Silicon-carbon nanocomposite materials are widely adopted in the anode of lithium-ion batteries (LIB). However, the lithium ion (Li⁺) transportation is hampered due to the significant accumulation of silicon nanoparticles (Si) and the change in their volume, which leads to decreased battery performance. In an attempt to optimize the electrode structure, we report on a self-assembly synthesis of silicon nanoparticles@nitrogen-doped reduced graphene oxide/carbon nanofiber (Si@N-doped rGO/CNF) composites as potential high-performance anodes for LIB through electrostatic attraction. A large number of vacancies or defects on the graphite plane are generated by N atoms, thus providing transmission channels for Li⁺ and improving the conductivity of the electrode. CNF can maintain the stability of the electrode structure and prevent Si from falling off the electrode. The three-dimensional composite structure of Si, N-doped rGO, and CNF can effectively buffer the volume changes of Si, form a stable solid electrolyte interface (SEI), and shorten the transmission distance of Li⁺ and the electrons, while also providing high conductivity and mechanical stability to the electrode. The Si@N-doped rGO/CNF electrode outperforms the Si@N-doped rGO and Si/rGO/CNF electrodes in cycle performance and rate capability, with a reversible specific capacity reaching 1276.8 mAh/g after 100 cycles and a Coulomb efficiency of 99%.

Silicon-based anode materials are used to improve the performance of next-generation high-energy-density lithium-ion batteries (LIBs). However, the inherent limitations and cost of these materials are hindering their mass production. Commercial graphite can overcome the shortcomings of silicon-based materials and partially reduce their cost. In this study, a high-performance, low-cost, and environmentally friendly composite electrode material suitable for mass production was developed through optimizing the silicon content of commercial silicon–graphite composites and introducing a small amount of graphene and carbon nanofibers. This partially overcomes the inherent limitations of silicon, enhances the interface stability of silicon-based materials and the cycle stability of batteries, and reduces the irreversible capacity loss of the initial cycle. At a silicon content of 15 wt%, the initial Coulombic efficiency (ICE) of the battery was 65%. Reducing the silicon content in the composite electrode from 15% to 10% increased the ICE to 70% and improved the first lithiation and delithiation capacities. The battery exhibited excellent cycle stability at a current density of 0.1 A g⁻¹, retaining approximately 65% of its capacity after 100 cycles, good performance at various current densities (0.1–1 A g⁻¹), and an excellent reversible performance.