<p>The construction of silicon–carbon (Si/C) composites containing graphite is the mainstream solution to overcome the key problems of volume expansion, insufficient conductivity, and poor interfacial compatibility of silicon-based anodes. However, most Si/C materials are still constrained by the long lithium-ion diffusion paths, sluggish kinetics, and lithium plating risks caused by excessively large graphite particle sizes. This study innovatively employs sand-milled small-sized flake-graphite (F-Gr) as the matrix, and successfully constructs F-Gr@Si@C-Fe/Fe₃C composite material through spray drying combined with annealing treatment, in which silicon, graphite, and Fe/Fe₃C multi-components are closely interconnected. The prepared F-Gr@Si@C-Fe/Fe₃C material can significantly overcome the aforementioned defects and exhibits good Coulombic efficiency and excellent battery performance. Notably, its reversible capacity after 1000 cycles at 1 A g⁻¹ is as high as 704 mAh g⁻¹, significantly higher than that of F-Gr@Si@C without Fe/Fe₃C doping. Comprehensive characterization indicates that: the carbon coating layer effectively enhances the material's electrical and structural stability, while the introduction of the Fe/Fe₃C structure significantly strengthens the material's interfacial compatibility, consequently enabling the composite material to exhibit superior electrochemical performance. More importantly, the F-Gr@Si@C-Fe/Fe₃C||LiCoO₂ pouch full battery assembled based on this material verifies its potential for practical application.</p> Graphical Abstract <p>The prepared F-Gr@Si@C-Fe/Fe₃C anode can suppress the volume expansion, improve the Li⁺ diffusion kinetics and interfacial compatibility, and finally effectively boost the battery performance.</p>