Bonding the Terminal Isocyanate-Related Functional Group to the Surface Manganese Ions to Enhance Li-Rich Cathode's Cycling Stability

Capacity fading of Li-rich cathodes in the cycling process is mainly caused by the irreversible side reactions at the interface of electrode and electrolyte by reason of the lack of a corrosion resistant surface. In this work, isocyanate-related functional groups (-N = C = O groups and polyamide-like groups) were tightly bonded on the surface of Li-rich oxides through a urea decomposition gas heat-treatment. The surface isocyanate functionalization inhibits the side reaction of PF5 hydrolysis to give LixPFyOz and HF species at the surface of Li-rich materials in the cycle process. As compared to the untreated Li-rich sample U0, the samples with the spinel-like layer and isocyanate functionalized surface exhibited an enhanced cycle stability. The capacity retention of the treated sample U3 reached as high as 92.6% after 100 cycles at the current density of 100 mA/g, larger than 66.8% for the untreated sample. Even at a higher current density of 1000 mA/g, sample U3 gives a capacity retention of 81.7% after 300 cycles. The findings of this work reveal the importance of surface isocyanate functionalization in restraining the surface side reactions and also suggest an effective method to design Li-rich cathode materials with better electrochemistry performance.