DE10033578A1 - Conductive polymer composition based on graphite - Google Patents

Abstract

The invention relates to a conductive polymer composition comprising A) graphite and/or at least one graphite compound, B) at least one binding agent and C) at least one polyurethane dispersion resin, in addition to a multilayered electrode material containing one such polymer composition, and also a method for producing said electrode material and the use thereof.

Description

The present invention relates to a conductive polymer tion, the graphite and / or at least one graphite compound, at least one binder and at least one polyurethane dispersant gierharz, a multilayer electrode material, which such a polymer composition comprises processes for the same Production and its use.

Graphite features due to its layered crystal lattice, where the carbon atoms are each only three σ bonds in one plane and an additional, non-localized π bond form, via anisotropic, electrical conductivity. by virtue of this layered lattice structure, graphite is still able to special forms of intercalation compounds, so-called Zwi to form grate or intercalation compounds. It who the foreign atoms or molecules in a stoichiometric or non-stoichiometric ratio in the spaces between the individual carbon levels. In the resulting laminar Connections remain in the electrical properties of graphite Generally obtained and can be significantly improved become. In this case, the storage layers by a sub different number of carbon levels (so-called levels) of separated and the occupation densities of the intercalations layers of different sizes or the layer grid strongly aufgewei be. Accordingly, a large number are partly chemical quite different graphite compounds known. Also the naturli Graphites are available in a variety of fineness levels offered. To achieve a good conductivity are in the Generally high-purity graphites used in a chemical Be were subjected to such action, eg B. to ash-forming components eliminate.  

Conductive compositions containing finely divided graphite or Gra containing phite compounds dispersed in a polymer component, are known. For the production and stabilization of conductive Dispersed graphite polymer compositions are disclosed in U.S. Pat Graphite specially adapted binders, dispersing resins and gege if necessary, further excipients required. A disadvantage of the be Known polymer compositions that is generally for each Graphittyp be provided its own binder system got to. Since the manufacturers of these Graphite or graphite compounds in Generally only the performance characteristics, such as Leit ability, glide and hardness, but not the chemical surface structure, are for identifying a for the optimum graphite composition optimum binder composition in space extensive extensive tests required. There is thus one Need for a binder system for making conductive poly merzusammensetzungen, which can be used more universally as the known compositions.

For dispersing the graphite in conductive polymer composition Tongues are often low molecular weight surfactants as dispersants used. A disadvantage of low molecular weight surfactants is that the in polymer compositions as plasticizers and their me reduce mechanical load capacity. Furthermore, they often increase the hydrophilicity of the compositions, which then, in particular at Long-term use, can absorb water. This leads to a Reduction in conductivity and mechanical strength the polymer compositions. In addition, an incompatibility of Surfactants with the binder to a partial segregation and egg ner local enrichment of surfactants, z. B. on the surface of Polymer compositions, resulting in the mechanical properties are also adversely affected. When used in Lithium-ion batteries are also low molecular weight surfactants in the Usually attacked by the lithium ions.  

To achieve the highest possible conductivity and a possible As good intercalation becomes a high graphite content of the poly desired compositions, d. H. the proportion of binders and other excipients should be as low as possible. To the verar Processing of conductive polymer compositions are often Lö used. The layer grid structure of the Gra phits are essentially preserved while processing a good conductivity of the resulting polymer layers and possible to ensure the best possible intercalation conditions. Of Furthermore, these solutions should be storage stable, so that no Ag glomerates occur that have the performance characteristics influence negatively. Should the solutions for the production of leit capable layers, eg. B. by pouring onto a substrate, turned be set, they must be well flowable, d. H. the behavior The viscosity and yield point should vary depending on the vary the chosen application method. The previously known conductive polymer compositions do not meet all previously ge called requirements at the same time and therefore could be improved dig.

EP-A-0 647 668 describes conductive binder compositions containing a graphite intercalation compound, carbon black Polyester binder and a solvent. Disadvantageous These compositions have their low electrochemical stability due to a cleavage of the polyester bonds. In addition is the storage stability and the rheology of these compositions ver improvement worthy.

In electrical components, eg. B. in lithium-ion batteries and -Bat become sheet-like multilayered electrode materials used, wherein a central conductive layer, for. B. a Kup ferfolie, with a conductive polymer composition on both sides is coated. The individual layer thicknesses are partly very low and are z. In a range of about 5 to 500 μm. In general, the production of this multilayer takes place  gene electrode materials by dispersing the graphite in one polymeric binder with melting in an extruder and on closing application to the carrier film. A disadvantage of this The method is that often agglomerates arise and the Gra phitstruktur can be partially destroyed, resulting in a verrin gerten conductivity leads. In addition, graphite is sensitive to so called over-dispersing, which also leads to a degradation of Layer grid structure and thus to a reduced conductivity leads. This can happen, in particular, when batteries are used during the Production process are compressed under high pressure.

Conductive polymer compositions for use in lithium Ion batteries must incorporate the lithium ions into the graphite enable grating. Neither the polymeric binder nor an optionally used dispersing agent through the lithium Ions are attacked. At the same time, these binders and optionally dispersion aids are such that a. Ion migration of the lithium ions and a transition to the graphite layer structure is made possible.

The present invention is based on the object, conductive To provide polymer compositions that are a bandage comprising a system which is suitable for dispersing a number of natural and synthetic graphites, of graphite ver and optionally other pigments. virtue wise, these compositions should be used to formulate Dis are those which have a high graphite or pigment content and still generally flow well. conductive Polymer compositions comprising this binder system, should preferably for the production of multi-layer Elek trodenmaterialien are suitable. Another object of the present invention It is an improved method for producing more layered electrode materials to provide.  

Surprisingly, it was found that the basis of the invention underlying tasks solved by conductive polymer compositions can be, in addition to graphite and / or at least one graphite compound containing a binder system, which at least one Binder and additionally at least one polyurethane dispersing resin includes.

The present invention thus provides a conductive Po lymerzusammensetzung comprising

• A) graphite and / or at least one graphite compound,
• B) at least one binder, and
• C) at least one polyurethane dispersing resin.

Preferably, the polymer compositions according to the invention comprise at least one pigment D) which differs from component A), which is selected from carbon black, metal chalcogenides and mixtures from that.

Component A)

For the conductive polymer compositions according to the invention, in general, all known electrically conductive graphi te and / or graphite compounds. Suitable graphite compounds are, for. B. graphite intercalation compounds containing electron donors or acceptors incorporated. In this case, in general, charge exchange between the incorporated compound and the Gra phit occurs, so that the electron occupation in the conduction band is changed compared to unmodified graphite. By suitable choice of the intercalated compounds, a significant improvement in the conductivity can generally be achieved. Suitable electric nendonatoren z. As alkali and alkaline earth metals, Übergangsme metals, preferably the V. to VIII. Subgroup, as well as the Lanthani de. Preferably, the electron donors are selected from Li, K, Rb, Cs, Ca, Sr, Ba, Eu, Yb, Sm, Mn, and mixtures thereof. Geeig designated electron acceptors are z. B. Halogens, such as Cl and Br. Geeig net are also the reaction products of graphite with Oxidationsmit stuffs, such as HNO ₃ , CrO ₃ , (NH ₄ ) ₂ S ₂ O ₈ etc., and the reaction products of graphite with strong acids, such as HClO ₄ , HNO ₃ , H ₂ SeO ₄ , H ₃ PO ₄ , in the presence of oxidants. The preparation of these Graphitinterka lationsverbindungen in a conventional manner known to the expert, for. Example by reacting natural or synthetic graphite under heating in the presence of vapors of the aforementioned metal le or in the presence of liquid acids and / or oxidizing agent or solutions thereof. The formation of the intercalation compounds may be at ambient pressure or, preferably, under elevated pressure. Suitable graphite compounds are, for. Example, the graphite intercalation lationsverbindungen, as described in EP-A-0 646 688, to which reference is made here.

Component B)

Suitable binders B) are z. As polymers containing at least one free-radically polymerizable, α, β-ethylenically unsaturated mono merized polymer. Suitable monomers are C ₂ to C ₈ monoolefins, such as. As ethylene, propylene, 1-butene, 2-butene, Isopro pen, vinyl aromatics, such as. As styrene, α-methyl styrene, ο-chlorostyrene or vinyl toluenes, halogenated monoolefins, such as Chlortrifluorethy len, tetrafluoroethylene, hexafluoropropene, vinyl and Vinylidenhalo genides such. As vinyl fluoride, vinylidene fluoride, vinyl chloride and vinylidene chloride, esters of vinyl alcohol with C ₁ - to C ₂₀ monocarboxylic acids, such as. As vinyl formate, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of α, β-monoethylenically unsaturated mono- and dicarboxylic acids with C ₁ - to C ₂₀ alkanols, preferably with C ₁ - to C ₈ alkanols, such as z. As esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and Crotonsäu re with methanol, ethanol, n-propanol, isopropanol, n-butanol, iso butanol and 2-ethylhexanol, maleic acid and Maleinsäu re-n-butyl ester, α, β ethylenically unsaturated nitriles, such as. As acrylonitrile and methacrylonitrile, amides of acrylic and Methacrylsäu re, non-aromatic hydrocarbons having 2 to 8 Kohlenstoffato men and at least two olefinic double bonds, such as. Butadiene, isoprene and chloroprene, and mixtures of these monomers.

Preferably, the binder B) comprises at least one polymer, which einpolyme at least one α, β-ethylenically unsaturated monomer which is selected from halogenated monoolefi such as chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropene, Vinyl and vinylidene halides, such as vinyl fluoride, vinylidene fluoride orid, vinyl chloride, vinylidene chloride and mixtures thereof. before The binder B) comprises at least one polyvinylidene fluoride Homopolymer and / or a polyvinylidene fluoride-hexafluoropropene Copolymer (PVDF / HFP copolymer). The polymers mentioned B) based on halogenated monomers may be particularly preferred as sole binders B) are used. Preferred as a binder tel B), however, are also polymer mixtures which are at least one polymer and based on halogenated monomers and at least one other Include polymer. Preferred further polymers are those in the Following polyurethanes. Preferably, their share at most 50 wt .-%, particularly preferably at most 25 wt .-%, bezo to the total amount of binder.

Preferably, the binder B) comprises at least one polymer which contains at least one copolymerized C ₂ - to C ₈ monoolefin as α, β-ethylenically unge saturated monomer. Preference is given to polyisobutenes. These preferably have a number average molecular weight in the range of about 400,000 to 5,000,000. The glass transition temperature is preferably in a range of et wa -70 to -10 ° C. Suitable polyisobutenes are the Oppanol® grades of BASF AG. The stated polyolefins can be used with particular preference as the sole binder B).

Suitable binders B) are also cellulose derivatives, for. Cel cellulose esters, preferably cellulose nitrates, cellulose acetates, cellulose seacetopropionate and cellulose acetobutyrate.  

Other suitable binders B) are epoxy resins, preferably Phenoxy resins, the z. As the reaction products of bisphenols, such as Bisphenol A, incorporated with epichlorohydrin.

According to a suitable embodiment, component B comprises we at least one polyurethane resin. Suitable polyurethane resins included at least one isocyanate group-containing component selected is among diisocyanates, polyisocyanates and isocyanate prepolymers, in copolymerized form. Suitable di-, tri- and polyisocyanates and Isocyanate prepolymers are described below in the component C ge Nannt. Furthermore, the polyurethane resins contain at least one Compound that is selected from compounds that have an or contain several active hydrogen atoms per molecule, einpolymeri Siert. This is z. B. selected from amines, polyamines, diols, Triols, polyols, aminoalcohols, compounds having at least two terminal, isocyanate-reactive groups which belong to additionally at least one further functional group selected under α, β-ethylenically unsaturated double bonds and epoxy contain per molecule, polymers with at least two end permanent, isocyanate-reactive groups, Verbindun gene with at least two terminal, opposite isocyanate groups reactive groups additionally having at least one polar function nelle group, selected from carboxylic acid groups, sulfonic acid group groups, phosphonic acid groups, phosphoric acid groups, their alkali metals tall and alkaline earth metal salts, amino groups and quaternary ammo have niumgruppen per molecule, and mixtures thereof. suitable Compounds containing one or more active hydrogens per mo Lekül are also described below in the component C called.

Suitable polyurethane resins are, for. As described in DE-A-32 27 163 and DE-A-32 27 164 binder for magnetic Materiali s, which are obtainable by crosslinking a polyisocyanate with a hyroxylgruppenhaltigen polyurethane prepolymer. The polyurethane prepolymer is a thermoplastic poly ureaurethane having an OH number between 10 and 120 (or 30 and 160), which consists of the components

• A) 1 mol of a polydiol having a molecular weight between 400 and 4000,
• B) 0.2 to 10 mol (or 0.2 to 9 mol) of a diol having 2 to 18 Carbon atoms,
• C) 0.1 to 4 moles (or 0.2 to 10 moles) of a primary or secondary aminoalcohols having from 2 to 20 carbon atoms,
• D) optionally 0.01 to 1 mol of a triol having 3 to 18 carbon atoms atoms and
• E) 1.20 to 13 moles of a diisocyanate having 6 to 30 carbon atoms men, wherein the proportion of NCO groups of the diisocyanate, based to the components IA to ID, 65 to 95% of the equivalent Amount of OH and NH groups is,

will be produced. In this case, the component IB can be wholly or partially by diamines or amino alcohols with primary or secondary amino groups, corresponding to the component IC. This comm Components serve to form hydroxyl-containing urea groups at the chain ends of the polyurethane prepolymer.

Suitable binders B) are also described in DE-A-32 27 163 Binder mixtures of the aforementioned hydroxylgruppenhal polyurea urethane and a physically drying bandage medium based on vinyl formal groups.

Suitable binders B) are also described in DE-A-39 29 164 be described polyurethane binders based on a fluorgruppenhal term, soluble in tetrahydrofuran, isocyanate group, ver branched polyurethane containing hydroxyl-containing urea groups at the chain ends and a molecular weight between 4000 and 30,000. This polyurethane binder is made

• A) 1 mol of a polyol having a molecular weight between 400 and 4000,
• B) 0.3 to 9 moles of a diol having 2 to 18 carbon atoms,
• C) 0.01 to 1 mol of a triol having 3 to 18 carbon atoms,
• D) 0.001 to 0.4 mol of a perfluoro compound with two opposite Isocyanate-reactive end groups and a molecular weight between 300 and 4000,
• E) 1.25 to 13 moles of a diisocyanate having 6 to 30 carbon atoms men, where the ratio NCO: OH in the sum of the components A, B, C and D is 1.05: 1.0 to 1.4: 1.0, and
• F) 0.05 to 4 mol of an OH group-containing, compared to isocyanates reactive, primary or secondary amine

manufactured. To form prepolymers having hydroxyl groups on the Chain ends are the components A to E to an isocyanate reacted group-containing intermediate and this subsequently reacted with the aminoalcohol F. Also suitable in the DE-A-39 29 165 described polyurethanes, wherein different from the DE-A-39 29 164 as component D 0.01 to 0.4 moles of an organofunction nelle polysiloxane compound with two isocyanate reacti ven end groups and a molecular weight between 300 and 4000 is used.

Also suitable are the bin described in DE-A-40 39 748 based on a thermoplastic, in tetrahydrofuran solution isocyanate group-free, branched polyurethane prepolymer with sulfonate groups along the polyurethane branches as well as hydroxyl  group-containing urea groups at the chain ends. The production The hydroxyl-containing polyurethane prepolymer is carried out as in DE-A-39 29 164, wherein instead of a perfluoro Binding a diol having at least one sulfonate group is set.

Suitable binders are also those in DE-A-197 57 670 be polyurethane resins which by crosslinking at least a polyisocyanate having at least one isocyanate group-free, at least three active hydrogen atoms containing polyurethane are available prepolymer, wherein the polyurethane prepolymer little at least two hydroxyl groups and at least one primary and / or se has a known amino group.

On the aforementioned writings is hereby fully Be taken.

The following are compounds that differ from acrylic acid and Methacrylic acid can be partially shortened by insertion the syllable "(meth)" in the derived from the acrylic acid compound designated.

Suitable dispersing resins C) are z. As polyurethane (meth) acrylates and / or polyurea (meth) acrylates based on hydroxyl-containing polymers containing at least one ester of an α, β-ethylenically unsaturated mono- and / or dicarboxylic acid with C ₁ - to C ₂₅ -, preferably C ₁ - to C ₈ alkanols, as well as, if appropriate, further free-radically polymerizable monomers in copolymerized form.

As α, β-ethylenically unsaturated mono- and / or dicarboxylic könks nen z. Acrylic acid, methacrylic acid, fumaric acid, maleic acid, Cro Tonsäure, Itaconsäure etc. and mixtures thereof are used. Preference is given to acrylic acid, methacrylic acid and mixtures thereof. Ge suitable alkyl radicals of the alkanols are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl,  n-pentyl, n-hexyl, n-heptyl, n-octyl, ethylhexyl, 1,1,3,3-tetrame butylbutyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, palmi tyl, margarinyl, stearyl, palmitoleinyl, oleyl or linolyl.

Suitable further monomers which contain the hydroxyl-containing polyme may contain polymerized in the binder, are the bindings B) vinylaromatics, α, β-ethylenically unsaturated Nitriles, vinyl halides, esters of vinyl alcohol, etc. Suitable other monomers are also bifunctional monomers, such as. Eg not aromatic hydrocarbons with at least two olefinic Double bonds, z. B. butadiene and divinylbenzene. For the introduction of hydroxyl groups, the polymers can esters of α, β-ethyls unsaturated carboxylic acids with polyhydric alcohols builds included. Suitable polyhydric alcohols are, for. B. usual Diols, triols and polyols, e.g. B. 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, Diethy glycol, 2,2,4-trimethylpentanediol-1,5, 2,2-dimethylpropanediol-1,3, 1,4-dimethylolcyclohexane, 1,6-dimethylolcyclohexane, glyce trimethylolpropane, erythritol, pentaerythritol, sorbitol, etc.

Preferably, the hydroxyl-containing polymers contain about 80 to 100 mol% of at least one ester of an α, β-ethylenically unsaturated mono- and / or dicarboxylic acid with a C ₁ - to C ₂₅ - alkanol and 0 to 20 mol% of at least one other monomer built-in.

For the preparation of the hydroxyl-terminated polymers preferably used radical initiators and / or regulators, the are suitable to introduce a hydroxyl function in the polymer Suitable initiators and regulators are known to the person skilled in the art. These include z. B. OH-containing initiators, eg. B. hydroperoxides such as tertiary butyl hydroperoxide, tetrahydrofuran hydroperoxide, cumene droperoxide, 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide) and Regulators such as amino alcohols and thioalkanols, e.g. B. 2-hydroxyethyl-3  mercaptopropionate, 3-hydroxypropanethiol and especially mercap toethanol.

The hydroxyl-containing polymers are with di- and / or Reverse polyisocyanates to isocyanate group-containing polymers puts. The molar ratio of NCO groups is the Di- and / or polyisocyanates to hydroxyl groups of the hydroxyl groups terminated polymers preferably in a range of about 1.2: 1 to 3.9: 1.

Suitable di- and / or polyisocyanates are preferably selected among compounds having from 2 to 5 isocyanate groups, isocyanate prepolymers ren with an average number of 2 to 5 isocyanate groups, and Mi of it. These include organic di-, tri- and poly isocyanates. Suitable diisocyanates are, for. B. tetramethylene diisocyanate nat, hexamethylene diisocyanate, 2,3,3-trimethylhexamethylene diisocyanate nat, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate, 1,4-phenyne lendiisocyanat, 2,4- and 2,6-toluene diisocyanate and their isomers mixed, 1,5-Naphthylendiisocyanat, 2,4- and 4,4'-Diphenylmethandi isocyanate. A suitable triisocyanate is z. B. triphenylmethane 4,4 ', 4 "-triisocyanate. Prepolymers with two are also suitable free isocyanate groups from at least two same or different those diisocyanates and the diols mentioned below and poly diols. Preference is given to isocyanate prepolymers having a number average molecular weight up to about 10,000, preferably in a Be rich of about 500 to 3000. These are z. B. by addition of aforementioned isocyanates to polyfunctional hydroxyl or amino containing group-containing compounds. Preference is given to polyisocyanates based on toluene diisocyanate, hexamethylene diisocyanate and / or isophorone diisocyanate used by polyaddition D1 or triols or by biuret or isocyanurate formation hen. Suitable diols and triols are those previously described in the hydroxylgrup penhaltigen polymers described as polyhydric alcohols. Particularly preferred are addition products of toluene diisocyanate  on trimethylolpropane and / or on diols, such as diethylene glycol, 1,3- Butanediol, 1,4-butanediol, neopentyl glycol, and mixtures thereof.

According to a suitable embodiment, the hydroxyl groups polymers also with a mixture of the aforementioned Isocy anate be implemented. Preferably z. B. mixtures of aliphati isocyanates. These preferably have on average 2 to 6, ins particular 3 to 6 NCO groups per molecule. A suitable Isocy Anatgemisch includes z. B. 0.1 to 10 wt .-% of at least one Diisocya nats, 20 to 80 wt .-% of at least one triisocyanate and 20 to 60 wt .-% at least one polyisocyanate having a functionality of 4 to 10.

In the implementation of the aforementioned hydroxyl-containing poly merisate with the aforementioned di- and / or polyisocyanates re add isocyanate group-containing prepolymers, which are then mixed with verbin which at least one isocyanate-reactive Group, to those in the inventive conductive poly Mermersetzungen as dispersing resins C) used Polyuret han (meth) acrylates or polyurea (meth) acrylates reacted you can.

According to a first preferred embodiment for producing the Polyurethandispergierharze C) are the isocyanate groups Prepolymers with ammonia or at least one compound vice which has a primary or isocyanate reactive primary or have secondary amino group per molecule. These include z. Me ethylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine etc. The molar ratio of Isocyanate groups of the prepolymer to isocyanate to re active groups is generally in the range of et 1.1: 1 to 3: 1, so that polyurethane urea (meth) acrylates resul animals, which essentially no more free isocyanate groups on point.  

According to a second preferred embodiment for preparing the polyurethane dispersing resins C), the prepolymers containing isocyanate groups are reacted with at least one compound which contains one or more active hydrogen atoms per molecule and which is selected from

• a) amines having 2 to 10, preferably 2 to 4, primary and / or se secondary amino groups per molecule,
• b) polyamines having at least 2 primary and / or secondary amino groups,
• c) diols having 2 to 18 carbon atoms,
• d) aminoalcohols having at least one primary or secondary amino group,
• e) triols and / or polyols having 3 to 25 carbon atoms.

Suitable amines a) are straight-chain and branched, aliphatic and cycloaliphatic amines having at least two primary and / or secondary amino groups per molecule, which is generally about 1 to 30, preferably about 1 to 20 carbon atoms. These include z. As ethylenediamine, propylenediamine, 4-aminopiperidine and its Al kylderivate, such as 4-amino-2,6-dimethylpiperidine, 4-amino-2,6-diethyl piperidine, 4-amino-2,6-di-n-propylpiperidine, 4-amino-2,6-diisopro pylpiperidine, etc., 1- (2-aminoethyl) piperazine, ethanolamine, Me ethylethanolamine, diethylenetriamine, dipropylenetriamine, triethylene tetraamine, 4-azaheptamethylenediamine, N, N'-bis (3-aminopropyl) -butane 1,4-diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diami nooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane,  1,12-diaminododecane, 4,9-dioxododecane-1,12-diamine, 4,4'-diaminodi phenylmethane, and mixtures thereof.

Suitable polyamines b) having at least two primary and / or sec The amino groups generally have a number-average molecule largeweight of about 400 to 4000, preferably about 700 to 2500 on. These include z. As polyalkyleneimines, preferably polyethyleneimines, by Hydrolysis of poly-N-vinylamides, such as. For example, poly-N-vinylacetamide, he vinylamines, copolymers containing α, β-ethylenically unsaturated Monomers with appropriate functional groups, eg. B. Aminomethy lacrylate, aminoethyl acrylate, (N-methyl) aminoethyl acrylate, (N-Me ethyl) -aminoethyl methacrylate, etc., in copolymerized form, and α, ω-diamines based on linear and branched, aminated Polyalkylene oxides.

As component c) diols having 2 to 18 carbon atoms, before preferably 2 to 10 carbon atoms, are used, such. For example, 1,2-ethane diol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2-methyl-2-butyl-1,3-pro pandiol, 2,2-dimethyl-1,3-propanediol, 2,2-dimethyl-1,4-butanediol, 2-Ethyl-2-butyl-1,3-propanediol, hydroxypivalic acid neopentyl glycol ester, diethylene glycol and triethylene glycol. The diols can be one or used as mixtures. The diols c) can also partly replaced by water.

Suitable components d) are amino alcohols having 2 to 16, preferably 3 to 8 carbon atoms, such as. Monoethanolamine, methyl isopropanolamine, ethylisopropanolamine, methylethanolamine, 3-amino propanol, 1-ethylaminobutan-2-ol, 4-methyl-4-aminopentan-2-ol, N- (2-hydroxyethyl) aniline. Diolamines are preferably used since by their attachment at the chain end, the hydroxyl number of the polymers is doubled. Particularly preferred are diethanolamine and diiso propanolamine.  

Suitable triols e) are compounds having 3 to 25, preferably 3 to 18, particularly preferably 3 to 6 C atoms. Examples of custom bare triols are glycerol or trimethylolpropane. Are also suitable low molecular weight reaction products of triols and polyols, eg. B. of trimethylolpropane, with alkylene oxides, such as ethylene oxide and / or Propylene oxide. As polyols, for example, erythritol, pen use taerythritol and sorbitol.

According to a third preferred embodiment for preparing the polyurethane dispersing resins C, the isocyanate group-containing prepolymers are first reacted with at least one compound having at least two isocyanate-reactive groups, wherein the molar ratio of isocyanate groups of the pre-polymer to reactive groups preferably in a range of about 2 : 1 to 7: 1. Subsequently, the excess free reactive groups are partially or completely reacted with a compound which is suitable for introducing acidic groups into the polyurethane dispersion resin. The groups which are reactive toward isocyanate groups are selected from functional groups which have active hydrogen atoms, such as primary and secondary amino groups, hydroxy groups and mercapto groups. Suitable compounds having at least two of these groups are the stated amines a) having 2 to 10 primary and / or secondary amino groups per molecule, polyamines b), diols c), amino alcohols d) and triols or polyols e). Also suitable are mercaptans, such as 1,2-thioglycol, thioalcohols, such as 2-mercaptoethanol, thioamines, such as (2-mercaptoethyl) methylamine, etc. Particularly advantageous are amines of the formula

H ₂ N (-CH ₂ -CH ₂ -NH) _x -HI,

where x has a value from 2 to 6, or the formula

H ₂ N-CH ₂ -CH ₂ -CH ₂ -NH (-CH ₂ -CH ₂ -NH) _y -CH ₂ -CH ₂ -CH ₂ -NH ₂ II,

in which y has a value from 0 to 4 proved. Finally, it will the reaction product with a compound that with the still free reacts reactive groups and by which acidic groups turned or mixtures of such compounds. When Substances reactive with the reactive groups can have many substances classes are used, for. B. alkyl halides, amides, epoxides, Esters, ketones or isocyanates having one or more in the molecule acidic groups or groups that easily turn into acidic groups, carry. Acid groups are especially sulfonic acid, phosphonic acid re, - phosphoric acid and especially carboxyl groups. examples for such compounds are alkyl halides such as chloroacetic acid, Amides such as succinic acid monoamide, epoxides such as glycidic acid, esters such as phthalic acid monomethyl ester or ketones such as acetylacetic acid. Particularly suitable compounds are the internal anhydrides of polybasic carboxylic acids, such as maleic anhydride, succinic acid Anhydride, phthalic anhydride and adipic anhydride, which at For example, with amino groups form amido groups, which with a Carbonyl group are substituted. In the case of hydroxyl groups as Reactive groups may be advantageous in addition to the mentioned Carbonsäu ren and carboxylic acid derivatives and inorganic acids, in particular Mineral acids, such as phosphoric acid and the oligomers and polymers such acids, or derivatives, such as esters or salts of such acids, through which acidic groups are introduced into the compound, or Mixtures of such compounds can be used.

According to a fourth preferred embodiment for producing the Dispersing resins C are the isocyanate groups described above containing prepolymers reacted with at least one compound, the at least one isocyanate-reactive group and to In addition, one or more acidic groups or groups that are light go into acid groups, carry per molecule. It can also Ge Mixed various of these compounds are used. Geeig Neten opposite isocyanate groups are the previously ge called. Suitable acidic groups are selected from sulfonic acid Re, phosphonic, phosphoric and especially Carboxylgrup  pen. Groups that easily turn into acidic groups are included For example, the ester group or salts of acids. examples for such compounds are hydroxycarboxylic acids, such as citric acid, Hydroxymethyl succinic acid, 6-hydroxycaproic acid or 12-hydroxy dodecanoic acid, aminocarboxylic acids, such as aminovaleric acid, mercapto carboxylic acids, such as mercaptosuccinic acid, phosphoric acid derivatives, preferably hydroxyalkyl phosphoric acid esters, such as phosphoric acid mono- (bis (2,3-hydroxymethyl)) - butyl ester or oligoethylene glycol Phosphoric acid esters, aminoalkyl phosphoric acid esters, such as phosphoric acid Re-mono (2-aminoethyl) ester sodium salt, phosphonic acid derivatives, preferably hydroxyalkylphosphonic acid esters, such as bis (N-2-hy droxyethyl) -aminoethyl-phosphonic acid diethyl ester, aminoalkyl phosphonic acid esters, such as diethyl 3-aminopropylphosphonate, or sulfonic acid derivatives, preferably hydroxysulfonic acids, such as 3-hydroxypropanesulfonic acid, or aminosulfonic acids such as N-methyl taurine.

Polyurethane (meth) acrylates and / or polyurea (meth) acrylates suitable as dispersing resins are in particular obtainable by:

• A) Reaction of a polymer P1 containing hydroxyl groups from:
  • a) 80 to 100 mol% of at least one ester of an α, β-ethylenically unsaturated mono- and / or dicarboxylic acid with a C ₁ - to C ₂₅ -alkanol,
  • b) 0 to 20 mol% of at least one other monomer and
  • c) at least one starter and / or regulator, by means of which the majority of the polymers P1) are terminated at one of their ketene ends by a hydroxyl group,
• B) with a di- or polyfunctional isocyanate to a poly Merisat P2), wherein the amount of isocyanate groups 1,2 to 3.9 moles per mole of the hydroxyl group are terminated,  
• C) III.1) reaction of P2) with ammonia or at least one Ver Bond, the isocyanate-reactive Amingrup pen, or
• D) III.2) Reaction of P2) with a compound opposite Isocyanate groups reactive groups to a polyme risat P3) and subsequent implementation of P3) with a Compound through which acidic groups in the polymer P3) be introduced or
• E) III.3) reaction of P2) with at least one compound, the ge has groups which are reactive toward isocyanate groups and introduced by the acidic groups in the polymer P2) become.

Suitable polyurethane dispersing resins C) are, for. In DE-A-41 41 838, DE-A-41 41 839, DE-A-44 46 383, DE-A-195 16 784, EP-A-0 547 432, EP-A-0 592 905, US 5,552,229 and US 5,556,918 which is hereby incorporated by reference.

The conductive polymer compositions according to the invention contain Preferably, the dispersing resin C) in an amount of 0.01 to 5 wt .-%, particularly preferably 0.02 to 3 wt .-%, based on the Total weight of the composition. In particular, the Disper Gierharz in small amounts up to 1 wt .-%, especially at most 0.3 wt .-%, based on the total amount of the components A) and D) used. Advantageously, the inventions can be Polymer compositions according to the invention, the at least one Disper gering resin C in a small amount, generally to formulate dispersions that have good rheological properties, as a low viscosity and / or a low yield point point.  

Component D)

The conductive polymer compositions according to the invention can in addition to the aforementioned components A) to C) at least a component D) selected from carbon black, metal chalcogenides and mixtures thereof.

Preferably, component D) comprises at least one industrially produced carbon black or a preparation thereof. Like graphite, carbon blacks are essentially composed of carbon-six-ring layers. In contrast to graphite, however, these are usually arranged concentrically around the center of a particle in the carbon blacks and are displaced irregularly relative to each other (turbostratical structure). The layer spacing is usually slightly larger than in Gra phit and is z. B. in a range of about 0.35 to 0.4 nm. Advantageously, carbon blacks also have, unlike graphite in general, an elastomer-enhancing effect. They show in the inventions to the invention compositions in general very good pigment properties both as reinforcing fillers, as well as a bridging component to improve the conductivity. Before preferably the specific surface of the invention according to a set carbon black, determined by the BET method, in a range of about 10 to 1000 m ² / g, more preferably 10 to 250 m ² / g.

If the conductive polymer compositions according to the invention are used in or as cathodes, component D) preferably comprises at least one metal chalcogenide selected in particular from V ₆ O ₁₃ , V ₂ O ₅ , MoO ₂ , TiS ₂ , MnO ₂ , V ₂ O ₅ , MoS ₃ , Cr ₃ O ₆ , FeS, NiS, CoO, CuO, LiCoO ₂ , LiMnNiO ₄ , spinels of general formula AB ₂ X ₄ wherein A is a divalent metal such as Mg, Fe (II), Zn , Mn, Co, Ni, Cu or Cd, B for a trivalent or tetravalent Me tall, such as. B. Al, Fe (III), V, Cr, Ti and X for O, S, or Se, stands, lithium compounds of the general formula Li _x V ₃ O ₈ and mixtures of Mi thereof. The metal chalcogenides used as component D) are preferably selected from among spinels, preferably LiMnO ₄ and LiCoO ₂ , LiMnNiO ₄ , MnO ₂ and mixtures thereof.

Be the conductive polymer compositions of the invention used in or as anodes, they preferably contain as Component D) carbon black. This is for use in or as anodes Weight ratio of the total amount of components A) and D) to the total amount of components B) and C) in a range of about 70: 30 to 99: 1, preferably 80: 20 to 98: 2, in particular 90: 10 to 97: 3.

Preferred polymer compositions for use in or as anodes include:

• A) 90 to 94 wt .-% graphite and / or at least one Graphitver binding,
• B) 2 to 6% by weight of at least one binder,
• C) 0.01 to 1 wt .-%, preferably 0.05 to 0.5 wt .-% at least a polyurethane dispersing resin and
• D) 2 to 6 wt .-% carbon black.

Be the conductive polymer compositions of the invention used in or as cathodes, they preferably contain a Component D) selected from Ru described above Shen, metal chalcogenides and mixtures thereof. This is preferably Weight ratio of the total amount of components A) and D) to the total amount of components B) and C) in a range of about 80:20 to 99: 1, preferably 90:10 to 98: 2.

Preferred polymer compositions for use in or as cathodes comprising:

• A) 1 to 3 wt .-% graphite and / or at least one Graphitver binding,
• B) 2 to 6% by weight of at least one binder,
• C) 0.01 to 1 wt .-%, preferably 0.05 to 0.5 wt .-% of at least one polyurethane dispersing resin,
  • 1. 88 to 92 wt .-% of at least one metal chalcogenide and
  • 2. 1 to 5 wt .-% carbon black.

Another object of the invention are dispersions containing tend:

• A) at least one conductive polymer according to the invention as described above,
• B) at least one inert diluent,
• C) optionally at least one other than I and II Additive.

Suitable diluents (dispersants) are z. B. apro table-polar solvents such as dialkylformamides such as dimethylfor mamide and dimethylacetamide, dimethyl sulfoxide, cyclic ethers, such as Tetrahydrofuran, dioxane, N-alkylpyrrolidones, such as N-methylpyrroli don, ketones such as acetone and methyl ethyl ketone, etc. and mixtures from that. Preference is given to a dispersion mixture of at least a low-boiling (≦ 100 ° C) and at least one high-boiling (≧ 150 ° C) solvent used. These include z. B. mixtures Tetrahydrofuran and N-methylpyrrolidone. Preferably, the Ge weight ratio of low-boiling to high-boiling Dis in the range of about 20:80 to 80:20. Advantage Proven to show the dispersions of the invention based on the aforementioned dispersion medium and in particular the mixtures of  Low and high boilers usually a good drying behavior They are generally advantageous for formulation pourable mixtures.

Preferably, the dispersions of the invention contain no low molecular weight dispersants such. B. surfactants. Thus be the disadvantages of surfactants known from the prior art avoided conductive polymer dispersions.

Surprisingly, can be with the leitfähi invention Polymer compositions based on at least one Polyuret Handispergierharzes formulate dispersions that have a high Gra have phite or pigment content and still good in the rule flowable and easy to process. A measure of the flowable speed of a polymer dispersion is its yield point, d. H. the small ones shear stress, measured in Pascal [Pa], above which they are rheologically behaves like a liquid. Preferably, the dispersions of the invention have a yield point in the range of about 10 to 100 Pa, preferably 15 to 75 Pa. The viscosity of he According to the invention dispersions is preferably in one range from about 20 to 400 mPa.s. Advantageously, the inventions The dispersions according to the invention generally have good gloss values. In space In general, the dispersions of the invention also show a good Storage stability.

Another object of the invention is a multi-layer Elek trodenmaterial, which at least one internal conductive metal-containing layer comprising at least one conductive Polymer composition as described above, both sides beschich tet or sheathed.

Suitable metals and metal alloys for use as a central conductive metal-containing layer or as a component thereof are known to those skilled in the art. Preferably metals and / or Metalllegierun conditions are used which have a high electrical conductivity, which z. B. at room temperature in a range of about 10 ⁶ to 10 ⁴ Ω ^-1 cm ^-1 . Depending on the field of application, half metals with a conductivity range of about 10 ¹ to 10 ⁶ Ω ^-1 cm ^-1 are also suitable. Suitable metals with high conductivity are z. B. the metals of the first subgroup of the periodic table, ie, Cu, Ag, Au, whose conductivity is in a range of about 6 × 10 ⁵ Ω ^-1 cm ^-1 . Also suitable are the lighter metals of the first and second main group and the second subgroup of Periodensy stems, such as Li, Na, K, Be, Mg, Cr, Zn, Cd, and the metals A1, In, Mo, W, Ru, Os , Co, Rh and Ni. Suitable conductive Metalllegierun conditions are for. As copper-nickel alloys, such as. The constantan (60% Cu, 40% Ni), carbon-nickel alloys, etc.

The central (inner) conductive metal-containing layer of If desired, the electrode materials according to the invention can be made from at least one of the aforementioned metals and / or Metalllegie exist. However, suitable as a central layer are also Ma materials where z. As a polymer with at least one of sheathed in said metals and / or metal alloys. Ge Suitable polymers are the customary, known to the expert Materials, such. For example, polyethylene terephthalates. On this polymer can z. B. applied at least one of the aforementioned metals his. Suitable application methods are also known to the person skilled in the art known. This includes z. As the electrodeposition and vapor deposition such as B. CVD. Preferably, as a central layer z. B. a mate used in which a polyethylene terephthalate with egg a first layer of copper and a second layer of nickel is sheathed.

The multilayer electrode material may, for. B. for electroplating Sheer elements usual compact form, such as chopsticks or plates form, exhibit.

Preferably, the multilayer electrode material is in the form a film, wherein a carrier film comprising at least one  conductive metal-containing layer or a central polymer film, umman with at least one conductive metal-containing layer telt is, on both sides with a conductive polymer composition, as described above, is coated. The layer thickness of in The underlying layer (s) is generally in a Be rich from about 5 to 100 microns, preferably 10 to 50 microns. Preferably is used as a carrier film, a metal foil in particular of copper, egg ner metal alloy based on copper, or aluminum, turned puts. Suitable metal foils are z. B. copper foils with a Layer thickness in the range of about 15 microns or aluminum foil with egg ner layer thickness in the range of about 20 microns.

The layer thickness of each individual conductive polymer layer is in a range of about 10 to 500 μm, preferably 50 to 120 μm.

A further subject of the invention is a method for the production of a film-shaped multilayer electrode material, comprising:

• a) providing a pourable dispersion of a fiction, proper polymer composition,
• b) applying the dispersion from step i) to a Trägerfo lie, the at least one conductive metal-containing layer to grasp and
• c) drying and optionally calendering the in step ii) applied dispersion at elevated temperatures.

Preferably, the castable dispersion has a viscosity in Be rich of about 30 to 500 mPa.s, preferably about 50 to 300 mPa.s, on. The determination of the viscosity can be carried out in conventional equipment, z. B. a Spindelrheomat done. The adjustment of the viscosity can by adding an appropriate amount of one of the previously ge  called diluent or optionally also by tempera increase in weight during the casting process.

The preparation of a pourable mixture of a dispersion, such as previously described, can be done in the usual way. This z. B. in a dispersing machine, such as a pot ball mill or a Agitator mill, from the graphite and / or the graphite compound A), optionally at least one compound DL of a solution of Binder B) in one of the aforementioned diluents and a solution of at least one polyurethane dispersing resin C) in egg In the aforementioned diluent, a graphite dispersion manufactured. If desired, the pourable mixture before the Apply, for. B. for the separation of agglomerates, according to customary Me be filtered.

According to a suitable embodiment of the method according to the invention rens, the pourable mixture is stirred at a rich from about 1 to 800 m / min, preferably 5 to 300 m / min, on the applied conductive metal-containing layer.

Suitable pouring devices for applying the pourable mixture are on the movably arranged conductive metal-containing layer z. B. reverse roll coater, kiss coater, squeegee, measuring energy ßer etc. After applying the pourable mixture on the leit capable metal-containing layer generally contributes to the mixture dried elevated temperatures and optionally calendered. The drying temperature is generally within a range from about 60 to 120 ° C, preferably 70 to 110 ° C. Be on little at least one side of the multilayered electrode material, two or three more conductive polymer layers on the central layer This can be done at the same time or with a time delay if appropriate after drying and / or hardening of the first polymer layer, respectively. If desired, the layers can also be used in one wet-on-wet application to the carrier, given if dried together and / or cured together. Ge  suitable method for simultaneous application of multiple layers are known in the art. This includes in particular the knife or Doctor blade casting, extrusion or Abstreifgießverfahren and the cascade casting process.

The coating of the two different sides of the central conductive metal-containing layer is preferably ver time puts. It can be the same for each side of the central layer or various of the aforementioned coating methods be set. If desired, this central carrier layer also on both sides with different invention conductive polymer compositions or with a unterschiedli chen number of layers of the inventive conductive poly merzusammensetzungen be coated. The resulting more layered electrode materials, optionally after a certain residence time, on conventional calendering machines by means Hin perform between heated and polished rolls at elevated Temperatures and optionally smoothed by applying pressure and condensed. The temperature during calendering is here as drying in the range of about 60 to 120 ° C, preferably about 70 to 110 ° C.

Advantageously result according to the Her Positioning method multilayer electrode materials, the Generally have more homogeneous layers than those from the state the art known electrode materials. This can be the Yield point and / or the viscosity of the inventive Disper Advantageously, about the amount of polyurethane used pergierharzes C) in a wide range. The result pourable dispersions enable the production of smooth layers that are generally free of holes. To In the method according to the invention, the layer thicknesses can be exactly to adjust. Furthermore, in general, layers with glat ter, open-pored surface. These properties allow chen a good ion migration, z. B. of metal ions, to the individual  layers. This is particularly advantageous if the inventions The multilayer electrode materials according to the invention for the production of batteries, such as As lithium-ion batteries are used.

Another advantage of producing the multilayer electric denmaterialien according to the inventive method is that, unlike the dispersion of graphite in the bandage by means of an extruder, generally less agglomerates te are present and / or the graphite structure less destroyed becomes.

Furthermore, in the case of the conductive polymer according to the invention Compositions advantageously on the use of low mols gular surfactants are dispensed with. As mentioned act low mols kular surfactants generally as plasticizers and worsen Thus, the mechanical properties of the conductive Polymerschich In addition, conductive polymer compositions based on low molecular weight surfactants generally by alkali metal ions, such as As lithium, attacked, so that they only conditionally to Production of lithium-ion batteries are suitable.

Another object of the invention is the use of more layered electrode materials in electronic components, such as z. As capacitors, preferably in batteries, such as lithium-ion batteries. Preferably, they are there as anode material, cathode material or used as a component thereof.

Another object of the invention are batteries and batteries, preferably lithium-ion batteries and batteries containing a multi-layered electrode material, as described above. In this case, the conductive electrode material according to the invention based on a graphite-containing conductive polymer composition according to the invention can generally be used both as an anode, as a cathode, as well as a component thereof. Suitable lithium-ion cells are the following types:

• 1. Solid cathode - organic electrolyte
• 2. Solid cathode - liquid electrolyte comprising a saline solution
• 3. Solid cathode - solid electrolyte

Cells with solid cathode and organic electrolyte contained in Generally, a cathode that is selected from carbon monofluoride polymers, manganese dioxide, cupric oxide, iron disulphide and silver chromate. Other suitable cathode materials are, for. B. Cupric sulfide, cupric fluoride, vanadium pentoxide, silver bis mutchromat, bismuth oxide, molybdenum trioxide, lead oxides and sulfur. Suitable electrolytes are z. As organic solvents, such as Ethers, esters and mixtures thereof. The electrodes can be z. B. be pin-shaped or wound.

Solid electrolyte cells are based z. On the systems Li-LiI-I ₂ , Li-LiI-PbI ₂ , PbS, Pb etc.

The conductive polymer compositions according to the invention and multilayer electrode materials are preferably suitable for use in rechargeable lithium-ion batteries. These include preferably lithium intercalation batteries with polymeric electrolyte. Such a battery typically comprises electrodes based on lithium intercalation compounds and intervening electrolytes based on flexible polymers containing at least one lithium salt dissolved in a polymer-compatible solvent The multilayer electrode materials according to the invention can be used both as an anode and as a cathode who the. Suitable conductive polymer compositions for use as the anode and as the cathode are those previously described. In this case, the cathode can be at least one metal chalcogenide, such as. LiCoO ₂ , LiMnO ₄ , LiMnNiO ₄ , etc. The polymeric electrolyte comprises we least one polymer, at least one lithium salt and a com patible solvent. Suitable polymers are, for. B. vinylidene fluoride homo- and copolymers. A suitable copolymer contains z. B. 70 to 95 wt .-% vinylidene fluoride and 5 to 30 weight percent hexafluoropropylene, based on the total amount of monomers built. Suitable lithium salts include at least one anion, preferably a weak base having a large ionic radius. These include z. B. I ^-, Br ^- SCN ^-, ClO ₄ ^-, BF ₄ ^-, PF ₆ ^-, AsF ₆ ^-, CF ₃ COO ^-, CF ₃ SO ₃ ^-, CF ₃ CO ₃ ^-, etc. Preferred electrolytes are z. B. LiAsF ₆ , LiClO ₄ , LiF ₃ SO ₃ , LiBF _4, etc. As the solvent, preferably low volatile aprotic polar solvents are used. These preferably have a boiling point of more than 80 ° C. These include z. As ethylene carbonate, propylene carbonate, γ-butyrolactone, 1,3-dioxolane, 2-methyltetrahydrofuran, etc. Also suitable are polar solvents with heteroatoms which are suitable for binding alkali metal cations. These include z. B. glyme, such as tetraglyme, hexaglyme, heptaglyme and Polyethylenglykoldialkylether, such as Po lyethylenglykoldimethylether.

The invention will be apparent from the following non-limiting examples games, explained in more detail.

Examples example 1

In a stirred ball mill with a volume of 15 l, filled with 2.7 kg of ceramic balls with a diameter between 1 and 1.5 mm, a mixture of 2400 g of N-methylpyrrolidone, 1160 g Te trahydrofuran, 1140 g of a 12 wt. -% solution of a Copolymeri sate of polyvinylidene fluoride and hexafluoropropylene in tetrahydrofuran, 273 g of a 20 wt .-% solution of a polyurethane Disper gierharzes with dispersing phosphate groups in tetrahydrofuran and 1367 g of a conductive carbon black (BET surface area 45 m ² / g ) Dispersed for 18 hours. Thereafter, the highlight (measurement of the reflection at a 60 ° angle) was constant at 56.

In a stirred tank equipped with a high-speed stirrer, were 2234 g of the resulting carbon black composition, 1260 g of N-methyl pyrrolidone, 967 g of tetrahydrofuran, 2650 g of a 12 wt .-% Lö  solution of a copolymer of polyvinylidene fluoride and hexafluoro propylene in tetrahydrofuran and 8000 g of a high purity graphite with pronounced intercalation properties intensively mixed and then filtered under pressure.

The dispersion thus obtained was coated on both sides by means of a conventional linearizer on a 15 μm thick copper foil and dried at 80 ° C. The coating weight of the dry layer was 220 g / m ² .

Comparative Example 1

The procedure was as in Example 1 except that the polyu Rethandispergierharz with dispersing phosphate groups by a commercial dispersant as commonly used in For used for secondary batteries has been replaced.

Application properties 1. Gloss measurement

On a sample doctor made swab, the Re Flexion measured at 60 ° angle.

2. Rheology

The yield point was determined according to DIN-53214 and the Determination of the viscosity was carried out in a rotary viscometer ter after the plate-cone system.

3. Resilience of the electrodes

Under load capacity of an electrode is the shortest possible Charging or discharging time understood. The assessment was made as in Table 1 below.  

Table 1 load-bearing capacity

Charge-discharge duration evaluation 1 h (1 C) poor / low 6 min (10 C) Well 3 minutes (20 C) very well

To assess the electrical properties of a lithium-ion battery was prepared, which summarizes an anode based on a fiction, multilayer electrode material according to Example 1 to. The preparation of a cathode of 90 wt .-% LiCoO ₂ , 4 wt .-% PVDF / HFP binder, 3 wt .-% of conductive carbon black and 3 wt .-% graphite was carried out according to the general procedure of Example 1, in place of the high-purity graphite a mixture of LiCoO ₂ and graphite was used. The preparation of a cell was carried out according to han delsüblichen method using a polymer electrolyte to summarize a PVDF / HFP polymer, diethyl carbonate and LiPF ₆ as elec trolyte salt.

The performance properties are shown in Table 2 as dergegeben.  

Table 2

Application properties

Claims (14)

A conductive polymer composition comprising

• A) graphite and / or at least one graphite compound,
• B) at least one binder and
• C) at least one polyurethane dispersing resin.

2. Composition according to claim 1, which additionally at least one A) comprises different pigment D) selected under carbon black, metal chalcogenides and mixtures thereof. 3. A composition according to any one of the preceding claims, wherein the component A) is selected from natural graphites, synthetic graphites, graphite intercalation compounds and Mixtures thereof. 4. A composition according to any one of the preceding claims, wherein the binder B) is selected from polymers which at least one radically polymerizable, α, β-ethylenic Containing unsaturated monomer in copolymerized form, polyurethane NEN, cellulose derivatives, epoxy resins and mixtures thereof. 5. A composition according to any one of the preceding claims, wherein the polyurethane dispersing resin C) at least one compound contains at least one polar functional Having group selected from carboxylic acid groups, Sulfonic acid groups, phosphonic acid groups, phosphoric acid groups pen, the alkali metal, alkaline earth metal and ammonium salts of these, amino groups, quaternary ammonium groups, siloxane groups pen and mixtures thereof. 6. Dispersion containing:

• A) at least one conductive polymer composition according to any one of claims 1 to 5,
• B) at least one inert diluent,
• C) optionally at least one additive.

7. Multilayer electrode material comprising at least one internal conductive metal-containing layer that with little at least one conductive polymer composition according to any one of Claims 1 to 5 coated or coated on both sides. 8. electrode material according to claim 7 in the form of a film. 9. The electrode material according to claim 8, wherein the layer thickness of inner layer (s) in a range of 5 to 100 microns lies. 10. The electrode material according to claim 8 or 9, wherein the layer thickness of each individual conductive polymer layer in a Be rich from 10 to 500 microns. 11. A method for producing a film-shaped multilayer electrode material, comprising:

• a) providing a pourable dispersion as defined in claim 6,
• b) applying the dispersion from step i) to a carrier foil which comprises at least one conductive metal-containing layer and
• c) drying and optionally calendering the dispersion applied in step ii) at elevated temperatures.

12. The method according to claim 11, characterized in that one the pourable dispersion at a speed in the range from 1 to 800 m / min, preferably 5 to 300 m / min, on the leit capable of applying metal-containing layer. 13. Use of multilayer electrode materials after egg nem of claims 7 to 10 in and for the production of electro niche components. 14. Batteries, preferably lithium-ion batteries and Batteries, which are a multi-layer electrode material after one of claims 7 to 10 included.