The demand for higher energy densities in rechargeable batteries has driven intensive research into next-generation anode materials that surpass the limitations of conventional graphite. Lithium metal, with its highest theoretical specific capacity (3.86 Ah g⁻¹) and lowest electrochemical potential, is a promising candidate but suffers from dendritic growth, unstable solid–electrolyte interphases (SEIs), and excessive lithium consumption, which compromise safety, efficiency, and cost. Silicon, though offering an even greater theoretical capacity (4200 mAh g⁻¹), faces similar challenges arising from severe volume fluctuations and interfacial degradation during cycling. This dissertation addresses these critical barriers through interphase and substrate engineering using tailored graphene hosts, integrating artificial interphase design with structural control to realize stable, high-capacity anodes for both lithium metal and silicon-based systems.An air-controlled electrospray process was developed to produce layered and crumpled graphene scaffolds from a common precursor. Crumpled scaffolds more effectively accommodated lithium, reduced nucleation overpotential, and suppressed dendritic deposition. When paired with NMC811 cathodes (N/P = 3:1), lithiated crumpled graphene achieved 1790 mAh g⁻¹ with 79 % retention over 200 cycles, outperforming both layered scaffolds and lithium foil. Extending this approach, copper free current collectors were developed using freestanding graphene (FSGr) and graphene coated polypropylene (PPGr) scaffolds. These lightweight architectures replace conventional copper foil and enable safer, more efficient anodes. The capacities, 1380 and 930 mAh g⁻¹ for FSGr and PPGr respectively, are calculated from the total anode weight, including the conductive host and substrate. Under this practical basis, both systems exhibit much higher capacities than graphite on copper, about 250 mAh g⁻¹, while reducing inactive mass and enhancing overall safety. Further progress was achieved through a one step, scalable gradient artificial SEI (ASEI) comprising a lithiophobic polymer rich upper layer and a lithiophilic inorganic rich lower layer within a three-dimensional porous framework. This stratified interphase directed lithium ion flux, reduced interfacial impedance, and enabled stable Li

Li pouch cell cycling for 5000 hours, along with improved full cell performance in both ether- and carbonate-based electrolytes. Finally, the dissertation introduces a low-cost graphene manufacturing route for silicon anodes. Graphene exfoliated from petroleum coke in a Taylor–Couette reactor was combined with silicon powder to form binder free hybrid electrodes that achieved high silicon utilization, capacities up to 2500 mAh g⁻¹ at 5 mAh cm⁻², and improved lithium ion transport kinetics. Collectively, this work establishes a scalable materials-design framework that combines graphene host architectures and engineered interphases to overcome the intrinsic instabilities of lithium metal and silicon anodes. The resulting principles provide practical guidance for translating next-generation anodes into pouch-cell and industrial battery formats, advancing the development of high-performance, cost-effective lithium-based energy storage.