This initial adsorption results in the localized expansion of C-C bonds due to the filling of π* antibonding orbitals. Localized interactions between adsorbed Na and C are evident in the ∆𝜌(𝑟) from adsorption models and are consistent with DFT calculations and Raman spectroscopy. Subsequently, sodium ions adsorb at lower binding energy surface defect sites, such as divacancies. As sodiation continues toward lower voltages within the slope region, sodium ions begin to transport and intercalate between graphene layers, coordinated by intralayer defect sites, causing the average interlayer spacing to increase, consistent with Na-C correlations seen in ∆𝜌(𝑟) 𝑏𝑟𝑜𝑎𝑑 . Sodium ions eventually reach the pores and adsorb at defect sites in the pore walls.