Graphene materials for electrochemical capacitors

Chemical activation has also been adopted for fabricating porous activated CMG to improve SSA. In this approach, graphite oxide powder prepared by a modified Hummers method was further treated though a microwave-assisted exfoliation process, which was denominated as microwave exfoliated graphite oxide (MEGO). First, fluffy MEGO powder were dispersed and soaked in an aqueous KOH solution for 24h. Then the solid cake obtained by vacuum filtration was dried and successively treated at 8000C for 1h in a horizontal tube furnace with an argon flow of 150 sccm and working pressure of about 400 Torr to generate activated MEGO' (a-MEGO) powder. The activation with KOH generated a continuous 3D pore structure with atom-thick walls and both microand mesopores (Figuse 1d). It was demonstrated that the BET SSAs of a-MEGO powder can be adjusted in the range of 760-3100 m2 g-1 by tuning activation temperature and the KOH/MEGO ration. The capacitive performance of a-MEGO-based EC was evaluated by testing in 1-bytyl-3-methyl-imidazolium tetraflouroborate (BMIMBF4)/acetonitrile (AN) electroyte. The CVs of this EC showed a quasi-rectangular shape in 0 to 3,5 V overa wide range of voltage scan rates (Figure 3a). The SCs of the a-MEGO-based EC were measured to be 165, 166, and 166 F g-1 from their galvanostatic discharge current densities of 1.4, 2.8, and 5.7 A g-1, (Figure 3b). The voltage drop at the initial stage of discharge is only 0,034 V ( at the current density of 1.4 A g -1), suggesting a very low equivalents series resistance (ERS) of the test cell. Nyquist plot shown in Figure 3c features a vertical curve, indicating a nearly ideal capacitive behavior of the cell with an ESR of 3,2 (Figure 3c, inset). Moreover, the a-MEGO electrodes are very stable as confirmed by 97% capacitance retention after testing for 10000 charge/ discharge cycles at a constant current density of 2,5 A g-1 in neat BMIMBF 4 electrolyte (Figure 3d). It also found that the SCs follow the trend of BET SSA of a-MEGO electrode: the higher the BET SSA, the larger the SC. These facts reinforced the correlation between high BET surface area and gravimetric capacitance for graphene-based material. LightScribe is a standard optical disc recording technique, and it has been applied to laser reduction of GO films. The laser-scribed graphene (LSG) films have 3D open networks with a larger SSA of 1520 m2- g-1 (Figure 1e). Furthermore, they are mechanically robust and electrically conductive (1738 S m-1) and thus can be directly processed without the requirement of polymer binder and current collectors. A superthin EDLC device with a total thickness of <100 m can be readily made by sandwiching an ion porouts separator between two identical LSG electrodes using polyethylene terephthalate (PET) as a thin flexible substrate and an aqueous electrolyte of 1.0 M H3PO4. The electrochemical performance was evaluated through CV and galvanostatic

charge/discharge experiments. It was demonstrated that CV of LSG-EC is nearrectangular in shape at a scan rate as high as 1.0 V s-1, being indicative of ideal capacitive behavior. The nearly triangular shape of the charge/ discharge curves at a high current density of 10 A g-1 also signifies the formation of an ideal EDL and fast ion transport within the LSG electrodes. The areal capacitance of the LSG-EC was caculated to be 3.67 mF cm-2 at A g-1. The device also showed a very high rate capability, maintaining a high SC of more than 1.84 mF cm-2 even at an ultrafast charge/ discharge rate of 1000 A g-1. The device displays a pure capacitive behavior, even at high frequencies of up to 158Hz with a resistance (RC) time constant of 33 ms. This rapid frequency response of the LSG-EC associates with the large and accessible surface area of the LSG. Additionally, the LSG-EC is electrochemicaly stable and exhibited 96.5% capacitance after charge/ discharging for 10000 cycles.

Figure 3: Supercapacitor performances of a-MEGO (SSA~2400 m2 g-2) inn the BMIM BF4/ AN electrolyte. (a) CV curves for different scan rates. (b) Galvanostatic charge/ discharge curves of a-MEGO-based supercapacitor under different constant currents. (c) NYquiuist plot, showing the laser