Double Nitrogenation Layer Formed Using Nitric Oxide for Enhancing Li⁺ Storage Performance, Cycling Stability, and Safety of Si Electrodes

To enhance Li storage properties, nitrogenation methods are developed for Si anodes. First, melamine, urea, and nitric oxide (NO) precursors are used to nitrogenize carbon-coated Si particles. The properties of the obtained particles are compared. It is found that the NO process can maximize the graphitic nitrogen (N) content and electronic conductivity of a sample. In addition, optimized N functional groups and O─C species on the electrode surface increase electrolyte wettability. However, with a carbon barrier layer, NO hardly nitrogenizes the Si cores. Therefore, bare Si particles are reacted with NO. Core-shell Si@amorphous SiN_x particles are produced using a facile and scalable NO treatment route. The effects of the NO reaction time on the physicochemical properties and charge–discharge performance of the obtained materials are systematically examined. Finally, the Si@SiN_x particles are coated with N-doped carbon. Superior capacities of 2435 and 1280 mAh g⁻¹ are achieved at 0.2 and 5 A g⁻¹, respectively. After 300 cycles, 90% of the initial capacity is retained. In addition, differential scanning calorimetry data indicate that the multiple nitrogenation layers formed by NO significantly suppress electrode exothermic reactions during thermal runaway.