International Conference on Mechanical, Materials and Automotive Engineering (ICMMAE'2012) April 13-15, 2012 Pattaya

Micro-Nano Sized Carbon Black as an Electrode Material for Electrochemical Double Layer Capacitors
M. Nasibi, Gh. Rashed, and M.A. Golozar

AbstractIn this paper, carbon black was evaluated as a possible

electrode candidate material for electrochemical capacitors. Mechanical pressing as a fast and easy method was used for electrode fabrication. Regarding the utility in supercapacitors, the electrochemical properties of the produced electrode was studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests in 2 M KCl electrolytes. The results obtained show that carbon black electrode has a specific capacitance as high as 33.58 Fg1, in the potential range of -0.15 to 0.55 V (vs. SCE) in 2 M KCl at scan rate of 10 mVs-1. Also, charge/discharge cycling test shows a good reversibility and confirms that the electrical resistance would increase after 100 cycles.

electrochemical capacitors using electrochemical techniques including cyclic voltammetry, electrochemical impedance spectroscopy. II. EXPERIMENTAL A. Materials Nickel foil (99.99% with 0.125 mm thickness) and polytetrafluoroethylene (<2 m) were purchased from Aldrich. All other chemicals used in this study were purchased from Merck. The mixture containing carbon black (CB) and 10 wt.% polytetrafluoroethylene (PTFE) was well mixed in ethanol to form a paste and then was pressed onto nickel foil (4107 Pa) which served as a current collector (surface was 0.785 cm2). The typical mass load of electrode material was 30 mg. The used electrolyte was 2 M KCl. B. Characterization The electrochemical behavior of carbon black electrodes was characterized using CV and EIS tests. The electrochemical measurements were performed using an Autolab (Netherlands) Model PGSTAT 302N. CV tests were performed within the range of -0.15 and +0.55 V (vs. SCE), using scan rates of 10, 20, 30, 50 and 100 mV.s-1. EIS measurements were also carried out in the frequency range of 100 kHz to 0.01 Hz at open circuit potential with ac amplitude of 10 mV. The specific capacitance C (F.g1) of the active material was determined by integrating either the oxidative or the reductive parts of the cyclic voltammogram curve to obtain the voltammetric charge Q (C). This charge was subsequently divided by the mass of active material m (g) in the electrode and the width of the potential window of the cyclic voltammogram E (V), i.e., C =Q/(Em) [4]. III. RESULTS AND DISCUSSION Fig. 1 shows the second CVs of carbon black electrodes at different scan rate in 2 M KCl electrolyte. CVs exhibit a rectangular shaped profile, which is characteristic of ideal capacitive behavior [4]. All of these electrodes exhibited almost potential-independent double-layer capacitance, over appreciable ranges of polarization voltage. As the scan rate increases (Fig. 1) the capacitance versus potential relation would deviate from the classical square waveform, expected for a pure capacitor. As discussed by some researchers this is due to the resistance effects down the pores [5]. In addition to
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KeywordsElectrochemical capacitor, Cyclic voltammetry, Electrochemical impedance spectroscopy . I. INTRODUCTION XPLOSIVE growth in electronic equipments and the urgent need for electronic and hybrid electronic vehicles demand for the high power and energy storage devices. Among different energy storage systems, ultracapacitors are recognized as highly attractive energy storage devices to satisfy the above needs [1]. Therefore, many laboratories are actively engaged in development of well-known type of supercapacitors, viz., electrochemical double-layer, pseudo and hybrid supercapacitors. Most research in this area has been focused on the development of the different electrode materials such as various forms of carbons, conducting polymers and transition metal oxides [2]. Carbon black is a high conductive carbon base material that the key properties of it are considered to be fineness (primary particle size), structure (aggregate size/shape), porosity, and surface chemistry [3]. In this paper, mechanical pressing as a fast and easy method was used to fabricate carbon black electrodes. The product was evaluated as a possible candidate electrode for

M. Nasibi is with the Petroleum University of Technology, Abadan, Islamic Republic of Iran (corresponding author to provide phone: +98 911 370 8480; fax: +98 631 442 3250; e-mail:m_nasibi@yahoo.com). Gh. Rashed, is the Petroleum University of Technology, Abadan, Islamic Republic of Iran (e-mail: rashed 545@yahoo.com). M.A.. Golozar is with the Materials Science and Engineering Department, Isfahan University of Technology, Isfahan, Islamic Republic of Iran (email:Golozar@gmail.com).

International Conference on Mechanical, Materials and Automotive Engineering (ICMMAE'2012) April 13-15, 2012 Pattaya

pore resistance, efficiency is another important parameter affecting the capacitance in high sweep rates. As the sweep rate increases, loss of energy increases and the stored charge on the electrode surface decreases causing the capacitance to decrease (Table I). Additionally, CV curves at such a high scan rate reveal a low current response on voltage reversal at each end potential. Meanwhile, this low current response on the voltage reversal represents a high equivalent series resistance of the electrodes and also the low diffusion of electrolyte ions in the electrodes [6].

Fig. 1 capacitance vs. potential curves obtained from different scan rates of carbon black electrodes.

Fig. 3 EIS curves after and before 100 CV cycles for Carbon black electrodes.
TABLE I CAPACITANCE OBTAINED FROM CARBON BLACK ELECTRODES AT DIFFERENT SCAN RATES IN 2 M KCL ELECTROLYTE
10 mV/s 33.58 20 mV/s 24.88 30 mV/s 17.95 50 mV/s 12.08 100 mV/s 6.59

IV. CONCLUSIONS In summary, electrochemical tests revealed that carbon black, as electrode material for electrochemical capacitors, has good electrochemical performance in the potential range of 0.15 to 0.55V (vs. SCE) in 2 M KCl electrolyte. It provides a double layer capacitance. Carbon black electrode has as high as 33.58 Fg-1 specific capacitance in 2 M KCl electrolyte at scan rate of 10 mVs-1 and shows a good cycling performance. ACKNOWLEDGMENT The cyclic stability of supercapacitors is a crucial parameter for their practical applications. So, the stability of carbon black electrode was evaluated by repeating the CV tests between -0.15 and +0.55 V (vs. SCE) using a scan rate of 10 mVs-1, for 100 cycles (Fig. 2). Simultaneously, EIS method was used to evaluate the electrode changes (Fig. 3). As shown in Fig. 3, the point of intersecting with the real axis of Nyquist curves in the range of high frequency is the equivalent series resistance. It indicates the total resistance of the electrode, the bulk electrolyte resistance and the resistance at electrolyte/electrode interface [2]. According to Fig. 3, Nyquist plots show a double layer capacitance and shift to higher impedances, which confirm the higher equivalent series resistance after 100 cycles. Electrolyte deposition and redox reactions could be the reasons for this resistance increment.
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Fig. 2 Representative cyclic voltammograms obtained from carbon black electrode at 10mV.s-1 in 2 M KCl electrolyte.

The authors are thankful to Petroleum University of Technology, Iran, for financial support of the project. REFERENCES
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