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Materials Letters 85 (2012) 4043

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

Nano iron oxide (Fe2O3)/carbon black electrodes for electrochemical capacitors


Mahdi Nasibi a,n, Mohammad Ali Golozar b, Gholamreza Rashed a
a b

Technical Inspection Engineering Department, Petroleum University of Technology, Abadan, Iran Department of Materials Engineering, Isfahan University of Technology, Isfahan 84156-83111, Iran

a r t i c l e i n f o
Article history: Received 8 May 2012 Accepted 28 June 2012 Available online 6 July 2012 Keywords: Nano iron oxide Microstructure Electrochemical capacitors Energy storage and conversion

a b s t r a c t
In this research, nano iron oxide (Fe2O3)/carbon black electrodes are prepared by mechanical pressing method and evaluated as possible electrodes for electrochemical capacitors. Electrochemical properties of the produced electrodes are studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests in 2 M KCl electrolyte at different scan rates. Scanning electron microscopy (SEM) is also used to characterize the microstructure and nature of the produced electrodes. Electrochemical stability of the electrodes is investigated by switching the electrode back and forth for 500 cycles at 20 mV s 1.The results obtained show a specic capacitance of as high as 40.07 F g 1 for 30:60:10 (carbon black:Fe2O3:polytetrauoroethylene) electrode in 2 M KCl at 10 mV s 1. The proposed electrode exhibits good cyclic stability and maintains 80% of the capacitance after 500 cycles. SEM images conrm the porous structure of Fe2O3/carbon black electrodes. Crown Copyright & 2012 Published by Elsevier B.V. All rights reserved.

1. Introduction Although the need for energy and energy storage will be far greater in the future, the problem of ensuring power quality is already upon us. Energy storage is being widely regarded as one of the potential solutions to deal with the variations of variable renewable electricity sources and it is the key to unlocking the door renewable energy. Among different energy storage systems, electrochemical capacitors store the electrical energy in interfaces formed at a solid/electrolyte interface. Positive and negative ionic charges within the electrolyte accumulate at the surface of the solid electrode and compensate the electronic charge at the electrode surface [1]. High cycle life, high life time, high energy efciency ranging from 85% up to 98% and high self-discharge rate are some of the characteristics of supercapacitors [2,3]. Today, many laboratories are actively engaged in development of well-known type of supercapacitors, viz., electrochemical double-layer, pseudo and hybrid supercapacitors, and most researches have been focused on the development of different electrode materials [4,5]. The aim of this work is to fabricate nano Fe2O3/carbon black electrodes using mechanical pressing as a fast method. Then the products were evaluated as possible candidate electrode for

electrochemical capacitors using cyclic voltammetry, electrochemical impedance spectroscopy and scanning electron microscopy.

2. Experimental Materials: High purity ( 4 99%) nano iron oxide (Fe2O3) ( o 50 nm), nickel foil (99.99% with 0.125 mm thickness) and polytetrauoroethylene ( o 2 mm) were purchased from Aldrich, USA. All other chemicals used in this study were purchased from Merck, Germany. In order to prepare the electrodes, the mixture containing different wt% Fe2O3 and carbon black (CB) and 10 wt% polytetrauoroethylene (PTFE) was mixed well in ethanol to form a paste and then was pressed onto the nickel foil (25 MPa), which served as a current collector (surface was 0.785 cm2). The typical mass weight of electrode material was 30 mg. The used electrolyte was 2 M KCl. Characterization: Electrochemical behavior of Fe2O3/carbon black electrodes was characterized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests. The electrochemical measurements were performed using an Autolab (Netherlands) potentiostat Model PGSTAT 302 N. CV tests were conducted at various scan rates (s) with recording of potential response currents, I, which is related by C I/s where C is the capacitance of the electrode interface. EIS measurements were also carried out in the frequency range from 100 kHz to 0.005 Hz at open circuit potential with ac amplitude of 10 mV. The specic capacitance C (F g 1) of the active material was

Corresponding author. Tel.: 98 911 3708480; fax: 98 631 4423520. E-mail address: 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.2012.06.109

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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 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) [6]. The morphology and the nature of porous electrodes were studied using scanning electron microscopy (TESCAN, USA).

a scan rate of 10 mV s 1. This electrode was selected for further investigation, i.e. scan rate and chargedischarge cycles. The CV curves at various scan rates between 10 and 100 mV s 1 for 30:60:10 electrodes are shown in Fig. 3(a). As the potential scan rate is increased no obvious distortion in the CV

3. Results and discussion Specic surface area and porosity are two important parameters to prepare high efcient electrodes for electrochemical capacitors. The morphology and the nature of the as-prepared electrodes were analyzed using SEM. As shown in Fig. 1, images show good dispersion of the nanoparticles on the surface of the electrodes. This increases the specic surface area and makes the surface of the electrodes porous. This porous surface greatly improves the charge storage and charge delivering capability of the electrodes. Fig. 2(a) shows the CVs of various Fe2O3-containing electrodes at the scan rate of 10 mV s 1 in 2 M KCl electrolyte. CVs exhibit a rectangular shaped prole (Fig. 2 (a)), which is a characteristic of ideal capacitive behavior [7,8]. The electrodes exhibited almost potential-independent capacitance for which current leakage may be the reason [7]. As the Fe2O3 nanoparticles were added to the electrode material, potential window was shifted to the negative direction of potentials to overcome the overcharging and/or overdischarging of the electrodes. This could result in a decrease in the active materials available for further cycling. As the nano material content increased (up to 80%) current peak decreased and caused to lower the calculated capacitance. This current peak reduction may be due to increase in the electrode resistance (Fig. 2(b)) in the presence of iron oxide nanoparticles. The point of intersecting with the real axis of Nyquist curves in the range of high frequency (Fig. 2(b)) 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 [9]. As shown in Fig. 2(b), an obvious difference observed among these three Nyquist spectra is the pseudo-charge transfer resistance (Rct) in high Fe2O3-containning electrodes. This could be attributed to the Faradic reactions of active materials on the electrode surface. Generally, by addition of Fe2O3 nanoparticles into the electrode material, the following three parameters will act simultaneously: Faradic reactions on the metal oxide particles, increase in the specic surface area in the presence of nanoparticles and increase in the electrical resistance of the electrode. Finally, it is concluded that the 30:60:10 electrode shows as high as 40.07 F g 1 capacitance in 2 M KCl electrolyte at

Fig. 2. (a) CV curves and (b) Nyquist diagrams for various Fe2O3-content electrodes in 2 M KCl electrolyte.

Fig. 1. SEM images obtained from 30:60:10 electrode showing porous surface.

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M. Nasibi et al. / Materials Letters 85 (2012) 4043

In order to gain the quantitative information on the utilization of 30:60:10 Fe2O3/CB electrodes, the voltammograms were analyzed as a function of scan rate, according to the procedure reported by Ardizzone et al. [11]. The scan rate dependence of the capacitance can be related to the less accessible surface area (pores, cracks, etc.) which become excluded as the rate reaction is enhanced. In charge and discharge cycles, the 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 n n n n n reaction sites, i.e., qn T qI qO, where qT, qI and qO are the total charge, and charges related to the inner and the outer surface, respectively. The extrapolation of qn to v 0 from 1/qn vs. v1/2 plot 1 gives the total charge qn cm 2 which is the charge T of 33.3 C g related to the entire active surface of the electrode. In addition, extrapolation of qn to v N (v1/2 0) from the qn vs. v 1/2 plot 1 gives the outer charge qn cm 2, which is the charge O, 9.80 C g due to the redox process on the most accessible active surface [12]. Therefore, this nanocomposite electrode shows low ratio of n the outer charge to total charge (qn O/qT) of 0.3, which conrms the low current response of the prepared electrodes at high scan rate. Regarding the practical applications, the cycle stability of supercapacitors is a crucial parameter. The cycle lives of both conducting polymers and metal oxides, as candidates for pseudocapacitive materials, are much shorter than those of the carbon base materials because of the loss of active materials [4]. Incorporation of carbon black into the pseudo-capacitive materials is an effective method to improve their cycle performance. In the case of nano Fe2O3/CB electrodes the cycle stability was evaluated by repeating the CV at a scan rate of 20 mV s 1 for 500 cycles (Fig. 3(b)). Simultaneously, EIS tests were used to evaluate the electrode changes (Fig. 3(c)). These electrodes were found to exhibit excellent stability over the entire cycle numbers (Fig. 3(b)). In these electrodes, carbon black can provide conductive channels due to the excellent conductivity; but, during the 500 chargedischarge cycles the equivalent series resistance increases (Fig. 3(c)) and the Nyquist plots shift to some higher values which can be attributed to the electrolyte decomposition on the electrode surface. Increased electrode resistance with increasing cycle number can decrease the capacitance (20% after 500 cycles). Electrolyte deposition and active material dissolution during cycling decrease the specic surface area. So fewer electrochemically active sites were available for energy storage.

4. Conclusions In summary, nano Fe2O3/carbon black is a good candidate electrode material for electrochemical capacitors at low scan rates. This is based on the good electrochemical performance observed in the potential range from 0.3 to 0.25 V (vs. SCE) in 2 M KCl electrolyte. The surface showed a porous structure that greatly improves charge storage and charges delivery of electrode capability. It shows a pseudo-capacitance characteristic and low n ratio of the outer charge to total charge (qn O/qT) of 0.3. The 30:60:10 (CB:Fe2O3:PTFE) electrode has as high as 40.07 F g 1 specic capacitance in 2 M KCl electrolyte at a scan rate of 10 mV s 1 and showed a good cycling performance.

Fig. 3. (a) CV curves obtained at various scan rates, (b) representative cyclic voltammograms obtained at 20 mV s 1 and (c) Nyquist plots before and after 500 CV cycles for 30:60:10.

curves is observed. Even at a high scan rate of 100 mV s 1, the CV curves still retain their rectangular shape. However, CV curves at such a high scan rate reveal a low capacitance (due to energy losses) and a low current response on voltage reversal at each end potential. It has been proposed that the low current response on the voltage reversal represents a high ESR of the electrode as well as a low diffusion of electrolyte ions within the pores of the electrode [10]. In the case of Fe2O3/CB electrodes, Fe2O3 particles ( o 50 nm) on the surface of the carbon black particles can greatly reduce the diffusion length of K during the chargedischarge processes.

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