusting Co/Ni Ratios and Mechanism Investigation Using in situ X-ray Diffraction and Online Continuous Flow Differential Electrochemical Mass Spectrometry

Owing to high specific capacity of ∼250 mA h g–1, lithium-rich layered oxide cathode materials (Li1+xNiyCozMn(3–x–2y–3z)/4O2) have been considered as one of the most promising candidates for the next-generation cathode materials of lithium ion batteries. However, the commercialization of this kind of cathode materials seriously restricted by voltage decay upon cycling though Li-rich materials with high cobalt content have been widely studied and show good capacity. This research successfully suppresses voltage decay upon cycling while maintaining high specific capacity with low Co/Ni ratio in Li-rich cathode materials. Online continuous flow differential electrochemical mass spectrometry (OEMS) and in situ X-ray diffraction (XRD) techniques have been applied to investigate the structure transformation of Li-rich layered oxide materials during charge–discharge process. The results of OEMS revealed that low Co/Ni ratio lithium-rich layered oxide cathode materials released no lattice oxygen at the first charge process, which will lead to the suppression of the voltage decay upon cycling. The in situ XRD results displayed the structure transition of lithium-rich layered oxide cathode materials during the charge–discharge process. The Li1.13Ni0.275Mn0.580O2 cathode material exhibited a high initial medium discharge voltage of 3.710 and a 3.586 V medium discharge voltage with the lower voltage decay of 0.124 V after 100 cycles.