Constructing LiF‐Enriched Solid Electrolyte Interface on Graphene Arrays with Abundant Edges on Microscale Si‐C Anodes Toward High‐Energy Lithium‐Ion Batteries

Abstract Silicon (Si) anodes offer excellent lithium storage capacity for lithium‐ion batteries but face practical limitations due to significant volume expansion and low intrinsic electrical conductivity. These issues lead to side reactions that consume the electrolyte and impede ion‐electron transport, resulting in low areal loading (<2 mg cm⁻²) and restricted energy density. To address this, a scalable method is developed using spray drying of commercial graphite flakes (s‐Gr) and nanosilicon particles (n‐Si), followed by chemical vapor deposition to create microscale Si/C anodes (s‐Gr/n‐Si/VGs). Thin vertical graphene nanosheets (VGs) are grown on the surfaces and within the internal pores, forming a robust, micron‐sized Si/C spherical composite material. The VGs construct the conductive network, allowing the electrodes to operate at high areal loadings without pulverization and promoting LiF‐enriched solid electrolyte interphase for improved cycling stability. The s‐Gr/n‐Si/VGs maintain a capacity of 641.9 mAh g⁻¹ after 1000 cycles at 11.0 mg cm⁻², retaining 95.9% capacity. In pouch cells with NCM811 cathodes, the 5.0 Ah‐level cells achieved 80.0% capacity retention after 510 cycles at 1.0 C. This research provides a feasible pathway for manufacturing high‐performance, low‐cost, and scalable Si/C anodes suitable for high‐energy‐density lithium‐ion batteries.