Electrochimica Acta 53 (2007) 710719

A study of the electrochemical behaviour of electrodes in operating solid-state supercapacitors

P. Staiti , F. Lufrano
CNR-ITAE, Istituto di Tecnologie Avanzate per lEnergia Nicola Giordano, Via Salita S. Lucia Sopra Contesse n.5, 98126 S. Lucia, Messina, Italy Received 16 March 2007; received in revised form 20 July 2007; accepted 21 July 2007 Available online 26 July 2007

Abstract The electrochemical behaviour of electrodes and of complete solid-state supercapacitors has been studied by cyclic voltammetry (CV) and galvanostatic charge/discharge (CD) measurements using two independent electrochemical equipments. The rst one controlled the execution of the test and recorded the voltage and current values of the complete supercapacitor while the other one recorded the potential changes of the single electrodes. In this work, two different types of capacitors were studied: (a) a symmetric supercapacitor using carbon electrodes, and (b) a hybrid (asymmetric) supercapacitor with ruthenium oxide/carbon in the positive electrode and carbon in the negative electrode. The studies evidenced that in the symmetric capacitors the positive electrode controlled the capacitive performance and an optimal mass ratio from 1.2:1 to 1.3:1 between the positive and the negative electrodes was found in the investigated conditions. For the hybrid supercapacitor it was observed that the ruthenium-based positive electrode inuenced the capacitive performance of carbon-based negative electrode and that an accurate balance of carbon loading in the negative electrode was necessary. 2007 Elsevier Ltd. All rights reserved.
Keywords: Electrochemical characterization; Polymer electrolyte; Positive electrode; Negative electrode; Supercapacitor

1. Introduction The electrochemical features of the electrodes of a supercapacitor are usually studied in a three-electrode cell, which includes a working electrode, a reference electrode, and a counter electrode [19]. The electrochemical measurements carried out in this type of cell allow studying the properties of the active materials contained in the working electrode and the electrochemical stability of electrolyte and solvent. On the other hand, the complete supercapacitors are usually studied in a two-electrode cell, in which both of the electrodes act as working electrodes [1014]. In this latter cell type, it is not possible to know the ranges of the effective working potentials of negative and positive electrodes. Since negative and positive electrodes can have different electrochemical behaviour in working supercapacitor, it would be more useful to know both the electrochemical characteristics of the supercapacitor and those

Corresponding author. E-mail address: staiti@itae.cnr.it (P. Staiti).

of the single electrodes. It is known that electrochemical performances and potential windows of electrodes investigated in three-electrode cells can differ from those of the same electrodes investigated in supercapacitor conguration. This type of observation was also reported from Khomenko et al. [15], who evidenced that the values of specic capacitance of electrodes with electronically conducting polymer (ECP), obtained by a three-electrode test cell were not comparable to those measured in a two-electrode system. Moreover, they found that the capacitance of ECP electrode was strictly dependent from the ranges of potential window in which the electrode was investigated. In this paper, we show as by means of an analytical procedure, that includes the use of two electrochemical equipments, it is possible to study with simple experiments the electrochemical behaviour of single electrodes and of complete supercapacitors. Some similar studies on supercapacitors, in which were simultaneously investigated negative and positive electrodes, and complete devices, were reported in literature [1619]. Laforgue et al. [16] showed results obtained by hybrid supercapacitors, with carbon in the negative electrode and an electronically conducting polymer (ECP) in the positive electrode. The hybrid

0013-4686/$ see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2007.07.039

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supercapacitors were tested in a non-aqueous electrolyte and used two different ECPs as active materials in the positive electrode, and an activated carbon in the negative electrode. The voltage proles of these supercapacitors and of their positive and negative electrodes obtained by galvanostatic charge/discharge tests were shown by the authors for evidencing the importance of this type of study to establish which of the capacitors and/or of electrodes was presenting the better electrochemical performances. Arbizzani et al. [17] reported a similar approach to investigate the specic capacitance of three different types of supercapacitors based on carbon/carbon, ECP/ECP and carbon/ECP. They showed the voltage proles of complete devices and of each single electrode as obtained by galvanostatic charge/discharge measurements. Similarly, Wang et al. [19] reported a study for three hybrid supercapacitors based on activated carbon at the negative electrode and lithium-ion intercalated material at the positive electrode. The stability of the positive electrode was evidenced by the shape of the galvanostatic charge/discharge curve recorded for this electrode. All the cited papers reported the voltage proles of positive and negative electrodes and those of supercapacitors as obtained from galvanostatic charge/discharge measurements. Our paper is different from previous studies because we report an electrochemical study performed on a particular type of supercapacitor using a solid polymer electrolyte [20]. The behaviour of electrodes and supercapacitors was studied by cyclic voltammetry and galvanostatic chargedischarge measurements. Two types of supercapacitors were investigated: (a) a symmetric capacitor with electrodes based on carbon material, and (b) a hybrid capacitor with negative electrode based on carbon material and positive electrode based on ruthenium oxide/carbon material. A solid polymer electrolyte was used as electrolyte separator between the electrodes of the supercapacitors. The inuence of the loading of the carbon material in the electrodes, and that of the presence of ruthenium oxide/carbon material in the positive electrode, on the specic capacitances of single electrodes and complete supercapacitors at various charge/discharge rates was studied. 2. Experimental 2.1. Preparation of electrodes and capacitors The composite electrodes used in the experiments were prepared by a casting technique [21] that consisted in spreading on a at glass plate an ink formed with the active material (carbon or RuOx nH2 O/carbon), the graphite bres, the solid polymer
Table 1 Characteristics of the electrodes tested in the supercapacitors Electrode AC1 AC2 AC3 AC4 ACR1 Composition

electrolyte and the solvent. The activated carbon used in the preparation of electrodes was Norit A Supra Eur furnished by Norit Italia S.p.A (Ravenna, Italy). The measured BET surface area of carbon was 1530 m2 /g, the pore volume 0.775 cm3 /g at P/P0 = 0.95 and the micropore volume 0.56 cm3 /g. Ruthenium oxide on carbon material was prepared by precipitating ruthenium oxide from an acidic solution of ruthenium chloride, impregnated for 72 h in activated carbon (Norit A Supra Eur), with a 0.1N NaOH solution. The obtained material was rinsed with distilled water and dried at 160 C for 90 min. The RuOx loading in the nal material was 40 wt%. The solid polymer electrolyte in solution form, used for the preparation of electrodes, was furnished by Fumatech GmbH, Germany and the additional N,N-dimethylacetamide solvent (purity 99.8%) for the ink preparation was purchased from Aldrich and used as supplied. After casting on the glass-plate, the solvent is evaporated from the ink at the temperature of 50 C for 15 h. The formed electrode layer was peeled off from the glass, dried in oven at 80 C and then washed in distilled water. The membrane and electrodes assemblies (MEAs), formed with the polymer electrolyte membrane sandwiched between two 4 cm2 samples of electrodes, were prepared by a hot-pressing procedure at 130 C and 10 kg/cm2 for 10 min. The MEAs, before their insertion into the test cell, were treated with 1 M H2 SO4 for 2 h and then repeatedly washed with distilled water until pH 5 was reached. The electrodes investigated in this work with their respective compositions are reported in Table 1. The polymer electrolyte membrane used for the preparation of assemblies was a per-uorinated sulfonic acid/PTFE copolymer with EW = 900 g/equiv. furnished by Fumatech GmbH. The size of membrane (thickness 150 m) in the MEA was larger than that of electrodes and this allowed to a saturated calomel electrode (SCE) to be contacted with membrane border in the test cell (see Fig. 1). 2.2. Cyclic voltammetry and charge/discharge measurements Cyclic voltammetry (CV) measurements were carried out in the complete supercapacitors with an AMEL electrochemical apparatus connected to the negative and positive electrodes. The negative electrode was also in contact with the reference electrode terminal of apparatus, thus allowing the control on voltage scan parameters. Through these connections, the electrochemical instrument also measured the voltage difference between the electrodes but did not give any information on the potential of

Thickness ( ) 155 140 215 305 150

Loading of the active material (mg/cm2 ) 5.5 (carbon) 5.0 (carbon) 8.5 (carbon) 13.8 (carbon) 7.8 (4.5 carbon3.3 RuOx nH2 O)

65% carbon5% graphite bres30% polymer electrolyte 65% carbon5% graphite bres30% polymer electrolyte 65% carbon5% graphite bres30% polymer electrolyte 65% carbon5% graphite bres30% polymer electrolyte 65% RuOx/carbon5% graphite bers30% polymer electrolyte

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positive electrodes, and on hybrid supercapacitors with activated carbon in the negative electrode and ruthenium oxide/carbon in the positive electrode. 3.1. Study of symmetric supercapacitors and discussion Some characteristic parameters of the two studied symmetric supercapacitors are reported in Table 1. The carbon loadings for the electrodes were 5.5 mg/cm2 for the AC1 electrode and 13.8 mg/cm2 for the AC4 electrode. Fig. 2(a)(d) shows the characteristic voltammograms of negative electrodes, positive electrodes and supercapacitors as obtained by the test station of Fig. 1. The differences of potential for negative and positive electrodes and the specic capacitances for complete supercapacitors as well as for each electrode are summarized in Table 2. In Fig. 2, the values of potential difference of electrodes and voltage difference of supercapacitors are always displayed with the positive sign and, the current is for all that measured for the supercapacitor. Analysing the voltammograms in Fig. 2 it is observed that the supercapacitor current is increasing almost proportionally with the increase of voltage scan rate, which should indicate a purely capacitive process that occurs at the electrodes. The specic capacitances of symmetric AC1/AC1 supercapacitor are 26.3 F/g at 5 mV/s and 24.5 F/g at 20 mV/s. The corresponding capacitances at 5 and 20 mV/s (vsr of supercapacitor) are varying from 117 to 113 F/g for the negative electrode and from 95.7 to 86.7 F/g for the positive electrode (see Table 2). As can be observed the specic capacitance of each electrode presents a slight variation as a function of the voltage scan rate of supercapacitor and, the capacitance of positive electrode is lower than that of negative electrode. Therefore, for a correct balance of the capacitance of AC1/AC1 capacitor it would be necessary to increase the mass of positive electrode of a factor of about 1.23 at 5 mV/s and 1.3 times at 20 mV/s. Moreover, when the scan rate is increased from 5 to 20 mV/s in the supercapacitor, an increase of the potential difference for the positive electrode (AC1) is observed. These effects may be ascribed to an increased difculty at the charges redistribution into the positive electrode that occurs at the higher voltage scan rate. This behaviour becomes more accentuated for the AC4/AC4 capacitor, with high carbon loading in the electrodes (Fig. 2(c) and (d)), that also show a more pronounced distortion from rectangular shape of the voltammogram of supercapacitor. The distortion is more evident at the voltage scan rate of 20 mV/s. For this capacitor, the optimal mass ratio, between positive and negative electrodes, is found to be 1.33 at 5 mV/s and 1.78 at 20 mV/s. In this supercapacitor, the increase of equivalent series resistance in the positive electrode is evidenced by the slow variation of the changing of current sign after inversion of voltage scan rate at 0 and 1 V. This increased difculty in the charge redistribution into the positive electrode may be due to the lower rate in accepting/releasing anions at the positive electrode than in accepting/releasing cations at the negative electrode. The calculated specic capacitances for the AC4/AC4 supercapacitor are 25.2 and 21.4 F/g at 5 and 20 mV/s, respectively, whereas the values of specic capacitance of the negative and positive electrodes are respectively 118 and 88 F/g at 5 mV/s and 119 and

Fig. 1. Scheme of the supercapacitor test station: (1) main electrochemical equipment; (2) auxilary equipment; (3) graphite plates; (4) positive and negative electrodes; (5) polymer electrolyte membrane; (6) gasket; (7) reference electrode.

each electrode. CVs were carried out within the voltage window 01 V and at the voltage scan rates of 5 and 20 mV/s for the supercapacitors. Galvanostatic charge/discharge (CD) measurements were carried out on the complete supercapacitors at the constant currents of 2.5 mA/cm2 and 10 mA/cm2 through continuous cycling tests within the voltage window 01 V. The test in this case was based on the control of the electric current owing through the supercapacitor that was obtained by connecting positive and negative poles to the apparatus. In addition to the main equipment, a second electrochemical apparatus was connected to the cell and had the function of measuring the potentials of the negative and positive electrodes in the CV and CD experiments. For these measurements, a reference electrode (a saturated calomel electrodeSCE) in contact with the membrane of the supercapacitor was used. The potential values of the electrodes were acquired when the CV or CD curves of supercapacitors were perfectly reproducible. Fig. 1 shows in detail the electrical connections of electrodes and reference electrode with the electrochemical equipments. The specic capacitance (Cs ) was calculated for supercapacitor (or electrode) applying the following formula: Cs = Q(Vw)1 , in which, Q, is the amount of charge discharged from the supercapacitor (or electrode) during the variation of voltage (or electrode potential) from Vmax to Vmin (V) and w the weight of the active material contained in both the electrodes (or electrode). In the CV tests, Q was measured by an integrator connected to the supercapacitor, whereas in CD tests it was calculated by multiplying current by discharge time. 3. Results and discussion The electrochemical measurements were carried out on symmetric supercapacitors with activated carbon in the negative and

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Fig. 2. Cyclic voltammograms obtained from symmetric supercapacitors at the voltage scan rates of 5 mV/s (a) and (c) and 20 mV/s (b) and (d). The carbon loading in the electrodes is 5.5 mg/cm2 (a) and (b) and 13.8 mg/cm2 (c) and (d).

67 F/g at 20 mV/s (see Table 2). If, from one side, the comparative study between the AC1/AC1 capacitor and the AC4/AC4 capacitor show relatively high differences of capacities, from the other side, the negative electrodes of both capacitors do not show substantial variation of specic capacitance in function of carbon loading and voltage scan rate. Thus, the main differences between the two supercapacitors are to attribute to the performances of positive electrodes. Therefore, even if this study is performed on a particular type of supercapacitor, i.e. a solidstate supercapacitor, the results conrm that it is essential to do an accurate mass balance of materials of electrodes for the

enhancement of capacitive performance. A direct comparison of the present results with others reported in the current literature is quite difcult to do because it is not easy to nd similar studies. For examples, the behaviour of electrodes for symmetric supercapacitors was studied by Mastragostino et al. [22] who reported values of specic capacitance of 125 and 158 F/g for the positive and negative electrodes, respectively for carbonbased supercapacitors and using 1 M NEt4 BF4 in acetonitrile as electrolyte. Wang et al. [23] showed difference of 16% of the specic capacitance between the positive electrode (87 F/g) and the negative electrode (102 F/g) for an AC/AC capacitor

Table 2 Electrochemical data of positive electrodes, negative electrodes and supercapacitors obtained by cyclic voltammetry tests Supercapacitor conguration (/+) Cyclic voltammetry at 5 mV/s V (V) () pole (+) pole AC1/AC1 AC4/AC4 AC2/ACR1 AC3/ACR1 AC4/ACR1 0.449 0.428 0.714 0.609 0.456 0.551 0.572 0.286 0.391 0.544 26.3 25.2 28.0 33.1 39.5 Specic supercap. capacitance (F/g) Specic capacitance (F/g) () pole 117.4 117.7 100.1 103.8 135.6 Cyclic voltammetry at 20 mV/s V (V) Specic supercap. capacitance (F/g) Specic capacitance (F/g) () pole 24.5 21.4 25.3 29.5 33.2 113.1 119.2 91.6 99.1 82.9 (+) pole 86.7 67.0 140.6 144.0 247.3

(+) pole () pole (+) pole 95.7 88.0 161.3 177.4 201.6 0.434 0.360 0.704 0.570 0.627 0.566 0.640 0.296 0.430 0.373

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in 1.5 M TEMAPF6 electrolyte in propylene carbonate (PC). Lozano-Castello et al. [24] reported higher capacitance for negative electrodes than for positive electrodes. The authors were using activated carbon materials in the preparation of both electrodes, and a standard three-electrode cell with 1 M LiClO4 electrolyte in propylene carbonate (PC) to perform the electrochemical measurements. Shiraishi et al. [25] showed higher capacitance for the positive electrodes than for the negative electrodes when studied electrodes based on different activated carbon bers (ACFs) in a standard three-electrode cell with 1 M LiClO4 electrolyte in PC. Chmiola et al. [26] reported higher specic capacitance for the positive electrodes than for the negative electrodes, although they found for the positive electrodes a remarkable dependence of capacitance from the pores size of carbons derived from metal carbide precursors. In the paper, the authors were using the tetraethylamonium tetrauoroborate salt in acetonitrile as electrolyte. Wen et al. [27] showed that the specic capacitance of the positive electrode was lower than that of the negative electrode. They studied the electrochemical characteristics of supercapacitors with nanoporous glassy carbons-based electrodes in aqueous KOH electrolyte. The analysis of our results and those of literature allows to evidence the difculty in obtaining clear and univocal ndings. Generally, the reported results [2224,27] are in agreement with

our own, in the attribution of higher capacitance at the negative electrode and in the afrmation that the adsorption/release of cations is favourite, but in some cases an opposite behaviour was observed [25,26]. These results show that the AC/AC symmetric supercapacitors, which normally are made with electrodes of equal weight and size, need to be optimised for the weight of the active material. The results above reported also evidence that the accessibility of pores to the ionic species (ion-sieving) could not be the only parameter that controls the specic capacitance of positive and negative electrodes because controversial results have been found by analysing different systems of supercapacitors. Our studied solid-state supercapacitors, at difference of those of literature, use a solid polymer electrolyte that is characterized to have a mobile cation (proton) in hydrated form, while the anion group (RSO3 ) is anchored to the polymer backbone. For such reason and also because the polymer micelles are of dimension in the range of 100200 nm, the xed anion species are not able to reach directly the internal surface of micro- and mesoporous carbons. Thus, the values of capacitance of 100120 F/g (e.g. 6.58 F/cm2 ), which are comparable to those currently reported in literature for liquid electrolyte-based supercapacitors should be explained by a different mechanism. We suppose that at the positive electrode (in solid-state supercapacitors) others weak anion species could participate at the

Fig. 3. Galvanostatic charge/discharge curves obtained from symmetric supercapacitors at the current of 2.5 mA/cm2 (a) and (b) and 10 mA/cm2 (c) and (d). The carbon loading in the electrodes is 5.5 mg/cm2 (a) and (b) and 13.8 mg/cm2 (c) and (d).

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Table 3 Electrochemical data of positive electrodes, negative electrodes and supercapacitors obtained by galvanostatic charge/discharge tests

The hybrid supercapacitors are formed of negative electrodes based on carbon (AC2, AC3, AC4) and positive electrodes based on ruthenium oxide/carbon (ACR1). The compositions of the electrodes are reported in Table 1 and the electrochemical results obtained from the supercapacitors by CV and CD tests are summarized in Tables 2 and 3, respectively. The behaviour of hybrid supercapacitors in dependence of the carbon loading in the negative electrodes (from AC2 to AC4) is more complex to explain compared to that of the symmetric supercapacitors. It is well known that redox phenomena associated with the ruthenium-based positive electrodes inuence the functionality of hybrid capacitors. The origin of pseudo-capacitance in RuO2 xH2 0 electrode has been attributed at different redox processes [2,28,29] in which protons and electrons are exchanged by ruthenium compound through the

() pole (+) pole

V (V)

Supercapacitor conguration (/+)

AC1/AC1 AC4/AC4 AC2/ACR1 AC3/ACR1 AC4/ACR1

0.480 0.452 0.691 0.603 0.498

0.520 0.548 0.309 0.397 0.502

27.9 27.5 32.9 31.2 41.5

3.2. Studies of hybrid supercapacitors and discussion

Charge/discharge at 2.5 mA/cm2

Specic supercap. capacitance (F/g)

formation of the double layer capacitance. These should be originate by charge exchanges between RSO3 groups and H2 O molecules. However, the strength of these charges or electric dipoles could never be equivalent to that of anions present in aqueous or non-aqueous electrolyte. Therefore, the high level of double layer capacitance measured in our solid-state supercapacitor remains, at this time, a not fully understood subject. In spite of our previous studies [10,11,20,21], in this work we are able to separate the capacitance of single electrodes from that of complete supercapacitor but the mechanism through which the cations and anions inuence the double layer capacitance remains at the moment without answer. Fig. 3(a)(d) shows the galvanostatic charge/discharge (CD) curves for the same reported supercapacitors performed at the current densities of 2.5 and 10 mA/cm2 . The experimental results are summarized in Table 3. It is evident from the proles of curves that the positive electrode is also in these tests the performance-limiting electrode. In fact, it always presents higher polarization during the charging process and its polarization increases with the increasing of the carbon loading and the current density. The calculated specic capacitances for the AC1/AC1 capacitor are 27.9 and 24.5 F/g at the currents of 2.5 and 10 mA/cm2 , respectively. The specic capacitances for negative electrode and positive electrode are respectively 116 and 107 F/g at 2.5 mA/cm2 and 121 and 82 F/g at 10 mA/cm2 . The specic capacitances for the AC4/AC4 capacitor are 27.5 and 22.7 F/g at the currents of 2.5 and 10 mA/cm2 , respectively. The specic capacitances for negative and positive electrodes are respectively 122 and 100 F/g, at 2.5 mA/cm2 and, 136 and 68 F/g, at 10 mA/cm2 (see Table 3). The electrochemical characteristics of electrodes and capacitors follow the same trend of those reported in Table 2 related at CV tests. The behaviour of the negative and positive electrodes observed through the voltammograms and CD curves (Figs. 2 and 3) suggests that a more functional symmetric supercapacitor should contain a higher mass of carbon in the positive electrode than in the negative electrode to balance its lower capacitance.

Specic capacitance (F/g)

(+) pole () pole () pole (+) pole (+) pole () pole

Charge/discharge at 10 mA/cm2

Specic supercap. capacitance (F/g) V (V) Specic capacitance (F/g)

116.5 121.9 121.5 99.0 130.3

107.5 100.5 175.4 164.9 229.4

0.404 0.334 0.673 0.595 0.421

0.596 0.666 0.327 0.405 0.579

24.5 22.7 30.6 28.9 35.8

121.5 136.1 115.9 92.9 133.0

82.4 68.2 153.9 149.7 171.6

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following mechanism: RuOx (OH)y + wH+ + we RuOxw (OH)y+w (0 w 2) The reaction indicates that the symmetric redox pairs can be observed by appearance of current peaks in the voltammograms, which are due to reversible gradual changes of ruthenium oxidation state from Ru2+ to Ru4+ with the variation of potential of the electrode. The capacitance is therefore inuenced from proton and electron conduction in the bulk and/or on surface of the material as well as from the particle sizes and the structure of ruthenium oxide. The water content plays an important

role in H+ transport, while the electron conduction is mainly inuenced by the crystalline degree of RuOx structure. Optimal water content and crystalline degree should be realized for a balanced mixing of protonicelectronic conduction, which should maximize the pseudo-capacitance delivered from ruthenium oxide. Further, the specic capacitance could be improved by supporting the oxide on carbon. This latter, in fact, should increase the available active surface area and should function as an electrolyte reservoir [30]. Recently, has been reported that the specic capacitance of RuO2 xH2 0 is given from three main contributes, which are: (a) electric double layer capacitance (CDL ), (b) reversible redox reaction due to electro-adsorption effects (CAD ), and (c) irreversible redox related charge (CIRR ) [31,32].

Fig. 4. Cyclic voltammograms obtained from the hybrid supercapacitors at the voltage scan rate of 5 mV/s (a), (c), and (e) and 20 mV/s (b), (d), and (f). The carbon loading in the negative electrodes is 5 mg/cm2 (a) and (b); 8.5 mg/cm2 (c) and (d); 13.8 mg/cm2 (e) and (f).

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The contribution of redox processes on the specic capacitance may depend from the characteristics of ruthenium oxide materials, e.g. anhydrous, amorphous, crystalline and/or porous form. Moreover, the electrochemical utilization of ruthenium oxide material is usually limited to very thin layer, while in the ACR1 electrode we have thickness as high as 150 m. However, being the ruthenium oxide supported on activated carbon material high particles dispersion can be obtained. Also for hybrid supercapacitors, the mass balance of the negative electrode has to be optimised for maximizing the capacitive performance. In fact, at a low (AC2) and medium (AC3) carbon loading in the negative electrode, it is this electrode to limit

the capacitive performance, as it is shown in Table 3. Further, the voltammograms of supercapacitor do not display rectangular shape because they present the effects of faradaic process occurring at the positive electrode. Nevertheless, the redox peaks in the voltammograms of supercapacitor result attenuated because at the positive electrode, with pseudo-capacitive property, it is coupled the negative electrode with pure double layer capacitance. Therefore, in hybrid supercapacitors the shapes of the voltammograms show that there is a reciprocal inuence between the positive and negative electrodes and that is important to make a correct balancing of materials for enhancing the capacitive performances. The specic capacitances of AC2/ACR1 capaci-

Fig. 5. Galvanostatic charge/discharge curves obtained from the hybrid supercapacitors at the current of 2.5 mA/cm2 (a), (c), and (e) and 10 mA/cm2 (b), (d) and (f). The carbon loading in the negative electrodes is 5 mg/cm2 (a) and (b); 8.5 mg/cm2 (c) and (d); 13.8 mg/cm2 (e) and (f).

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tor at 5 and 20 mV/s are 28.0 and 25.3 F/g, respectively. Those of the negative and positive electrodes are 100.1 and 161.3 F/g at 5 mV/s and 91.6 and 140.6 F/g at 20 mV/s, respectively. By increasing the carbon loading of the negative electrode (carbon loading is in electrode AC2 < AC3 < AC4, see Table 1), the polarizations of the negative electrodes, which are measured through the CVs at 5 mV/s, gradually decrease (Fig. 4(a), (c), and (e)). The AC4/ACR1 supercapacitor with the highest carbon loading achieves the highest value of specic capacitance of 39.5 F/g, and the respective correspondent values for the negative and the positive electrode are 135.6 and 201.6 F/g. In such better situation, the negative electrode efciently redistributes a large amount of charges and presents lower polarization than that of positive electrode. At the voltage scan rate of 20 mV/s (Fig. 4e), the behaviour of AC4/ACR1 supercapacitor presents some difference from that expected because the negative electrode turns to be the more polarised electrode because it is affected by high ionic resistance that contrasts the rate of charge redistribution. This effect was not observed in the experiments conducted at 5 mV/s because probably it would appear at higher values of carbon loading than those here investigated. The hybrid supercapacitors were also studied by galvanostatic CD tests. The respective experimental curves are reported in Fig. 5(a)(f) and the results summarized in Table 3. From the tests performed at 2.5 and 10 mA/cm2 , we have found at each current a gradual decrease of polarization of negative electrode with the increase of the carbon loading. The comparison of the CD curves of supercapacitors at the same carbon loading and at different charge-discharge currents evidences that for the low (Fig. 5(a) and (b)) and medium carbon loading (Fig. 5(c) and (d)), there is not sensible variation in the behaviour of electrodes, apart of a slight decrease of capacitance by increasing the CD current. With the AC4/ACR1 supercapacitor at high carbon loading, the increase of the CD current from 2.5 to 10 mA/cm2 causes a pronounced lowering of the polarization of the negative electrode (Fig. 5(e) and (f)) that produces a sensible increase of the specic capacitance of this electrode. In such condition, the calculated specic capacitances are 133.0 F/g for the negative electrode, 171.6 F/g for the positive electrode and 35.8 F/g for the supercapacitor. The highest capacitance performance in CD tests, with a value of 41.5 F/g, is obtained for the capacitor with the highest carbon loading in the negative electrode at the current density of 2.5 mA/cm2 . The specic capacitances for negative and positive electrodes are 130.3 and 229.4 F/g, respectively. The behaviour of negative electrode of the same supercapacitor previously observed in the voltammograms of Fig. 4(d) and (f) varying from medium to high the carbon loading is apparently different from that observed in Fig. 5(d) and (f) referred to CD tests. In fact, in the CD curves a regular decrease of the polarization is evidenced for the negative electrode varying from low, to medium, to high the carbon loading, while this effect is not observed in the voltammograms. A possible explanation for this different behaviour is that in the CD curves a lower current (10 mA/cm2 ) ows in the cell respect to that measured during the CV tests at 20 mV/s (about 15 mA/cm2 ). It is reasonable to expect also in CD tests that a higher polarization for the negative electrode would be obtained at higher currents than those

here investigated, when substantial effects of equivalent series resistance in negative electrode would be apparent. The analysis of Tables 2 and 3 and Figs. 4 and 5 shows that in the investigated hybrid capacitors the electrodes are reciprocally inuenced and that their specic capacitances are function of parameters such as the active material loading and the electric current ow. The analysis of the results reported in this paper evidence, for example, that the values of specic capacitance of negative electrodes for symmetric and hybrid supercapacitors were found to vary up to 35% (from 100 to 135.6 F/g). This means that for any given carbon the specic double layer capacitance is not an invariant property of material, but rather it is a characteristic value that is valid in the specic condition of measurement. This study also demonstrates that the specic capacitance of an electrode obtained in a three-electrode system may be much different from that measured in a real supercapacitor because of the reciprocal inuence between the electrodes. 4. Conclusions In this work, we report a study performed on symmetric and hybrid solid-state supercapacitors in which the electrochemical features of the complete capacitors and of the positive and negative electrodes were studied by two electrochemical equipments connected to the test cell. In particular, the study showed that an optimisation mass ratio, between the positive and negative electrode was essential for maximizing the capacitance performances of symmetric solid-state supercapacitors. We found that the mass of carbon in the positive electrode must be 1.21.3 times than that of negative electrode in determined operative conditions. Moreover, it was found that the positive electrode is that controlling the capacitive performance of symmetric supercapacitor because it showed higher polarizations. However, high value of specic capacitance of 26.3 F/g at 5 mV/s were found for the symmetric AC1/AC1 supercapacitor and specic capacitances of negative and positive electrodes of 117 and 95.7 F/g, respectively. The study of hybrid supercapacitors has demonstrated that an optimal capacitance performance may be obtained by optimising the carbon loading in the carbon based negative electrode. In fact, it was evidenced that the behaviour of one electrode, inuences that of other electrode and that of complete supercapacitor. Furthermore, we have found that the specic capacitance for a given carbon material may vary very much in dependence of composition of electrodes and working conditions, and a variation up to 35% was recorded in our tests. This is meaning that the specic capacitance of an active carbon material may not be considered as a characteristic property, but a characteristic value that is valid for those specic experimental conditions. Acknowledgements The authors acknowledge Fumatech GmbH (Germany) that has supplied the polymer electrolyte solution and membrane, and Norit Spa Ravenna (Italy) that has furnished activated carbon material for our experiments.

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