Electrochemically cathodic exfoliation in room temperature ionic liquids N-butyl, methylpyrrolidinium bis(trifluoromethylsulfonyl)-imide (BMPTF2N) has been developed for few-layer graphene sheets, demonstrating low levels of oxygen (2.7 at% of O) with a nearly perfect structure (I-D/I-G < 0.05). The mechanism of cathodic exfoliation in BMPTF2N involves the intercalation of ionic liquids cation [BMP](+) under highly negatively charge followed by graphite expansion. Porous activated graphene sheets were also obtained by activation of graphene sheets in KOH. Transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy were used to characterize these graphene materials. The electrochemical performances of the graphene sheets and porous activated graphene sheets for lithiumion battery anode materials were evaluated using cyclic voltammetry, galvanostatic charge-discharge cycling, and electrochemical impedance spectroscopy.