Silicon (Si) is considered a promising anode material for lithium-ion batteries (LIBs) due to its high performance. However,

when Si is exposed to an electrolyte, it forms a solid electrolyte interphase (SEI) film and the following electrode decomposition

results in poor performance of the LIB. Effective coverage of Si by carbon materials is an interesting potential solution to

solve this problem. In this study, we prepared carbon nanotubes–reduced graphene oxide–silicon (CNTs–RGO–Si) composite

materials by eco-friendly processes and showed that they can be used as a high-performance anode material for LIBs. Fabrication

of the CNTs–RGO–Si composites was composed of three steps. The first step was the preparation of well-dispersed

CNTs–GO colloids by bead milling without any chemical treatment and then co-assembly of the CNT–GO–Si composites by

spray drying the colloidal mixture. Finally, the CNT–RGO–Si was fabricated by thermal reduction of GO in the CNTs–GO–Si

composite. The morphology of the as-fabricated CNTs–RGO–Si composites was generally the shape of a crumpled paper

ball and the size of the composites showed a distribution of 1–5 μm. The highest capacity of the CNT–RGO–Si composite

after milling three times of CNTs–GO colloids was about 1634 mAh g−1 during the 100-cycle charge and discharge test at 1

C high current density. The CNT–RGO–Si composites exhibited coulombic efficiency of over 96% with excellent stability.