Electron and Proton Conducting Polymers PDF

Electrochimica Acta 45 (2000) 2403 2421 www.elsevier.
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Electron and proton conducting polymers: recent developments and prospects

G. Inzelt a,*, M. Pineri b, J.W. Schultze c, M.A. Vorotyntsev d
Department of Physical Chemistry, Eot6os Lorand Uni6ersity, Budapest 112 PO Box 32, H-1518, Hungary b CENG Grenoble Cedex 9, 38054 France c AGEF e.V.-Institut an der Heinrich-Heine-Uni6ersitat Dusseldorf, D-40225 Dusseldorf, Germany d Labatoire LSEO, Faculte des Sciences Gabriel, LSEO-UMR 5632CNRS Uni6ersite de Bourgogne, 6 Boule6ard Gabriel, F-21000 Dijon, France
a
Papers received in Newcastle, 20 December 1999
Abstract The most important topics of the rapidly developing eld of conducting polymers are surveyed. Particular emphasis is laid on the problems of synthesis, structure, thermodynamics and kinetic behaviour of these systems. The relevant experiences, existing models and theories are outlined. Abundant examples of the growing applications are also discussed. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Conducting polymers; Thermodynamics; Models
1. Introduction Traditionally polymers were thought of as insulators and any electrical conduction in polymers was generally regarded as an undesirable phenomenon. The residual conductivity in common polymers can mostly be assigned to loosely bound protons. In the last decades an opposite trend has started inasmuch as examinations directed to the utilization of ionic conductivity of polymeric systems. The active research on thermodynamic and kinetic properties of ion conducting polymers has led to the wide use of polymer electrolytes and polyelectrolytes in electrochemical systems, e.g. in power sources, sensors, and the development of all-solid-state electrochemical devices [13]. Also in the 1970s somewhat surprisingly a new class of polymers possessing high electronic conductivity (electronically conducting polymers) in partially oxidized (or less frequently reduced) state has been discovered. Electrochemistry has
* Corresponding author. Tel.: +36-12090555; fax: +3612090602. E-mail address: inzeltgy@para.chem.elte.hu (G. Inzelt)
played a signicant role in the preparation and characterization of these novel materials. Electrochemical techniques are especially suitable for controlled synthesis of these compounds and for tuning of a well-dened oxidation state. The preparation, characterization and application of electrochemically active, electronically conducting polymeric systems are still in the foreground of research activity in electrochemistry. There are at least two major reasons for this intense interest. First is the intellectual curiosity of scientists that focuses on understanding the behaviour of these systems, in particular on the mechanism of charge transfer and charge transport processes occurring in the course of redox reactions of conducting polymeric materials. Second is the wide range of promising applications in the eld of energy storage, electrocatalysis, organic electrochemistry, bioelectrochemistry, photoelectrochemistry, electroanalysis, sensors, electrochromic displays, microsystem technologies, electronic devices, microwave screening and corrosion protection etc. Several excellent monographies have been published e.g. [1,2,4 9] mostly reviewing the knowledge accumulated
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regarding the development of polymer lm electrodes and their applications. These novel materials with interesting and unanticipated properties have attracted the whole scientic community including polymer and synthetic chemists [10], material scientists [10], organic chemists [11], analytical chemists [12], as well as theoretical and experimental physicists [10]. After 20 years the fundamental nature of charge propagation on the whole is understood, i.e. the transport of electrons can be assumed to occur via an electron exchange reaction (electron hopping) between neighbouring redox sites in redox polymers and by the motion of delocalized electrons through conjugated systems in the case of socalled conducting polymers (polyaniline, polypyrrole). (In fact, several conduction mechanisms, such as variable range electron hopping, uctuation-induced tunneling, have been considered). In almost every case, the charge is also carried by the motion of electroinactive ions during electrolysis, i.e. these materials constitute mixed conductors. Owing to the diversity and complexity of these systems, just to think of the chemical changes (dimerization, cross-linking, ion-pair formation etc) and polymeric properties (chain and segmental motions, changes in the morphology, slow relaxation), much research is still needed to achieve a detailed understanding of all processes related to the dynamic and static properties of several interacting molecules, which are conned in a polymer network. It is intended here to discuss the topics those are of the greatest interest at present and possibly in the future, to outline of some relevant experiences, existing models and theories, and last but not least to draw attention to the unsolved problems. It is hoped that despite the incompleteness and subjectivity this paper will be helpful to the colleagues who are interested in this quickly developing eld of science. Considering the pace of the ever growing applications of polymers in electrochemical cells it may be declared that electrochemistry is in transition from the bronze age (i.e. typically using metals) to the era of polymers.
2. Electron conducting polymers
2.1. Synthesis and structure

Polymers can be prepared by using chemical or electrochemical methods of polymerization. The majority of the redox polymers have been synthesized by chemical polymerization. Electrochemically active groups are either built in the polymer structure inside the chain or as a pendant group (pre-functionalized polymers), or incorporated into the polymer phase in the course of the polymerization, or xed at the polymer network in an additional step after the coating procedure (post-
coating functionalization) in the case of the polymer lm electrodes [1 12]. The latter approach is typical for ion-exchange polymers. Several other alternative synthetic approaches exist, in fact virtually the whole arsenal of synthetic polymer chemistry have been exploited. From the applied point of view the electrochemical polymerization of cheap, simple aromatic benzoid or nonbenzoid (mostly amines, e.g. aniline, o-phenylenediamine) and heterocyclic compounds (e.g. pyrroles, thiophenes, indoles, azines) is of utmost interest. The reaction is usually oxidative polymerization. Chemical oxidation [13 15] can also be applied (e.g. the oxidation of pyrrole by Fe(ClO4)3 leads to conducting polypyrrole), but electrochemical polymerization is preferable especially if the polymeric product is intended to use as a polymer lm electrode, thin layer sensor, in microtechnology etc. because the potential control is a precondition of the production of goodquality material and the polymer lm is formed at the desirable spot that serves as an anode during the synthesis. Chemical route is recommended if large amount of polymer is needed. The polymers are obtained in an oxidized, high conductivity state containing incorporated counterions from the solution used in the preparation procedure. It is easy to change the oxidation state of the polymer electrochemically e.g. by potential cycling between oxidized, conducting and the neutral, insulating state, or by using suitable redox compounds. In addition, the variation of the composition of the contacting solution or that of the gas may also lead to the change of conductivity. For instance, the increase of the pH of the solution [13,16] or the presence of an electron donor molecule (e.g. NH3) in the gas phase result in a decrease of the conductivity of polyaniline (PANI) or polypyrrole (PP) lms [17 19]. By further chemical reactions the structure and conductivity can be altered. The mechanism and the kinetics of the electropolymerization, especially in the case of polyaniline [13,14,20 44] and polypyrrole [45 63] have been investigated by many researchers since the rst reports [20,21,45]. Two points have been addressed, i.e. the chemical reaction mechanism and kinetics of the growth on a conducting surface. Owing to the chemical diversity of the compounds studied a general scheme cannot be given. However, it has been proved that the rst step is the formation of cation radicals. The further fate of this highly reactive species depends on the experimental conditions (composition of the solution, temperature, potential or the rate of the potential change, galvanostatic current density, material of the electrode, state of the electrode surface etc). In favorable case the next step is a dimerization reaction and then stepwise chain growth proceeds via association of radical ions (RR-route) or that of a cation radical with a neutral monomer (RS-route) [1,2,9,11,12]. Even there
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might be parallel dimerization reactions leading to different products or to the polymer of a disordered structure. The inactive ions present in the solution may play a pivotal role in the stabilization of the radical ions. Potential cycling is usually more efcient than potentiostatic method, i.e. at least a partial reduction of the oligomer helps the polymerization reaction. It might be the case if RS-route is preferred, and the monomer carries a charge, e.g. a protonated aniline molecule (PANI can be prepared only in acid media, at higher pH values other compounds, such as p-aminophenol, azobenzene, 4-aminodiphenylamine, are formed). A relatively high concentration of cation radicals should be maintained in the vicinity of the electrode. The radical cation and the dimers can diffuse away from the electrode, usually intensive stirring of the solution decreases the yield of the polymer production. The radical cations can react with the electrode or take part in side reactions with the nucleophilic reactants (e.g. solvent molecules) present in the solution. Usually the oxidation of the monomer is an irreversible process and takes place at higher positive potentials than that of the reversible redox reaction of the polymer. However, in the case of azines (e.g. 1-hydroxy-phenazine [64], methylene blue [6567], neutral red [68]) reversible redox reactions of the monomers occur at less positive potentials and this redox activity can be retained in the polymer, i.e. the polymerization reaction, that takes place at higher potentials does not alter substantially the redox behavior of the monomer. For instance, the catalytic activity of methylene blue towards oxidation of biological molecules (e.g. hemoglobin) is preserved in the polymer [67]. The knowledge of kinetics of the electrodeposition process is also of utmost importance. It depends on the same factors enlisted above, although the role of the material and the actual properties of the electrode surface is evidently more pronounced. For example, the oxidation of aniline at Pt is an autocatalytic process. The specic interactions, the wetting may determine the nucleation and the dimensionality of the growth process. Two or more stages of the polymerization process can be distinguished. In the case of PANI it has been found that rst a compact layer (L 200 nm) is formed on the electrode surface via a potential-independent nucleation and a two-dimensional (2-D, lateral) growth of PANI islands. In the advanced stage 1-D growth of polymer chain with continuous branching leading to an open structure takes place [38,42]. It is established that in accordance with the theory [69] the density of the polymer layer decreases with the lm thickness, i.e. from the metal surface to the polymer/solution interface. The lm morphology (compactness, swelling) is strongly dependent on the composition of the solution, notably on the type of counterions present in the solution, and the plasticizing ability of the solvent
molecules [35,41]. The formation of the polymer involves about 2 mol electrons referred to 1 mol of aniline [1,2,7 9,22]. The growth rate is proportional, except for the early induction period, to the 0.5 power with respect to the lm volume, and it is rst order with respect to aniline concentration [24]. Owing to the autocatalytic nature of the electropolymerization the positive potential limit of cycling can be decreased after two to ten cycles which is a common practice in order to avoid the degradation of the polymer due to the hydrolysis of the oxidized PANI (pernigraniline form) [23,25,30]. Although it is still debated the appearance of the middle peak most likely reects the occurrence of oxidative hydrolysis and degradation, and it can be assigned to the redox reaction of benzoquinone [33]. Beside the head-to-tail coupling resulting in the formation of p-aminodiphenylamine, tail-to-tail dimerization (benzidine) also occurs, however, the latter is considered as a minor dimer intermediate because the rate constant of dimerization for RR coupling to produce the former product (k is ca. 108 dm3 mol 1s 1) is about 2.5 times higher than that for the tail-to-tail dimer [33]. The degradation process should be considered for other polymer lms but similarly it can be controlled electrochemically [48]. If the conditions are not carefully optimized generally a mixed material is deposited on the surface containing electrochemically active and conducting as well as inactive and insulating parts [48]. It has been demonstrated that in the synthesis of polypyrrole (PP) the current density is a crucial parameter [49,51,52]. At low current densities the structure of PP is dominated by one-dimensional chains, while at high current densities two-dimensional microscopic structures of the polymer are formed [51,52]. The structure substantially affects the conductivity of the polymer phase, the conductivity of the 2-D form is higher and its temperature dependence is lower, which is of importance when this polymer is used for practical purposes. Detailed studies have shown that the higher conductive 2-D islands are interconnected by short 1-D chain segments acting as tunneling barriers [52]. It has also been demonstrated by scanning microscopies that the lm growth at sub-mm or mm-structured substrates is not restricted to conductive substrate domains. Instead, after the lm thickness has risen to the level of the surrounding insulator a lateral outward growth on the non-conductive part also occurs [70]. This is a phenomenon that should be taken into account in microtechnical applications. Although the region close to the electrode surface shows a more or less well-dened structure, in general the polymer layer can be considered as an amorphous material [28,34,38,42,47]. However, there are rare reports on crystalline structure, too. For instance, poly (p-phenylene) lms obtained by electrooxidation of benzene in concentrated H2SO4 emulsion show a highly crystalline structure [71].
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The conditions of polymerization was found crucial also in the case of polythiophene and polybithiophene lms [48,53,7277]. The relatively high potential required for the oxidation prevents the use of many metallic substrates. The electrochemical oxidation of substituted thiophenes and thiophene oligomers yields conducting polymers and these compounds can be electropolymerized at less positive potentials, therefore it is a good strategy to use these derivatives instead of thiophene [1,2,77]. Another approach is the deposition a thin polypyrrole layer that ensures the deposition of polythiophene on these substrates (e.g. Ti, Au) [72]. Interesting other polymers, e.g. poly(thionaphthene-indole) [78], polyazulene [9], poly(o-phenylenediamine) [79,80], poly(5-carboxyindole) [81] as well as copolymers and composites [37,39,43,54,57,61,62,74,75,8285] can also be synthesized. Higher electronic conductivity has been achieved by template synthesis with using polycarbonate membranes [15] and this method has also been exploited to obtain nanostructures [56]. Spectacular fractal patterns can be obtained by utilizing a needle-to-circle electrode conguration [50]. The application of combined electrochemical and non-electrochemical techniques, such as piezoelectric microgravimetry at EQCM [41,46,47,62,66,80], radiotracer [22,23], spectroscopies [40,49,65,73,74,78], microscopies [15,33,34,36,44,50,70,71,75,76,81,82], ellipsometry [29,42,47], conductivity [53] probe beam deection [86] has allowed a very detailed insight into the nature of electropolymerization and deposition processes, and consequently now the production of conducting polymers, polymeric lms, and composites with the desired properties is a well established area of electrochemical and material sciences.
of the nature and mechanism of the redox processes occurring in these systems [4 9,12].
2.2. Kinetic beha6iour and thermodynamical considerations

The electron conducting polymers can easily be switched between conducting and insulating states just by changing the potential, i.e. by electrochemical (or chemical) oxidation and reduction, respectively. (As has been mentioned the change of the composition of the contacting uid media, e.g. by varying H+-ion activity of the solution or the NH3, NO concentration in the gas phase, may also lead to similar effect). This is a unique property in comparison with the majority of electron conducting materials. When the oxidation state of the polymers is varied not only their conductivity is altered but other properties (e.g. colour) also change. It is the very feature that can be exploited in many practical applications. The rate of this change is of utmost importance virtually in all cases, consequently much effort has been made concerning the elucidation
2.2.1. Characterization For the determination of the rate of the charge transfer and charge transport processes in the electrochemically active polymer lms especially the electrochemical impedance spectroscopy (EIS) [54,75,87 115] proved to be the most reliable and powerful technique. A combination of different techniques, such as piezoelectric microgravimetry at EQCM [43,62,66,116 124], radiotracer [22,23,125,126], probe beam deection (PBD) [64,86,127 129], spectroscopies [65,130 140], microscopies [141 151] and conductivity measurements [10,15,16,52,53,89,114,152 162] with electrochemical methods has supplied the most valuable informations about the ionic and electronic charge transfer and charge transport processes. The study of ionic charge transport accompanying the redox transformation by EQCM and radiotracer techniques has contributed not only to the knowledge of the kinetics of these processes but also to the establishment of the chemical reaction mechanism and to gain a deeper understanding of the kinetics and equilibrium of swelling. However, it has also been revealed that the sorption/desorption of solvent molecules that causes the swelling/deswelling of the polymer and therefore affects the chain, and segmental motions, the contact of the electron donor and acceptor sites, may play a crucial role in the kinetic behaviour. This situation arises especially when a neutral lm is converted into a polyelectrolyte as a function of the potential, in fact during the redox transformation a new polymeric material is created having substantially different chemical and physical properties from the initial one. The elucidation of the structure and properties of polymer (polyelectrolyte) layers as well as the changes in their morphology caused by the potential and potentialinduced processes and in other parameters (e.g. temperature, electrolyte concentration) set a entirely new task for electrochemists. Owing to the long relaxation time characteristic to polymeric systems the equilibrium or steady-state situation often has not been reached within the time scale of the experiment [41,125,163 177]. Consequently, even slow sweep rate cyclic voltammetry does not supply reliable thermodynamical quantities which otherwise can be derived by analyzing the changes in the peak potentials. The manifestation of the polymeric nature of these systems is most striking in the relaxation phenomena which are in connection of the changes of the conditions (potential, temperature, etc). and appear in different effects, such as hysteresis, rst cycle and memory effects [41, 163 177]. Two advanced models, i.e. the electrochemically stimulated conformational relaxation [171,172] and the percolation theories [165 170] should be mentioned.
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2.2.2. Nature of the charging process Although conjugated polymers may be charged positively or negatively, the study of the charging mechanisms has mostly been devoted to the case of p-doping. Initially, the latter had been carried out by the chemical treatment leading to a material containing mobile electronic species and counterions rested from the oxidizing agent, e.g. I inside the polymer matrix [10]. It does not allow one to vary the charging level for the same lm, unlike that at the electrode surface which may be charged and discharged repeatedly by the mere change of the potential in a cyclic manner. The measurements of the electronic conductivity revealed a drastic change of this characteristic (up to 1012 orders of magnitude) from its low value for the initial (non-charged) state of the lm corresponding to a semiconductor or even an insulator, to the values within 1103 S cm 1 (even up to 105 S cm 1 for polyacetylene [178,179]) comparable to metals [180 182]. It is worth to note that the mobility of initial portions of the incorporated electronic charge is rather low. At higher charging levels the conductivity increases much more rapidly than the charge and then leveled out, or even decreases. This onset of the conductivity has been interpreted as an metal-insulator transition due to various electron-electron interactions although its description still represents a eld of vivid discussions [183,184]. Moreover, the temperature dependence of the conductivity in the highly charged state does not correspond in most cases to the metallic type [185]. In conformity with quantum-chemical expectations the ESR measurements demonstrated the presence of unpaired spins inside the lm [186]. However, their concentration passes through the maximum at a relatively low charging level (before the conductivity onset) and then vanishes [187]. These data led to the polaron-bipolaron model of the charging process [184,188] where the ESR data are attributed to polarons, single charged cation radicals at the polymer chain (coupled with its local deformation), which are transformed into spinless dications (forming a complex with a counterion), bipolarons, at higher charging levels. Later, the interactions between those species were incorporated into this model [187]. The steady-state cyclic voltammetric response in the background electrolyte solution (without monomer) represents in most cases a combination of broad anodic and cathodic peaks with a plateau of the current at higher potentials. The current is proportional to the scan rate (see, e.g. [180,181]), i.e. from the electrical point of view the lm in quasi-static conditions behaves like a capacitor. However, this simple result is the consequence of a complicated phenomenon which includes the faradaic process (generation of charged electronic entities at the polymer chains near the electrode surface by the electron transfer to the metal), the trans-
port of those species throughout the lm, the ion exchange at the lm/solution interface (to keep the overall electroneutrality). Despite the above mentioned quasi-equilibrium character of the CV curve, they demonstrate usually a pronounced hysteresis, i.e. a considerable difference between the anodic and cathodic peak potentials (up to 0.4 0.6 V [77,165 176,189]). Its initial explanations (slow heterogeneous electron transfer, effects of local rearrangements of polymer chains, slow mutual transformations of various electronic species etc) are overviewed in [85]. The phase transition of the rst order due an S-shaped energy diagram [190], e.g. due to attractive interactions between the electronic and ionic charges [191], or the insufcient conductivity of the lm at the beginning of the anodic process [192] have also been proposed as possible origins of the hysteresis. An important additional information has been provided by the CV studies of polyphenylene lms with different anodic or cathodic limits of the potential variation [77]. They have obviously demonstrated the existence of at least three different electronic species inside the lm, two of them (at low and higher degrees of charging) following the potential variation in an almost reversible manner while the third charged component undergoes irreversible transformations within the potential ranges corresponding to the CV peaks. An indication to the possible mechanism of the latter process is provided by the experiments with dissolved short-chain oligomers of the same chemical type [193 196] electrogenerated cation radicals are subjected to a very rapid dimerization reaction. In the above approaches the attention has been paid to only one factor, the electronic charging of the lm due to its interfacial exchange with the metal. However, the global process must always include an ion exchange between the lm and the solution, to retain the overall electroneutrality of the lm [197,198] (except for a small disbalance of the charge related to the electric double layer species inside the metal or the solution parts of the interfaces). If one describes it as a single polymer phase (may be, containing macropores, see below), then the overall electrode potential represents a sum of two interfacial contributions corresponding to the metal/polymer and polymer/solution interfaces [199,200]. The ratio between their variations at the change of the overall polarization inuences the chargepotential relation (charging isotherm), quasi-equilibrium CV curves, ion exchange with the solution, and kinetics of the redox reactions at polymer-coated electrodes. The theoretical analysis [201] of the potential distributions across the metal/lm/solution has found the existence of two limiting cases. At sufciently high concentrations of co-ions inside the lm the potential
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drop at the polymer lm/solution interface is almost constant, and the proles of the potential at the equilibrium are similar to those for a redox polymer lm coated electrode [202205]. In the opposite limiting case the potential prole shows a gradual transformation (as function of the charging level) from this form to the electron-counterion type where the both interfacial potential drops vary with comparable rates [206]. The study with the use of various scanning probe techniques (SEM, AFM, STM, Kelvin microscopy etc, see [143153]) has revealed a pronounced heterogeneity depending on the substrate, synthesis conditions, composition of the solution, thickness of the lm. Theoretically, one has to distinguish between macropores (whose diameter exceeds considerably 10 nm) and nanopores (which represent solvent molecules and ions between the polymer chains). In the former case the thermodynamic and transport properties of the electrolyte solution inside such pores are close to those of the bulk solution, the space-charge regions (electric double layers) are formed at the interface between the polymer phase and the solution whose thickness is much lower than the characteristic sizes of those macroelements (brils, grains and pores). The polymer phase itself consists of a polymer matrix with incorporated ions and solvent molecules which do not form a separate continuous phase. Strong coulomb attractions between the electronic and ionic charges prevent their separations at the distance signicantly exceeding the Debye screening length of the medium (a few angstrom in the charged state). Two alternative approaches have been developed for its description. One of them treats it as a specic polymer phase containing all above components and possessing certain thermodynamic and transport properties [90,106,200,204,206]. In equilibrium its state is determined by the equality of the electrochemical potentials for the species transferred across the corresponding interface, with the metal (electrons) or with the solution (ions, solvent). Both the electronic and ionic species inside this phase participate in the formation of the space charges at the interfaces with the surrounding media, metal or solution. Another approach separates polymer chains and ions+ solvent, respectively into two different phases [98115] whose properties (generally they must be strongly different from those of the bulk phases, e.g. those of the bulk solution) are considered in the same manner as those of the innite media. A similar simplication is also used for the interfacial properties, e.g. electric double layers. A great number of characteristic parameters has to be introduced within this model. Despite seemingly opposite ways of describing the polymer phase in those approaches, the results turned out to be often similar or even identical.
A further development should be expected in this area which must clarify the relations between the characteristics found in both models, as well as to analyze the real macroporous structure of those systems. Porosity effects in the charging process have been implicated for a long time in the discussion of the faradaic and capacitive contributions to the current [77,207 210]. Several ways to distinguish between them experimentally have been proposed: analysis of the form of the CV curve, e.g. the peaks are attributed to the faradaic process while the plateaus of the current are considered as the indication to the capacitive term. However, this straightforward analogy to the metal/solution interface does not work in reality, e.g. the obviously faradaic process of a redox transformation of the surface layer does not lead to a direct current, unlike a similar reaction for solute species. As it has been pointed out above, the CV curves represent a superposition of several different processes, and the above simple interpretation is not applicable; purely capacitive behavior of the low-frequency impedance, Z$ ( jC) 1, is sometimes interpreted as an indication to the double-layer type of the charging. Again, this nding is a direct consequence of the possibility to charge the lm to different levels as a function of the applied potential, with no direct current passage; there have been numerous attempts to separate the above contributions to the CV curve by its comparison with optical measurements, assuming that only the faradaic charge can give a response. However, the chemical nature of all electronic species (like polarons, etc) participating in the formation of the double layers at the surface of the macro- or nanopores inside the lm, is quite identical to that of the bulk polymer species. Therefore, all these electronic species must give a similar contribution to the optical signal so that the latter cannot be used for their discrimination at all.
2.3. Reactions at conducting-polymer coated electrodes: electrocatalysis

Starting from the pioneering study by Diaz et al [21] numerous reactions of solute species at the polymercoated electrodes have been investigated. It was initially assumed that these lms in their insulating state should inhibit the reaction at the polymer/solution interface so that such kinetic measurements might be used as an indicator of the lm conductivity [211]. In accordance with this concept the oxidation of species having formal redox potentials in the insulating potential range of the polymer is usually shifted to the interval of the lm conductivity onset while the reduction reactions are suppressed at all (at
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least for polymers without n-doping). For example, Fe2 + reaction at several polymers [212] does not take place at either negative (insulating lm) or high positive (overoxidation) potentials while it occurs in the intermediate range (one can argue whether it is due to a greater size of those species, or to their positive charge which prevents their penetration into the polymer phase because of the electrostatic repulsion) [213,214]. For small non-polar gas molecules (H2, O2) [212] the deposition of an insulating lm leads to a greater overpotential, the kinetics being strongly dependent on the metal substrate nature, an indication to the reaction localization at the metal/polymer interface, or at the bare metal surface not covered by the polymer due to its porous structure. Within the interval where the lm is electronically conducting there are numerous examples of the reaction catalysis by the polymer lm, compared to the bare electrode, e.g. oxygen reduction [215,216], Fe2 + [217], I, Br, ferrocyanide [218], hydrazine [219] and hydroquinone [220,221] oxidation at PANI, oxygen [222] and bromine [223] reduction at PPP. On the other hand, the rate of some other reactions is diminished by the lm even in its conducting state, e.g. ferrocene oxidation at polythiophene [224]. The above simple relation between the polymer conductivity and its effect on the reaction kinetics has turned out not to be valid universally. Iodine reduction on polythiophene [225] as well as viologens at polyaniline [226] take place within the insulating range of those polymers. The reduction of oxygen [216] and naphthoquinone-sulfonate [226] at PANI starts within the conducting range but continues at more negative potentials. These observations testify in favor of the generation of positively charged electronic species at the polymer matrix by those reagents, similar to the dark hole injection at insulator or semiconductor electrodes [225,226]. The interpretation of these kinetic data assumes in most cases (usually without a detailed analysis) the reaction localization at the lm/solution interface. For a qualitative consideration the lm having a sufciently high electronic conductivity is identied to the metal electrode which means the attribution of the whole potential drop (i.e. its varying part) to the lm/solution interface. Quite opposite view (practical constancy of the latter interfacial potential) [199,204] means a close analogy to the case of redox polymer lms [202,203]. Thermodynamic analysis of the charging process taking into account both the electron exchange with the metal and the ion exchange with the solution [191,201,206] (see chapter 2.2) provides an evidence in favor of an intermediate variant, the both interfaces are markedly polarizable. Then, the relations for the reaction constants should have a more complicated form, modied Tafel equation at high charging levels and some fea-
tures similar to inorganic semiconductor electrodes at lower potentials. Existing experimental verications of these hypotheses, e.g. [191,227], are not sufcient for a certain conclusion, especially in view of the still existing problem of an adequate description of the charging process. More globally, much work has still to be done to establish the reaction zone since the reagents in certain cases may cross the lm/solution and react inside the polymer phase, or even at the metal/polymer interface, especially at low charging degrees of the lm. Besides, one has to distinguish between the reaction at the outer or inner (with macropores) polymer/solution boundary. Another hot topic in this area are the conducting polymer lms modied by catalytic centers, clusters of transition metals [228 235], polyoxometallates [43,236,237], porphyrines, phthalocyanines and their analogs [216,238], other transition metal complexes [239 241], biomolecules [54], arenes and rotaxane [242,243], etc., see [244 248] for review. The centers can be incorporated into the polymer matrix with the use of several techniques: as a counterion added to the solution before the electrosynthesis. This electrostatic coupling is not always sufciently stable, and the species may later leave the lm, especially during its reduction; generated chemically or electrochemically inside the lm, or on its surface, after the synthesis, e.g. by the destructive oxidation or reduction to produce metal or oxide clusters; bonded chemically to the monomer species before the synthesis; included directly into conjugated chains, e.g. in shish-kebab metallo-porphyrine polymers [249 251]. The catalytic centers inside conducting polymers accelerate numerous reactions, oxidation of hydrogen and various organic molecules, reduction of oxygen and carbon dioxide, electrohydrogenation of organic species, etc. Another application of such functionalized polymer lms is for chemical sensing [244,252]. In the composite lm containing PANI and dimercapto-thiadiazole the conducting matrix plays a catalytic role in the process of DMcT polymerization transferring the electrons between those species and the electrode [253]. This system has got prospects of its battery applications in view of its high energy density.
2.4. Applications of conducting polymers 2.4.1. Material properties of conducting polymers On a rst view, the most interesting property of the intrinsically conducting polymers (ICPs) is the high, almost metallic conductivity of a material which has a good corrosion stability. This is important for the dry state. The second point is given by the advantage that
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Table 1 Qualitative properties of ICPs according to their charging state Charging state Stoichiometry Content of solvent Volume Colour Electronic conductivity Ionic conductivity Diffusion of molecules Surface tension Reduced Without anions (or with cations) Small Increase with oxidation Transparent or bright Semiconducting Smaller Dependent on structure Hydrophobic Oxidized With anions (or without cations) Higher Dark Metallic High Hydrophilic
ICPs can be deposited from a liquid phase even in complex topographies. Finally, ICPs belong to a small class of materials changing their properties by a reversible intercalation process similar to bronzes (e.g. NaxWO3), graphite, TiS2, and others. Thus, in conctact with an electrolyte, the redox properties of ICPs become dominant. Due to that redox process combined with the intercalation of anions (or cations, resp.), chemical, optical and ionic properties can be switched. These values can be changed by a variation of anion size and preparation techniques, e.g. inclusion of other chemical species (see earlier). Qualitative data are given in Table 1. Typical regions of application can be described in a double logarithmic plot of Fig. 1. For orientation, the position of ideal metals, semiconductors and insulators is given on top of the diagram. Constant properties exist at high ionic resistance, i.e. at top of the diagram. Here, the application of ICPs in the dry state in a inert atmosphere can be discussed. In contact with the electrolyte, a much wider eld of applications can be speculated dependent on the special ionic and electronic resistance given by the charging state: here we nd applications in batteries, displays, sensors etc.
2.4.3. Topography and microstructuring For application in advanced systems, mechanical and topographic properties must be checked rst. The lling of moulds, holes and gaps often is a problem which depends on the preparation. Here the advantage of ICPs must be mentioned. For example the electrochemical polymerisation can be carried out in a hole or mould. Sometimes, the growth preferentially takes place at the edges. Even that can be used as an advantage for the deposition of chemicals [257]. The minimum size of a hole to be lled is given by the molecular size of the polymer and the hydrophilicity of the hole. Even the nano-sized channels of porous silicon or Al2O3 could be lled [258,259]. Chemical polymerisation by soluble (Fe3 + ) or solid oxidants (MnO2) can also be used. A detailed review of the use of conducting polymers for micro system technologies and silicon planar technology was given by [260]. Local deposition of
2.4.2. General and special functions of ICPs for application General, important functions are given by the application in thin lm processes, by the intrinsic pore structure, and the redox process. This yields a rst grouping of applications described in Table 2. A specic function as wettability, optical or membrane properties, leads to applications in special systems, e.g. displays, or processes, e.g. metallisation of holes. This table gives some characteristic examples and references which will be discussed in more detail in the following sections. These are arranged, however, under a complementary grouping given by the technological elds, e.g. energy technology, sensors and others. For extended descriptions see the reviews in [254256].
Fig. 1. Applications of ICPs in a double logarithmic plot of ionic and electronic resistances.
G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421 Table 2 General and special functions of ICP for application General function Special function Application
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System/reference
Thin lm technologies in macro-or microscopic systems
e-Conducting lm e-Conducting lm in holes e-Conducting lm Band structure, optical transitions
Antistatic coating
PEDT [261,262]
Printed circuit boards, through PEDT/epoxy hole plating resin [264] Capacitor metal/dielectric/ PEDT [296] LEDs Metal/PPV/ITO [280] Sensors Membrane, sparation Offset-printing Smart windows Active mass of batteries Actuators (articial muscle) Corrosion protection PANI/glucoseoxidase [290] Py [281] PT [271] PEDT [278] PT/Li [269] PPy [277] PANI/Fe [285]
Material for llings, porous membranes, composites Redox process
Matrix/membrane for functional molecules Membrane Wettability Optical properties Intercalation Change of volume and length Inhibition, protection
Others
polybithiophene is possible on n-type silicon by laser assisted deposition. The production of negative and positive microstructures with high aspect ratio and precision is possible. Different concepts like direct laser writing, prestructuring of the silicon substrates by mask techniques or poststructuring of already deposited polymer lms were realised [260].
2.4.4. Application of ICPs in 6arious elds of technologies 2.4.4.1. Thin lm deposition and microstructuring of conducting materials. In thin lm technologies, ICPs can be used as conducting layer. A eld with a wide technical importance is the antistatic protection [261,262] and the electromagnetic interference shielding by conducting polymers [263]. PANI, PPy and PT derivatives have been predominant. They are incorporated as llers in common polymeric materials like polyvinylchloride, polyvinylacetate or others to substitute carbon black lled materials. Poly(3,4-ethylendioxithiophene) (PEDT) is used as a protective layer for photographic lms [261,262]. A large scale technological process was realised with the through hole plating of printed circuit boards [264 266]. The insulating epoxy board is oxidised by KMnO4. The resulting thin lm of MnO2 x is used as an oxidiser for the oxidative polymerisation of EDT. The thin lm of PEDT is conductive even at low potentials in acidic solution. Therefore, the hole covered with conducting polymer can be directly electroplated with copper. In microelectronics ICPs may be applied as charge
dissipators for electron beam lithography. Electron beam lithography is a direct writing method with a very high resolution in the sub-micron range. The charging of the insulating electron beam resist can lead to a deection of the electron beam and so it results an image distortion. To avoid the problem, conducting resists or layers must be applied. Water-soluble PANI was introduced by IBM as a discharge solution [267].
2.4.4.2. Materials for energy technologies. The possibility of a reversible switching of conducting polymers between two redox states rose speculations for rechargeable batteries. The rst prototypes of commercial batteries with conductive polymers used Li/ polypyrrole (Varta-BASF) or Li/polyaniline [268]. The actual development is focused on new cathode materials for lithium batteries. Good results were obtained with substituted polythiophenes and poly(1,2-di(2thienyl)ethylene). Open problems are the insufcient cycle stability compared with inorganic systems and the high discharge rate. A detailed review is given in [269]. Another eld of application is given by the excellent ionic conductivity allowing high discharge rates. The use as electrode materials in supercapacitors is a good example. Supercaps require high capacitance and quick charge/discharge electrode materials. Compared with classical used carbon materials conducting polymers shows promising characteristics [270]. Further, ICPs are now used as electrode material in capacitors [271,272]. They show an enlarged stability against breakdown phenomena because of the loss of conductivity at higher eld strength.
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The use of organic semiconductor is of special interest because of the possibility to deposit large areas with low costs and to synthesize tailored materials for special affords. A rst device using a bilayer structure of copper phthalocyanine and a perylene derivative is described by [273]. Due to the conducting properties polythiophenes can only be used in photovoltaic devices in their reduced state. The reduction must take place electrochemically before the vapour deposition of the top electrode. Different layer structures and combinations of PT%s with PPV or C60 were studied [274,275]. Devices of Al/C60 modied PTs/ITO show a conversion efciency of 15% with zero bias and 60% with a bias of 2 V (for u= 500 nm, 1.5 mW cm 2).
was observed for doped lms compared with undoped (reduced) lms. This could be explained with structural changes and an increase in hydrophilicity during the oxidation [281]. Membranes of 3-hexyl-PT show a decrease of the permeability for dopamine with increasing oxidation [282]. Different permselectivity for anions was found and studied by [283]. Despite the possible switching of the selectivity and the excellent separation effect for some systems the technical realisation is scarce due to the missing stability and the lack of pinhole free materials.
2.4.4.3. Electroluminescent and electrochromic de6ices. Electrochromic devices could be realized with ICPs. In that case, the response time of the conducting polymers must be fast enough (100 ms [276]) and a reversibility of the charging/discharging must be achieved (up to 105 cycles or more [277]). Smart windows based on a sandwich structure of ITO/ PEDT-PSS/ITO between glass were developed [271,278]. Organic electroluminescent devices (LEDs) are a possible alternative to liquid crystal displays and cathodic tubes, especially for the development of large displays. The principle set-up of a polymeric LED is ITO/light-emitting polymer/metal. A thin ITO electrode on a transparent glas or polymeric substrate serves as anode, metals like Al, Ca or Mg were used as cathode materials. After the application of an electric eld electrons and holes were injected into the polymer. The formation of e/h+-pairs leads to the emission of photons. One of most important opportunities of the use of polymeric LEDs is the chemical tuning of the HOMO-LUMO gap of the light-emitting polymers by a tailored synthesis. Typical materials are polyparaphenylene (PPV) and its derivatives or substituted polythiophenes. The use of PANI is reported as a rst layer on the ITO electrode to enlarge the efciency of the LED [279]. Quantum efciencies of 3%, light densities up to some thousand cdm 2 and light efciencies of 5 lm W 1 become possible. A good overview of recent developments is given by [280]. 2.4.4.4. Use as membrane and ion exchanger. Conducting polymers can be regarded as membranes due to their porosity. They could be used for the separation of gas or liquids. Free standing (on supporting substrates) chemically prepared PANI lms are permeated selectively by gases. In general, the larger the gas molecule the lower the permeability through the lm. Several studies reported a switchable permeability for water and organics dependant on the redox state. For electrochemically formed PANI and PPy on metal or conducting grids a large increase of water permeability
2.4.4.5. Corrosion protection. Conducting polymers can be deposited as corrosion protection layer. PANI, PPy and PT (and their derivatives) were used [284 286]. Favourite substrate of the investigation is mild steel, but also dental materials are discussed [286]. The application of the conducting materials takes place directly by electrodeposition on the active material or by coating of formulated solutions of these polymers. The efciency and mechanism of corrosion protection are not yet classied. On iron an anodic protection is discussed [287]. Due to the redox processes taking place, thicker layers of iron oxide are formed and are stabilised against dissolution and reduction. An inhibition is also reasonable due to a geometric blocking and a reduction of the active surface. 2.4.4.6. Sensors. The use of conducting polymers in sensor technologies consists as an electrode modication to improve selectivity, to impart selectivity, to suppress interference and to support as a matrix for sensor molecules. All electrochemical transducer principles can be realised with conducting polymer modied electrodes. The role of the conducting polymer may be active (for instance as catalytic layer, as redox mediator, as switch, or as chemical modulated resistor) or passive (for instance as matrix) [288]. Sensors with conducting polymers exist for a lot of different substances, for example for gases like SO2 and NO2 [289], glucose [290], urea [291], hemoglobin [66,291], xanthin [292] or humidity [293]. Other examples and commercial applications are given in [288]. 2.4.4.7. Articial muscles. Conducting polymers show a swelling with increasing oxidation (doping). The ingress of counter-anions into the polymer leads to a structural change of the polymer backbone and to an increase in volume up to 30% [294]. These electromechanical properties are used in actuators like the polymer based articial muscle. Bi-layer structures on the base of PPy [277] are described. Three layer muscles, formed of two layers of conducting polymers divorced by a exible insulating foil, are developed to avoid the use of a separate, metallic counterelectrode [295].
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3. Proton conductive polymers Ion conductive materials have found applications as cell separators in electrochemical processes to improve the efciency of the electrosynthesis by preventing undesirable reactions at the electrodes. In the past only inorganic materials like asbestos were used with a continuous shift from inorganic to composites and now organic ion exchange membranes. Such membranes are used in applications where either ionic or proton conductivity is necessary. Cation or proton conductivity is possible along the polymer backbone because of the presence of carboxylated or sulfonated groups with a cationic counterion whose mobility can be increased by water swelling. The main properties required for these ion exchange membranes to be used in these electrochemical processes are: -low electrical resistance which can be obtained by increasing the ion exchange capacity, the water content and decreasing the membrane thickness; -high permselectivity for anions and nonionised molecules; the permselectivity decreases with the water swelling and a compromise has to be found between conductivity and selectivity; -good mechanical and chemical stability over long periods of use in presence of oxidising species. The main applications of these membranes are in chlor-alkali electrolysis, efuent treatment, recycling and energy production in fuel cells. In this last application like in water electrolysis the membrane is used as proton conductor. Proton conductivity in these materials is due to the existence of ionic domains which swell in the presence of water and percolate to permit the proton conduction through the membrane. Selectivity may be due to ionic interactions which depend on the extent of swelling and also on the structure of the intercluster phase.
molecular weight of the SO2F containing monomer. The chemical structure of these polymers is given below:
with x =610 and y, z=1. Naon membranes with equivalent weight (grams of polymer per mole of H+) of 1200 (Naon 120), 1100 (Naon 117 and 115), 1000 (Naon 105) have been successively developed with continuous improvements in the performances in fuel cell because of the increase of intrinsic conductivity associated with a higher exchange capacity and also because of a decrease in the membrane thicknesses (7 ml (0.007 in.) for the Naon 117 down to 5 ml for the Naon 105 and 115).
3.1. Peruorinated sulfonic acid membranes

As proton conductive membranes, one of the largest potential aplications is for low temperature fuel cells for electrical cars. Above mentioned requirements for electrochemical processes extended to the fuel cell application have been met by the development of Naon peruorinated membranes during the sixties by Du Pont [297,298] with continuous improvements along the years and development of other similar materials by Dow [299], Asahi Glass (Flemion) and Asahi Chemical (Aciplex) [300]. These polymers result from the copolymerization of peruorinated ethylene monomers with a SO2F containing peruorinated ether monomer. The thermoplastic lms so obtained are functionalized by soaking in a aqueous solution of sodium carbonate around 80C. The exchange capacity of the membranes depends on the degree of copolymerization and on the
with x= 310 and y= 1. Because of the shorter side groups, equivalent molecular weights lower than those of Naon are obtained (800 850) with thicknesses around 5 ml. Evidence of phase separation between the ionic water swollen phase and the hydrophobic peruorinated matrix has been given mainly from X-rays and neutron small angle scattering experiments [301 303]. For high water contents the generally accepted model consists of a continuous water-ions phase dispersed in a partially crystallized peruorinated matrix which acts as physical crosslinks preventing a complete dissolution at moderate temperatures. At low water contents ionic clusters already exist; different theoretical models to explain the experimental data have been proposed [304,305]. Conductivity measurements can be performed by using complex impedance spectroscopy but a more signicant approach can be made from measurements in fuel cell conditions where the interface limitations are minimized by hot pressing the membrane between two electrodes with a recast ionomer lm in the active layer. Analysis of proton exchange membrane fuel cell performances has recently been made for the Aciplex-S 1104, Dow 800 and Naon 115 membranes, approximately 125 mm thick in the dry state [306]. At 50C and with 1 atm for the H2/O2 gas, resistances 0.18 V cm 2 for the Aciplex and Dow membranes and 0.35 V cm 2 for the Naon membranes have been measured. These resistance values correspond for these swollen membranes to conductivities around 10 1 S cm 1. Low temperature conductivity measurements per-
2414
formed on Naon-propylene carbonate gels show that there is no conductivity discontinuity down to temperatures of 40C [307]. A similar behaviour may be expected for the water swollen membranes since no water freezing of the ionic phase has been evidenced down to these low temperatures. The membranes obtained from these polymers are particularly adapted to the fuel cell application with long life time ( \10 000 h), limited ohmic losses specially when using reinforced materials (GORE type) which permit to decrease the overall thickness and consequently the associated ohmic losses.
tained with a preferential grafting in the amorphous part of the semi- crystalline polymers. Large ionic domains corresponding to the swollen polyelectrolyte are then distributed inside the polymer lm and the high conductivity values result from percolation of these ionic domains at high water content. In fuel cell applications there are however severe limitations for these membranes because of degradations due to HO. and HO2. radicals formed on the anode side from the incomplete reduction of O2 which has diffused from the cathode to the anode [313 315].
3.4. Sulfonated thermostable polymers 3.2. Alternati6e proton conducti6e membranes

Several reasons have induced the development of new membranes: The high cost of peruorinated ionomer membranes ( 600 $ m 2) which is at least one order of magnitude too high for the fuel cell application in electrical cars where at least 6 to 10 m2 of membrane is necessary to get the 50 kW power for a middle size car. Running a cell at temperatures higher than 100C is interesting in terms of yield and also for fuel cells because of the catalyst poisoning by CO is much less important at high temperatures. Peruorinated membranes cannot be applied in this temperature range because of lower swelling and lost of mechanical properties. In electrodialysis application high temperature extension is also necessary. Methanol may be the energy vector of the future for fuel cells, which imply the development of membrane having a high selectivity for water versus methanol. Environmental considerations have also to be taken into account to use protonated rather than uorinated polymers specially for the high amounts of membrane potentially necessary for the car application. New polymers have been considered according to the following criteria: resistance to high temperatures and to corrosion, presence along the backbone of an aromatic ring for sulfonation. The following polymers have therefore been checked as possible candidates for new proton conductive polymers: Polyamideimide (PAI), Polybenzimidazole (PBI), Polyetherethercetone (PEEK), Polyethersulfone (PES), Polyimide (PI). Different polyethersulfone (Udel, Victrex) have been sulfonated along different sulfonation processes [316 320]. Exchange capacities up to 3 mmol g 1 have been obtained. After sulfonation the polymer is soluble in different solvents like DMF, DMS, NMP, TEP and mixtures of dichloroethane/isopropanol or dioxane/ methyl ethyl ketone. Membranes are then made by casting and evaporation of solvent. Swelling in water is a key parameter which controls the conductivity and the mechanical properties. Increasing the degree of sulfonation induces large swelling and conductivity but possible mechanical cracking of the membrane. Crosslinking obtained during the casting procedure by addition of molecules reacting with the sulfonic groups permits to get a balance. These membranes have been tested in fuel cell conditions. Conductivity performances are good enough to obtain polarization data similar as those obtained with Naon and Dow membranes. Long term data are limited, Ballard gives life times of 500 h for these membranes [320]. Sulfonated polyether ketones have also been developed by several groups [321,322]. Similar casting procedures permit to get membranes with possible post crosslinking by annealing at temperatures around 120C. Good performances in terms of conductivity and aging have been claimed for these membranes in hydrogen and methanol/air fuel cells. Because of the better chemical resistance of uorinated polymers in fuel cell conditions, Ballard has developed a membrane (BAM 3G) based on triuorostyrene [323]. Longetivity tests exceeding 4000 h have been conducted with these membranes with conductivity performances better than Naon and even Dow membranes. Applications in water and chloralkali
3.3. Irradiation grafted membranes.

Radiation grafting of partially or totally uorinated polymers has been used by different groups to produce proton conductive membranes by further sulfonation or carboxylation of the grafted monomers [308312]. The membranes are usually made in a three steps process: (1) irradiation of the base polymer lm with the formation of free radicals; (2) grafting of monomers (3) sulfonation or carboxylation of the grafted monomers. Membranes obtained have ion exchange capacities up to 4 mmol g 1 depending on the degree of grafting and functionalisation. Swelling in water is important (several tens of percent) and induces high proton conductivities (up to 0.1 S cm 1). A uniform distribution of the ionic groups across the thickness has been ob-
2415
electrolysis, electrodialysis, chromatography or as electrode separators have been claimed for these membranes. Sulfonation of polybenzimidazole can be made either directly on the backbone [324] or by grafting of benzylsulfonate [325]. Conductivity similar to Naon has been obtained for 75% of benzyl sulfonate grafting. Limitations in the use of such membranes may be due to britleness resulting from dehydration and also from possible degradation at the Ca position. Sulfonated polyimides have been synthesized by polycondensation of already sulfonated diamines with dianhydrides [326]. By using a two steps polymerisation process, it is possible to vary the distribution of the charge groups along the backbone from statistical to different size blocks. Changing the dianhydrides and diamines in the hydrophobic sequences permits to adjust the solubility in different solvents and also to modulate the permeation properties of the resulting cast membranes. Conductivity similar to those of Naon type membranes has been obtained. Longetivity tests over more than 3000 h in fuel cell conditions have shown the interest of this kind of polymer [327,328]. High selectivity and permselectivity, which can be adjusted by chemical modications, induce potential applications in different electrochemical applications.
supplies) or for other electrochemical applications (electrode coatings, actuators, articial muscles). Chemical stability at room temperature is good enough to permit 4000 h running in fuel cells.
3.7. Composite electrolytes

The aim of this approach is to separate the conductivity function and the mechanical strength. Several ways have been tested: By lling the interconnected pores of a polymer matrix [320,332 334] or a porous substrate of randomly orientated individual bres [335] by a solution of a proton conductive polymer. Gore type membranes are formed by lling a microporous PTFE by a peruorinated ionomer ( Naon type) and have given excellent results in fuel cell because of low ohmic losses resulting from a limited thickness of the conductive polymer. By lling a microporous polymer matrix with inorganic proton conductors like tungstophosphoric acid [336]. By making bilayer or trilayer membranes with each layer bringing selectivity, mechanical strength and high conductivity. Such composite membrane has been successfully used in chloralkali technology [337] and has been patented for fuel cell use [338]. By blending a proton conductive polymer with noncharged polymers [339,340]. The aim of such procedure is to increase either the ion permselectivity for electrodialysis processes or the water/methanol selectivity for direct methanol fuel cells. By modifying an ion exchange membrane by precipitation inside the membrane of silicon oxide [341] or of water insoluble salts in order to decrease the water content [342]. By dispersing in the membrane inorganic llers either nonconductive or conductive [343,344] with the goal to reduce the fuel crossover for fuel cells, to increase the proton conductivity when dispersing inorganic proton conductors and to enhance the water transport [345].
3.5. Proton conducti6e polymers obtained by acid complexation

Polybenzimidazole is one of the polymers able to be complexed by strong acids because of its basic character (pK= 5.5). Complexation by phosphoric acid makes conductive materials [325,329] whose conductivity, depending on the acid content, may go up to 2.10 2 S cm 2 at 130C. The absence of electrosmotic water drag in such a membrane is interesting for high temperature applications including fuel cells above 100C. Cell performance of these membranes show a good stability in performances for 200 h runs at 150C [330]. Applications in direct methanol fuel cells may be also of interest because of a better selectivity water/methanol compared to existing membranes.
3.6. Hydrocarbon based block copolymers for fuel cells operating at ambient temperatures
Commercially available styrene/ethylene-butylene/ styrene triblock polymers have been sulfonated to give highly conductive membranes (approaching 0.08 S cm 1 for high sulfonation levels) [331]. These low cost materials have potential applications either for fuel cells in the portable power source arena (outdoor recreational products, domestic emergency power devices, portable power supplies for military personnel, tradesperson tool and site power, portable equipment power
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Electrochimica Acta 45 (2000) 2403 2421 www.elsevier.

Electron and proton conducting polymers: recent developments and prospects

Papers received in Newcastle, 20 December 1999

G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421

2. Electron conducting polymers

2.1. Synthesis and structure

G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421

G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421

2.2. Kinetic beha6iour and thermodynamical considerations

G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421

G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421

2.3. Reactions at conducting-polymer coated electrodes: electrocatalysis

G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421

G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421

Thin lm technologies in macro-or microscopic systems

e-Conducting lm e-Conducting lm in holes e-Conducting lm Band structure, optical transitions

Material for llings, porous membranes, composites Redox process

G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421

G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421

3.1. Peruorinated sulfonic acid membranes

G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421

3.4. Sulfonated thermostable polymers 3.2. Alternati6e proton conducti6e membranes

3.3. Irradiation grafted membranes.

G. Inzelt et al. / Electrochimica Acta 45 (2000) 24032421

3.7. Composite electrolytes

3.5. Proton conducti6e polymers obtained by acid complexation

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