DE102004013634A1 - Composition useful for forming a coating useful in electrical double layer capacitors to form electronic apparatus and power supplies comprises a mixture of a conductive polymer in colloidal form and carbon - Google Patents

Abstract

A composition comprises a mixture (preferably at least two) of a conductive polymer in colloidal form and carbon. Independent claims are included for the following: (a) manufacture of the composition involving dispersing the conductive polymer and carbon, and optionally additives in a liquid dispersion medium and optionally drying the liquid dispersion after application on a substrate; and (b) an electrical or electronic article comprising the composition or a composite material containing the composition.

Description

Conductive materials are known and used in many different forms and applications. Carbon based conductive materials are available in a variety of physical and chemical morphology, shape and composition. Pure or predominantly pure carbon is available in the form of carbon black (which also contains predominantly oxygen-based impurities), graphite (pure), carbon nanotubes and fullerenes and others. Carbon-based organic compounds are available in the form of (intrinsically) conductive polymers that have found some initial applications. These many different types of carbon-based conductive materials have at least one property in common, conductivity, and other properties may be unique to one or the other of this group of materials, or may vary widely, such as particle size (graphite in the range of a few to several some 10 μm, fullerenes in the range of angstroms), specific surface area (carbon black and carbon nanotubes with higher values of up to about 1000 m ² / g, graphite with low values of only a few m ² / g) or redox chemistry ( Polyaniline, one of the representatives of conductive polymers, which has a rich redox chemistry, PEDT or PEDOT (Polyethylendioxythiophen), which have a moderate or rich redox chemistry and on the other hand, graphite or carbon black (no reversible redox chemistry).

Therefore It is sometimes of interest to materials with widely varying Combining properties to a combination of properties to provide that would otherwise be unreachable.

The Combination of conductive Polymers such as polyaniline, polyethylenedioxythiophene, polypyrroles or their derivatives with carbon-containing Materials (soot, Graphite, carbon nanotubes and fullerenes) has sometimes been tried. While simple mixtures of mentioned materials are not significant or reproducible Offer advantage and therefore no commercial or technological Gaining attraction are chemical methods of combination from, for example, conductive Polymers and carbon black or conductive Polymers and carbon nanotubes been extensively studied. For example, the company Eeonyx Soot, up its surface Polyaniline was polymerized as a development product in the market offered ("Eeonomer"), see G. Du, A. Epstein, K. Reimer, presentation at the meeting of the American Physical Society in March 1996, Session M23, presentation M23.09; the laboratory chemicals supplier Aldrich has such a chemical produced mixture advertised in his catalog. However, one offered such product obviously no interesting advantages.

One the areas where soot / polyaniline blends could offer an interesting technological advantage, that could Be the area of the so-called "supercapacitors", often also called "double layer" or "redox capacitors". This area brings the highest Number of publications in which carbon and conductive polymers are mixed or have been provided in the form of a mixture.

• – einfaches Mischen von Pulvern von Ruß und Polyanilin durch einerseits Kugelmahlen (US-Patentanmeldung 2002/0114128) oder auf andere Weise (keine Beschreibung angegeben, Journal of Power Sources 11, 2003, 185–190, und Journal of the Electrochemical Society, 148, 10, 2001, A1130-A1134), wobei Polyanilin oder ein Polythiophenderivat mit Rußpulvern gemischt wurden.
• – Chemische oder elektrochemische Polymerisation von verschiedenen leitfähigen Polymeren auf der Rußoberfläche.

For this purpose, mainly two mixing procedures have been used:

• Simple mixing of powders of carbon black and polyaniline by one hand ball milling (US patent application 2002/0114128) or otherwise (no description given, Journal of Power Sources 11, 2003, 185-190, and Journal of the Electrochemical Society, 148, 10, 2001, A1130-A1134), wherein polyaniline or a polythiophene derivative was mixed with carbon black powders.
• - Chemical or electrochemical polymerization of various conductive polymers on the carbon black surface.

The last method has been extensively studied in the patent and scientific literature. The European patent application EP 1 329 918 reports a composite material for a negative electrode made of carbon and polyaniline or polypyrrole, in which the conductive polymer has been electrochemically polymerized. The positive electrode was made of lead. It has been found that the proportion of conductive polymer at 10 to 15 wt .-% is optimal. The capacitor formed using this composition was made by an electrode combination including a positive non-polarizable and a negative-polarizable electrode, whereby the positive non-polarizable electrode was made of lead. US Patent Application 2002/0089807 reports an intrinsically conductive polymer which is polymerized directly onto highly porous carbon black material by chemical or electrochemical means. By electrochemical polymerization, polyaniline was polymerized on a carbon airgel made from polyacrylonitrile (Journal of Applied Eletrochemistry 33, 465-473, 2003), which is consistent with the electrochemical polymerization of pani on porous activated carbon (Journal of Power Sources 117, 273-282, p. 2003 and 10, Carbon 41, 2865-2871, 2003). In the conference report of ANTEC '98, Volume 2, 1197 ff., 1998 The authors report the polymerization of polyethylenedioxythiophene on high surface area carbon layers on a platinum collector. In the same publication, it was reported that polyaniline was cast from hexafluoro-isopropanol solutions onto the same type of carbon layers.

In Electrochimica Acta, Vol. 41, No. 1, 21-26, 1996, has been published on various Redox supercapacitors in symmetrical or asymmetrical electrode arrangement form reported in which various conductive polymers such as polypyrrole or polythiophene derivatives and used on the substrate in one comparable procedure, as in US Patent 5,527,640, 1996, used, polymerized, wherein polythiophene derivatives polymerized on carbon substrates by electrochemical means were.

[Detailed description the invention]

[Technical field, the the invention concerns]

The The present invention relates to conductive materials consisting of (intrinsically) conductive Polymers and carbon-based materials, Process for their preparation and use for high capacity capacitors with electric double layer for use in various electronic Devices, Energy plants and the like.

[State of the art]

As explained above are carbon black / conductive polymer blends often used for use in so-called "supercapacitors". These capacitors are also often called "double layer capacitors", "electrochemical" or "electrical Double Layer Capacitors "or" Redox Capacitors "and sometimes referred to as" Pseudo Capacitors ".

Conventionally, a double-layer capacitor is an energy device in which two electrodes - at least one of which is obtained by coating a collector plate with a porous carbonaceous material having a high surface area between and above about 100 and 1000 m ² / g to a collector plate - face each other With a separator disposed therebetween, a voltage is applied to the electrodes in the presence of an electrolyte solution to create an electric double layer on at least one of the electrodes, and from which energy can be taken. The structure of a type of double-layer capacitor using the porous carbonaceous material as the electrode material is classified as disclosed in the specification and drawings of US Pat. No. 5,150,283 as the type in which a pair of electric double layer electrodes (each comprising a polarizable electrode connected to a collector plate) wound up and contained in a container and the button type in which a pair of electric double layer electrodes are laminated.

The wound version has an arrangement in which a lead wire for the discharge of Energy to the outside is attached to a collector plate, for example, from a etched Aluminum foil is composed with a thickness of 20 to 50 microns, wherein the aluminum foil is coated with a paste that consists of a Mixed powder is composed by mixing together activated carbon powder with a desired one Binder and a desired conductive Means of forming a conductive Layer is made, a polarizable electrode made of a predominantly composed of activated carbon activated carbon layer composed is on the conductive Layer is formed to an electric double-layer electrode and a pair of these electric double layer electrodes with a separator disposed therebetween opposite each other arranged and wound up.

In addition, will the electric double layer electrodes assembled by a method in the polarizable compound composed of activated carbon layers Sufficiently impregnated electrode and separator with an electrolyte solution, the dissolved in vacuum Contains electrolytes that Electrodes and the separator in an aluminum or the like manufactured housing be introduced and an opening portion of the aluminum housing sealed using a gasket. In general this assembly is cylindrical.

On the other hand, the knob type has an arrangement in which a polarizable electrode composed of an activated carbon layer is formed on a disc-shaped metal sheet of a valve metal, and a pair of these electric double-layer electrodes are interposed with an insulating separator therebetween, and this assembly is assembled in a two-piece Me tallbehälter is included. In the two electric double layer electrodes, their disk-shaped metal valve sheets are respectively fixed to inner sides of a lower part and an upper cover part of the metal container, the lower part and the upper cover part being connected to each other, hermetically sealing with an annular sealing gasket on a peripheral edge part thereof are sealed, and the inside of the container is filled with a non-aqueous electrolyte solution, which is sufficiently supplied to the electric double layer electrodes and the separator. As a nonaqueous electrolytic solution, for example, a solution prepared by adding tetraethylammonium tetrafluoroborate to propylene carbonate is used.

It There are several other common ones Arrangements of double-layer capacitors or redox capacitors (often called "supercapacitors"), here not described in detail.

It a high capacity electrochemical capacitor is proposed in which electrochemically active inorganic substances or organic (intrinsic) conductive polymers as electrode materials in combination with or instead of the above porous carbonaceous material Materials) are used and in which an electrical energy storage, based on the formation of electrical double layers, in the same manner as in the ordinary electric double layer capacitor, the above porous Carbon-containing material is used and used simultaneously an electrical energy store is used on both electrodes which is accompanied by an oxidation / reduction reaction Oxidation / reduction potential based, thereby achieving a high capacity.

For example becomes an electrochemical capacitor using ruthenium oxide as an electrode-active substance (Physics Letters, 26A, p. 209 (1968)) as with the highest capacity the currently known electrochemical capacitors using evaluated inorganic oxide, and it has been confirmed that this one Energy density of 8.3 Wh / kg and an output density of 30 kW / kg having.

In In recent years, capacitors are using others investigated inorganic oxide mixing systems as electrode material (J. Power Sources, Vol. 29, p. 355 (1990)).

moreover For example, electrochemical capacitors have been under considerable research in recent years having been used as electrode material a so-called (intrinsic) conductive Polymer that has the oxidation / reduction property of an organic Substance with n-conjugated system exploits, and of the above-mentioned inorganic Metal oxides are different.

The electrochemical capacitors using the conductive polymers are has been studied in many research institutes, and it has been regarding the properties reported that, for example, the use of polypyrrole as electrode material has a capacity of 86 C / g and an energy density of 11 Wh / kg, the use of a Mixture of polypyrrole and polythiophene has a capacity of 120 C / g and an energy density of 27 Wh / kg and the use of Poly 3- (4-fluorophenyl) thiophene a capacity of 52 C / g and an energy density of 39 Wh / kg (J. Power Sources, Vol. 47, p. 89 (1994)).

Unlike the above, in carrying out the use of intercalation for a high-capacitance capacitor, a layer structure substance (TiS ₂ , MoS ₂ , CoO ₂ , V ₆ O ₁₃ ) is generally used as the electrode material. In this case, the device is assembled with asymmetric electrodes in many cases (Japanese translations of PCT for Patent Nos. 2002-525864, 2002-542582).

moreover are composites that are different from the above Electrode materials are produced, evaluated in some cases they have been much higher capacities compared to conventional Achieve capacitors that only the porous carbonaceous material as electrode material.

[By the invention too expectorant Tasks]

In spite of intensive research is not a mixture of carbon-containing Materials and (intrinsic) conductive polymers industrial in use. The reasons for that can predominantly in a bad homogeneity the mixture on a nanoscopic scale and a bad one Reproducibility of properties due to the manufacturing process used (as described above).

On the other hand, the above-mentioned conventional electric double-layer capacitors are use a porous carbonaceous material for polarizable electrodes, limited in capacity, although they are good at fast charge / discharge characteristics. For example, as described in Japanese Patent Laid-Open No. 2003-338437, a capacitor using activated carbon obtained by activating porous carbonaceous material (surface area: 650 m ² / g) has an electrostatic capacity of 18.3 F / g. which is lower than those of electrochemical capacitors.

As with the ratio between the electrostatic capacity and the specific surface area of the porous carbonaceous material, an electrostatic capacity of about 22 F / cm ^{3 is} obtained when the specific surface area is in the range of 1500 to 2600 m ² / g, however Capacity is not further increased but tends to decrease when the specific surface area is above the range ("Electrical Double Layer Capacitors and Electric Power Storage Systems", The Nikkan Kogyo Shimbun, Ltd., p. 9).

From the above various other examples of an electrode material, the porous one Carbon-containing material used are in the Japanese Patent Publication Nos. 2003-217982, 2003-81624, 2002-373835 and the like, however, each of the examples gives in comparison to those of electrochemical capacitors a smaller capacity, which is particularly when used for motor vehicles and the like is important.

Besides that is in the case of using only the porous carbonaceous material for electrodes necessary to add acetylene black or the like to the binder the conductivity too increase, however, the interface resistance is even with such an addition very high, which is a serious problem represents.

On the other hand, the electrochemical capacitors using a metal oxide use a conductive metal as described above. Although these electrochemical capacitors have very high capacities as compared with the cases of using the above-mentioned porous carbonaceous material, the electrochemical capacitors are disadvantageous because of production cost because the metal of the metal oxide is generally noble metals. For example, at the 5th International Seminar on Double Layer Capacitors and Similar Energy Storage Device, held in Florida, USA in 1995, it has been reported that pseudocapacitance capacitors utilizing a thin layer of ruthenium oxide or indium oxide as the electrode material have an electrostatic capacity of 160 Have F / cm ³ in an aqueous system.

In addition, show the electrochemical capacitors, which are a conductive polymer material as electrode material, generally a much higher capacity in comparison to those of capacitors containing the above porous carbon-containing Use material, however, can their properties in dependence of the method for forming the electrodes vary. For example, if the conductive polymer on collector plates by an electrolytic polymerization process, as in Japanese Patent Laid-Open Nos. Hei 6-104141 and Hei 6-104142 described, has the capacitor a capacity of 3.7 F and an internal resistance of 13.9 Ω and the formation of electrodes by the electrolytic polymerization process generally brings a serious problem regarding the productivity of the same with himself.

Therefore are many suggestions been submitted, combinations of carbonaceous materials (predominantly Soot) and intrinsically conductive To use polymers. As described above, only two Process for the preparation of these mixtures has been used - a dry mixing process of powders (by ball milling and the like) and the polymerization of the conductive Polymers in the presence of the carbon black.

The Process for the synthesis of a conductive polymer by chemical Oxidation polymerization and for the production of a composite material from the conductive Polymer and further conductive inorganic material is obviously a relatively simple one Technology for the formation of electrodes and many examples of these Technology has been published in recent years. However, that is their reproducibility bad and therefore are not such mixtures in practical use, because the problems are enormous in the Attempt to scale up (scale up) and the development of a reproducible process are.

For example, Japanese Patent Laid-Open No. 2002-265598 discloses the use of a composite of organic conductive oligomer and inorganic material as an electrode material. However, in this case, the organic conductive oligomer can not be expected to have a high conductivity So that it is necessary that the inorganic material has a very high conductivity in order to lower the internal resistance.

In addition, can as a similar one Case of using conductive Polymer material a method of polymerizing the conductive polymer in a porous Carbon-containing material (Japanese Patent Laid-Open No. 2001-210557) no conductive Polymer with a high conductivity generate leads but to an increase in the internal resistance of the capacitor.

As So far described above is a large number of examples of one Condenser known, which is an electrochemically active conductive polymer or inorganic oxide used. However, the use of the inorganic leads Material to a problem in terms of production costs, whereas the use of the conductive Polymers difficulty in controlling conductivity, control of particle size and reproducibility entails what causes that the capacitors are not sufficient performance exhibit.

Therefore It was the object of this invention to provide a carbon material / conductive polymer blend to create a reproducible production and superior Performance values, in particular in the production of supercapacitors, allows.

[Detailed description the invention]

Most surprising may be a mixture of (intrinsic) conductive polymer / conductive polymers Carbon-based materials such as carbon black, graphite, carbon nanotubes or Fullerenes are produced reproducibly when the conductive polymer (the conductive Polymers) in colloidal form and the colloidal form of conductive Polymer is mixed with the carbon-based material.

preferred embodiments The present invention is disclosed in the dependent claims.

An embodiment of the present invention resides in electrodes for a high capacity capacitor comprising porous carbonaceous material or valve metal, at least one of the electrodes being formed of a composition containing an electrochemically active substance and the composition dispersing primary particles in a liquid dispersion medium dispersed conductive polymer, wherein the primary particles have an average particle diameter of less than 500 nm and a specific surface area of more than 15 m ² / g, measured according to BET method. In particular, the electrochemically active substance material is prepared by dispersing the conductive polymer in water or organic solvent, and in particular, by controlling the particle size of the conductive polymer, it is possible to firmly bond the porous carbonaceous material and form a stable electrode or electrodes. While a nonconductive organic binder has been used in the art as a binder to bind the porous carbonaceous material, the conductive material of the present invention makes it possible to form the electrode without using a binder. In addition, the adhesion force for adhesion to a collector plate can be sufficiently ensured by controlling the particle diameter. As another effect, the dispersion of particles of the conductive polymer makes it possible to increase the specific surface area required for forming an electric double layer, and is very advantageous for impregnation with an electrolytic solution. The conductive polymer is not particularly limited, and examples thereof include polyaniline, polyaniline derivatives, polythiophene, polythiophene derivatives, polypyrrole, polypynol derivatives, polythianaphthene, polythianaphthane derivatives, polyparaphenylene, polyparaphenylene derivatives, polyacetylene, polyacetylene derivatives, polyparaphenylenevinylene, polyparaphenylenevinylene derivatives, polynaphthalene and polynaphthalene-polynaphthalene derivatives. The method for polymerizing the conductive polymers is not particularly limited, and the usable methods include electrolytic oxidation polymerization, chemical oxidation polymerization, and catalytic polymerization. The polymer obtained by the polymerization method as mentioned is neutral and not conductive per se. Therefore, the polymer is subjected to p-type doping or n-type doping. By doping, the polymer can be made a conductive polymer. The substance used for doping is not particularly limited; In general, a substance such as a Lewis acid capable of accepting an electron pair is used. Examples of the substance include hydrochloric acid, sulfuric acid, organic sulfonic acid derivatives such as paratoluenesulfonic acid, polystyrenesulfonic acid, alkylbenzenesulfonic acid, campfersulfonic acid, alkylsulfonic acid, sulfosalicylic acid, etc., iron chloride, copper chloride and iron sulfate.

A another embodiment of the invention concerns the conductivity of the conductive Polymers and wears especially to a reduction of the equivalent series resistance at the capacitors. While It is common practice to use acetylene black or the like as a conductivity-imparting material in the case of an electrode for to add a capacitor which is a porous carbonaceous material used is the material of the invention characterized in that the conductive polymer by adjustment the conductivity to 100 S / cm or above in itself the function as conductivity-conferring Material has what the special addition of conductivity-imparting Material unnecessary power. Since it is not necessary, conductivity-conferring material admit it is possible the capacity of the actual Product to enlarge. In this case is the conductivity of the conductive Polymer necessarily at least 100 S / cm, preferably 200 S / cm or above and especially 500 S / cm or above. The conductivity is preferably as high as possible, because she has a big one Influence on the internal resistance of the capacitor to be produced Has.

A another embodiment of the invention consists in an electrode composition for a capacitor in which the conductive one Polymer is dispersed in water or an organic solvent. In particular, the specified composition for the case where the electrolyte in the condenser is water, and in case in which the electrolyte is an organic solvent, conditionally separated be used. In particular, when the electrolyte liquid Water is, the use of conductive, is in organic solvent dispersed polymer for the stability the electrode advantageous.

A another embodiment of the invention relates to an electrode composition for a capacitor in which the conductive one Polymer dispersion component solid components in a concentration of not more than 20% by weight. Especially at the time of formation of the electrodes affects the concentration solid components productivity and costs greatly. However, the solid components in the conductive polymer dispersion component affect also the stability the dispersion. Therefore, amounts the concentration of solid components is not more than 20% by weight, if production costs are taken into account and the concentration is not more than 10% by weight, preferably not more than 5% by weight, if the stability the dispersion is also considered.

A another embodiment of the invention relates to an oxidation / reduction reaction of the conductive polymer. Especially if the stability, those with a structural chemical reaction change is considered, has the attitude of a minimal proton movement has a good effect on the lifetime the device. Preferred examples of such a conductive polymer material shut down Polyaniline, polyaniline derivatives, polypyrrole and polypyrrole derivatives.

Another embodiment of the invention relates to the specific surface area of the porous carbonaceous material. The present definition refers to the capacitance of the capacitor, and a sufficient capacitance can be obtained by using the carbonaceous material having a specific surface area of not less than 100 m ² / g, preferably 500 m ² / g, and more preferably 1000 m ² / g become. This porous carbonaceous material is dispersed in the conductive polymer dispersion component. In order to achieve a highly dispersed state, the dispersing method can be carried out by using a conventional ball mill, a planetary ball mill, a homogenizer or an ultrasonic dispersing machine. When the planetary ball mill is used, stirring is preferably performed for at least 30 minutes. Stirring for a long time involves a problem such as a rise in the temperature of the solvent; therefore, in the case that stirring is not less than 1 hour, cooling is required.

Another embodiment of the invention relates to the added amount of the porous carbonaceous material. It is necessary to add the porous carbonaceous material in an amount of at least 5% by weight. The amount of addition is closely related to the charge / discharge speed of the capacitor. It is desirable, in the case of fast charge / discharge devices, to add the porous carbonaceous material in a larger amount, and in the case of slow charge / discharge devices, the conductive polymer to add in a larger amount. Therefore, according to the invention, it is sufficient to control the addition amount according to the device requirements. In order to obtain a capacitor device having a capacitance at least greater than that of a capacitance device using only the porous carbonaceous material, it is necessary to add the conductive polymer in an amount of not less than 5% by weight based on solid components. In order to obtain a sufficient oxidation / reduction effect, it is necessary to use the conductive polymer based on solid components in an amount of preferably not less than 10% by weight.

A another embodiment of the invention consists in electrodes for a capacitor connected to the separator between them opposite each other are arranged, both electrodes of the same type of conductive polymer are composed. This arrangement has the advantage of providing a very reasonably priced one Device under consideration productivity the same.

A another embodiment of the invention consists in electrodes for a capacitor, wherein the compositions used to form the two opposite ones Electrodes are used with the interposed separator, composed of different types of conductive polymers are. This is based on the consideration of the general fact that many conductive Polymers under a positive voltage and under a negative Voltage show different efficiencies. In other words, A method for obtaining a high-capacity device is described in U.S.Patent Use of a conductive Polymer material, which is the highest shows electrical effectiveness when the voltage is reversed.

A another embodiment of the invention consists in electrodes for a capacitor connected to the separator between them opposite each other are arranged, wherein one of the two electrodes of porous carbon-containing Material is formed and the other made of a composite body porous Carbonaceous material / conductive polymer as defined herein is composed. With this arrangement, a high capacity in case the use of an intercalation electrode as a porous carbon-containing Electrode can be expected.

A another embodiment of the invention consists in electrodes for a capacitor connected to the separator between them opposite each other are arranged, wherein one of the two electrodes of metal oxide and the other composite porous carbonaceous material / conductive polymer composite body as defined here is composed. This arrangement is special in the case of obtaining a high capacity by using the oxidation / reduction properties the metal oxide electrode effectively. Particularly desirable examples of Materials of the metal oxide electrode are ruthenium oxide and indium oxide.

If the composite body of inorganic material / conductive Polymer in the present invention to a film or a other shaped product, stabilizing agents, Light stabilizer, filler, Binder, conductivity-imparting Means and the like may be added as needed.

[Way of carrying out the Invention]

Experimental Example 1: Production process from composite electrode of porous Carbonaceous material / conductive polymer

Powdered activated carbon from coconut shells (not yet activated) in an amount of 18 g became conductive in 90.9 g Polymer dispersion material (ORMECON 7301-026-002; solvent: xylene; solid components: 2.2%), and the mixture became with a planetary ball mill Stirred for 60 minutes. To the porous one Carbonaceous material / conductive polymer slurry Further, 57.3 g of xylene was added and the mixture was stirred Stirred for 30 minutes, to a dispersion of porous Carbonaceous material / conductive polymer.

The Electrodes for A capacitor requires an exchange of collector plates in dependence of an electrolyte solution. In this experiment, platinum plates were used as electrodes in the case the use of aqueous Sulfuric acid solution (1 mol / l) as electrolyte solution used, and aluminum was for the electrodes used in the case of using propylene carbonate for the electrolytic solution. If platinum for the Collector plates in the actual Electrodes for The capacitor is used first, the surfaces of the Platinum plates roughened with a file and then with a predetermined Amount of the porous carbonaceous material / conductive polymer dispersion prepared above coated. Then the coated platinum plates are left for 1 hour long at 100 ° C in a high temperature tank placed to the organic solvent sufficiently remove. The electrodes thus formed become one Weighed out the electrode active substance and were directly as electrodes for used the capacitor.

Then were in the case of using 1 mol / l solution of tetraethylammonium tetrafluoroborate in propylene carbonate as an electrolyte solution based on organic solvent Aluminum plates used as collector plates. The aluminum collector plates were roughened with a file and with a given amount the dispersion of porous Carbonaceous material / conductive polymer on the same As in the case of using the platinum plates as collector plates coated. It was then dried at 100 ° C for 24 hours carried out, to remove moisture sufficiently.

The Components of the dispersion material used to form the composite electrodes made of porous Carbonaceous material / conductive polymer can be used, are listed in the following table.

Experimental Example 2: Production the capacitor cell

each Electrode plate with an electrode-active substance in close connection with that prepared in Experimental Example 1 becomes circular discs punched out with a diameter of 1 cm to produce two electrodes. A glass fiber filter becomes a circular shape with a diameter punched out by 1.5 cm, and the circular product is used as a separator used. Further, an aqueous 1 M sulfuric acid solution as electrolyte solution in the case of an aqueous Systems used. A 1 M solution of tetraethylammonium tetrafluoroborate in propylene carbonate is in Case of an organic solvent system as electrolyte solution used.

rating the capacitor properties

Measuring instruments: The internal resistance of each capacitor cell was measured using an impedance meter YHP 4192A measured. The measurements during a charge / discharge test were performed using a TOYO system TOSCAT-31000.

The Results of the charge / discharge test of capacitors under Use of the electrode-active substances listed in Experimental Example 1 are listed as examples in the following table.

The results of the evaluation of the internal resistance are in 1 and 2 shown. The measurement was carried out using a capacitor cell formed using the electrodes using the dispersion components of Example 2 and Example 5 and using a 1 M sulfuric acid solution as the electrolytic solution.

1 shows the internal resistance of the capacitor using the porous carbonaceous material having a specific surface area of 1600 m ² / g.

2 shows the internal resistance of the capacitor using the porous carbonaceous material having a specific surface area of 1100 m ² / g.

Comparative Example:

[Effects of the Invention]

As has been described above, the present invention provides a electric double layer capacitor in which a pair of polarizable electrodes, each containing a solid electrolyte made of conductive Comprising polymer contained in an activated carbon layer, with a separator disposed therebetween opposite each other are arranged. In particular, by increasing the particle diameter and the conductivity of the conductive Polymers an electric double layer capacitor with a low Internal resistance and a high capacity can be obtained.

Claims (25)

Composition leading to the formation of a coating is suitable and a mixture of conductive polymer in colloidal Form and carbon includes. A composition according to claim 1, wherein the conductive polymer from polymers of anilines, thiophenes, pyrroles and substituted ones Derivatives thereof selected is. A composition according to claim 1 or claim 2, where two or more different conductive polymers are present. A composition according to any one of the preceding claims, wherein the carbon has a specific surface area greater than 100 m ² / g as measured according to the BET method. A composition according to any one of the preceding claims, wherein the carbon is selected from graphite, carbon black, nanotubes and fullerenes. A composition according to claim 5, wherein the carbon Active soot is. A composition according to claim 6, wherein the active carbon black has a specific surface area greater than 750 m ² / g. A composition according to any one of the preceding claims, wherein the average particle size (number average) of the conductive polymer is less than 500 nm. A composition according to any one of the preceding claims, wherein the conductivity of the conductive polymer is greater than 10 ^-5 S / cm. A composition according to claim 9, wherein the conductivity greater than 10 S / cm is. A composition according to claim 10, wherein the conductivity greater than 100 S / cm is. A composition according to any one of the preceding claims, wherein the weight ratio of the conductive Polymer to carbon ranges from 1:50 to 50: 2. A composition according to any one of the preceding claims which furthermore a liquid one Dispersing agent in a concentration of 40 to 99.5 wt .-% wherein the dispersant liquid is under ambient conditions is vaporizable, and other non-volatile additives in a concentration from 0 to 10 wt%, wherein the conductive polymer and the carbon components are present in a concentration of 0.5 to 60 wt .-%, wherein all Weight percentages are related to the entire composition. A composition according to claim 13, wherein the liquid dispersant Water and / or organic) solvent includes. Process for the preparation of a composition according to one of the preceding claims, where the conductive Polymer and carbon and optionally additives dispersed in a liquid dispersant be and the liquid Dispersion optionally dried after application to a substrate becomes. The method of claim 15, wherein the conductive polymer in a first liquid is dispersed and the carbon separated in a second liquid is dispersed, the liquids are the same or different, and the respective dispersions are then mixed together with optional additives before, during or after the separate Dispergierschritten be added. The method of claim 15, wherein the conductive polymer in a liquid is dispersed and the carbon separated in the absence of liquid is ground and in which the dry ground carbon then the liquid colloidal dispersion of the conductive Polymer is added and dispersed therein. Composite material comprising the composition according to a the claims 1 to 14 or by the method according to one of claims 15 to 17 composition obtained in the form of a coating on a Substrate comprises. The composite of claim 18, wherein the substrate from the group consisting of metals, semiconductors, plastics, Ceramics and wood products is selected. Electrical or electronic article containing the Composition according to one the claims 1 to 14 or the composite material according to claim 18 or claim 19 includes. An article according to claim 20, wherein the article is made from the group consisting of conductors, energy storage, sensors, switches, Capacitors, capacitors and supercapacitors, double-layer capacitors and redox capacitors selected is. An article according to claim 21, wherein the article is a Capacitor is, the electrolyte and a pair of electrodes with one interposed separator, wherein at least one the electrodes, the composition according to any one of claims 1 to 14 or the composite material according to claim 18 or claim 19. A capacitor according to claim 22, wherein both electrodes the composition according to one the claims 1 to 14 or the composite material according to claim 18 or claim 19 include. A capacitor according to claim 22, wherein an electrode the composition according to one the claims 1 to 14 or the composite material according to claim 17 or claim 18 and the other electrode comprises a conventional capacitor electrode is. A capacitor according to claim 24, wherein the other Electrode includes a pantograph, which has a composition coated, the intrinsically conductive polymer, but no Contains carbon.