We use density functional calculations to determine the binding sites and binding energies of Li+ at graphene edges and prismatic graphite surfaces. Binding is favorable at bare and carbonyl terminated surfaces, but not favorable at hydrogen terminated surfaces. These findings have implications for the exfoliation of graphitic anodes in lithium-ion batteries that happens if solute and solvent co-intercalate. First, specific adsorption facilitates desolvation of Li+. Second, chemisorption lowers the surface energy by about 1 J m−2 prismatic surface area, and gives graphite additional stability against exfoliation. The results offer an explanation for experiments that consistently show exfoliation for hydrogenated graphite, but show no exfoliation for oxygenated graphite.