In Hyuk Son

Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density

Silicon is receiving discernable attention as an active material for next generation lithium-ion battery anodes because of its unparalleled gravimetric capacity. However, the large volume change of silicon over charge–discharge cycles weakens its competitiveness in the volumetric energy density and cycle life. Here we report direct graphene growth over silicon nanoparticles without silicon carbide formation. The graphene layers anchored onto the silicon surface accommodate the volume expansion of silicon via a sliding process between adjacent graphene layers. When paired with a commercial lithium cobalt oxide cathode, the silicon carbide-free graphene coating allows the full cell to reach volumetric energy densities of 972 and 700 Wh l−1 at first and 200th cycle, respectively, 1.8 and 1.5 times higher than those of current commercial lithium-ion batteries. This observation suggests that two-dimensional layered structure of graphene and its silicon carbide-free integration with silicon can serve as a prototype in advancing silicon anodes to commercially viable technology.

CO2 Enhanced Chemical Vapor Deposition Growth of Few-Layer Graphene over NiOx

The use of mild oxidants in chemical vapor deposition (CVD) reactions has proven enormously useful. This was also true for the CVD growth of carbon nanotubes. As yet though, the use of mild oxidants in the CVD of graphene has remained unexplored. Here we explore the use of CO2 as a mild oxidant during the growth of graphene over Ni with CH4 as the feedstock. Both our experimental and theoretical findings provide in-depth insight into the growth mechanisms and point to the mild oxidants playing multiple roles. Mild oxidants lead to the formation of a suboxide in the Ni, which suppresses the bulk diffusion of C species suggesting a surface growth mechanism. Moreover, the formation of a suboxide leads to enhanced catalytic activity at the substrate surface, which allows reduced synthesis temperatures, even as low as 700 °C. Even at these low temperatures, the quality of the graphene is exceedingly high as indicated by a negligible D mode in the Raman spectra. These findings suggest the use of mild oxidants in the CVD fabrication as a whole could have a positive impact.

Graphene Coating of Silicon Nanoparticles with CO2‐Enhanced Chemical Vapor Deposition

Understanding the growth of graphene over Si species is becoming ever more important as the huge potential for the combination of these two materials becomes more apparent, not only for device fabrication but also in energy applications, particularly in Li-ion batteries. Thus, the drive for the direct fabrication of graphene over Si is crucial because indirect approaches, by their very nature, require processing steps that, in general, contaminate, damage, and are costly. In this work, the direct chemical vapor deposition growth of few-layer graphene over Si nanoparticles is systematically explored through experiment and theory with the use of a reducer, H2 or the use of a mild oxidant, CO2 combined with CH4 . Unlike the case of CH4 , with the use of CO2 as a mild oxidant in the reaction, the graphene layers form neatly over the surface and encapsulate the Si particles. SiC formation is also prevented. These structures show exceptionally good electrochemical performance as high capacity anodes for lithium-ion batteries. Density functional theory studies show the presence of CO2 not only prevents SiC formation but helps enhance the catalytic activity of the particles by maintaining an SiOx surface. In addition, CO2 can enhance graphitization.