Materials Letters 91 (2013) 323325

Contents lists available at SciVerse ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Nanoporous carbon black particles as an electrode material for electrochemical double layer capacitors
Mahdi Nasibi a,c,n, Mohammad Ali Golozar b, Gholamreza Rashed a
a

Technical Inspection Engineering Department, Petroleum University of Technology, Abadan, Iran Department of Materials Engineering, Isfahan University of Technology, Isfahan, Iran c Health and Safety Engineering (HSE) Ofce, National Iranian Oil Rening and Distribution Company (NIORDC), Yazd zone, Yazd, Iran
b

a r t i c l e i n f o
Article history: Received 27 July 2012 Accepted 26 September 2012 Available online 5 October 2012 Keywords: Electrode material Electrochemical double layer capacitors Microstructure Energy storage and conversion

abstract
The aim of this work is to investigate the nanoporous carbon black particles as a possible electrode candidate material for electrochemical double layer capacitors using cyclic voltammetry and electrochemical impedance spectroscopy tests in 2 M KCl electrolyte at different scan rates. Scanning electron microscopy is also used to characterize the microstructure and nature of the produced electrodes which conrms the nanoporous ( o 10 nm in diameter) structure of the prepared electrodes. This nanoporous structure increases the specic surface area and electrical resistance of the electrodes, simultaneously. Proposed electrode shows a specic capacitance as high as 33.58 F g 1, in the potential range from 0.15 to 0.55 V (vs. SCE) at a scan rate of 10 mV s 1. It shows the low ratio of the outer to total charge * (q* O/qT) of 0.11 which conrms the low current response. Additionally, charge/discharge cycling test shows good reversibility after 100 cycles. Crown Copyright & 2012 Published by Elsevier B.V. All rights reserved.

1. Introduction Explosive growth in electronic equipments and the urgent need for electronic and hybrid electronic vehicles demand 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]. High cycle life, high life time, high energy efciency and high self-discharge rate are some of the characteristics of supercapacitors [2,3]. Today, most researches in this area have been focused on the development of different new porous carbons and porous pseudocapacitive electrode materials [47]. These porous structures can provide a very short diffusion pathway for ion as well as large active surface area, leading to improved charge storage capability [6]. According to Ge et al. [7], one of the signicant properties of these materials during cycling is the structure and/or volume changes due to the Faradic reactions, electrolyte decomposition and active material losses. Among different carbon base materials, carbon black is a highly conductive material such that the key properties of it are considered to be neness (primary particle size), structure (aggregate size/shape), porosity, surface chemistry and its low cost [8]. The aim of this work is to investigate the nanoporous carbon black particles as a low cost material for supercapacitors. Mechanical pressing as a novel, fast and easy

method was used to fabricate the electrodes. Then the product was evaluated as a possible candidate electrode for electrochemical double layer capacitors using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM).

2. Experimental Materials: High purity nickel foil (99.99% with 0.125 mm thickness) and polytetrauoroethylene ( o 2 mm) as a polymeric binder were purchased from Aldrich, USA. Nanoporous ( o 10 nm in diameter) carbon black (CB) as an active material ( o 2 mm) was purchased from Degussa, Germany. All the other chemicals were purchased from Merck, Germany. The electrode material containing 90% CB and 10 wt% polytetrauoroethylene was well mixed in ethanol to form a paste and it was then pressed onto nickel foil (4 107 Pa) which served as a current collector (surface was 0.785 cm2). The typical mass load of the electrode material was 30 mg. The electrolyte used was 2 M KCl. Characterization: Electrochemical behavior of the electrodes was characterized using the CV and EIS tests. The electrochemical measurements were performed using an Autolab (Netherlands) model PGSTAT 302N. The CV test was performed within different ranges of potential, using scan rates of 10, 20, 30, 50, 100 and 200 m V s 1. EIS measurements were carried out in the frequency range from 100 kHz to 0.01 Hz at open circuit potential with ac amplitude of 10 mV. The specic capacitance C (F g 1) of the

Corresponding author. Tel.: 98 9113708480; fax: 98 6314423520. E-mail addresses: m_nasibi@yahoo.com, mahdi.nasibi@gmail.com (M. Nasibi).

0167-577X/$ - see front matter Crown Copyright & 2012 Published by Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.matlet.2012.09.088

324

M. Nasibi et al. / Materials Letters 91 (2013) 323325

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 DE (V), i.e., C Q/(DEm) [9]. Finally, morphology and the nature of the prepared electrodes were investigated by scanning electron microscopy (TESCAN, USA).

3. Result and discussion Specic surface area, pore size distribution and conductivity of the electrode materials are important parameters to prepare highly efcient electrodes for electrochemical capacitors. CB is characterized by high porosity and small particle size [8,10]. These porosities also vary from mild surface pitting to the actual hollowing out of particles. Additionally, the surface area of CB is generally considered to be more accessible than the other forms of high surface area carbons; this ne highly branched structure of the CB particles makes them ideally suited for lling inter-particle voids created between coarse particles which improves the electrical contact between them. As shown in Fig. 1, SEM images conrm the nanopores on the used CB particles, on the surface of the investigated electrodes. This nanoporous structure (Fig. 1) increases the specic surface area and will change the charge storage and charge delivering capability of the electrodes. It may result in a difculty in the motion of the electroactive ions in these small pores, and accordingly a decrease in the usable surface area and an increase in the internal resistance of the electrode. This situation becomes especially conspicuous at high discharge rates, at which the electrolyte within the pores contribute a lot to the internal resistance of the electrodes. Therefore, cyclic voltammetry was used to investigate the effect of different charge/discharge scan rates on the charge storage capability of the electrodes. As the scan rate increases (Fig. 2(a)) the CV curves would deviate from the classical square waveform, expected for pure capacitance. Due to a marked decrease in the accessible surface area at such a high scan rate and the resistance down the nano-sized pores [11], capacitance and accordingly the energy delivered decreases dramatically (Fig. 2(a)). The efciency is

another important parameter affecting the capacitance in these high sweep rates [12,13]. In order to gain quantitative information on utilization of the prepared CB electrodes, voltammograms were analyzed as a function of scan rate, according to the procedure reported by Ardizzone et al. [14]. Scan rate dependence of the capacitance can be related to the less accessible surface area (pores, cracks, etc.) which becomes excluded as the reaction rate is enhanced. In charge and discharge cycles, total charge can be written as the sum of an inner charge from the less accessible reaction sites and an outer charge from the more * * * * * accessible reaction sites, i.e., q* T qI qO, where qT, qI and qO are the total charge and charges related to the inner and the outer surface, respectively. Extrapolation of q* to v 0 from 1/q* vs. v1/2 plot 1 (Fig. 2(b)) gives the total charge q* cm 2 which is T of 19.61 C g the charge related to the entire active surface of the electrode. In addition, extrapolation of q* to v N (v 1/2 0) from the q* vs. v 1/2 1 plot (Fig. 2(c)) gives the outer charge q* cm 2, which is O, 2.04 Cg the charge on the most accessible active surface. Therefore, this nanoporous electrode shows a low ratio of the outer charge to total * charge (q* O/qT) of 0.11, which conrms the low current response of the electrodes at high scan rates. One explanation can be that such a high scan rate limits the diffusion of electroactive anions (Cl and OH ) and/or cations (K and H ) through the whole volume of the electrode and consequently some pores and voids remain inaccessible at high sweep rates. Finally, it is concluded that two counter acting parameters would act simultaneously on this nanoporous structure: increasing the specic surface area in the presence of the nano-pores and decreasing the electrode conductivity due to the resistance down the pores. The prepared CB electrodes show specic capacitance as high as 33.58 F g 1 in 2 M KCl electrolyte at the scan rate of 10 mV s 1. Regarding the practical applications the cycle stability of the supercapacitors is a crucial parameter. The cycle life of the carbon base materials is much longer than that for both conducting polymers and metal oxides as candidates for pseudo-capacitive materials due to the structure and/or volume changes [14]. The long-term cycle stability of the electrodes was also evaluated in this study by repeating the CV test between 0.15 and 0.55 V (vs. SCE) at a scan rate of 10 mV s 1 for 100 cycles (Fig. 3(a)). The nanoporous CB electrodes are found to exhibit excellent stability over the entire cycle numbers (Fig. 3). According to Fig. 3(b), the

Fig. 1. Scanning electron microscopy images obtained from CB electrodes.

M. Nasibi et al. / Materials Letters 91 (2013) 323325

325

Fig. 3. (a) Representative cyclic voltammograms obtained from CB electrode at 10 mV s 1 in 2 M KCl electrolyte. (b) EIS curves obtained from CB electrodes after and before 100 CV cycles.

Fig. 2. (a) Capacitance vs. potential curves obtained from different scan rates of CB electrodes in 2 M KCl electrolyte. Variation of the voltammetric charge density (q) with respect to scan rates, (b) extrapolation of q to v 0 from the q 1 vs. v0.5 plot given the total charge and (c) extrapolation of q to v N from the q vs. v 0.5 plot given the outer charge for CB electrodes.

Nyquist plots show a double layer capacitance and shift to higher impedances after 100 cycles. As shown in Fig. 3(b), the point of intersection with the real axis of the Nyquist curves in the range of high frequency is the equivalent series resistance (ESR). It indicates the total resistance of the electrode, the bulk electrolyte resistance and the resistance at the electrolyte/electrode interface [4]. After 100 cycles, the anodic and cathodic currents decrease, but the C/V curves remain in their rectangular shaped proles (Fig. 3(a)) and the capacitance decreases only by 11% of the initial capacitance demonstrating good cycle stability. The decrease of the specic capacitance could be attributed to the electrolyte deposition and redox reactions on the electrode surface which increase the electrical resistance of the electrodes.

nanoporous electrodes: increasing the specic surface area in the presence of the nano-pores and decreasing the electrode conductivity due to the resistance down the pores. This nanoporous structure shows a double layer characteristic and a low * ratio of the outer charge to total charge (q* O/qT) of 0.11 which conrms the low current response on voltage reversal. The proposed CB electrode shows specic capacitance as high as 33.58 F g 1 in 2 M KCl electrolyte at the scan rate of 10 mV s 1. Finally, charge/discharge cycling tests conrm a good cycling performance of the electrodes. References
[1] Chau KT, Wong YS, Chan CC. Energy Convers Manage 1999;40:102139. [2] Hadjipaschalis I, Poullikkas A, Efthimiou V. Renew Sustain Energy Rev 2009;13:151322. [3] Sharma P, Bhatti TS. Energy Convers Manage 2010;51:290112. [4] Zhang Y, Feng H, Wu X, Wang L, Zhang A, Xia T, et al. Int J Hydrogen Energy 2009;34:488999. [5] Banerjee N, Krupanidhi SB. J Alloys Compd 2011;509:43815. [6] Rakhi RB, Chen W, Cha D, Alshareef HN. Nano Lett 2012;12(5):255967. [7] Ge M, Rong J, Fang X, Ch Zhou. Nano Lett 2012;12(5):231823. [8] Pandolfo AG, Hollenkamp AF. J Power Sources 2006;157:1127. [9] Babakhani B, Ivey DG. J Power Sources 2010;195:21107. [10] Donnet JB, Bansal RC, Wang MJ. Carbon black science technology. 2nd ed. New York: Marcel Dekker; 1993. [11] Conway BE, Pell WG. J Power Sources 2002;105:16981. [12] Nasibi M, Golozar MA, Gh. Rashed. J Power Sources 2012;206:10810. [13] Sun G, Song W, Liu X, Qiao W, Long D, Ling L. Mater Lett 2011;65:13925. [14] Ardizzone S, Fregonara G, Trasatti S. Electrochim Acta 1990;35:2637.

4. Conclusion In summary, nanoporous carbon black was studied as an electrode material for electrochemical double layer capacitors. Two counter acting parameters act simultaneously on these