An electrochemical methodology, “cathodic exfoliation” has been developed for the fabrication of graphene sheets. The mechanism of cathodic exfoliation was proposed, involving the intercalation of solvated TAB⁺, graphite expansion and solvent decomposition. The graphene sheets (GS) show promising application as anode materials for use in Li-ion batteries. Such work is highly important as it holds promise for the potential scale up of graphene production.