Conducting Polymers: Past, Present, Future

J. Electrochem. Sci. Eng. 8(1) (2018) 3-37; DOI: http://dx.doi.org/10.5599/jese.
448
Open Access : : ISSN 1847-9286

www.jESE-online.org
Review article
Conducting polymers: past, present, future

György Inzelt
Department of Physical Chemistry, Institute of Chemistry, Eötvös Loránd University, Pázmány Péter
sétány 1/A, 1117 Budapest, Hungary
E-mail: [email protected]
Received: September 29, 2017; Revised: October 30, 2017; Accepted: November 2, 2017
Abstract
In my plenary lecture delivered at the 6th Regional Symposium on Electrochemistry of
South-East Europe (RSE-SEE) that was held between June 11 and 15, 2017, in
Balatonkenese, Hungary I surveyed the developments in the field of conducting polymers
based on my 40 years of experience in this area. It is intended to give an overview including
thermodynamical considerations, redox transformations and transport processes,
methods of investigation, redox polymers, electropolymerization, characterization, and
applications with abundant examples from my research results.
Keywords
Synthesis; Redox behaviour; Composites; Sensors; Biosensors; Supercapacitors; Electrocatalysis
Introduction
The preparation, characterization and application of electrochemically active, electronically
conducting polymeric systems are still at the foreground of research activity in electrochemist-
try [1-3]. There are at least two major reasons for this intense interest. First is the intellectual
curiosity [1-4] of scientists, which focuses on understanding the behavior of these systems, in
particular on the mechanism of charge transfer and on charge transport processes that occur during
redox reactions of conducting polymeric materials [2, 4-6]. Second is the wide range of promising
applications of these compounds in the fields of energy storage, electrocatalysis, organic
electrochemistry, bioelectrochemistry, photoelectrochemistry, electroanalysis, sensors, electro-
chromic displays, microsystem technologies, electronic devices, microwave screening and corrosion
protection [2]. After 40 years of research in the field, the fundamental nature of charge propagation
is now in general understood; i.e., the transport of electrons can be assumed to occur via an electron
exchange reaction (electron hopping) between neighboring redox sites in redox polymers, and by
the movement of delocalized electrons through conjugated systems in the case of so-called
intrinsically conducting polymers (e.g., polyaniline, polypyrrole). (In fact, several conduction
doi:10.5599/jese.448 3
J. Electrochem. Sci. Eng. 8(1) (2018) 3-37 CONDUCTING POLYMERS
mechanisms, such as variable-range electron hopping and fluctuation-induced tunneling, have been
considered.) In almost every case, the charge is also carried by the movement of electroinactive ions
during electrolysis; in other words, these materials constitute mixed conductors [2,5,6]. Owing to
the diversity and complexity of these systems — just consider the chemical changes (dimerization,
cross-linking, ion-pair formation, etc.) and polymeric properties (chain and segmental motions,
changes in the morphology, slow relaxation) associated with them, the discovery of each new
system brings new problems to solve, and much more research is still needed to achieve a detailed
understanding of all of the processes related to the dynamic and static properties of various
interacting molecules confined in a polymer network.
Although the conductivity of these polymers is an interesting and a utilizable property in itself,
their most important feature is the variability of their conductivity, i.e., the ease with which the
materials can be reversibly switched between their insulating and conducting forms (Figure 1). (The
conductivity of copper is still better but not variable!)
An evidence of the existence of the mobile electrons in the system is the practically uniform
absorbance at high wavelengths in half-oxidized state (emeraldine form of polyaniline). It is
characteristic to the metals (metallic conduction) since the excitation of the mobile electrons needs
small and practically the same energy. At lower wavelenghts the variation of the spectra indicates
the color change related to the leucoemeraldine – emeraldine – pernigraniline transitions (Figure 2).
Figure 1. Variation of the resistance of polyaniline as a function of potential (charging state) in contact with
1 mol dm−3 H2SO4 (compiled from the results of [7])
We can utilize the variation of the conductivity in electronic devices including thin film transistors
and insulated gate field effect transistors or in gas sensors; the color change in electrochromic
display devices or in smart windows, the electroluminescence in light emitting devices, the swelling-
deswelling accompanying the charging-discharging processes in artificial muscles, the charge
storage capacity in energy technologies (batteries, supercapacitors). There are properties, which are
useful in a certain application, e.g., volume change, however, those may cause problem in other
utilization. In fact, during the redox transformations generally we create a polyelectrolyte from an
uncharged polymer, which alter many physical and chemical properties. For instance, the charged,
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G. Inzelt J. Electrochem. Sci. Eng. 8(1) (2017) 3-37
salt-form is insoluble, while the neutral form is soluble in certain organic solvents. The overcharging
(overoxidation) may lead to the hydrolytic degradation of the polymer. In some cases the
mechanical properties including adhesion is of importance, e. g., in corrosion protection or in
membranes where gas evolution occurs, which are less crucial in batteries. In the early period
several attempts were made to vary the morphology and the swelling properties by using different
counterions. The derivatization of the monomers frequently lead to more flexible polymers.
Figure 2. UV–VIS–NIR spectra of PANI obtained in situ at different potentials:

(1) −0.35, (2) −0.25, (3) −0.15, (4) −0.05, (5) 0.05, (6) 0.15, (7) 0.25, (8) 0.35, (9) 0.45, (10) 0.55, and
(11) 0.65 V. Solution: 1 mol dm−3 H2SO4 [8]
In the last decade the researchers have started to apply novel approaches. The new trend is the
fabrication of composites including nanocomposites of polymers and other materials such as carbon
nanotubes, graphene or inorganic compounds having special structure and properties. In sensors
and biosensors of different kinds (conductometric, impedimetric, potentiometric, amperometric
and voltammetric) conducting polymers are used as active, sensing or catalytic layers, however, in
the the majority of application those serve as matrices entrapping enzymes or other biologically
active compounds. The biocompatibility of several conducting polymers provides opportunity for
the application in medicine as artificial muscles and limbs, as well as artificial nerves. The biomimetic
(bionic) applications certainly will continue in the future. (References [1-6] contain hundreds of cited
papers which were considered by the author as the most important ones. Therefore, most of the
citations in this review are the author’s works in connection with the results presented. It is worth
to mention that the total number of papers on counducting polymers until 2017 according to the
scientific database is ca. 300 000 [1].)
Historical background
Somewhat surprisingly, a new class of polymers possessing high electronic conductivity
(electronically conducting polymers) in the partially oxidized state was discovered. Alan J. Heeger,
Alan G. MacDiarmid and Hideki Shirakawa played a major role in this breakthrough, and they
received the Nobel Prize in Chemistry in 2000 “for the discovery and development of electronically
conductive polymers” [9-14]. The preparation of polyacetylene and the discovery of the large
doi:10.5599/jese.448 5
increase in its conductivity after “doping” actually launched this new field of research. However, as
Thomas Mann wrote: “Very deep is the well of the past”. Our case is also curious because the most
important representatives of these materials, polyaniline and polypyrrole, were already being
prepared by chemical or electrochemical oxidation in the nineteenth century. Of course, for a long
time they were not called polymers, since the existence of macromolecules was not accepted until
the 1920s. Therefore, it is somewhat interesting to review the story of polyaniline here, because it
provides an insight into the nature of the development of science. One may recall that aniline was
prepared from the coal tar residues of the gas industry in the first half of the nineteenth century,
and later played a fundamental role in the development of organic chemistry and the chemical
industry. First, aniline dyes replaced dyes from natural sources. Then coal tar dyes found use in
medicine (to stain tissues), and the selective toxicity of these compounds was also discovered. This
initiated the chemical production of medicines, and the establishment of the pharmaceutical
industry. In 1862 Dr. Henry Letheby, who was a physician and a member of the Board of Health in
London, was interested in aniline because it was poisoning workers. Letheby observed that a bluish-
green precipitate was formed at the anode during electrolysis, which became colorless when it was
reduced and regained its blue color when it was oxidized again [15]. In 1840 Fritzsche observed the
appearance of a blue color during the oxidation of aniline in acidic media [16]. In 1950 Khomutov
and Gorbachev discovered the autocatalytic nature of the electrooxidation of aniline [17]. In 1962
Mohilner, Adams and Argersinger reinvestigated the mechanism of the electrooxidation of aniline
in aqueous sulfuric acid solution at a platinum electrode. They proposed a free radical mechanism,
and wrote that “the final product of this electrode reaction is primarily the octamer emeraldine, or
a very similar compound” [18].
The first real breakthrough came in 1967, when Buvet delivered a lecture at the 18th Meeting of
CITCE (later ISE), and this presentation appeared a year later in Electrochimica Acta [19]. Here we
cite the first sentence of this paper, which speaks for itself: “Polyanilines are particularly
representative materials in the field of organic protolytic polyconjugated macromolecular
semiconductors, because of their constitution and chemical properties”. They also established that
polyanilines “also have redox properties,” and that “the conductivity appears to be electronic“. It
was also shown that ”polyanilines are also ion-exchangers“. Finally, they proposed that
“polyanilines... can be utilized for making accumulators with organic compounds”. While Josefowicz
et al. used chemically prepared PANI pellets as an electrode and for conductivity measurements,
investigations of the mechanism of electrochemical oxidation also continued, and the name
polyaniline became generally accepted. The paper of Diaz and Logan that appeared in 1980 [20]
initiated research into polymer film electrodes based on polyaniline, which continues even today.
Definition and classification

Electrochemically active polymers can be classified into several categories based on the mode of
charge propagation (note that insulating polymers are not considered here except for those with
variable conductivity). The mode of charge propagation is linked to the chemical structure of the
polymer. The two main categories are electron-conducting polymers and proton (ion)-conducting
polymers. We will focus on electron-conducting polymers here.
We can also distinguish between two main classes of electron-conducting polymers based on the
mode of electron transport: redox polymers and electronically (intrinsically) conducting polymers
(ECPs or ICPs).
6
Redox polymers contain electrostatically and spatially localized redox sites which can be oxidized
or reduced, and the electrons are transported by an electron exchange reaction (electron hopping)
between neighboring redox sites if the segmental motions enable this. Redox polymers can be
divided into several subclasses: i) polymers that contain covalently attached redox sites, either built
into the chain, or as pendant groups; the redox centers are mostly organic or organometallic
molecules; ii) ion-exchange polymeric systems (polyelectrolytes) where the redox active ions
(mostly complex compounds) are held by electrostatic binding.
A simple distinction between the intrinsically conducting and redox polymers is that in dry state
the ICPs are conducting while redox polymers are not. In the case of redox polymers water (or other
solvent) acts as a plasticizer, and makes the chain and segmental motions possible which is
inevitable to ensure the electron hopping between the localized redox groups.
Conducting polymers are mostly used as polymer film electrodes by electrochemists. A polymer
film electrode can be defined as an electrochemical system in which at least three phases are
contacted successively in such a way that between a first-order conductor (usually a metal) and a
second-order conductor (usually an electrolyte solution) is an electrochemically active polymer layer
which is usually a mixed conductor. The polymer layer is more or less stably attached to the metal,
mainly by adsorption (adhesion).
Methods of investigation
Conducting polymers have been studied using the whole arsenal of methods available to
chemists and physicists [2]. Electrochemical techniques, mostly transient methods such as cyclic
voltammetry (CV), chronoamperometry (CA) and chronocoulometry (CC), are the primary tools used
to follow the formation and deposition of polymers, as well as the kinetics of their charge transport
processes. Electrochemical impedance spectroscopy (EIS) has become the most powerful technique
used to obtain kinetic parameters such as the rate of charge transfer, diffusion coefficients (and
their dependence on potential), the double layer capacity, the pseudocapacitance of the polymer
film, and the resistance of the film [21].
The application of combinations of electrochemical methods with non-electrochemical
techniques, especially spectroelectrochemistry (UV-VIS, FTIR, ESR), the electrochemical quartz
crystal nanobalance (EQCN), radiotracer methods, probe beam deflection (PBD), various
microscopies (STM, AFM, SECM), ellipsometry, and in situ conductivity measurements, has
enhanced our understanding of the nature of charge transport and charge transfer processes,
structure–property relationships, and the mechanisms of chemical transformations that occur
during charging/discharging processes. In several cases to elucidate more complicated reaction
mechanism it is necessary to apply the combination of more than one technique, e.g., transient
electrochemical technique with UV-VIS spectroelectrochemistry and ESR, or with
spectroelectrochemistry and EQCN.
It is not necessary to deal with these techniques in detail here, since there are several books,
monographs and papers on the subject [2, 21-24].
Preparation of conducting polymers

Both redox and electronically conducting polymers can be prepared using chemical and/or
electrochemical methods of polymerization, although most redox polymers have been synthesized
by chemical polymerization. Electrochemically active groups are either incorporated into the
polymer structure inside the chain or included as a pendant group (prefunctionalized polymers),
doi:10.5599/jese.448 7
added to the polymer phase during polymerization, or fixed into the polymer network in an
additional step after the coating procedure (post-coating functionalization) in the case of polymer
film electrodes. The latter approach is typical of ion-exchange polymers. The electrochemical
polymerization is preferable, especially if the polymeric product is intended for use as a polymer
film electrode, thin-layer sensor, in microtechnology, etc., because potential control is a prerequisite
for the production of good-quality material and the formation of the polymer film at the desired
spot in order to serve as an anode during synthesis. A chemical route is recommended if large
amounts of polymer are needed.
Electropolymerization
In the majority of cases the polymers are prepared by electrooxidation of the respective
monomer compound. The oxidation of the monomer results in the formation of a cation radical.
The chain propagation occurs via dimerization of the radicals formed and elimination of hydrogen
ions. The dimer is oxidized (more easily than the monomer) and a next coupling step takes place
with a monomeric cation radical. The radical cation—radical cation coupling (RR coupling) −due to
the strong Coulombic repulsion− is considered less likely than the radical cation—substrate coupling
(RS coupling), i.e., the coupling of a charged and a neutral species. However, in condensed phase RR
coupling can proceed in a substantial rate. The nature of the rate-determining step (rds) depends
on the conditions; since the rate of the deprotonation, the solubility of the oligomer, the stability of
the cation radical depend on the nature of the solvent (e.g., its effect on the proton elimination),
electrolyte (especially on the nature of the anion which may stabilize the cation), and temperature
[2, 25, 26]. One has to consider also the deposition step which strongly depends on the nature of
the substrate (metal, carbon etc.). Some metals can catalyze the oxidation of the monomer or a first
layer of monomers may be formed due to the chemisorption on the metal which is characteristic in
several monomers on Pt or PtO [27].
During the very first potential cycle a characteristic loop (a crossing pattern that appears in the
cyclic voltammogram on reverse scan) (Fig. 3) can be observed which is due to the energy needed
for the nucleation. According to another view in some cases the loop is due to a homogeneous
comproportionation reaction [25] which facilitates the oxidation of the monomer.
Figure 3. The 1st cyclic voltammogram (–) and the simultaneously detected EQCN response (–) during the
electrooxidation of 6-aminoindole (1.5  10-2 mol dm-3) on Au in 1 mol dm-3 H2SO4 solution. Scan rate: 25 mV
s-1, switching potential: 0.5 V [27].
8
A huge anodic current appears and simultaneously the EQCN resonant frequency starts to
decrease which continues until anodic current flows. This indicates a deposition of the oxidation
product on the gold surface. The –5 Hz frequency decrease corresponds to a ca. 0.7 nm thin film,
assuming 1.2 g cm-3 for the density of the film or a surface concentration of 6-aminoindole, Г = 6.7
 10-10 mol cm-2. It follows that barely a monolayer or even submonolayer film was formed, i.e., it
can be considered just a nucleation. While the nucleation process is somewhat hindered, the growth
of the film is a much faster process. In Fig. 3 the so-called nucleation loop, i.e., the crossing pattern
of the anodic current and the current after switching is not well seen, because the switching
potential was limited to 0.5 V in order to avoid the overoxidation. However, it exists, and well-seen
when a higher positive switching potential was applied during the first scan. It has been interpreted
as the start of the nucleation process.
The progress of the electropolymerization and the deposition of the polymers can be nicely seen
on the cyclic voltammograms since the peak currents (and the charge under the waves) related to
the redox responses of the conducting polymer increases. By using electrochemical quartz crystal
nanobalance the increase of the deposited mass can be monitored directly. It can be seen in the
following figures (Fig. 4 polyaniline, Figs. 5-7 polyindole and poly(4-aminoindole, respectively).
Figure 4. The cyclic voltammograms and the simultaneously detected EQCN frequency changes during
the electropolymerization of aniline at a platinum electrode. Scan rate: 100 mV s−1.
Solution composition: 0.2 mol dm−3 aniline in 1 mol dm−3 HClO4 [28].
The mechanism of polyaniline formation is influenced by the deposition of oligomers, and the
highest growth rate in cyclic electropolymerization occurs during the cathodic potential scan. The
film morphology (compactness, swelling) is strongly dependent on the composition of the solution,
notably on the type of counter-ions present in the solution, and the plasticizing ability of the solvent
molecules. Due to the autocatalytic nature of the electropolymerization, the positive potential limit
of cycling can be decreased after 2–10 cycles, which is a common practice used to avoid the
degradation of the polymer due to the hydrolysis of the oxidized polyaniline (pernigraniline form).
The head-to-tail coupling that results in the formation of p-aminodiphenylamine, tail-to-tail
dimerization (benzidine) also occurs; however, the latter is considered to be a minor dimer
intermediate because the rate constant of dimerization for RR coupling that produces the former
product is about 2.5 times higher than that for the tail-to-tail dimer. Two types of nucleation
(instantaneous and progressive) and three types of growth (1-, 2-, and 3-dimensional) have been
observed in the case of different polymers and conditions. Although the region close to the
electrode surface exhibits a more or less well-defined and compact structure, in general the polymer
doi:10.5599/jese.448 9
layer can be considered to be an amorphous material with decreasing density as a function of the
distance of the substrate.
Figure 5. Cyclic voltammograms and the simultaneous change of the EQCN frequency (Δf) during the
oxidative electropolymerization of indole (1 mmol dm−3) in 1 mol dm−3 HClO4 on Pt during 40 consecutive
cycles. Scan rate: 10 mV s−1 [29]
Figure 6. Cyclic voltammograms and the simultaneous change of the frequency (Δf) during the
electropolymerization of 4-aminoindole (1 mmol dm−3) in 1 mol dm−3 HClO4 on Pt,
during 20 consecutive cycles. Scan rate: 10 mV s−1 [29]
While the usual representation, i.e., the decrease of the EQCN frequency (or the increase of the
surface mass) during consecutive voltammetric cycles can be found in the majority of papers
(Figs. 5 and 6), displaying the variation of the EQCN frequency as a function of time can be more
instructive. In this case the changes in the course of each cycle are much better seen (Figs. 7). It is
well seen that while the surface mass increases from cycle to cycle (continuous decrease of the
frequency at the beginning of the subsequent cycles), there is a change during each cycle. In the
case of indole this change is getting higher and higher (Fig. 7a) since during the oxidation and
reduction counter-ions enter and leave the surface film, respectively, and as the film is getting
thicker more and more counter-ions (in this case anions) enter or leave the film in the charge-
compensating process. In the case of 4-aminoindole the Δf vs. time curve resembles a staircase (Fig.
7b). This dependence reflects that the deposition occurs with the same rate from cycle to cycle and
the frequency variation is independent of the film thickness. It is only possible if there is no
movement of ions of considerable mass, i.e., the transport of H+ ions should be considered instead
of anions.
10
Figure 7. Comparison of the electropolymerization of indole (a) and 4-aminoindole (b) under the same
circumstances on the same type of electrode (1.37 cm2 Pt) in 40 and 20 cycles, respectively. Cyclic
voltammograms and the simultaneously detected frequency curves. The frequency curves are plotted as
function of the time. cmonomer = 1 mmol dm-3, electrolyte: 1 mol dm-3 HClO4. Scan rate: 10 mV s–1 [30].
While electrochemical impedance spectroscopy has become a basic tool in the study of the rate
of charge transport processes, film resistances and capacitances of polymer film electrodes, it is
relatively seldom used to follow the electropolymerization process. Figures 8 and 9 show such
results and the respective electrical equivalent circuit [30].
Figure 8. Three-dimensional representation of the (a) Bode and (b) Nyquist plots of the measured
impedance data during the electrodeposition of polyindole on Pt at 0.7 V in 0.1 mol dm−3 H2SO4 solution [31]
doi:10.5599/jese.448 11
Figure 9. Electrical equivalent circuit describing the EIS response of polyindole deposition on platinum. Zdl
represents the impedance of the double layer, Rct,indole and ZW,indole are the charge transfer and diffusional
impedances of indole, respectively, Ca,anion is the capacitive impedance related to the counter-ion adsorption
(on Pt surface), Rct,anion is the charge transfer resistance associated with the counter-ion adsorption/desorp-
tion, ZW,anion is the diffusional impedance of the counter-ions, and Rs is the solution resistance. The equivalent
electric circuit has been elucidated based on a priori chemical knowledge about this system [31].
Following the variation of the characteristic parameters several conclusions could be drawn
concerning the events at the surface (adsorption of indole and ions, polymerization etc.). The charge
transfer resistance and Warburg coefficient associated with indole itself vary with time, providing
evidence that after an inductive period, the process of generation of active centers is at its maximum
contributing to noticeable diffusion limitations. The apparent rate coefficient reflects the relative
contribution of slow and fast electrochemical stages involving the interfacial charge transfer during
the film growth. In general, formation of nuclei of a new phase is considerably slower than their
growth. At higher times the surface of Pt is covered by the polymer film, so that the growth at the
Pt/polyindole boundary is suppressed. However, the diffusion coefficient of the indole molecules
in/at the relatively thick indole film is decreased. The sulfate adsorption capacitance significantly
changes during the polymer film growth. At the anodic potential selected for polymerization, it is
known that the sulfate surface coverage is ~0.2 monolayer (ML) in H2SO4, and the adsorption
capacitance is approximately a few μF cm-2 as the adsorbate layer is almost “saturated”. After 5 min
of indole electropolymerization, the adsorption capacitance increases up to ~200 μF cm-2. This value
roughly corresponds to 0.1 ML of sulfates adsorbing and desorbing during the low-amplitude ac
probing, i.e. ~50 % of the available adsorbed sulfates are “disturbed” during initial stages of
polymerization. However, after ~10 min, the adsorption capacitance decreases (~100 μF cm-2) and
remains approximately constant. The non-zero values of the adsorption capacitance after ~10 min
indirectly suggest that redox transformations at the polymer/Pt interface still significantly disturb
the adsorbed sulfate layer.
Overoxidation
The overoxidation is a general problem in the course of the electropolymerization and also the
investigation or the use of conducting polymer modified electrodes. The choice of positive potential
limit in the case of electropolymerization or the application of proper oxidant (redox couple which
does not possess too positive equilibrium potential) in the case of chemical oxidation is essential to
12
have a good quality polymer. At high anodic potentials the further oxidation of the polymer occurs,
and this oxidation product undergoes a chemical reaction, e.g., in the case of polyaniline quinone
groups appear due to hydrolysis reaction. It manifests itself in the so-called “middle peak” between
the two main voltammetric peaks (see Fig. 10).
Figure 10. The consecutive cyclic voltammograms during the electropolymerization of aniline at a platinum
electrode. Scan rate: 100 mV s−1. Solution composition: 0.2 mol dm−3 aniline in 0.5 mol dm−3 H2SO4
In the case of the electropolymerization of 4-aminoindole it can be seen that during the
consecutive cyclic voltammograms (2-6th and 7-9th) the current continuously decreases during the
cycling together with a shift of the peak potential. The rate of the frequency change shows also
decreasing characteristics from cycle to cycle (Fig. 11). By using positive potential limits above 0.6 V
an overoxidation and hydrolysis occur and the electroactivity and conductivity of the film become
negligible. Nevertheless, a bluish-purple layer, which was formed, remained on the surface. Similar
phenomenon can be observed practically for all indole derivatives as shown in Figures 12-14 in the
case of 6-aminoindole.
Figure 11. Effects of the extended positive potential limit. The figure shows the first cycle (black), from the
2nd to the 9th cycle (red), and the 19th and 20th cycles (yellow) from a series of measurements.
Solution: 1 mmol·dm 3 4-aminoindole in 0.5 mol·dm 3 H2SO4. Pt electrode, v = 20 mV·s 1 [29].
doi:10.5599/jese.448 13
Figure 12. Subsequent cyclic voltammograms and the simultaneously detected EQCN responses during the
electrooxidation of 6-aminoindole (1.5  10-2 mol dm-3) on Au in 1 mol dm-3 H2SO4 solution.
Scan rate: 25 mV s-1. After the 17th cycle the switching potential was decreased to 0.48 V [27]
Figure 13. Subsequent cyclic voltammograms and the simultaneously detected EQCN responses during the
electrooxidation of 6-aminoindole (1.5  10-2 mol dm-3) on Au in 1 mol dm-3 H2SO4 solution. Scan
rate: 50 mV s-1. The first 46 cycles between –0.1 V and 0.55 V without changing the switching potential [27].
Figure 14. Cyclic voltammograms and the simultaneously detected EQCN responses during the electro-
oxidation of 6-aminoindole film on Au in contact with 1 mol dm-3 H2SO4. The change of the color of the film
by using the original photos of the electrode is also displayed. The positive potential limit was increased
during the consecutive cycling. The responses of the clean gold electrode in the potential range between –
0.3 V and 1.40 V (1). Positive potential limits were as follows: 0.55 V (2), 0.65 V (3),
and 1.4 V (4-6) (three subsequent cycles) [27].
14
The oxidation peak of the polymer, appearing at 0.27 V in the course of the first cycles when
0.5 V potential limit was kept, gradually shifts into the direction of more positive potentials. Its
height shows decreasing tendency with cycling to higher positive switching potentials (curves 2-4 of
Fig. 14). The oxidation peak of the monomer appears at 0.6 V, the frequency decrease related to
the deposition of the polymer gradually increases (curves 2 and 3 of Fig. 14). During continuous
cycling using higher and higher positive potential limits the deposited mass increases. However, the
peak height and the charge consumed during the oxidation of the monomer (together with the
oxidation of the film) decreases, and eventually both the charge and the frequency observed earlier
by applying a given switching potential gradually diminishes (for the sake of clarity not all cycles are
shown in Fig. 14). When 1.4 V switching potential was applied (curves 4-6) the effect described
above is well seen. Finally, during cycling 7 Hz frequency variation can be observed, which is
approximately equal to the magnitude of the usual double layer charging, i.e., no further deposition
takes place, and the film redox activity also diminishes. Nevertheless, a bluish-purple layer, which
was formed, remained in the surface. Because of the loss of electrochemical activity it can be
concluded that the conjugated polymer bonds break down, and an indigo or indirubin-like insoluble
but colored layer is formed.
Thermodynamical considerations
Thermodynamical considerations (the question of equilibria)
No equilibrium (adsorption equilibrium) exists between the surface phase and the solution with
respect to the polymer. In most cases no chemical bonds exist between the substrate and the
polymer, the polymer layer remains at the surface due to the van der Waals forces between the
substrate and the polymer, as well as between the polymer chains in multilayer films. The
adsorption model of de Gennes predicts a diminishing layer density which has been observed,
indeed, i.e., the polymer film is more compact close to the substrate surface.
Equilibrium situation is seldom established within the time scale of the experiments since the
relaxation process of the polymer network (gel) may be extremely long. It is true not only with
respect to the polymer morphology (conformation) but also to the membrane equilibria with
participation of ions and solvent molecules. In the first approach the surface polymer layer can be
treated as an amorphous swollen gel with a uniform structure and density in contact with a solution
containing solvent molecules and ions. In this case, both non-osmotic and osmotic membrane
equilibria, as well as the mechanical work done in swelling the polymer, must be taken into account.
In most cases the situation is even more complicated than that usually treated using membrane
equilibrium, since the charge in the polymer changes during the redox reaction; in most cases a
neutral polymer is transformed into a polyelectrolyte, and vice versa.
Membrane equilibria
Even in the case of a neutral polymer one should consider the partitioning equilibria of the
solvent molecules, the neutral salt and the ions formed by dissociation. The solvent content in the
polymer phase obviously depends on the difference between the standard chemical potentials of
the solvent molecules in the two contacting phases. Ions enter the film if their van der Waals and
ion-dipole interactions with the polymer are large. Ions can be solvated (hydrated) by both the
polymer and the solvent. When the polymer is hydrophobic and the solvent is hydrophilic the
interaction energies between the polymer segments and between the solvent molecules are higher
than those between the polymer segments and the solvent molecules. In this case, the polymer
doi:10.5599/jese.448 15
segments are not solvated by the solvent molecules, and hence there is no solvent swelling of the
polymer film. If the neutral polymer contains polar groups, water molecules will enter the polymer
and the polymer phase will eventually contain substantial amounts of water.
The situation is different when the interface is not permeable for one of the ions; i.e., the polymer
film behaves like an ion-exchange membrane. This is the case when the polymer is charged, which
is usually achieved by oxidation or reduction; however, this can also be the result of protonation.
Two cases should be considered: (i) non-osmotic membrane equilibrium; (ii) osmotic membrane
equilibrium. In the latter case, where solvent molecules can enter the surface layer or the
membrane, the situation is more complicated since mechanical equilibria are also involved. The
non-osmotic membrane equilibrium is illustrated in Fig. 15.
Figure 15. Charged polymer in contact with an electrolyte solution. Non-osmotic membrane equilibrium [2]
In the case of osmotic membrane equilibrium incorporation of ions and solvent molecules into
the polymer phase, a swelling of the polymer layer occurs, i.e., the state of the polymer phase
depends on the potential. For the thermodynamical description of the expansion or contraction of
the polymer network a mechanical work term has to be considered. The deformation of the polymer
layer: plastic (break-in period) or elastic (reversibly coupled to the redox reaction).
Redox transformations and the accompanying processes

The electron transfer taking place at the metal│polymer interface is accompanied by ionic charge
transfer at the polymer│solution interface, in order to maintain the electroneutrality within the
polymer phase. Counter-ions usually enter the polymer phase. However, less frequently the
electroneutrality is established by the movement of co-ions present in the polymer phase, e.g., in
so-called “self-doped” polymers. Oxidation reactions are often accompanied by deprotonation
reactions, and H+ ions leave the film, removing the excess positive charge from the surface layer. It
should also be mentioned that simultaneous electron and ion transfer is also typical of
electrochemical insertion reactions; however, this case is somewhat different since the ions do not
have lattice places in the conducting polymers, and both cations and anions may be present in the
polymer phase without any electrode reaction occurring. A general scheme of the charge transport
and the accompanying processes is shown in Fig. 16.
16
Figure 16. The charge transport and the accompanying processes in the case of a polymer film electrode
Owing to the complexity of the system and its redox transformations to gain a deeper
understanding of the mechanism combined techniques should be applied. In many cases even the
combination of more techniques is necessary. Two examples will be presented below. The
considerable difference between the anodic and cathodic peak potentials of the cyclic
voltammograms for the poly(tetracyanoquinodimethane) (TCNQ) redox electrode has been
explained by the formation of dimeric species; i.e., the slow formation of mixed-valence dimers
during reduction (charging) and the fast re-oxidation of dimer dianions resulting in mixed-valence
dimers during the discharging process [31]. The concentrations of the anion radicals and the dimer
dianions were derived from UV-VIS spectroelectrochemical data. The concentration of the mixed-
valence dimer was calculated from the variation in the ESR intensity and the concentration of the
other paramagnetic species, TCNQ.- and TCNQ.-2 (Fig. 17). It is striking evidence that even UV-VIS
spectroelectrochemistry is not enough to reveal all the intermediate products since the mixed-
valence dimer, TCNQ.-2 is silent within the available spectral lengths.
In order to monitor the transport and equilibria of ions and solvent molecules the
electrochemical quartz crystal nanobalance (EQCN) and radiotracer techniques are relatively simple
but highly effective methods. A comparison of the behavior of polyindole and poly(4-aminoindole)
serves as an illustration (Figures 18 and 19).
The reduction peak belonging to the first oxidation peak is rather undeveloped and suppressed
by the second one. The frequency change follows the charging–discharging processes. The apparent
molar mass, that corresponds to the Δf/Q quotient is 90.6 g mol−1 (n = 1). Therefore, ClO4--anions
enter and leave the film during its oxidation and reduction, respectively.
doi:10.5599/jese.448 17
Figure 17. Distribution diagram for the species formed during the electroreduction of poly(tetracyanoquino-
dimethane). A = TCNQ, A- = TCNQ-, A2- =TVNQ2-, A2 =TCNQ2 , and S = cTNCQ- + cTNCQ2- [32]
2- 2-
In the case of poly(4-aminoindole) based on the frequency change vs. potential curve three
processes can be distinguished in both scan directions (Fig. 19).
Figure 18. Cyclic voltammogram with the Figure 19. Cyclic voltammograms and the corresponding
frequency change curve of a polyindole film frequency curves of a poly(4-aminoindole) layer on Au,
in 1 mol dm–3 HClO4. Scan rate: 10 mV s−1 [29] measured in (1 mol dm-3 HClO4) at 10 mV s−1 [29]
In the positive scan direction, from 0.1 V an increasing current can be detected. Simultaneously
a mass increase starts, which is attributable to anion incorporation. However, the apparent molar
mass value (M = 10 g mol−1) that can be calculated from the mass vs. charge function is much lower
than the molar mass of the perchlorate ions. While the frequency decrease during the ascending
part of the cyclic voltammetry wave is evident, its value is rather small especially compared to the
relatively substantial charge consumed. This observation can be elucidated by assuming simulta-
neous anion sorption and deprotonation, and the latter process is the dominant one. Together with
18
protons water molecules also leave the film, i.e., desorption of hydrated H3O+ can be considered.
From 0.3 V, a strange frequency increase-decrease pattern can be detected before the next
frequency decrease section. This type of changes has been detected in the cases of other systems,
and has been assigned to a structural rearrangement which occurs simultaneously with a partial
deprotonation and dehydration of polymer layer. Further charging results in anion incorporation
and deprotonation again. The EQCN technique can resolve the events occurring under the wide
voltammetric wave, and these results reveal that the charge compensating processes are more
complicated than that are usually expected. Therefore, at least three consecutive processes can be
considered despite the single pair of peaks that appears in the current response.
A direct way to monitor the ion exchange processes can be achieved by radiotracer technique.
Using the radiotracer method, the strength of the ion–polymer interactions can also be studied,
which is certainly a special advantage of this technique. When unlabeled species are added to the
solution phase in great excess, the sorbed species are exchanged provided that there are no strong
interactions (chemical bonds) between the ions or molecules and the polymer. At a given potential
the mobility of the ions can be tested (Fig. 20).
Figure 20. The exchange of labeled SO42- ions sorbed in polypyrrole film with unlabeled SO42- ions added to a
solution phase containing 10−5 mol dm−3 35S-labeled H2SO4 and 10−2 mol dm−3 HClO4 at the moment indicated
by the arrow. E = 0 V. Final H2SO4 concentration: 2×10−2 mol dm−3 [33]
The results presented in Fig. 20 attest that ions embedded in polypyrrole (PP) film are mobile,
despite the fact that the interactions between PP and SO42- are much stronger than those between
PP and ClO4- ions, since ClO4- ions are present at a concentration that is three orders of magnitude
greater.
The periodical sorption/desorption of Cl− ions during four consecutive potential cycles in the case
of a polypyrrole electrode can be seen in Fig. 21. As expected Cl− ions enter the PP film during
oxidation and leave it during reduction.
A comparison of the data obtained by radiotracer and piezoelectric nanogravimetric techniques
(EQCN) is especially useful, because the latter supplies information on the total surface mass change
due to the deposition or sorption of different species, while the contributions originating from the
different species can be unambiguously separated by labeling the respective molecules or ions.
doi:10.5599/jese.448 19
Figure 21. The change in the amount of Cl− ions in a polypyrrole electrode during four consecutive oxidation-
-reduction cycles. Solution: 2×10−4 mol dm−3 36Cl-labeled HCl. Scan rate: 0.4 mV s−1. [33]
Recently, a new software controlled electrochemical measuring system for the simultaneous
measurements of surface mass changes and optical absorbance spectra has been developed [34].
By using an EQCN, extremely useful quantitative information about electrode processes such as
adsorption, deposition and dissolution, ion and solvent exchange between the surface film and the
solution can be obtained. However, by using EQCN only the total mass change can be measured
even in the case of ideal behavior. Therefore, one can draw reliable conclusion concerning the
mechanism, if the nature of the intermediates and products of the electrochemical reactions will be
determined by an independent technique. If the formed products or intermediates are colored
species, spectroelectrochemistry is a plausible choice. The simultaneous use of the EQCN technique
with spectroscopic UV-VIS measurements certainly helps to solve this problem (Fig. 22).
Figure 22. Absorbance of the polyaniline layer during a single anodic potential scan. Bare ITO crystal was
taken as reference. Scan rate: 10 mV s-1, electrolyte: 0.1 mol dm-3 H2SO4, caniline = 0.01 mol dm–3 [34]
Polymeric (polyelectrolyte) properties

Effect of temperature. Difference between redox and conducting polymers
The increase of temperature enhances the chain and segmental motions, therefore a more
reversible, surface cyclic voltammetric behavior can be observed due to the more effective electron
transport (Fig. 23). Of course, the rate of the counter-ion’s motion also increases, however, in the
case of redox polymers the polymeric motion and consequently the rate of the electron hopping is
usually the rate-determining process.
20
In the case of intrinsically conducting polymers usually the intrachain electron transport is
dominating, and consequently the temperature has no or a minor effect on the cyclic
voltammograms (Fig. 24). Albeit in the case of polyaniline at higher pH values a strange effect can
be observed, i.e., shift of the voltammetric wave occurring at more positive potentials. It is related
to the temperature dependence of the protonation constant of the weak base, therefore similar
phenomenon appears with pH variation (Fig. 25).
Figure 23. Cyclic voltammograms of a poly(tetracyanoquinodimethane) (TCNQ) electrode

(Γ= 5.1×10−8 mol cm−2) in contact with aqueous 10 mol / dm3 LiCl. Scan rate: 6 mV s−1.
Temperatures: (1) 22.5, (2) 34.2, (3) 43, (4) 50.5, (5) 61, and (6) 77 °C [35]
Figure 24. Temperature dependence of cyclic voltammetric response of a polyaniline film at different
temperatures. Temperatures: 1.5 (1), 4 (2), 13 (3) 29 °C (4); 1 mol dm−3 HCl pH = 0 v = 60 mV s-1 [36]
The electrochemical responses and also the change of other properties, e.g., color changes
remain still fast at rather low temperatures. This is of practical importance because it allows using
this system in electrochromic display devices at very low temperatures where the usual displays
based on liquid crystals fail (Fig. 26).
doi:10.5599/jese.448 21
Figure 25. Temperature dependence of cyclic voltammetric response of a polyaniline film at different
temperatures. Temperatures: 19 (1), 29 (2), 36 (3), 46 (4), 58 (5), 66 °C (6);
0.9 mol dm−3 Na2SO4 mol dm−3 + 0.2 NaHSO4 pH = 2.65 (lower part). v = 60 mV s-1 [36]
Figure 26. Temperature dependence of cyclic voltammetric response of a polyaniline film in contact with
moist acetonitrile containing 0.1 mol dm−3 H2SO4, 0.1 mol dm−3 tetrabutylammonium perchlorate and
0.01 mol dm−3 HCl (water content: 1.5 %) at different temperatures.
Temperatures: –42 (1), –36.5 (2), –31 (3), –26.5 (4), and –21 °C (5). v = 25 mV s-1 [36]
Effect of the electrolyte concentration

The swelling and shrinking of a polyelectrolyte gel are strongly affected by the concentration of
the contacting electrolyte solution and the temperature. Thermodynamic theory, which considers
three contributions to the free energy of the gel (i.e., mixing of constituents, network deformation,
and electrostatic interactions), predicts gel shrinkage as the salt concentration is increased. The
shrinking process usually occurs smoothly, but under certain conditions the process becomes
discontinuous, and the addition of a tiny amount of salt will lead to the collapse of the gel; i.e., a
drastic decrease in the volume to a fraction of its original value. These effects have strong influence
on the cyclic voltammograms especially in the case of redox polymers (Figs. 27 and 28).
In a more compact structure the rate of electron hopping may increase since the concentration
of redox sites is high; however, deterioration in the film’s permeability to the counter-ions due to
22
the decrease in the free volume is expected at the same time. The maximum observed in the peak
current versus salt concentration curve is the result of the balanced effects of the enhanced
electron-exchange process and the hindered counter-ion motion. The abrupt change in the free
volume of solvent-filled cavities causes a sharp decrease in the charge transport diffusion
coefficient. A rigorous theoretical treatment which takes into account the extension and contraction
of the polymer chain as it is electrochemically converted into a polyelectrolyte is very difficult if not
impossible due to the complexity of the polyelectrolyte systems and the lack of an appropriate set
of data. These effects were modeled in an empirical approach by scaling the concentration of
electroactive sites in the polymer film and the effective charge transport diffusion coefficient (Dct)
with cs1/2 [4, 37].
Figure 27. Cyclic voltammograms of a Figure 28. Cyclic voltammograms of a poly(tetra-

poly(tetracyanoquinodimethane) electrode in cyanoquinodimethane) electrode in contact with
contact with lithium chloride solutions of different calcium chloride solutions of different concentra-
concentrations: (1) 0.625, (2) 1.25, (3) 2.5, (4) 5.0 tions: (1) 0.15, (2) 0.31 (3) 0.625, (4) 1.25, (5) 2.5,
and (5) 10.0 mol dm−3. Scan rate: 60 mV s−1 [37] (6) 5.0 mol / dm3 CaCl2. Scan rate: 25 mV s−1 [37]
By employing the empirical equations:
c  Z (1  Bcs1 / 2 ) (1)
and
Dct  Dct0 (1  H ' c) (2)
semi-quantitative description of the effect of concentration on peak currents and peak potentials
has been obtained. Dcto is the effective diffusion coefficient of charge transport through the polymer
doi:10.5599/jese.448 23
film in the absence of the addition of supporting electrolyte; Z, B, and H' are empirical parameters
characteristic of the system under study. The values of these parameters depend on the nature of
the solvent, on the counter-ions (their size and charge), and the polymer forming the film.
Combining (1) and (2) with the Randles–Ševčík equation, as well as the appropriate Nernst equation,
gives the relationships:

Ip  Ki 1  H 1  Bcs1 / 2  1  Bc 
1/2 1/2
s
(3)
and
Ep  K E 
RT
zF

ln cs 1  H 1  Bcs1 / 2 1/2
 (4)
where
K i  2.69 x 105 Dcto1/2 Av 1 / 2 Z and H = ZH'
RT
K E  E c
'  ln K  0.0285 .
zF
The constant in the equation of the peak current (Ki) includes the quantities in the Randles–
Ševčík equation; i.e., A is the electrode area, v is the scan rate, and the charge number of the
electrode reaction is assumed to be 1. The constant in the equation of the peak potential (KE)
contains the formal potential ( E c ' ) and the formation constant of the salt, ion pair, or complex (K).
+0.0285 V and −0.0285 V, respectively, have to be used for the anodic and cathodic peak potentials.
Where a + or a − sign appears before the term of (RT / zF) lnK depends on the type of ions exchanged.
When counter-ions enter the polymer film it is + for reduction and − for oxidation, respectively. For
instance, for the reduction of TCNQ the sign is positive. However, when co-ions leave the film, the
opposite sign applies, i.e., during oxidation the sign is positive. The most remarkable conclusion of
these calculations is the fact that the variation in the Ip and Ep values with cs can be described with
the same set of parameters for a given system. In addition, the variation in Z, which is characteristic
of the chemical structure of the film, B, which in turn is linked to the swelling (solvent–polymer and
ion–polymer interactions) and H, which expresses how the permeability of the film depends on the
sizes of the penetrating ions and the solvent-filled cavities (the free volume in the film), exhibited
rather reasonable, systematic changes as the solvent was replaced with a better one or univalent
ions were substituted for bivalent ones.
Hysteresis and relaxation phenomena
Despite the quasi-equilibrium character of the cyclic voltammetric curves, a pronounced
hysteresis (i.e., a considerable difference between the anodic and cathodic peak potentials)
appears. Slow heterogeneous electron transfer, effects of local rearrangements of polymer chains,
slow mutual transformations of various electronic species, first-order phase transition due to an S-
shaped energy diagram (e.g., due to attractive interactions between the electronic and ionic
charges), dimerization, and insufficient conductivity of the film at the beginning of the anodic
process have been proposed as possible explanations for the hysteresis (Fig. 29).
Owing to the long relaxation times characteristic of polymeric systems, the equilibrium or steady-
state situation is often not reached within the time-scale of the experiment. Fig. 30 shows the
change in the resistance of polyaniline after potential steps. The achievement of a constant
resistance value takes a rather long time, especially during the conducting-to-insulating transition.
24
Figure 29. The change in the resistance of a polyaniline film in contact with 1 M H2SO4 as a function of the
potential [7]. Arrows indicate the anodic and cathodic directions of the measurements, respectively
Consequently, even slow sweep rate cyclic voltammetry does not supply reliable thermodynamic
quantities that can otherwise be derived by analyzing the changes in the peak potentials. It is even
more striking when the mass change is followed after potential steps. Due to the limited rate of the
ion transport and especially the slower solvent transports the constant swelling is achieved often
after tens of minutes [38].
Figure 30. The current transients and the respective resistance–time curves obtained after performing
potential steps (a) from 0.2 to 0.15 V and (b) from 0.15 to 0.2 V for a PANI electrode in contact with
2 mol dm−3 H2SO4 [7]
While the effect of potential-induced relaxation phenomena has been studied extensively, less
effort has been expended in exploring the effect of temperature. One notable exception is a
temperature shock experiment on a poly(tetracyanoquinodimethane) electrode. It was found that
when the electrode returned from elevated temperature to room temperature, a relatively long
time (>30 min) was needed to restore the original room-temperature voltammetric response, as
seen in Fig. 31.
Apparently, the polymer adopts an extended, perhaps solvent-swollen conformation at elevated
temperatures that requires a long time to revert back to the room temperature structure. Such
behavior is observed in studies of polymer gels, where varying the temperature results in the
hysteresis of macroscopic polymer properties such as swelling, elasticity, turbidity, and so forth.
doi:10.5599/jese.448 25
Figure 31. Cyclic voltammograms obtained for a

poly(tetracyanoquinodimethane) electrode in contact
with 10 M LiCl at (1) 69 °C and (2–6) after rapid cooling
at 22 °C, recorded after delays of (2) 4, (3) 9, (4) 13.5,
(5) 22.5, and (6) 38.5 min [39]
Break-in and first cycle effects

For a range of neutral polymer films freshly deposited on metal substrates by solvent evaporation
techniques several potential sweeps are required for the films to become fully electroactive. This
phenomenon has been referred as the break-in effect. The break-in effect is attributed to the
incorporation of solvent molecules and ions into the film phase during electrolysis, as well as to
potential-dependent morphological changes. The rate of the diffusive transport of solvent mole-
cules depends on the structure of the polymer and the motion of polymer segments. In crystalline
and crosslinked polymers, or below the glass transition temperature, the movement of the
incorporating species may be rather slow. On the other hand, solvent molecules act as plasticizers,
and therefore increase the rate of diffusion for both neutral and ionic species inside the film.
The first cycle or waiting time effects (where the shapes of the cyclic voltammograms and the
peak potentials depend on the delay time at potentials at which the polymer is in its neutral / dis-
charged state: see also as “secondary break-in”) have been interpreted in terms of slow morpho-
logical changes and / or the difficulty removing the remaining charges from insulating surroundings.
Figure 32. “Break-in effect,” as observed in cyclic voltammetric and simultaneous EQCN measurements
performed with a virgin and thick poly(tetracyanoquinodimethane) electrode. Γ = 7×10−8 mol cm−2.
Electrolyte: 2.5 M LiCl. Scan rate: 6 mV s−1. a) Consecutive cyclic voltammograms; b) simultaneously
obtained EQCM frequency curves [40]
26
Figure 33. Cyclic voltammograms (two cycles) a) and the simultaneously detected EQCN frequency changes
b) for a polyaniline film (L = 2.9 μm) in contact with 1M H2SO4. Scan rate: 100 mV s−1 [38]
Charging/discharging (or redox switching) processes are usually fast, but are rather complex in
nature. The steady-state cyclic voltammograms in the case of polyaniline exhibit a combination of
broad anodic and cathodic peaks with a plateau in the current at higher potentials (Fig. 33). The
current is proportional to the scan rate, i.e., from an electrical point of view the film behaves like a
capacitor, however, this simple result is the consequence of a complicated phenomenon which
includes a faradaic process (the generation of charged electronic entities at the polymer chains near
the electrode surface by electron transfer to the metal), the transport of those species throughout
the film, as well as the ion exchange at the film│solution interface. A closer inspection of the curves
of Fig. 33 reveals two effects of importance. First, the so-called first-cycle effect, i.e., the first anodic
cycle after starting the investigation of a virgin film or after a long waiting time at negative potentials
where the polymer is its reduced state, differs from the subsequent ones. The main reason is the
incorporation of ions and solvent molecules, and the transformation and relaxation of the structure
of the polymer layer. Second, at pH 0 in the beginning of the oxidation the mass change is minor,
although a substantial amount of charge has already been injected. The low mass change is due to
the low molar mass of H+ ion, which is the species that leaves the surface layer. The incorporation
of the anions, which have a much higher molar mass, clearly manifests itself in the observed EQCN
frequency decrease in a later phase of oxidation at higher anodic potentials. Owing to the very high
repulsion forces between the nearest-neighbor sites in the polymer chain, it is unfavorable that
protons on the nitrogen atom and the benzenoid ring filled with a hole (polaron) should exist next
to each other simultaneously. Consequently, deprotonation is a necessary process when positive
charges are injected into the polymer.
Characterization
The complete characterization of conducting polymer and composite films, layers, membranes
etc. includes the determination of all electrochemical properties (formal potential of the redox
reaction, charge storage capacity, rates of electron transfers, rates of ionic and electronic charge
transport processes, rate of solvent transport and phase equilibria, the mechanism and kinetics of
the electrochemical-chemical reactions, the film morphology and all the useful properties, e.g., the
changes of color or conductivity. In order to achieve this goal usually several experimental
techniques and their combination are needed as it had been mentioned. Furthermore, it is always
worth to apply the variation of experimental conditions because in this, relatively simple way
essential information can be obtained about the reaction mechanism, different interactions
doi:10.5599/jese.448 27
between the polymer and the ions and molecules present. Two examples will be shown: the effect
of the nature of electrolyte and the pH dependence.
Already the cyclic voltammograms reveal the strength of interaction between the polymer and
the counter-ions but by using combined methods e.g., EQCN, the transport and sorption of ions and
solvent molecules can be understood by the help of such easy experiments.
Poly(vinylferrocene) is more swollen in the presence of SO42- ions than in NO3- or ClO4-- containing
electrolytes. This means that the different anions enter the film together with their hydration
spheres, since the magnitude of the mass change is as follows: sulfate > nitrate > perchlorate. This
corresponds to the order of degree of hydration of these anions. On the other hand, the ion-pair
formation constant for the oxidized sites and the ClO4- - ions is greater than that for NO3- or SO42-
ions, which is reflected in the more positive formal potential of the ferrocene/ferricenium redox
couple in Na2SO4 or NaNO3 solutions compared with NaClO4 electrolyte, as seen in Fig. 34. The more
pronounced swelling also reflects the more extensive interaction between water and the charged
ferricenium sites in the presence of SO42- - or NO3- - compared to ClO4- -containing electrolytes.
Figure 34. Cyclic voltammograms (a) and the simultaneously recorded EQCN curves (b) for an
electrochemically deposited poly(vinylferrocene) film in contact with (1) NaClO4; (2) NaNO3; and (3)
Na2SO4│H2SO4 pH 3.4, respectively. Electrolyte concentration: 0.5 mol dm−3. Scan rate: 10 mV s−1. [40]
Because the polymers under study are organic compounds and/or contain groups available for
protonation the execution of the experiments at different pH values is inevitable since the electron
transfer steps are accompanied by protonation or deprotonation. As an example, the cyclic
voltammograms obtained at different pH values in sulfate electrolytes for a poly(copper
phthalocyanine) [poly(CuPc)] layer are presented (Fig. 35). It is evident that H+ ions participate in
the redox processes since with increasing pH the voltammetric peaks shift into the direction of the
more negative potentials by ‒65 ± 5 mV/pH. Therefore, we can conclude that the redox reaction of
poly(CuPc) is basically a 1 H+/1 e- or 2 H+/2 e- reaction. Albeit this reaction is much more complicated,
and the electron transfers are accompanied with dimerization and morphological changes, the pH
dependence serves as a starting point [41].
28
Figure 35. Au│poly(CuPc) electrode in

contact with sulphate electrolytes (H2SO4
or H2SO4 + Na2SO4 or Na2SO4 + NaOH)
pH values: 0.3 (1), 1.18 (2), 2.17 (3) 2.57,
(4), 7.8 (5), 11.1 (6) and 12.7 (7). Scan
rate: 10 mV s-1. The total concentration
of the sulfate ions was kept practically
constant at 0.5 mol dm-3 [41]
Applications
Material Properties of Conducting Polymers
Electronically conducting polymers can be prepared from cheap compounds such as aniline,
pyrrole, thiophene and their derivatives by relatively simple chemical or electrochemical polyme-
rization processes. Redox polymers are also applied in special cases, such as in biosensors or elec-
trochromic display devices. Redox processes combined with the intercalation of anions or cations can
therefore be used to switch the chemical, optical, electrical, magnetic, mechanic and ionic properties
of such polymers. These properties can be modified by varying the anion size and preparation
techniques; by including other chemical species for example. A qualitative summary of the
relationship between the properties of a conducting polymer and its charge state is given in Table 1.
Table 1. Qualitative properties of conducting polymers that conduct in their oxidized state, as a function of
their charge state [6]
Properties/Charging state Reduced Oxidized

Stoichiometry without anions (or: with cations) with anions (or without cations)
Content of solvent smaller higher
Volume smaller higher
Color transparent or bright dark
Electronic conductivity insulating, semiconducting semiconducting, metallic
Ionic conductivity smaller high
Diffusion of molecules dependent on structure
Surface tension hydrophobic hydrophilic
Typical areas in which conducting polymers are applied can be described using a double
logarithmic plot of ionic resistance versus electronic resistance, as shown in Fig. 36.
The positions of ideal metals, semiconductors and insulators in the diagram are shown at the top.
Constant properties exist at high ionic resistances, i.e., towards the top of the diagram. Here, ICPs
can be applied in the dry state in an inert atmosphere. Contact with an electrolyte leads to a much
wider field of applications, depending on the specific ionic and electronic resistances associated with
the charge state, such as in batteries, displays, sensors, etc.
doi:10.5599/jese.448 29
Figure 36. Double logarithmic plot of

ionic resistance versus electronic
resistance for conducting polymers,
showing areas of application [6]
Gas sensors
Gas sensors made of conducting polymers have high sensitivities and short response times, and
—a great advantage compared with most commercially available sensors based on metal oxides—
work at room temperature. The sensing principles employed in gas sensors using conducting
polymers as active sensing materials vary. The principle used depends on the variables (resistance,
current, absorbance, mass, etc.) measured and the type of interaction between the gas (analyte)
and the polymer. The oxidation state (the charge or doping level) of the polymer is altered by the
transfer of electrons from the analyte to the polymer, which causes a change in the properties
(resistance, color, work function, etc.) of the polymer.
For instance, electron-donor gases such as NH3 increase the resistance of polyaniline (PANI)
because the electrons transferred neutralize the positive sites (polarons), and the polymer becomes
neutral. Interestingly this is a reversible process; after flushing the polymer with air, the conductivity
of the polymer (sensing layer) is recovered (Figs. 37-39).
Figure 37. Layout designs of thin-film and thick-film polymer gas sensors [42]
30
Figure 38. The response of a PANI gas sensor (relative resistance vs. time curves at 20 oC). 10 ppm ammonia
was injected into the air at times indicated by the arrows. The total concentrations were: (1) 0, (2) 10, (3)
20, (4) 30, (5) 40, (6) 50 ppm; and (7) after flushing with clean air again [43]
Figure 39. The response of a PANI ammonia sensor (log relative resistance–gas concentration plot) for
different gases and vapors: (1) ammonia; (2) methanol; (3) ethanol; (4) CO; and (5) NO; at room
temperature [43]
Other sensors and biosensors

The use of conducting polymers as amperometric sensors, where the detection signal is amplified
due to the catalytic properties of the polymer and / or built-in catalytic entities, is straightforward,
although the application of these systems as ion-selective electrodes in potentiometry is
problematic because redox state and acid–base or ionic equilibria need to be controlled
simultaneously.
Poly(methylene blue) is a very good catalyst for the oxidation of hemoglobin. This property has
been utilized in an amperometric sensor (see Figs. 40 and 41). A good correlation was found
between the results of the electrochemical method and those of the spectrophotometric
cyanidation analysis method, which is used in clinical practice as a standardized protocol [44].
doi:10.5599/jese.448 31
Figure 40. Chronoamperometric responses for consecutive injections into a flow cell of samples of whole
blood diluted 1:10 in phosphate buffer (pH 6.24) and 0.5 mol dm−3 NaCl on a poly(methylene blue) electrode
at E = 0.4 V vs. SCE. Flow rate: 4 ml min−1. The tall and short waves are the responses to 6 cm3 and 4 cm3
dilute solutions, respectively [44]
Figure 41. Comparison between electrochemical and cyanidation methods for the analysis of blood samples
provided by five donors. Blood samples 2 and 3 were from females, while 1 and 4 were from male patients.
Patients 1–4 were healthy, while patient 5 was a potentially ill donor. Experimental conditions were the
same as for Fig. 40 [44]
Electrochromic display devices
Figure 42. Photos of a PANI-based flexible electrochromic display device containing 25 pixels. The display
region and the connections were made by depositing gold on a plastic sheet using an appropriate mask and
an evaporation technique. Each pixel can be driven separately. Left: PANI is in its oxidized state in all pixels.
Right: PANI is reduced in two pixels (the bleached ones)
32
Due to its many advantageous properties (low cost, fast color change, good contrast, stability,
etc.), PANI is also a favorite material for use in electrochromic display devices. Pictures of a PANI-
based flexible device are shown in Fig. 42. The display pattern, which consists of 25 pixels and the
connections that allow each pixel to be driven separately, was fabricated by depositing gold onto a
plastic sheet. Another plastic sheet covers the display. The electrochemical switching is executed
using a counter electrode, which also serves as a reference electrode, and an acidic gel electrolyte
is placed between the two sealed plastic sheets.
Supercapacitors
In electric and hybrid vehicles during acceleration a high power density is needed or in backup
power devices the fast response is crucial. Supercapacitors are ideal for these purposes, and that is
the very reason for the intense quest regarding electrode materials, which can meet the
requirements of reversibility, long-term stability, the high storage capacity and the fast
charging/discharging characteristics.
Among the different metal oxides, the properly prepared hydrous RuO2 shows the best
properties. Its commercial use is, however, hindered due its high cost and limited availability.
Another class of materials, which in principle is suitable for supercapacitor applications are the
electrically conducting polymers. These materials are cheap, show reversible redox behavior and
high capacitance, but their long-term stability is not good enough. The combinations of RuO2 with
conducting polymers seem to be a promising attempt to have a possible synergic effect, i.e.,
simultaneously improving the electron transport, stability and decreasing the cost. A simple method
resulting in a well-defined, well-dispersed RuO2–polyaniline composite on the electrode surface is
the use of the oxidation power of Ru (IV) that is the ability of RuO2 crystals attached to the electrode
surface to oxidize the aniline which process resulting in the formation of PANI on the external and
internal surfaces of RuO2 crystals [45]. The EQCN frequency decrease indicates the deposition of
polyaniline (Fig. 42). The reduced ruthenium sites can be regenerated by using short positive
potential pulses (Fig. 43).
Figure 42. (a) The EQCN frequency change vs. time curve (blue) observed for an Au│RuO2 electrode after the
addition of aniline into 0.5 M H2SO4 solution at open-circuit potential (0.85 V). The RuO2 has been oxidized
previously (current peak) [45]
The respective cyclic voltammograms and EQCN curves are displayed in Figs. 44-46. After the first
deposition step the response of the polyaniline appears, however, the response originating from
RuO2 dominates. Following further deposition steps the mass change during cycling also becomes
higher, however, in the potential region of the leucoemeraldine – emeraldine transition, i.e., from
doi:10.5599/jese.448 33
–0.1 to 0.15 V the frequency change is mostly due to processes occurring simultaneously with the
oxidation of the lower valence Ru sites. In acid media the EQCN response of the PANI is minor
because only deprotonation takes place, and H+ ions leave the surface phase. On the other hand,
after the peak the incorporation of anions manifests itself in a frequency decrease. The effect of
PANI is even better seen when a more positive switching potential is applied. At more positive
potentials the second pair of waves due to the transition of the emeraldine form to pernigraniline
form is nicely seen. In this case the redox transformation is accompanied by the desorption of anions
and H+ ions which causes a substantial mass loss.
Figure 43. The continuation of the experiment presented in Fig. 42. The EQCN frequency change vs. time
curve observed for the Au│ RuO2 electrode after two additional reoxidation pulses [45]
4999.46
0.15
-1
5 mV s
0.10
4999.44
0.05
f / kHz
I / mA
4999.42
0.00
-0.05 4999.40
-0.10
4999.38
-0.1 0.0 0.1 0.2 0.3 0.4 0.5
E / V vs. SCE
Figure 44. Cyclic voltammogram (red) and the Figure 45. Cyclic voltammogram (red) and the si-
simultaneously obtained EQCN frequency response multaneously obtained EQCN frequency response
(blue) for the Au│ RuO2 + PANI electrode prepared (blue) for the Au│ RuO2 + PANI electrode after three
above. Scan rate: 5 mV s-1, Potential range: successive activation pulses. Scan rate: 5 mV s-1,
–0.15 – 0.5 V. Electrolyte: 0.5 M H2SO4 [45] Potential range: –0.15 – 0.5 V.
Electrolyte: 0.5 M H2SO4 [45]
Fig. 46 shows the cyclic EQCN responses by using an extended potential range at pH 3.5.
One of the important features of the RuO2/PANI composite is that the electrochemical activity of
the polyaniline is remarkably preserved at higher pH values even at pH 7 a reasonable capacitive
response can be obtained. For the RuO2 samples used in this study in contact with 0.5 M H2SO4
solution the specific capacitance was found to be 540  40 F g-1 in the potential range of –0.1 and
0.85 V at a scan rate of 20 mV s-1. By PANI deposition, the specific capacitance can be increased as
high as by 50 % without practical deterioration of the response time or stability. After successive
34
cycling in sulfuric acid the capacitance loss is not higher than 10-15 % after 1000 cycles. Even in
some cases there is an increase of capacitance during cycling which is most likely due to the
completion of hydration and sorption of electrolyte which enhances the ionic charge transfer in the
pores of RuO2 and polyaniline.
Figure 46. Cyclic voltammogram (red) and the simultaneously obtained EQCN frequency response (blue) for
the Au│ RuO2 + PANI electrode after three successive activation pulses. Scan rate: 50 mV s-1,
Potential range: - 0.15 – 0.9 V. Electrolyte: 0.5 M H2SO4 + Na2SO4 pH 3.5 [45]
New trends
In the last two decades the researchers have started to apply novel approaches. The new trend
is the fabrication of composites including nanocomposites of polymers and other materials such as
carbon nanotubes, graphene or inorganic compounds having special structure and properties. In
sensors and biosensors of different kinds (conductometric, impedimetric, potentiometric,
amperometric and voltammetric) conducting polymers are used as active, sensing or catalytic layers,
however, in the majority of applications those serve as matrices entrapping enzymes or other
biologically active compounds. The biocompatibility of several conducting polymers provides
opportunity for the application in medicine as artificial muscles and limbs, as well as artificial nerves.
The biomimetic (bionic) applications certainly will continue in the future. Microsystem technologies
have been replacing by nanosystem technologies. More sophisticated and combined techniques
have been developed, and have become widespread tools in the laboratories all around the world;
e.g., scanning microscopies, or the new versions of electrochemical quartz crystal nanobalance.
In the recent years we have reached a deeper level of understanding of the behavior of these
systems that we can use to improve the performance of the devices based or use conducting
polymers. The improvement occurs either by a fine-tuning of already promising systems or by using
more sophisticated compositions and structures. Less often a quest of entirely novel applications
has also been reported, however, most of the directions have already been set out 10-30 years ago.
The use of the derivatives of the monomers or copolymerization of different monomers may be an
option to obtain conducting polymers, which are more flexible or rigid or even crystalline for e.g.,
heterojunction solar cells, as well as which are mechanically and chemically more stable, have a
more advantageous processability etc. The functionalization of conducting polymers, which leads to
smart materials interacting and responding to their environment, is also a great opportunity. The
preparation of self-doped polymers is also a good way to overcome the problems of the ionic charge
doi:10.5599/jese.448 35
transport during redox switching and other limitations of the use of the polymer. The other
possibility is a combination of the arsenal of materials science with chemistry (electrochemistry) to
improve the properties for special purposes. Nanocomposites, hybrid materials based on
conducting polymers certainly become and will be important materials in the future. There is a high
expectation concerning electroconducting nanomaterials such as nanofibers, nanorods and other
nanostructures based on the supramolecular self-assembly of conducting polymers, e.g., in the
enhancement of the photoluminescence efficiency by utilization of the energy and charge transfer
effect in surface resonance coupling. Manipulation of the microstructures of polymers may improve
the performances of both the polymer-based transistors and electrochemical cells. There will be
tasks for the chemists, electrochemists in the production and characterization of new materials, for
the theoreticians to explain the phenomena observed or will be observed and to predict new
opportunities, and also engineers to give a final form of the devices. The conducting polymers are
relatively cheap materials; however, the specially improved properties can give a further boost
concerning the mass production, which makes the products much less expensive. For instance,
making ink from conducting polymers opens up new horizons for printing sensors, electronic
circuits, solar cells, light emitting displays etc. The new trends can nicely be followed by studying the
literature including papers and the topics of conferences.
Conclusions
Based on the review of the achievements during the last 40 years we can draw the conclusion
that the development in the field of conducting polymers is unbroken, and we still expect new
discoveries and novel utilizations in several areas such as energy storage and power sources,
photovoltaics, health care, and different technologies.
References
[1] G. Inzelt, Recent advances in the field of conducting polymers. Journal of Solid State Electrochemistry
21 (2017) 1965–1975.
[2] G. Inzelt, Conducting polymers - A new era in electrochemistry, 2nd edn. In: F. Scholz (ed) Monographs
in electrochemistry, Springer, Heidelberg, Berlin, Germany, 2012.
[3] G. Inzelt, Journal of Solid State Electrochemistry 15 (2011) 1711-1718.
[4] G. Inzelt: Mechanism of Charge Transport in Polymer Modified Electrodes, In: Electroanalytical
Chemistry, A Series of Advances, A.J. Bard (ed.), Vol. 18, Marcel Dekker, Inc., New York, USA, 1994.
pp. 89-241.
[5] G. Inzelt, Charge transport in polymer modified electrodes, Encyclopedia of Electrochemistry, A.J.
Bard, M. Stratmann (eds.) Functions and applications of modified electrodes Vol. 10, I. Rubinstein, J.
Rusling, M. Fujihara (eds.), Weinheim, Wiley-VCH, 2007. Ch. 9, pp. 651-683.
[6] G. Inzelt, M. Pineri, J.W. Schultze, M.A. Vorotyntsev, Electrochimica Acta 45 (2000): 2403-2421.
[7] E. Csahók, E. Vieil, G. Inzelt, Journal of Electroanalytical Chemistry 482 (2000) 168-177.
[8] G. Inzelt, E. Csahok,V. Kertész, Electrochimica Acta 46 (2001) 3955-3962.
[9] H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chiang, A. J. Heeger, Journal of Chemical Society
Chemical Commununications (1977) 579-580.
[10] C. K. Chiang, C. R, Fischer, Y.W. Park, A. J. Heeger, H. Shirakawa, E. J. Louis S. C. Gau, A. G.
MacDiarmid, Physical Review Letters 39 (1977) 1098-1101.
[11] C. K. Chiang, M. A. Druy, S. C. Gau, A. J. Heeger, E. J. Louis, A. G. MacDiarmid, Y. W.Park, H. Shirakawa,
Journal of American Chemical Society 100 (1978) 1013-1015.
[12] H. Shirakawa Angewandte Chemie International Edition 40 (2001) 2574-2580.
[13] A. G. MacDiarmid, Angewandte Chemie International Edition 40 (2001) 2581-2590.
[14] A. J. Heeger, Angewandte Chemie International Edition 40 (2001) 2591-2611.
[15] H. Letheby Journal of Chemical Society 15 (1862) 161-163.
36
[16] J. Fritzsche, Journal für praktische Chemie, 20 (1840) 453–457.

[17] N. E. Khomutov, S. V. Gorbachev Zhurnal Fizichekoi Khimii 24 (1950) 1101-1106.
[18] D. M. Mohilner, R. N. Adams, W. J. Argersinger, Journal of Electrochemical Society 84 (1962) 3618-
3622.
[19] R. deSurville, M. Josefowicz, L. T. Yu, J. Perichon, R. Buvet, Electrochimica Acta 13 (1968) 1451-1458.
[20] A. F. Diaz, J. A. Logan, Journal of Electroanalytical Chemistry 111 (1980) 111-114.
[21] G. Inzelt, G.G. Láng: Electrochemical Impedance Spectroscopy (EIS) for Polymer Characterization In:
Electropolymerization (eds. S. Cosnier and A. Karyakin) Wiley-VCH, Weinheim, Germany, 2010, pp. 51-
76.
[22] Electroanalytical Methods, Guide to Experiments and Applications 2nd, revised and extended edition
(ed. F. Scholz), Springer-Verlag, Berlin Heidelberg, 2010.
[23] Cs. Visy, In situ combined electrochemical techniques for conducting polymers, Springer, Berlin,
Heidelberg, 2017.
[24] G. G. Láng, C. A. Barbero, Laser techniques for the study of electrode. In: F. Scholz (ed) Monographs in
electrochemistry. Springer, Berlin, Heidelberg, 2012.
[25] J. Heinze, B. A. Frontana-Uribe, S. Ludwigs, Chemical Reviews 110 (2010) 4724-4771
[26] Electropolymerization (eds. S. Cosnier and A. Karyakin) Wiley-VCH, Weinheim, Germany, 2010.
[27] B. B. Berkes, Á. Nemes, C. E. Moore, F. Szabó, G. Inzelt, Journal of Solid State Electrochemistry 17
(2013) 3067–3074.
[28] S. Pruneanu, E. Csahók, V. Kertész, G. Inzelt, Electrochimica Acta 43 (1998) 2305-2323.
[29] B. B. Berkes, G. Inzelt, E. Vass, Electrochimica Acta 96 (2013) 51-60.
[30] B. B. Berkes, G. Inzelt, Electrochimica Acta 122 (2014) 11-15.
[31] B. B. Berkes, A. S. Bandarenka, G. Inzelt, Journal of Physical Chemistry C – Nanomaterials and
Interfaces 119 (2015) 1996-2003.
[32] G. Inzelt, R.W. Day, J.F. Kinstle, J.Q. Chambers, Journal of Physical Chemistry 87 (1983) 4592-4598.
[33] G. Inzelt, G. Horányi, Journal of Electroanalytical Chemistry, 230 (1987) 257-265.
[34] B. B. Berkes, S. Vesztergom, G. Inzelt, Journal of Electroanalytical Chemistry 719 (2014) 41–46.
[35] G. Inzelt, L. Szabó, J. Q. Chambers, R. W. Day, Journal of Electroanalytical Chemistry, 242 (1988) 265-275.
[36] G. Inzelt, Journal of Electroanalytical Chemistry, 279 (1990) 169-178.
[37] G. Inzelt, J. Q. Chambers, J. Bácskai, R. W. Day, Journal of Electroanalytical Chemistry, 201 (1986) 301-
314.
[38] G. Inzelt, Electrochimica Acta 45 (2000) 3865-3876.
[39] J. Bácskai, G. Inzelt, Journal of Electroanalytical Chemistry 310 (1991) 379-389
[40] G. Inzelt, J. Bácskai, Electrochimica Acta 37 (1992) 647-654.
[41] K. Borsos, G. Inzelt, Journal of Solid State Electrochemistry 19 (2015) 2565–2577.
[42] G. Harsányi, M. Réczey, R. Dobay, I. Lepsényi, Zs. Illyefalvi – Vitéz, J. Van den Steen, A. Vervaet, W.
Reinert, J. Urbancik, A. Guljajev, Cs. Visy, Gy. Inzelt, I. Bársony, Sensor Review, 19 (1999) 128 – 134.
[43] I. Lepcsényi, A. Reichardt, G. Inzelt, G. Harsányi, Proceeding of 12th European Microelectronics and
Packaging Conference, Harrogate, UK, 1999. pp. 301-305.
[44] C. M. A. Brett, G. Inzelt, V. Kertesz, Analytica Chimica Acta, 385 (1999) 119-123.
[45] S. Sopcic, M. Kraljic-Rokovic, Z. Mandic, G. Inzelt, Journal of Solid State Electrochemistry, 14 (2010)
2021-2026.
©2017 by the authors; licensee IAPC, Zagreb, Croatia. This article is an open-access article
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(http://creativecommons.org/licenses/by/4.0/)
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Open Access : : ISSN 1847-9286

Conducting polymers: past, present, future

Figure 2. UV–VIS–NIR spectra of PANI obtained in situ at different potentials:

Definition and classification

Preparation of conducting polymers

Redox transformations and the accompanying processes

Polymeric (polyelectrolyte) properties

Figure 23. Cyclic voltammograms of a poly(tetracyanoquinodimethane) (TCNQ) electrode

Effect of the electrolyte concentration

Figure 27. Cyclic voltammograms of a Figure 28. Cyclic voltammograms of a poly(tetra-

By employing the empirical equations:

Figure 31. Cyclic voltammograms obtained for a

Break-in and first cycle effects

Figure 35. Au│poly(CuPc) electrode in

Properties/Charging state Reduced Oxidized

Figure 36. Double logarithmic plot of

Other sensors and biosensors

Electrochromic display devices

[16] J. Fritzsche, Journal für praktische Chemie, 20 (1840) 453–457.

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