To meet the escalating demand for high-energy-density lithium-based batteries, this study investigates the development of novel anode materials and interfacial engineering strategies to enhance the electrochemical performance and stability of lithium metal and silicon-rich anodes.First, free-standing graphene (FSGr) and polypropylene-supported graphene (PPGr) electrodes were fabricated via an electrospray technique. The anode’s gravimetric capacity was significantly improved by eliminating the conventional copper current collector. The graphene is able to form alloy with lithium, thereby regulating lithium deposition. Its 3D structure effectively suppresses dendrite formation, buffers volume expansion, and promotes uniform lithium nucleation. The incorporation of Sn nanoparticles further enhances lithiation capacity and cycling stability. Second, a synergistic strategy was developed by integrating graphene hosts with a conformal zwitterionic polymer artificial solid electrolyte interphase (ASEI) layer using initiated chemical vapor deposition (iCVD), forming an organic/inorganic bilayer ASEI. This configuration optimizes lithium-ion transport by forming intermediate lithium polysulfides with lower bond energy. Meanwhile, the zwitterionic polymer provides a robust protective layer that suppresses dendrite growth and improves interfacial stability, lithium nucleation behavior, and long-term cycling performance. Finally, a cost-effective and scalable strategy was proposed to prepare reduced exfoliated petroleum coke (rPC) from waste petroleum coke (PC) using a Taylor–Couette reactor(TCR). Following exfoliation, nano-silicon particles were mixed with the PC flakes and thermally treated under an inert atmosphere to remove oxygen-containing groups. The resulting binder-free Si@rPC composite anodes outperformed commercial graphene additives in terms of specific capacity, initial Coulombic efficiency, rate capability, and cycling performance. Collectively, these findings offer practical and scalable pathways for advancing next-generation lithium-based energy storage system.