Electrochimica Acta 46 (2001) 4083 4094 www.elsevier.

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On the faradaic and non-faradaic mechanisms of electrochemical processes in conducting polymers and some other reversible systems with solid-phase reagents
V.Z. Barsukov a,*, V.G. Khomenko a, S.V. Chivikov a, I.V. Barsukov b, T.I. Motronyuk c
a

Kie6 State Uni6ersity of Technologies & Design, 2 Nemiro6ich-Danchenko str., Kie6 02011, Ukraine b Superior Graphite Co, 4201 W. 36th Street, Chicago, IL 60632, USA c National Technical Uni6ersity of Ukraine, 37 Pobedy prosp., Kie6 03056, Ukraine Received 15 January 2001; received in revised form 15 May 2001

Abstract The electrochemical peculiarities of classical redox systems with solid-state reagents (non-soluble quinones, intercalation compounds of graphite) as well as polyaniline-type conducting polymers have been considered. The conducting polymers show a signicant non-faradaic component of the electrochemical mechanism. The essential differences of faradaic and non-faradaic systems in equilibrium behavior, trends of galvanostatic charge discharge curves and cyclic voltammograms have been shown, and criteria for the identication of these mechanisms are proposed. Our investigations of the current-producing mechanism for the polyaniline electrode have shown that at least within a narrower range of potentials DEn from 0.30 0.40 to 0.80 0.90 V versus SHE (depending on pH value) the capacitor model of ion electrosorption/desorption in well conducting emeraldine salt phase is more preferable. Nevertheless, such a model should take into account the transport of both anions and protons (cations in a general case). Besides the possibilities of redox processes at the limits and beyond this range of potentials DEn should be taken into account. At the same time, these processes can lead to the fast formation of thin passive layers of new poorly conducting phases (leucoemeraldine salt, leucoemeraldine base, etc.) near the current collector. The formation of such phases, even in a small amount, rapidly inhibits and discontinues the electrochemical process. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Conducting polymers; Polyaniline; Quinones; Graphite; Mechanisms

1. Introduction Reversible electrochemical systems with solid-phase reagents (for instance, non-soluble quinoid compounds, intercalation compounds of graphite or some carbons with cations and anions, conducting polymers, etc.) are more and more widely used in modern technology as
* Corresponding author. Tel.: + 380-44-2901603. E-mail address: chemi@mail.kar.net (V.Z. Barsukov).

active materials for primary and rechargeable batteries, double-layer super-capacitors, electrochemical sensors, electro-chromic devices and so on. That is why the investigation of the nature and mechanisms of electrochemical processes in such systems has a signicant fundamental and applied value. One of the central problems in the investigation of the mechanisms in such systems is the identication of faradaic and non-faradaic criteria of the current-producing process, which is of great theoretical and ap-

0013-4686/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved. PII: S 0 0 1 3 - 4 6 8 6 ( 0 1 ) 0 0 7 1 5 - 0

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plied importance for the optimal development of appropriate devices. For example, in double-layer super-capacitors the compounds with mainly non-faradaic (capacitor) current-producing mechanisms are normally used as active materials to enable fast charging discharging and creation of capacitors with very high current densities and specic power. In the effective rechargeable batteries compounds with mainly faradaic (redox) current-producing mechanism are used to achieve a relatively stable voltage during the charge and especially discharge (so called horizontal galvanostatic chargedischarge curves) and a high specic energy. The formal equations which describe the overall processes in such systems in terms of redox and capacitor mechanisms are quite similar: S1 +ne +nH+US3 S1 +ne nA US2

such slightly-soluble quinone derivatives as chloranil, duroquinone, anthraquinone-9,10, etc., has a faradaic nature (see [1 3] and references therein). The electrochemical processes in graphite intercalation compounds (GIC) can involve not only cations H+, Li+, etc. (so called donor-type of GIC) but also strong acids anions AZ = SO2 , BF, etc. (so called accep4 4 tor-type of GIC). Moreover, these anions are solvated by the molecules of acid and/or H2O; thus, they are rather large particles. The current-producing process for the acceptor-type of GIC can be described by Eq. (2a), which is similar to Eq. (2): Cx + yHAe + A U[Cx AyHA] (2a)

(1) (2)

where Si (i =1, 2, 3) is a solid phase; A is an anion (AZ in the general case); H+ is a proton (cation in the general case). However, real mechanisms are different. To elucidate the difference needs answering the following questions: 1. Are electrochemical charging discharging processes connected with mass (H+; A) transfer across the phase boundary (the redox model) or only with electron and ion charge redistribution in the double layer (the capacitor model)? 2. Does the proton form a strong chemical bond with the solid phase S1 giving a new solid phase S3 or does only the formation of a hydrogen bond, electrostatic or other weak interaction take place? 3. Does the anion A form a strong chemical bond with the solid phase S1 or does only electrostatic interaction take place? Let us answer these questions as applied to the solidstate reagents under consideration. The electrochemical process in quinoid compounds is accompanied by transfer of protons across the phase boundary and causes modication of the whole system of chemical bonds in the solid phase: (1a)

The initial quinone phase (S1) transforms into the completely new hydroquinone phase (S3). The equilibrium (stationary) electrode potential E corresponds to the quinone/hydroquinone equilibrium. This equilibrium is described Eq. (1a), which is similar to Eq. (1). No doubt has been found in literature that the solid-phase electrochemical mechanism of reactions in

The existence of so called graphite salts [Cx AyHA] was proved by X-ray phase, electrochemical and chemical analysis [4 8]. Intercalation of graphite occurs over a wide Cx A range: from CA and up to the maximum attainable degree of intercalation C2A through several sequential stages: C96A, C72A, C48A, C24A. Certain peaks or waves in cyclic voltammograms (CV) correspond to each of these compounds [4,5]. To describe the mechanism of the current-producing process in conducting polymers (CP) is much more difcult. The ratio of the faradaic and non-faradaic components of the polymer charge discharge process continues to be a point at issue. Numerous spectral and spectroelectrochemical studies published do not usually take into account equilibrium and galvanostatic behavior of CP and fully ignore the capacitor process. For example, in very interesting papers [9,10] in situ ESP and UV Vis spectroelectrochemical studies of polyaniline (PAN) lms were carried out. The theoretical base for both papers served the model based on interaction of polaronic and bipolaronic states and on the description of soliton soliton interactions derived by Brazovskii and Kirova [11]. In Ref. [10] there were pointed out three phenomena giving a shift of the driving force during the charging process: (a) the distribution of different conjugation lengths in the electrochemically prepared conductive polymers due to some structural units different from the linear model; (b) the interaction between polaronic and bipolaronic segments in the chain and (c) the acid/base equilibrium connected with a change of the pH value inside the polymer layer during charging. Nevertheless, the authors concluded that the processes (a) and (b) cannot describe the large peak separation in the cyclic voltammograms and the hysteresis in the spectroscopic signals. The third effect (c) should be depressed at low pH values, but the current plateau does not disappear with of 0.1 M sulphuric acid added.

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It seems to be not very convincing to explain an electrochemical mechanism and peculiarities of CP electrochemical behavior using only ESP/UV Vis spectroelectrochemical studies and the polaronic/ bipolaronic approach, which we try to show below. Let us suppose, for example, that reactions (1) and (2) in CP proceed not by redox, but only by the capacitor mechanism. In this case, only electron and ion charge redistributions will take place in the double layer, solid and liquid phases of electrochemical system under applied external potential E. If the current collector receives a negative charge, it can lead to the formation of anion-radicals in the solid-phase facing of the dl capacitor according to following equation:
S1 +ne US1

(3)

At the same time, the cations will be attracted to this negative facing S and the anions will be withdrawn 1 from this one in a liquid part of such a dl capacitor during its charging discharging. Of course, an efcient ESP/UVVis spectral signal can be recorded, which corresponds to the formation of the anion-radical S and change in the electronic state 1 of the solid phase S1. Nevertheless, such a signal does not prove the redox mechanism of the electrochemical process, because such charging discharging processes are not accompanied with mass transfer (H+; A) across the phase boundary. Polaronic/bipolaronic models (see, for instance [11]) can often be useful to account for the nature of conductivity in some solid-phase systems. In our opinion, however, it is not necessary to use such quasi-particles for the description of systems with poly-p-conjugated bonds like some forms of PAN (emeraldine salt), which have high electronic conductivity. The conductivity of such forms can be explained in most cases by analogy to that for graphite due to the possibility of p-bond delocalization within the limits of the whole macromolecule. It is interesting to note that the electronic interaction between intercalated ions and carbon layers of graphite leads to substantially increasing specic conductivity in the direction which is parallel to the orientation of the carbon layers [12]. The appearance of noticeable conductivity in CPs just after doping by ions has, probably, a similar nature. Feldberg [13] was among the rst scientists who drew attention to the necessity of taking into account the capacity of the double electric layer (dl). In [13] it was suggested that peaks in CV should correspond to redox reactions and the at region corresponds to the dl recharge. However, this theoretical model does not explain the separation and large asymmetry of CV peaks, does not t the experimental data even at small deviations from the specic conditions formulated in his model.

Based on investigations by impedance and CV methods, Tanguy and Hoclet proposed a model of charge redistribution in a polymer [14]. During the electrochemical cycling of a polymer lm, which is accompanied by the intercalation and withdrawal of anions, the polymer becomes divided into aggregates 6 nm in diameter. The capacity of the dl that is formed in this case reaches almost 200 F/cm2. In terms of this approach the capacitive behavior of CPs can be only dictated by their porosity and conductivity. Volfkovich et al. [15] established the porous structure of PAN using the standard porosimetry method (SPM). A high lm porosity (several tens of per cent) and large specic surface areas of 80 400 m2/cm3 were demonstrated. It was conrmed that high dl capacity values are observed in CPs. Ref. [16] proposed a pure capacitor model of current-producing process in PAN. This model explains well the trend of galvanostatic charging discharging curves and CVs of PAN in the main working potential range and allows one to estimate theoretically a maximum possible dl capacity Cmax 400800 F/g. It was also shown that in the case of a slightly narrower of the 0.300.40 V to potential sweep range DEnDEn from 0.80 0.90 V versus SHE (depending on pH value) all peaks on CV disappear. The experimental CV in such a range has shown a shape close to a parallelogram with two smoothed over angles, which corresponds ideally to the theoretical one. It seems to convincing proof that there is an absence of redox processes at least over the DEn range of potentials. Moreover, a very simplied model proposed in Ref. [16] makes it possible to account for the two sharp peaks in the CV over a complete possible potential range, which are connected with a sharp change (by several orders of magnitude [17]) in PAN resistance at the limits of the complete potential range DEmax. However, there exist some difculties in describing more diffuse small CV peaks in CV and trends of galvanostatic charging discharging curves in the whole DEmax range as well as in some special conditions of testing. It stimulates further investigation into the nature of the electrochemical process, rst of all, outside the DEn range. It can be supposed that the dened theoretical model adequately characterizes the electrochemical behavior of the system over the complete possible potential range DEmax if it is capable to explain the following minimum necessary complex of experimentally observable properties of the system with a solid-state reagent: 1. electrochemical equilibrium (the value and nature of equilibrium (stationary) potential E; character of E variation with time and the degree of system oxidation/reduction); 2. trend of cyclic voltammograms; 3. trend of galvanostatic charge discharge curves.

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Properties (1) (3) were usually reported as studied with different theoretical and applied goals. This is why it appears to be practically impossible to nd in references all the properties (1) (3) simultaneously for the same object in the similar conditions. That is why the paper goals are as follows: 1. to consider this main complex of properties for various typical systems, which can be described by Eqs. (1) and (2); 2. to determine what mechanism corresponds to the appropriate complex of the properties (1) (3).

2. Experimental Electrochemical measurements were performed by using three-electrode electrochemical cells. The reference electrode was an Ag/AgCl electrode; a Pt wire was the counter electrode. The cyclic voltammetric measurements were carried out on a PI-50-1 potentiostat. The chrono-amperometric experiments were carried out using an automatic battery test system with computer-aided recording of results. Twice-distilled water was used to prepare all solutions. All standard chemicals were analytical reagent grade and were used without further purication.

and 50 wt% acetylene black. A plug type anthraquinone electrode contained MAQ = 200 mg of active mass. The acti6e graphite mass consisted of natural graphite akes (88 wt%) from Kropfmuhl Normalocke (Munich) and acetylene black (12%). Acetylene black was used for increasing of porosity in the electrode due to its more dispersed structure. Before pressing into the polyethylene plug 1.5 2.0 wt% PTFE emulsion was added to the active mass. A plug type graphite electrode contained MC = 280 mg of active mass. We used H2SO4 or HBF4 as a working electrolyte for the plug type of anthraquinone and graphite electrodes.

2.2. Technique for the preparation and in6estigation of PAN electrodes

Aniline was puried by simple distillation and the fraction (colorless) boiling at 180 C was used for the formation of the polymer. PAN was precipitated using multiple cyclic voltammetry (6= 100 mV/s) in the range 0.01.0 V versus SHE. Polymer lms were prepared using 0.1 M of aniline in 1 M CF3COOH acid solution. The thickness of the lms was estimated considering that lms with a passed charge of 0.1 1.0 mC/cm2 for the 0300 mV voltage range in 1 M HCl solution have , a thickness of about 200 1000 A. The working electrode was Pt, the geometric area being 0.2 cm2. The useful volume of the cells was 2 ml. Cyclic voltammetric and chrono-amperometric experiments were carried out at 20 C in an acidied (pH 0.5) 1 M KCl solution. The acidication of the solution was performed using CF3COOH.

2.1. Technique for the preparation and in6estigation of anthraquinone and graphite electrodes
For investigations of anthraquinone-9,10 or graphite active mass, we have developed a special plug type of working electrodes. An active mass was pressed into a polyethylene plug of 11 mm inside diameter. Before pressing, a spiralled thin platinum wire was inserted into an opening, pierced in a plug wall. For the preparation of an acti6e anthraquinone-9,10 mass we used a mixture of 50 wt% anthraquinone-9,10

3. Results and discussion

3.1. Anthraquinone-type quinoid compounds

Anthraquinone-type quinoid compounds belong to the group of quinones, which are practically non-soluble in aqueous solutions (solubility less than 10 8 M/l). The stationary potential of electrode in 1.5 M H2SO4 is E :0.05 V versus Ag/AgCl. Moreover, an electrode acquires this potential in any case when the current is switched off. Fig. 1 shows the typical CVs for the anthraquinone electrode in 1.5 M H2SO4 during the rst 300 cycles of potentiodynamic charging discharging. CV has two sharp peaks. E can be easily determined from the CV. The background current is negligible. Fig. 2 shows typical galvanostatic charge discharge curves for the anthraquinone electrode taken at the current density j =5 mA/cm2. The charge and discharge potentials demonstrate a very high stability. The charge

Fig. 1. Typical experimental CVs for the anthraquinone-9,10 electrode in 1.5 M H2SO4 during the rst 300 cycles of potentiodinamic charging discharging. Sweep rate 6 = 10 mV/ s. MAQ = 200 mg. E vs Ag/AgCl electrode.

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Fig. 2. Typical experimental galvanostatic charge discharge curves for the anthraquinone-9,10 electrode in 1.5 M H2SO4 taken at the current density j= 5 mA/cm2. MAQ = 200 mg. E vs Ag/AgCl electrode.

Fig. 3. Typical experimental CVs for the graphite electrode in 4 M HBF4; 6 =50 mV/s; MC = 280 mg. E vs Ag/AgCl electrode. Emax =1.6 (1), 1.7 (2), 1.8 (3), 1.9 (4), 2.0 V (5).

and discharge capacities are equal to each other. The stationary potential can be determined from these chargedischarge curves too, and is E: 0.05 V. Thus, it is clear that the current-producing process at the anthraquinone-9,10 electrode occurs in full accordance with the faradaic mechanism, which can be described by equations similar to Eq. (1a). The main electrochemical proofs of such faradaic process are as follows: stable and easily determinable equilibrium (stationary) potential E; sharp peaks in CV on both sides of E; horizontal charge discharge curves on both sides of E.

is switched off, the electrode potential moves to its stationary value E in this solution. The same conclusion about the reversible intercalation potential Eint : 1.55 V can be made from CVs for graphite electrode (see Fig. 3). It follows from Fig. 3 that if the maximum oxidation potential Emax is higher (intercalation process), a higher deintercalation peak current and discharge capacity will be obtained by reduction process. In any case the reversible intercalation potential Eint corresponds to the stationary potential value E : 1.55 V. As follows from the relatively high positive potential of intercalation, a certain rate of oxygen formation is always coupled with the intercalation process. The presence of these two processes is clearly seen from comparison of galvanostatic charge and discharge curves (Fig. 4). The rst plateau in the charge curve corresponds to the process of BF intercalation into graphite and the 4 second one to the process of oxygen formation from the electrolyte. The plateau in the discharge curve corresponds to the process of BF deintercalation from 4 GIC. It is very simple to estimate the stationary potential value E :1.55 V from the galvanostatic charge discharge curves too. Thus, we can also observe all features (a), (b) and (c) of the faradaic mechanism during the current-producing process at the graphite electrode, which occurs in accordance with reaction (2a).

3.3. Polyaniline-type conducting polymers 3.3.1. Ion exchange in the absence of oxygen Electrochemical equilibrium has been investigated by taking chrono-potentiometric curves at a PAN electrode without the presence of oxygen in the cell, after giving the electrode a certain charge (Fig. 5). It is well known that when the current is switched off, the potential of redox electrode tends to return back to its stationary value. In contrast to this classical variant, in the case of a PAN electrode, after switching off the current, the potential settled at a value which was practically the same as that achieved at the moment of charging discharging (Fig. 5a). So, PAN does not display the potential of any own redox equilibrium in the absence of oxygen. Along with this, when the PAN electrode acquired even a small quantity of electricity Q, the value of stationary potential E(Q) considerably changed (Fig. 5b). The curves obtained under the above conditions (Fig. 5a, b) possess one more feature: after passing a certain quantity of electricity in one direction and the same quantity in the reverse direction, we come to the initial potential value. Thus, the experimental curves shown in Fig. 5 represent a quasi-equilibrium dependence of

3.2. Graphite intercalation compounds

Let us consider, for example, the formation of acceptor-type GIC with tetrauoroborate anions. The stationary potential of GIC electrode in 4 M HBF4 is E:1.55 V versus Ag/AgCl. When the current

Fig. 4. Typical experimental galvanostatic charge discharge curves for the graphite electrode in 4 M HBF4 taken at the current density j =3 mA/cm2. MC = 280 mg. E vs Ag/AgCl electrode.

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Fig. 5. Plots of the PAN electrode potential vs time with constant current in the system (1) and with the current switched off (2, 3) (a); the stationary potential vs the degree of charging Q/Qmax (b).

electrode potential on the degree of polymer charging Q/Qmax. During the common electrochemical redox process, the degree of charging Q/Qmax is a measure of the ratio of concentrations (activities) of the oxidized and reduced forms. For instance, if we assume that during chargedischarge the quantity of passed electricity is spent only on changing the degree of polymer oxidation (which is quite reasonable since in the potential range 00.9 V there are no side processes at the electrode in the absence of oxygen), the standard potential E must obey the classical Nernstian equation. Logarithmic dependence of the potential E on the Q/(Qmax Q) are known to correspond to this theoretical equation, which does not agree with the experimentally observed linear dependence E versus Q/Qmax (Fig. 5b). Besides, as follows from Fig. 5b, when the degree of oxidation of polymer is changed by a factor of two, the electrode potential changes by about 450 mV. If the system were described by the Nernstian equation, a change of no less than seven orders of magnitude in the degree of oxidation of polymer should correspond to this potential change. The PAN electrode potential shifts proportionally with the quantity of electricity Q, which is typical for any capacitor. These results are in a good agreement with the proposed capacitor model [16] and are, in our view, difcult to explain in terms of redox processes in PAN. Nevertheless, some redox reaction can proceed within the practically important potential range at a PAN electrode in an oxygen atmosphere. The effect of the catalytic reduction of air oxygen on a PAN lm electrode was established for the rst time in Ref. [18]. To

make this effect manifest, corresponding conditions should be created.

3.3.2. Ion exchange under oxygen atmosphere at equilibrium and at low rates of process If the special measures to withdraw oxygen from solution are not taken, a PAN electrode in a salt and acid solution (for instance in ZnCl2 at pH 5) usually shows a stationary potential of about 0.40 V (versus SHE). The discharge curve at a low current density ( j 50.5 mA/cm2) exhibits a plateau of non-estimated length in the same range of potential (Fig. 6). Taking into consideration basically possible ranges of oxygen reduction equilibrium potentials, it is possible to assume that electrochemical process normally occurs with hydrogen peroxide formation (E 0.3 0.5 V for

Fig. 6. Galvanostatic discharge curve for a thin PAN lm under conditions of good oxygen supply, j=0.25 mA/cm2.

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Fig. 7. Typical experimental galvanostatic discharge (1) and charge (2, 3) curves for a PAN electrode at j] 1 mA/cm2. Curve 3 recorded on a PAN electrode with the initial treating at the potential E = 0 V. The curves obtained in a 1 M aqueous solution of KCl and CF4COOH (pH 0.5).

usual oxygen concentrations in the solution). Such a theoretical assumption was conrmed experimentally using the reaction of H2O2 with KI solution [19]. This qualitative reaction proved the formation of H2O2 in the solution. H2O2 concentration increases with time and on application of current. Addition of KI indicator to the electrolyte conrmed that the polymer electrode is the source of H2O2 formation. In the case of a good oxygen supply to the PAN lm and relatively slow processes, CVs taken at sweep potential rate 6= 1 mV/s exhibit an external pair of peaks with the average potential in between about 0.40 V. Nevertheless, this pair of peaks can not be recorded at more rapid sweep potential rates (for instance, at 6=10 mV/s). This effect can be easily explained by the fact that the share of oxygen reduction current is usually much lesser than that of the current for the mean process of charging discharging of electrode. However, decrease of sweep potential rate makes this process more pronounced. The phenomenon of catalytic reduction of air oxygen at PAN lm observed, rst of all has a great signicance for understanding the mechanism of current-producing processes in conducting polymers. The pair of peaks (with average potentials of about 0.40 V) that appear at slower sweep potential rates must not be interpreted from the viewpoint of main redox process of charging discharging the electrode. It is possible to explain the phenomenon of PAN catalytic activity in terms of the electronic theory of catalysis by Pisarzhevsky and the capacitor concept [16]. Let us suppose that the system of poly-p-conjugated bonds for a conductive form of PAN persists unchangeable during the electrode charge discharge. Such a system is characterized by the possibility of easy delocalization of electrons. An oxygen molecule can be, for instance, easily ionized under the sorption on such a conductive surface. This creates conditions for PAN catalytic activity towards oxygen reduction.

Experiments show that in the lm PAN electrode the current density (cd) of oxygen reduction is usually less than 0.5 1.0 mA/cm2. That is why an optimal carbon substrate with a high conductivity, stability to oxidation, low density and sufcient specic surface is necessary for developing a gas-diffusion porous electrode with a practically interesting cd (a few dozen of mA/ cm2 depending on potential). PAN composites with different types of graphite and carbon blacks were prepared and selected. The best results in such composites were demonstrated by thermally exfoliated graphite from Superior Graphite Co., Chicago, IL. By the way, the above results can nd practical application for development of PAN/exfoliated graphite catalysts in quite efcient air metal power sources [20]. Specic energy attained in mockups of air Zn and air Mg batteries is about 150 200 Wh/kg. The discharge curve of such batteries is practically horizontal since it is determined by the oxygen reduction potential.

3.3.3. Gal6anostatic charge discharge cur6es in any atmosphere at the real currents At discharge (charge) current density values of j \ 1 mA/cm2, the electrode potential decreases (increases) with time practically linearly both in the absence and in the presence of oxygen in the main working range of potentials 0 B EB0.9 V (Fig. 7, curves 1, 2). This effect can be easily explained by the fact that the share of oxygen reduction current is usually much less than that of the main current for the electrode chargingdischarging process. According to the capacitor concept [16], the main current-producing process is bound up with the chargedischarge capacity of the inner double electric layer, which is abnormally high in the system under consideration due to the peculiarities of its structure. For instance, under the positive electrode potential anions from a solution are incorporated in the structure of polymer. In the same time, cations inside polymeric lm go out from polymer in a solution. There is only electrostatic interaction between anions and solid state. Thus, it is not necessary to apply great energy (or voltage) for the effect of such a electrosorption desorption process, which occurs with a very low polarization. By the way, that is why the conducting polymers can nd an effective application for extraction of ions out of sewage [21]. A deviation from the linear shape of charge discharge curves is observed at the limits and outside of this range (Fig. 7). We can observe an appearance of sharp electrode passivity outside a working range of potentials 0 B EB 0.9 V both with discharging (1) and with charging (2). Moreover, we performed the initial treating of the PAN electrode at the edge potential E= 0 V. For such a

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case an additional delay of a potential (plateau) is recorded during the process of charging (curve 3). So, a further development of a model [16] for whole potential range DEmax is necessary for explanation of these edge effects.

3.3.4. Cyclic 6oltammograms of a PAN electrode in a whole potential range Cyclic voltammetry is widely used to study conductive polymers. The shape of CV is, rst of all, a test for the quality of polymer lms and characterized well the chargedischarge process. A typical CV for our PAN lm in a 1 M aqueous solution of KCl and CF4COOH (pH 0.5) is shown in Fig. 8. The curve obtained by us on a PAN electrode is similar to CVs that are reported by many investigators. This corroborates the fact that our PAN is similar in chemical nature. A feature peculiar to the CV is the steep anodic peak at the onset of the process. A at plateau follows after that peak. During backward potential sweep, a cathodic peak with a potential shift relative to the anodic peak appears at the end of the plateau. The current magnitude of the cathodic peak is lower than that of the anodic peak (the areas of the anodic and cathodic portions of the CV being approximately equal). At more negative potentials, the currents are practically zero, and there are no maxims because the lm has a low electronic conductivity in this potential range [22]. This behavior is not typical of ordinary redox lms. The CV has a relatively large plateau with approximately constant current magnitude and exhibits a po-

tential shift between the cathodic and anodic peaks as well as an asymmetry of the peaks. To elucidate the nature of the processes that occur in the polymer lm during discharge and charge, it is necessary to answer the following questions: 1. What processes take place in CV? 2. How do they affect the electroactivity of polymer? 3. What factor predominates? Examination of the CV in Fig. 8 allows three pairs of peaks to be distinguished. When discussing the electrochemical behavior of PAN, it should be noted that the second pair of peaks (E 0.7 0.8 V versus SHE) is not specic for PAN proper. Its appearance is marked by the beginning of loss of PAN electroactivity, which is observed on overoxidation. In an aqueous medium, degradation leads to the formation of soluble products, which may be a quinone/hydroquinone couple [23]. Ref. [24] suggests, on the basis of theoretical considerations, that electroactive oligomers with a length of the order of ten aniline members may exist in this potential range. The appearance of the peak can be avoided by removing these oligomers. The study of the third pair of peaks (E 0.9 1.1 V versus SHE) is difcult because an irreversible oxidation of PAN is observed on cycling, which also gives rise to a loss of polymer electroactivity. In view of that said above, we shall consider the electrochemical behavior of a polymer lm in the working potential range 0 0.9 V versus SHE, where there is a so-called window of PAN stability. In this potential range, PAN can be cycled many times, for there are no side processes, which lead to degradation.

Fig. 8. Typical CV recorded on a PAN electrode with a scan rate 6 =100 mV/s in a 1 M aqueous solution of KCl and CF4COOH (pH 0.5).

3.3.5. Theoretical models and additional experiments The fact that emeraldine salt is the only electrically conductive form of PAN is considered now to be exactly established. Therefore, when analyzing various process schemes, one should pay special attention to the fact that during any redox process a practically nonconducting phase must be formed. The electric eld strength in the solid phase, which is the driving force of the process in similar systems, is maximal near the current collector and decreases rapidly with distance [25,26]. Therefore, if the faradaic process is initiated at denite potentials, it will occur at the highest rate near the current collector. As soon as the adjacent polymer monolayer (or several monolayers) changes to practically non-conducting state, the circuit opens, and further occurrence of the electrochemical process is impossible. Therefore, the predominant process in the electrochemical behavior of PAN must be, in our view, dl chargedischarge, and the share of the faradaic process be very small since it gives a sharp decrease of polymer electroactivity.

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Fig. 9. The scheme of positive/negative ions transfer during the charging of polymer which takes into account the formation of the poorly conducting layer near the current collector.

Fig. 10. A model of a thin layer of conducting polymer. RS, the resistance of poorly conducting layer controlled by potential (RS  as the switch); C, the effective DL capacitance of the PAN electrode; R, the effective resistance of the PAN electrode without taking into account a slightly-conducting layer near the current collector.

The nature of the electrochemical behavior of PAN can be approximately described by the scheme reported in our previous work [16], which is, nevertheless to be supplemented with the following considerations: 1. taking into account the possibility of formation of a poorly conducting layer near the electrode surface; 2. taking into account the fact that dl charge discharge can result both from proton and anion transport in the polymer lm [27,28]. A basic feature of this dl formation model is that each of the polymer chains in principle can be regarded as a microelectrode. Thus, dl is formed at a molecular level. Taking into account the scheme in Fig. 9, the equivalent circuit of a thin PAN electrode can be presented by following an electric equivalent (Fig. 10). The poorly conducting very thin layer in the substrate acts as a variable resistor or even as a switch in such an equivalent. Let us analyze the main peculiarities of the electrochemical behavior of a PAN electrode, which follow from the above models. It is easy to understand that for galvanostatic conditions the function E(t) must be linear for the main working potential range. A deviation from linear shape observed at the potentials of about 0 and 0.9 V, is due to an holmic drop since when these potentials are reached, the poorly conducting layer fully blocks the current collector surface. It should be noted that when the current is switched off, the potential reached by the electrode remains constant. Taking into account the capacitive nature of current variation in CV, we calculated the current traversing the capacitor C as a function of potentials. This current Ic is called capacitive current. In Fig. 11 we plotted the current obtained by cyclic voltammetry and the previously calculated current Ic from equation [29]: Ic = Cd6/dt[1 exp(t/RC)] (4)

Fig. 11. The fragments of experimental (dashed line) and calculated (curves 2, 3) CVs of a PAN electrode. Dashed line represents the fragment of experimental CV in a 1 M aqueous solution of KCl and CF4COOH (pH 0.5); potential limits: 0.10.9 V; 6= 100 mV/s. Curves 1 and 1% represent a conventional capacitor current as a function of the potential calculated step-by-step by the equation Ic = Cd6/dt[1 exp ( t/RC)], where d6/dt =100 mV/S. Inc, a non-capacitor current calculated as the difference between the total cathode CV current and capacitor current (curve 1%). The anodic capacitor current (curve 2) is calculated by the equation I= I0exp( t/ RC)+ Cd6/dt[1exp(t/RC)] when the isolated layer disappears in a PAN electrode.

The striking point is that the capacity curve being symmetric in the oxidation and reduction processes, the capacitive current is symmetric, too. On the contrary, the non-capacitive Inc current exhibits a large hysteresis. This can be interpreted in terms of the formation of an insulating monolayer near the electrode surface which leads to the disconnection of the bulk of polymer from the electrode. Therefore, in the case of linear sweep in the anodic direction, a DE potential shift is needed to switch the insulating layer to the electrically conducting state. It follows that the capacitor C is connected with more positive potentials, in which case a jump in current must arise. It is the factor that is responsible for the anodic peak observed in CVs, which is often attributed to a pure faradaic process. Using the equation: I= I0 exp(t/RC)+ CdV/dt[1 exp(t/RC)] (5)

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Fig. 12. Experimental fragment of CVs (curves 1, 2) on a PAN electrode with a scan rate 6 = 100 mV/s in a 1 M aqueous solution of KCl and CF4COOH (pH 0.5). Curve 2 recorded with the initial treating of the electrode at the potential E =0 V. The anodic Ic current (curve 3) is calculated by the equation I= I0exp( t/RC)+ Cd6/dt[1 exp( t/RC)].

where I0 =DE/R for the equivalent circuit in Fig. 10 and the experimental value of potential delay DE 0.2 V, we obtain an Ic(E) curve, which is shown in Fig. 11 (dotted line). When the electrode is kept at negative potentials, a thicker insulating layer is possibly formed. This is corroborated by galvanostatic measurements. For instance, the galvanostatic charge curve 3 (Fig. 7) exhibits

Fig. 14. Potential-step curves on a PAN electrode at a different range of potentials. Electrode potential stepped in the following ranges (vs SHE): from 0.3 to 0.6 V and after that from 0.6 to 0.3 V; from 0.0 to 0.3 V and after that from 0.3 to 0.0 V.

Fig. 13. Experimental fragments of CV curves on a PAN electrode at different potentials of switching: 1, E1 = 0; 2, E2 =0.3; 3, E3 =0.4 V. Electrolyte is a 1 M aqueous solution of KCl and CF4COOH (pH 0.5); a scan rate 6= 100 mV/s.

a constant-potential region after keeping the PAN electrode at the potential E =0 V. Due to the thicker poorly conducting layer, the DE value increases in CV, which is usually attributed to the rst-cycle effect. Fig. 12 shows a CV which was taken after keeping the electrode at the potential E =0 V. Anodic curve 3 in Fig. 12 calculated by Eq. (5) shows an increase in current with increasing potential, which is in a good agreement with experimental data (curve 2, Fig. 12). Eq. (5) fails to describe absolutely accurately the experiments due to the simplied cycling at potentials of 0.4 0.9 V, no peaks are observed in CVs (Fig. 13). In this potentials range, the capacity of the polymer lms is purely capacitive in nature as was shown earlier [16]. The effect of insulating layer formation can be clearly observed in chrono-amperometric measurement. Fig. 14 shows current variation as a function of stepwise potentials variation. It is evident from the gure that when potentials vary forwards the formation of a poorly conducting phase, a decrease in current magnitude in the chrono-amperogram is observed. Calculations of capacity from chrono-amperograms show a decrease of 37% in electrode capacity on stepwise potentials variation in this direction. Thus, the thin dielectric polymer layer causes the electrode to be blocked and the current-producing process to cease. The model in Fig. 10 allows one to account for not only the complex of properties (1) (3) for PAN-type CP, but also more specic yet important properties, e.g.

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memory effect (see [30 34] and references therein). Many assumptions were reported to account for this effect, some of them being mutually exclusive. Some assumptions were connected with the formation of poorly conducting layers. It is obvious that convincing deduction can only be made in constructing a general electrode model and revealing factors limiting the electrode process on the whole. The memory effect multiple manifests itself in our experiments connected with electrode treating at the some potentials (Fig. 7, curve 3; Fig. 11, curve 2; etc.). This effect can be easily accounted for in terms of the model in Fig. 10 with taking into account the fact that the internal poorly conducting layer formed at the some potentials becomes the limiting factor of the whole process; its thickness being dependent on the potential value and time of treating.

References
[1] H. Alt, H. Binder, A. Kohling, et al., Electrochim. Acta 17 (1972) 873. [2] G. Matricali, A. Kergreis, B. Auclair, M. Guillon, C.R. Acad. Sci. 278 (1974) 829. [3] O. Ksenzhek, V. Barsukov, V. Matveev, Reports of USSR Acad. Sci. (Doklady Akademii Nauk SSSR) 232(5) (1977) 1120 (in Russian). [4] S. Aronson, S. Lemont, J. Weiner, Inorg. Chem. 10 (1971) 1296. [5] F. Beck, H. Junge, H. Krohn, Electrochim. Acta 26 (1981) 799. [6] J.O. Besenhard, E. Wudy, H. Mohwald, et al., Synth. Met. 7 (1983) 185. [7] I.G. Chernysh, I.I. Karpov, G.P. Prikhodko, V.M. Shai, Physico-Chemical Properties of Graphite and its Compound, Naukova Dumka, Kiev, 1990 (in Russian). [8] V.Z. Barsukov, T.I. Motronyuk, I.V. Barsukov, in: J. Przyluskii, S. Roth (Eds.), New Materials: Conjugated Double Bond Systems, vol. 191, Trans. Tech. Publications, Switzerland, 1995, p. 261. [9] G. Paasch, P.H. Nguyen, A. Fischer, Chem. Phys. 227 (1998) 219. [10] A. Neudeck, et al., Synth. Met. 107 (1999) 143. [11] S.A. Brazovskii, N.N. Kirova, JETP Lett. 33 (1982) 4. [12] M.X. Karapetyanc, S.I. Drakin, General and Inorganic Chemistry (Obshaya i Neorganicheskaya Khimiya), Khimiya, Moskwa, 1981 (in Russian). [13] S.W. Feldberg, J. Am. Chem. Soc. 106 (1984) 4671. [14] J. Tanguy, M. Hoclet, Synth. Met. 43 (1991) 2995. [15] Yu.M. Volfkovich, A.G. Sergeev, Electrochim. Acta 44 (1999) 1543. [16] V. Barsukov, S. Chivikov, Electrochim. Acta 41 (1996) 1773. [17] E.W. Paul, A.J. Ricco, M.S. Wrighton, J. Phys. Chem. 89 (1985) 1441. [18] S.V. Chivikov, V.Z. Barsukov, N.V. Korneev, Fundamental Problems on Electrocatalysis, Abstr. III All-Union Conference on Electrocatalysis, Moscow, 1992, p. 155 (in Russian). [19] S. Chivikov, T. Motronyuk, M. Danilov, V. Barsukov, WEEPF-97 (2nd Int. Workshop on Electrochemistry of Electroactive Polymer Films), Volume of Abstracts, Dourdan, France, 1997. [20] V.G. Khomenko, S.V. Chivikov, V.Z. Barsukov, Problems of Chemistry and Chemical Technology/Voprosy Khimii i Khimicheskoy Tekhnologii (Ukrainian Journal) 1 (2000) 247 (in Russian). [21] S. Chivikov, V. Khomenko, T. Motronyuk, V. Barsukov, 49th ISE Meeting, Kitakyushu, Japan, Extended Abstracts, 1998. [22] S.U. Glarum, J.H. Marshall, J. Electrochem. Soc. 134 (1997) 142. [23] T. Kobayashi, H. Koneyama, H. Tanura, Electroanal. Chem. 177 (1984) 281. [24] S.U. Glarum, J.H. Marshall, J. Phys. Chem. 92 (1988) 4210. [25] V.Z. Barsukov, B.E. Rogoza, L.N. Sagoyan, Rus. J. Electrochem. (Electrokhimiya) 20 (1984) 1631 (in Russian).

4. Conclusion Analysis of different systems with solid-phase reagent conrms the fact that in such systems as slightly soluble quinones, acceptor- or donor-type GIC, etc., the electrochemical process occurs by the classical faradaic mechanism. In PAN-type CP the electrochemical process is mainly non-faradaic in nature. Our investigations of current-producing mechanisms for a PAN electrode have shown that at least within a narrower range of potentials DEn from 0.30 0.40 to 0.80 0.90 V versus SHE (depending on pH value) the capacitor model of ion electrosorption desorption in a well conducting emeraldine salt phase is more preferable. Nevertheless, such a model should take into account the transport of both anions and protons (cations in a general case). Within the limits and outside this range of potentials DEn it is also necessary to take into account the possibilities of redox processes. At the same time, these processes can lead to the fast formation of thin passive layers of new poorly conducting phases (leucoemeraldine salt, leucoemeraldine base, etc.) near the current collector. The formation of such phases even in a small amount inhibits and discontinues the electrochemical process quickly and allows one to account for the memory effect and other peculiarities of electrochemical behavior of CP.

Acknowledgements The nancial support of this research in the frame of the NATO c 973849 SfP project is highly acknowledged.

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V.Z. Barsuko6 et al. / Electrochimica Acta 46 (2001) 40834094 [29] J. Tanguy, N. Mormilliod, M. Hocles, J. Electrochem. Soc. 134 (1987) 795. [30] C. Odin, M. Nechtschein, Synth. Met. 43 (1991) 2943. [31] C. Odin, M. Nechtschein, R. Hapiot, Synth. Met. 47 (1992) 329. [32] C. Odin, M. Nechtschein, Synth. Met. 55 (1993) 1281. [33] M. Lapkowski, A. Zagorska, I. Kulszewiecz-Bajer, A. Pron, Synth. Met. (1993) 1570. [34] C. Barbero, R. Kotz, M. Kalaji, L. Nyholm, L.M. Peter, Synth. Met. (1993) 1545.

[26] V.Z. Barsukov, B.E. Rogoza, L.N. Sagoyan, 34th ISE Meeting, Extended Abstracts, O-112, Erlangen, Germany, 1983. [27] V. Khomenko, S. Chivikov, V. Barsukov, T. Motronyuk, WEEPF-2000 (NATO ARW on Electrochemistry of Electroactive Polymer Films), Extended Abstracts, 14, Poraj near Czestochowa, Poland, 2000. [28] C.M. Elliott, C.A. Salzer, WEEPF-2000 (NATO ARW on Electrochemistry of Electroactive Polymer Films), Extended Abstracts, 11, Poraj near Czestochowa, Poland, 2000.