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Journal of Electroanalytical Chemistry 612 (2008) 140–146 www.elsevier.com/locate/jelechem

Short Communication

The measurement of specific capacitances of conducting polymers using the quartz crystal microbalance
Graeme A. Snook
a

a,b,*

, George Z. Chen

a,*

School of Chemical and Environmental Engineering, University of Nottingham, University Park, Nottingham NG7 2RD, UK b CSIRO Division of Minerals, Clayton South, Victoria 3168, Australia Received 24 April 2007; received in revised form 30 August 2007; accepted 31 August 2007 Available online 8 September 2007

Abstract Mass specific capacitance (F gÀ1) of conducting polymers is an important factor in selecting these materials for use in supercapacitors. Presented in this work is a new method for measuring the mass specific capacitance of conducting polymers using the electrochemical quartz crystal microbalance (EQCM). It can be done by one of two ways: (1) using one thin deposit, calculating the capacitance and dividing by the deposition mass, or (2) conversion of the capacitance per deposition charge (for thick deposits) to capacitance per mass using Faraday’s Law and the EQCM data (for thin deposits). Using the new method, specific capacitances of polyaniline, polypyrrole and poly[3,4-ethylenedioxythiopene] comparable to those quoted in the literature are found. Such obtained mass specific capacitance should effectively be the theoretical maximum capacitance that can be extracted from a thick film. The standard plots of mass vs. potential were converted to ‘‘massograms’’ by differentiating the mass with respect to time. As the mass variation rate, dM/dt, is proportional to the current, I, the plot is directly comparable to the voltammogram. The onset of polymerisation and nucleation loops are made more apparent using the massogram plot. Using this data, the ideal deposition potentials for the conducting polymers can be determined. Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Supercapacitor; Mass specific capacitance; Conducting polymers; Electrochemical quartz crystal microbalance; Massogram

1. Introduction The electrochemical quartz crystal microbalance (EQCM) is a powerful technique for studying solid state reactions [1,2]. This technique involves using quartz crystals with metal discs (typically gold) coated on both sides with one side used as a working electrode. This device utilises the piezoelectric properties of quartz crystals to measure the attached mass (down to nanogram levels) on the electrode surface. A change in the resonant frequency can be related to a change in the mass according to the Sauerbrey equation [3].

Corresponding authors. Address: School of Chemical and Environmental Engineering, University of Nottingham, University Park, Nottingham NG7 2RD, UK. Tel.: +44 115 9514171; fax: +44 115 9514115. E-mail addresses: graeme.snook@csiro.au (G.A. Snook), george.chen@ nottingham.ac.uk (G.Z. Chen). 0022-0728/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jelechem.2007.08.024

*

The EQCM has been used extensively to study conducting polymers such as polypyrrole [4–12], poly(3,4-ethylenedioxythiopene) [12–17] and polyaniline [18–27]. This technique can be used for three main purposes in studying conducting polymers. Firstly, it can be used to monitor the deposition of the conducting polymer from the monomer solution. Secondly, the EQCM can be used to study the intercalation of ions into the deposited conducting polymer layer. Finally, something that few publications calculate, the EQCM can be used to calculate the mass specific capacitance (Cspec, F gÀ1) of the polymer layer. This can firstly be done by capacitance measurements (Cthin) on a single thin deposit (of measured mass, Dmthin):   C thin C spec ¼ ð1Þ Dmthin Alternatively, it can be extended to thicker layers by converting the capacitance per deposition charge (F CÀ1)

There are significant currents flowing between 0. These crystals had gold disks (5 mm diameter) vapour deposited on each side and resonated in air at 8 ± 0. According to theory. that further confirms that polymer growth is via a nucleation and growth mechanism. This observation has been previously reported for polypyrrole [4]. In this paper. Snook. Polyaniline (PAni) was deposited from an aqueous solution of 0. Also. As long as the deposition is reasonably thin. Poly-(3. N the number of moles reacted. Using constant potential deposition data (Qthin and Dmthin). None of the reports cited in this paper uses massograms [28] to investigate the conducting polymer systems. Polypyrrole (PPy) was deposited from either an aqueous solution of 0. Working electrodes were 13 mm diameter AT-cut a-quartz crystals (CH Instruments). 2 resonated at 10 ± 0. Q = nNF = n(M/Meq)F. n the number of electrons.0 M HCl. The auxiliary electrode was a platinum wire. Aldrich)..2 M EDOT and 0. potential reveals a more apparent mass loop.5 M lithium chloride or from an aqueous solution of 0. 2. Results and discussion 3. Q the deposition charge. Sigma) were all used as purchased. Meq = (Mpolymer + McounterÀion)/(2 + c).4-ethylenedioxythiophene (EDOT) (Bayer). Mass data for polymer depositions The EQCM results are presented in Fig. Chen / Journal of Electroanalytical Chemistry 612 (2008) 140–146 141 for thick deposits to Cspec using Faraday’s Law. 3. again using Faraday’s Law: M eq ¼ F Á Dmthin Qthin ð3Þ and the Maclab 8s system. massograms more clearly show the optimal potential for deposition of the polymers so that over-oxidation is avoided. lithium chloride (99%. no significant mass change occurs in the same potential range.2 M EDOT and 0. Potsdam. Meq = 74 g molÀ1 eÀ1. Given c % 0. The typical values of c are given in Table 2 [31]. The massogram plot of dM/dt vs. aniline (Ani) (98%. Ag/AgCl).0 ± 2 °C).1 M Py and 0.5 M lithium perchlorate.05 MHz.3 for PEDOT. However. Fluka). dopant level) in the oxidised polymer and (2 + c) is the number of electrons withdrawn from one monomeric unit during anodic deposition of the polymer [30]. Distilled water was used for preparation of electrolytic solutions. i. The crystals used for Fig. Rowville. it was found Meq = 87 ± 16 g molÀ1 eÀ1. The mass plot shows that significant deposition begins to occur at 1.5 M Py and 0. which are directly comparable to voltammograms as dðDMÞ / I.6 mm diameter platinum disc as the working electrode for PPy and PEDOT and using a 6. which means these currents are background currents resulting in no deposition of PEDOT onto the electrode surface. USA). tetrabutylammonium bromide (>99%. which is indicative of nucleation and growth [29] of the polymer. Previous work [30] suggests this is the reaction of gold adsorbed EDOT species.5 M lithium perchlorate. Voltammograms and massograms were recorded using the CH Instruments 440 Potentiostat or the EG&G PAR Model 173 Potentiostat coupled with the EG&G PAR Model 175 Universal Programmer (Princeton Applied Research Corp.0 V.A.25 M Ani and 1. Australia).5 mm diameter graphite disc as the working electrode for PAni.4-ethylenedioxythiophene) (PEDOT) was deposited from an acetonitrile solution of 0.G. The reference half cell was Ag/AgCl in 3. potential. An accurate calculation of this value allows the usefulness of a variety of conducting polymers as supercapacitor materials to be determined. Massograms are the plots of differentiated mass vs. Consequently. May & Bayer) and potassium chloride (>99%.e. Ag/AgCl). Table 1 indicates this as a suitable potential for constant potential deposition of thicker deposits. the equivalent mass per electron calculated should be very accurate.0 M KCl(aq).05 MHz (Bright Star Crystals. massograms will be used to invesdt tigate the deposition of the polymers.0 V to avoid over-oxidation and to deposit a polymer layer of sufficient thickness.e. All experiments were carried out at ambient temperatures (20.8 V (vs.5 M potassium chloride. where F is Faraday’s constant. There is a slight current loop.Z. taking into account possible solvation of the cation and experimental errors. AC impedance of the thicker deposits was recorded using the Autolab PGSTAT30 potentiostat using a 1.0 V (vs. Victoria. 3. The equivalent mass per electron was also calculated for a thick layer (30 C cmÀ2) which was removed from a platinum electrode and weighed using a mechanical balance. In addition. NY) . it can be seen from the massogram that significant deposition begins to occur at 1. The value where Dmthin and Qthin are respectively the deposition mass and charge of the thin layer. A list of values is given in Table 2. Aldrich). the authors recommend a constant deposition potential of 1. Hence. Data acquisition was assisted by the Elchema EQCN (Elchema. Nucleation loops [29] are made more apparent in the massogram plot and confirm that the growth of the polymers is via a nucleation and growth mechanism. where c is the molar ratio of dopant ions and monomeric units (i. M the mass of the deposited polymer and Meq the equivalent polymer mass per electron transferred during polymerisation:   C C F C spec ¼ ¼ ð2Þ M Q M eq where C/Q is the slope of a plot of capacitance vs. the QCM data matches closely with theory. Experimental Pyrrole (Py) (98%.5 V and 0. deposition charge for thick deposits. G. New Jersey. 1 for the deposition of PEDOT from an acetonitrile solution of 0. The value of Meq can be calculated from the EQCM data from deposition of a thin layer. This calculation of capacitance per gram of material is very important when evaluating conducting polymers as possible supercapacitor materials.1.

. G.7 V (vs.3 Mass specific capacitance (F gÀ1) 240 530 92 Cited from Ref.142 G. There is no significant or obvious background current.7 0.1 M pyrrole/0. using the constant potential deposition data. There is a reverse peak observed when the voltammetry is carried out back to more negative potentials. Table 1 Recommended deposition potentials Polymer PPy PAni PEDOT Deposition potential (V) 0.5 M LiClO4 (ACN) solution. yields a value of 40 ± 5 g molÀ1 eÀ1 compared Table 2 Constant voltage deposition data Polymer PPy PAni PEDOT a Capacitance per charge (F CÀ1) 0. 2 shows the deposition using 0. Multiple scans are shown. The authors recommend a deposition potential of 0.15 0. which agrees qualitatively with the EQCM measurement. Chen / Journal of Electroanalytical Chemistry 612 (2008) 140–146 Fig.Z. Ag/AgCl). (a) Cyclic voltammogram (50 mV sÀ1). Fig. The EQCM results for the deposition of PPy from an aqueous solution of Py/ClÀ have been previously published by this group [4].0 calculated was approximately 100 g molÀ1. The voltammetric current rapidly rises at around 0.5 0. (b) mass plot and (c) massogram for the deposition of PEDOT from a 0.2 M EDOT/0. 1. in which the magnitude of the polymer redox chemistry (current) increases with continuing deposition. The mass plot confirms a significant deposition of mass at this potential.083 Measured Meq(g molÀ1 eÀ1) 40 27 87 Theoretical Meq(g molÀ1 eÀ1) 34 44 74 ca 0.5 M LiCl(aq) and sweeping to more negative potentials than the previous publication. as the voltammetry was not extended to a sufficiently negative range. Snook.A. The equivalent mass per electron calculation.7 V to avoid over-oxidation of the polymer and for sufficiently rapid coating of the electrode.9 1.33 0. This is the de-intercalation and reduction of the polymer. 2 for PEDOT. [31]. This was not seen in Fig.10 0.

(b) mass plot and (c) massogram for the deposition PPy from a 0. this plot has not been used before to calculate the . Meq(MQ). Fig. To the best of our knowledge. which becomes significant at 0. in the previous section (and shown in Table 2) are all from constant potential deposition. In this section.2. (3). Meq(MPP). charge from which Meq(MQ) is calculated.5 M LiCl(aq) solution (Cycles 2–3).Z. Ag/AgCl). is using the slope from a plot of mass vs. 3 shows the 8th cycle of the deposition of PAni as measured by the EQCM using an aqueous solution of 0. 3. Again the EQCM measurement is higher than the theoretical value but the difference is within experimental errors.A. This is attributed to the expulsion of chloride from the oxidised polymer. that the mass decreases at below approximately 0. Again there is a reverse (reduction) peak (this time much closer to the deposition potential) at 0.55 V).G. Snook. The next calculation. once the potential direction is reversed.9 V (vs.1 M pyrrole/0. This can be explained by the observation of the formation of coloured/soluble oligmers of Ani [18] that contribute to the current/charge but not the deposited mass. It is observed. with the theoretical equivalent mass of 34 g molÀ1 eÀ1 (see Table 2). The nucleation loop is not apparent as the scan has been reversed at too high a potential. The reverse (reduction) peak for the other two polymers occurs at below 0.0 M HCl.25 M aniline and 1. Ag/AgCl). 2. is the calculation of equivalent mass using the mass (from the mass potential plot [MPP]) and the charge from the integrated cyclic voltammogram using Eq. G. The mass plot shows a mass increase. This is the suggested deposition potential for growing thicker deposits of the polymer as shown in Table 1. 4a shows the plot of mass vs. The massogram supports this interpretation as the massogram peak matches the voltammetric reduction peak (both occurring at around 0.55 V (vs. Fig. charge (effectively gives a straight line) and converting to Meq by multiplying by Faraday’s constant.8 V (vs. Ag/AgCl). (a) Cyclic voltammogram (20 mV sÀ1).0 V (vs. a number of calculations will be done for Meq from the cyclic voltammetry data. Meq. The value of Meq calculated from QCM data is significantly lower than theory. These are summarised in Table 3 along with the constant potential data (last column). Ag/AgCl). Alternative calculations of equivalent mass from cyclic voltammetry measurements Calculations of the equivalent mass. Chen / Journal of Electroanalytical Chemistry 612 (2008) 140–146 143 Fig. The equivalent mass per electron is calculated (using constant potential deposition data) as 27 ± 6 g molÀ1 eÀ1 (compared with a theoretical equivalent mass per unit of 44 g molÀ1). The first calculation.

Meq(MG). massogram plot minus background (BG). (5): Looking at the data for PPy. and constant potential deposition (CP).0 V to 0. Fig. Table 3 Values of equivalent polymer mass per electron transferred in electrochemical polymerisation (Meq. Chen / Journal of Electroanalytical Chemistry 612 (2008) 140–146 Fig. The final calculation. (a) Cyclic voltammogram (20 mV sÀ1).0 M HCl(aq) solution (Cycle 8). Q plot (MQ). g molÀ1 eÀ1) calculated from different dataa Polymer PPy PAni PEDOT Meq(MPP) 29 28 44 Meq(MQ) 25 31 38 Meq(MG) 27 26 38 Meq(dMdtI) 29 35 42 Meq(BG) – – 62 Meq(CP) 40 27 87 a The original data used for the calculation of Meq are from the mass potential plot (MPP). This suggests growth is very similar in both types of depositions and that similar proportions of oligimers are lost to the solution giving a lower equivalent mass than expected. by calculating the value of the slope of a plot of dM/dt vs.144 G. This particular plot is using PPy but only scanning in the range where deposition occurs (ie 0. massogram plot (MG).1 M aniline/1. done for PEDOT. The third calculation. I (which again gives a straight line) and equating to molecular weight by multiplying by Faraday’s constant. (b) mass plot and (c) massogram for the deposition PAni from a 0. the cyclic voltammetric data consistently gives lower values of Meq compared to the constant potential data. The PEDOT cyclic voltammetry data are also consistent for the different methods of calculation but give . Ag/AgCl). 4b shows the example plot for this calculation. employs the value of dM/dt from the massogram plot and the current from the cyclic voltammogram (at the switching potential) using the following equation: M eq ¼ F Á dM=dt I ð4Þ M eq ¼ F Á dM=dt I À I BG ð5Þ The fourth calculation is Meq (dMdtI). slope of mass vs. G.A. The PAni cyclic voltammetry data are also consistent for the different methods of calculation of Meq and this time match well with the value obtained under constant potential conditions.Z. slope of dM/dt vs. The most likely explanation for this is the different mode of deposition resulting in different morphology and hence a different c value (dopant level).7 V vs. subtracts the background current (IBG) from the cyclic voltammogram (I) to calculate the equivalent mass according to Eq. Snook. equivalent mass per electron. 3. I (dMdtI).

Table 2 shows the calculated value of capacitance per deposition charge for each polymer. Fig. In the column Meq(BG) the background current has been subtracted in the calculation of equivalent mass and gives a value much closer to the Meq values as calculated theoretically or from constant potential data. considerably lower values than the constant potential method. Snook. 5.7 V vs.5 ± 0. 1) was done with PPy [4]. This is most likely due to the background currents discussed previously.4 V vs. Calculation of mass specific capacitance of the polymers Using Eqs. and (b) plot of dM/dt vs. The value could still be too low. 4. This limited depth of penetration has been seen previously for solid organometallic compounds abrasively attached onto electrode surfaces [32]. For the tetrabutylammonium bromide. 5 shows the plot of capacitance vs. Using 0. The lines on the graph are the linear parts of the depositions. a capacitance of 2. The PEDOT shows Cspec = 92 F gÀ1. Therefore. charge for PPy. compared with PPy with 240 F gÀ1 and PAni with a very large 530 F gÀ1. current for PPy (deposition from 0. deposition charge (2 significant figures). the capacitance per deposition charge (F CÀ1) can be converted to the mass specific capacitance (Cspec. between 0. we use the previously derived Meq values to calculate Cspec for thick deposits. The thin deposit calculation (from Eq. corresponding to Cspec = 217 ± 15 F gÀ1. F gÀ1) using Faraday’s Law and the EQCM (constant potential) data. Ag/AgCl). generally agree with the literature and hence validate the calculated Meq values.3.5 M Py/ 0.5 lg deposit gave an average (over different scan rates) of 2. and PEDOT (potentiostatic deposition).0 V and 0.7 ± 0. PAni has a high value due to its high dopant level (high c value.5 M KCl(aq) as the electrolyte a 11. Including in the graph is the calculated slope of the capacitance vs. The low Cspec value of PEDOT is mainly due to the molecular weight per monomer unit (138 g molÀ1) being very large compared to PPy (67. due to different morphologies growing using the different methods of deposition.1 g molÀ1). deposition charge for thick deposits of PAni (galvanostatic deposition). . Dividing by the mass deposited (11. Capacitance vs. PPy.Z. So for PPy the line only goes through the points up to around 5 C cmÀ2 as the capacitance tails off at the higher deposition charges.G.A.5 V vs. (2) and (3).2 mF was obtained. Essentially. and PEDOT deposits (bias potential = 0. (a) Plot of mass vs. This agrees with the previous calculation.1 g molÀ1) and PAni (93. PPy deposits (bias potential = 0. G. Meq and the resulting Cspec. 3. the larger counter ion results in a lower Cspec value most likely due to the slow kinetics due to steric effects impeding fast and deeper intercalation. deposition charge as calculated using AC impedance (amplitude = 10 mV) for PAni. The values of PEDOT and PPy agree with the literature and the large values for PAni have been seen before. as seen in Table 2). It has been shown in earlier work [30] that constant potential deposition gives the most favourable morphology for thick growth and rapid kinetics in PEDOT. These Cspec values Fig. Chen / Journal of Electroanalytical Chemistry 612 (2008) 140–146 145 Fig. Ag/AgCl).5 M KCl at 50 mV sÀ1.5 lg) gives Cspec = 235 ± 9 F gÀ1.1 mF. Ag/AgCl).

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