Method for preparing polymer capacitors, conductive polymer compositions, and their use as conductive layers in electronic devices

Abstract

1. A method for preparing a polymer capacitor having a porous anode body, comprising the step of introducing a conductive polymer formulation into at least a portion of the porous anode body, the conductive polymer dispersion comprising at least one oligothiophene or polythiophene and a polymeric polyanion, the polymeric polyanion having a polydispersity of 3 or less and a weight average molecular weight (Mw) of 25 to 175 kDa. [Formula 1] TIFF2025529241000017.tif84125

Description

[Technical Field]

[0001] The present invention relates to a method for preparing a polymer capacitor and to a polythiophene / polyanion composition for use in the method. [Background technology]

[0002] Environmental concerns over greenhouse gas emissions have stimulated demand for battery electric vehicles and (plug-in) hybrid electric vehicles, increasing battery capacity. The electrical systems inside these vehicles operate at higher voltages than traditional internal combustion engines. The electronic control devices in these vehicles contain multiple polymer capacitors.

[0003] Polymer hybrid aluminum electrolytic capacitors are often used in this field. These capacitors consist of an etched Al / Al2O3 foil that serves as one electrode and a dielectric layer covered with a conductive polymer layer that serves as the other electrode. The conductive polymer complex poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT / PSS) is commonly used, which is applied to the Al / Al2O3 substrate by dip coating as an aqueous formulation.

[0004] A key aspect of the fabrication of such capacitors is the infiltration of conductive polymer particles into Al / Al2O3 foils. To increase the surface area, etched Al foils are used, which are then anodized to create a thin layer of Al2O3. This process creates a porous Al / Al2O3 substrate, which is then dip-coated with an aqueous PEDOT / PSS dispersion. Therefore, the particle size of the conductive polymer particles determines the polymer's ability to infiltrate the pores of the Al / Al2O3 substrate. As a result, smaller particle sizes in the conductive polymer dispersion result in better coating and lower equivalent series resistance (ESR) for the capacitor. Additionally, reducing the surface resistance of the PEDOT / PSS layer reduces ESR and improves capacitance.

[0005] Therefore, developing PEDOT / PSS dispersions with smaller particle sizes and lower surface resistance of the coating layer could improve the characteristics of polymer capacitors. This goal can be achieved by using a better-defined PSS with low polydispersity within a specific molecular weight range.

[0006] The synthesis of poly(styrene sulfonate) (PSS) has been described by Tosoh in numerous patent applications (e.g., U.S. Patent No. 5,629,297; ... and U.S. Patent No. 5,629,297). However, these patent applications do not disclose, for example, the preparation of PEDOT in the presence of the disclosed poly(styrene sulfonate). U.S. Patent No. 5,629,297 discloses the preparation of PEDOT / PSS using high-purity para-styrene sulfonate. However, these PEDOT / PSS dispersions have not been used to prepare polymer capacitors.

[0007] Non-Patent Document 1 reports the polymerization of polystyrene sulfonate from p-styrene sulfonate using atom transfer radical polymerization (ATRP). This paper demonstrates the synthesis of polymers with weight-average molecular weights of 23 to 480 kDa and polydispersities of 1.06 to 1.29. However, the preparation of PEDOT:PSS using such polystyrene sulfonate has not been reported. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP5760326 [Patent Document 2] WO2014061357 [Patent Document 3] JP2020158574 [Patent Document 4] WO201373259 [Non-patent literature]

[0009] [Non-Patent Document 1] Balding et al. (Balding, P., Cueto, R., Russo, PS and Gutekunst, WR (2019), ``Synthesis of perfectly sulfonated sodium polystyrene sulfonate over a wide molar mass range via reversible-deactivation radical polymerization'', J. Polym. Sci. Part A: Polym. Chem., 57: 1527-1537) Summary of the Invention

[0010] An object of the present invention is to provide a method for preparing a conductive polymer capacitor having a lower equivalent surface resistance (ESR) and a higher capacitance.

[0011] The object of the present invention is achieved by a method for preparing a conductive polymer capacitor as defined in claim 1.

[0012] Another object of the present invention is a conductive polymer formulation for the preparation of conductive polymer capacitors.

[0013] Further objects of the present invention will become apparent from the following description. DETAILED DESCRIPTION OF THE INVENTION

[0014] definition The term "monofunctional", for example when referring to a monofunctional polymerizable compound, means that the polymerizable compound has one polymerizable group.

[0015] The term "difunctional", for example when referring to a difunctional polymerizable compound, means that the polymerizable compound has two polymerizable groups.

[0016] The term "multifunctional", for example when referring to a multifunctional polymerizable compound, means that the polymerizable compound has more than two polymerizable groups.

[0017] The term "alkyl" refers to all possible variations of alkyl groups of each carbon atom number, such as methyl, ethyl, n-propyl and isopropyl for those with 3 carbon atoms, n-butyl, isobutyl and tert-butyl for those with 4 carbon atoms, n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl and 2-methylbutyl for those with 5 carbon atoms, etc.

[0018] Unless otherwise specified, substituted or unsubstituted alkyl groups are preferably C1-C6-alkyl groups.

[0019] Unless otherwise specified, a substituted or unsubstituted alkenyl group is preferably a C2-C6-alkenyl group.

[0020] Unless otherwise specified, a substituted or unsubstituted alkynyl group is preferably a C2-C6-alkynyl group.

[0021] Unless otherwise specified, a substituted or unsubstituted alkaryl group is preferably a phenyl or naphthyl group carrying one, two, three or more C1-C6-alkyl groups.

[0022] Unless otherwise specified, the substituted or unsubstituted aralkyl group is preferably a C-C alkyl group having a phenyl or naphthyl group. 20 - is an alkyl group.

[0023] Unless otherwise specified, the substituted or unsubstituted aryl group is preferably a phenyl group or a naphthyl group.

[0024] Unless otherwise specified, a substituted or unsubstituted heteroaryl group is preferably a five- or six-membered ring substituted with one, two, or three oxygen, nitrogen, sulfur, or selenium atoms, or a combination thereof.

[0025] Unless otherwise specified, a substituted or unsubstituted alkylene group is preferably a C1-C6-alkylene group.

[0026] The term "substituted," when referring to, for example, a substituted alkyl group, means that the alkyl group can be substituted with atoms other than those normally present in such a group (i.e., carbon and hydrogen). For example, a substituted alkyl group can contain a halogen atom or a thiol group. An unsubstituted alkyl group contains only carbon and hydrogen atoms.

[0027] Unless otherwise specified, substituted alkyl, alkenyl, alkynyl, aralkyl, alkaryl, aryl, and heteroaryl groups are preferably substituted with one or more members selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl, ester, amide, amine, ether, thioether, ketone, aldehyde, sulfoxide, sulfone, sulfonate ester, sulfonamide, -Cl, -Br, -I, -OH, -SH, -CN, and -NO2.

[0028] polymer capacitor A polymer capacitor (also called a polymer electrolyte capacitor) is an electrolytic capacitor that contains a solid conductive polymer electrolyte.

[0029] Electrolytic capacitors utilize the chemical property of forming an insulating oxide layer by anodizing certain special metals, often referred to as valve metals. By applying a positive voltage to the anode material in an electrolytic bath, an oxide barrier layer can be formed, the thickness of which depends on the applied voltage. This oxide layer acts as the dielectric of the electrolytic capacitor. To increase the capacitor capacitance, the anode surface is roughened, thereby roughening the oxide layer surface.

[0030] To complete the capacitor, a counter electrode must conform to the rough insulating oxide surface. This is accomplished by the electrolyte, which acts as the cathode electrode of the electrolytic capacitor. In polymer electrolyte capacitors, this counter electrode consists of one or more layers of a conductive polymer, preferably a polythiophene conductive polymer.

[0031] The main difference between polymer capacitors is the anode material and its oxide used as the dielectric: - Polymer tantalum electrolytic capacitors use high purity sintered tantalum powder as the anode with tantalum pentoxide (Ta2O5) as the dielectric; and -Polymer aluminum electrolytic capacitors use high-purity, electrochemically etched (roughened) aluminum foil as the anode with aluminum oxide (Al2O3) as the dielectric.

[0032] A porous metal layer (anode) coated with an oxide layer (dielectric) of that metal is referred to herein as a porous anode body.

[0033] Preparation of polymer capacitors A method for preparing a polymer capacitor according to the present invention comprises the step of incorporating a conductive polymer formulation, as described below, into at least a portion of a porous anode body.

[0034] The polymer capacitor formulation can be introduced into the porous anode body by any known process, such as impregnation, dipping, pouring, dripping, jetting, spraying, knife coating, brushing, or printing, such as inkjet printing, screen printing, or tampon printing.

[0035] Preferably, the polymeric capacitor formulation is introduced into at least a portion of the porous anode body by immersing the porous anode body in the polymeric capacitor formulation, thereby impregnating the porous anode body with the formulation.

[0036] Immersion in or impregnation with the polymer capacitor formulation is preferably carried out for a period ranging from 1 second to 120 minutes, more preferably from 5 seconds to 60 minutes, and most preferably from 10 seconds to 15 minutes. Introduction of the formulation into the anode body can be facilitated, for example, by increased or reduced pressure, vibration, ultrasound, or heating.

[0037] After impregnation of the porous anode body with the polymer capacitor formulation, the solvent contained in the formulation is preferably at least partially removed to obtain a solid electrolyte. This solid electrolyte completely or partially coats the dielectric, thereby forming the capacitor body. The coverage of the dielectric with the solid electrolyte is preferably at least 10%, more preferably at least 25%, and most preferably at least 50%. The coating can be as described in DE-A-10 2005 043 828.

[0038] The solvent is preferably removed by removing the electrode assembly from the formulation and drying it, with the drying step preferably being carried out at a temperature of 20°C to 260°C, more preferably 50°C to 220°C, and most preferably 80°C to 200°C.

[0039] The dipping and drying steps can be repeated one or more times to tailor the thickness of the solid electrolyte layer deposited on the dielectric or the degree of electrolyte filling in the electrode body to specific requirements.

[0040] It may be advantageous to use both so-called self-doped and externally doped polythiophenes to form polymer cathode layers. Polythiophenes typically have a positive charge located on the polymer backbone. This positive charge is preferably at least partially counterbalanced by anions. When anions are covalently bonded to the polymer, the polymer is often referred to as a self-doped polymer or an intrinsically conductive polymer. The monomers used to make such self-doped polymers, i.e., monomers having anionic groups, are also referred to as self-doped monomers.

[0041] When the anion is a separate compound, the polymer is typically referred to as an externally doped polymer or an extrinsically conductive polymer. The anion added as a separate compound is preferably a polyanion.

[0042] Both types of polythiophene polymers can be combined into a single polymer capacitor formulation as described above. However, it is preferred to incorporate both types of polythiophenes into the capacitor using different polymer capacitor formulations, each containing a self-doped polythiophene or an externally doped polythiophene. Preferably, the self-doped polythiophene is first incorporated into the porous anode body, followed by the externally doped polythiophene. The use of both self-doped and externally doped polythiophenes is disclosed, for example, in WO 2014 / 048562 (Heraeus) and US 2016 / 0351338 (AVX).

[0043] After the capacitor bodies are produced in this way, they can be further modified by methods and in a manner known to those skilled in the art. In the case of tantalum electrolytic capacitors, the capacitor bodies can be coated with a polymer outer layer, for example, as disclosed in DE-A-10 2004 022674 or DE-A-10 2009 007 594, and / or coated with a graphite layer and a silver layer, as known from DE-A-10 2005 043 828. In the case of aluminum wound capacitors, the capacitor bodies are assembled in an aluminum beaker and mechanically tightly sealed by clamping with sealing glass, in accordance with the teachings of US 749879. The capacitors can then be aged in a dielectric in a known manner to render them defect-free.

[0044] Conductive Polymer Compounds The conductive polymer formulation is typically prepared from the conductive polymer dispersion by adding various additives to the conductive polymer dispersion. The conductive polymer formulation used in the method for preparing the polymer capacitor according to the present invention is prepared from the conductive polymer dispersion described below.

[0045] Conductive polymer dispersion A dispersion containing a conductive polymer is referred to herein as a conductive polymer dispersion.

[0046] Conductive dispersions according to the present invention comprise a conductive polymer and a polyanion, both as described below.

[0047] The dispersion medium of the conductive polymer dispersion is preferably selected from water, a water-soluble organic solvent, or a mixture thereof. Suitable organic solvents are protic organic solvents, such as alcohols or acids. The dispersion medium is preferably water.

[0048] The conductive polymer dispersion may contain other ingredients such as a dispersant.

[0049] The conductive polymer dispersion is preferably prepared as described below.

[0050] The median particle size (d 50 ) is preferably 1 to 100 nm, more preferably 2 to 75 nm, most preferably 5 to 50 nm, and particularly preferably 10 to 40 nm. 50 Particle size is preferably measured by liquid phase centrifugal sedimentation particle size analysis.

[0051] conductive polymer The conductive polymers according to the invention are oligothiophenes or polythiophenes obtained by polymerization of monomers according to formula I, [ka] During the ceremony, A represents a substituted or unsubstituted C1-C5 alkylene bridge; R is a linear or branched, substituted or unsubstituted C1-C 18 -Alkyl groups, substituted or unsubstituted C5-C 12 -Cycloalkyl groups, substituted or unsubstituted C6-C 14 -aryl group, substituted or unsubstituted C7-C 18 - selected from the group consisting of aralkyl groups, substituted or unsubstituted C1-C4-hydroxyalkyl groups, and hydroxyl groups; s represents an integer of 0 to 8.

[0052] The term C1-C5 alkylene bridge, as used in Formula I, means an alkylene bridge containing from 1 to 5 carbon atoms.

[0053] The C1-C5 alkylene bridge is preferably methylene, ethylene, n-propylene, n-butylene, or n-pentylene.

[0054] C1-C 18 - as alkyl radicals, straight or branched C1-C 18alkyl radicals, such as methyl, ethyl, n- or isopropyl, n-, iso-, sec-, or tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, or n-octadecyl;

[0055] C5-C 12 -cycloalkyl radical represents for example cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl.

[0056] C6-C 14 -aryl radical represents, for example, phenyl or naphthyl.

[0057] C7-C 18 -aralkyl radical represents, for example, benzyl, o-, m-, p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-xylyl or mesityl.

[0058] Suitable substituents are alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, halogen groups, ether groups, thioether groups, disulfide groups, sulfoxide groups, sulfone groups, sulfonate groups, amino groups, aldehyde groups, keto groups, carboxylic acid ester groups, carboxylic acids, carbonate groups, carboxylate groups, cyano groups, alkylsilane groups, and alkoxysilane groups, and carboxamide groups.

[0059] A in formula I is preferably an ethylene bridge.

[0060] In a particularly preferred embodiment, the monomer according to Formula I is 3,4-ethylenedioxythiophene (EDOT).

[0061] The conductive polymer can be a homopolymer or a copolymer.

[0062] The conductive polymer is preferably poly(3,4-ethylenedioxythiophene) (PEDOT).

[0063] Polyanions The polymeric polyanion comprises at least one monomer unit according to formula II: [ka] During the ceremony any of R1-R5 selected from the group consisting of hydrogen, halogen, ether, and substituted or unsubstituted alkyl groups, with the proviso that at least one of R1-R5 is represented by a substituent according to formula III; [ka] During the ceremony n represents 0 or 1; R6 and R7 are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted alkaryl groups, and substituted or unsubstituted aryl or heteroaryl groups; R6 and R7 may also represent the atoms necessary to form a five- to eight-membered ring; B represents a functional group selected from the group consisting of sulfonic acid or a salt thereof, sulfuric acid ester or a salt thereof, and carboxylic acid or a salt thereof; The dashed line represents the covalent bond to the styrene ring; The polymeric polyanion is characterized by a polydispersity of 3 or less and a weight average molecular weight (Mw) of 25 to 175 kDa.

[0064] In preferred embodiments, R6 and R7 are preferably independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group, with hydrogen being most preferred.

[0065] In an even more preferred embodiment, n represents 0.

[0066] In another preferred embodiment, only one of R1-R5 is represented by a substituent according to formula III. In a particularly preferred embodiment, one of R2, R3, and R4 is represented by a substituent according to formula III. In a further particularly preferred embodiment, all substituents, other than those represented by a substituent according to formula III, represent hydrogen.

[0067] The polymeric polyanion can be a copolymer of different monomers according to formula II, but is preferably a homopolymer.

[0068] The polymeric polyanion preferably comprises at least 80 mol %, more preferably at least 90 mol % of monomer units according to Formula II, and most preferably the polymeric polyanion is made up entirely of monomer units according to Formula II.

[0069] The polymeric polyanions are functionalized with sulfonic acids or their salts.

[0070] In a particularly preferred embodiment, the polymeric polyanion is poly(4-styrenesulfonic acid) or a salt thereof.

[0071] The polydispersity of the polymeric anion is 3 or less, preferably 2.5 or less, and more preferably 2 or less.

[0072] The weight average molecular weight of the polymeric anion is 25 to 175 kDa, preferably 30 to 150 kDa, more preferably 35 to 100 kDa, most preferably 40 to 90 kDa, and particularly preferably 50 to 80 kDa.

[0073] The polymeric polyanion is preferably prepared by radical polymerization, more preferably by controlled radical polymerization. A particularly suitable controlled radical polymerization technique is atom transfer radical polymerization (ATRP). ATRP allows for better optimization of the polydispersity and molecular weight (Mw) of the resulting polymeric polyanion.

[0074] Typically, five key components are used in ATRP: monomer, initiator, catalyst, ligand, and solvent.

[0075] The monomer is according to formula II.

[0076] Non-limiting examples of monomers according to Formula II are disclosed in Table 1. [Table 1-1] [Table 1-2]

[0077] Suitable initiators are water-soluble organic halides, such as 4-(bromomethyl)benzoic acid or 2-hydroxyethyl 2-bromoisobutyrate. Preferably, 4-(bromomethyl)benzoic acid is used.

[0078] Suitable catalysts are transition metal complexes, preferably copper salts. More preferably, copper halides are used. Most preferably, CuCl or CuBr is used.

[0079] Suitable ligands are nitrogen-containing organic ligands, such as 2,2-bipyridine, tris(2-dimethylaminoethyl)amine, or N,N,N',N',N''-pentamethyldiethylenetriamine. Preferably, 2,2-bipyridine or tris(2-dimethylaminoethyl)amine is used. Most preferably, 2,2-bipyridine is used.

[0080] Suitable solvents include water or a mixture of water and a water-soluble organic solvent, such as methanol, ethanol, propanol, butanol, dimethylformamide, or dimethyl sulfoxide. Preferably, a water / methanol mixture is used, more preferably in a ratio of 80 / 20% to 20 / 80% (v / v), and most preferably in a ratio of 60 / 40% to 40 / 60% (v / v).

[0081] The ATRP polymerization reaction is carried out using specific molar ratios of monomer, initiator, catalyst, and ligand components. The monomer to initiator ratio is preferably 70 / 1 to 500 / 1, more preferably 135 / 1 to 444 / 1, and most preferably 222 / 1. The catalyst to ligand ratio is preferably 1 / 3. The initiator to catalyst ratio is preferably 2 / 1 to 1 / 2, more preferably 2 / 1 to 1 / 1, and most preferably 2 / 1.

[0082] The temperature of the reaction mixture is preferably 5 to 100°C, more preferably 10 to 70°C, and most preferably 20 to 55°C.

[0083] The concentration of the reactant, expressed as the amount of monomer per solvent (g / mL), is preferably 0.059 g / mL to 0.178 g / mL, more preferably 0.071 g / mL to 0.178 g / mL, and most preferably 0.089 g / mL to 0.178 g / mL.

[0084] The reaction period is preferably 3 to 24 hours.

[0085] To adjust the pH, an acid or a base can be used. Preferably, an aqueous solution of an inorganic acid or an inorganic base is used. Preferably, hydrochloric acid or sodium hydroxide is used.

[0086] Preparation of conductive polymers The polythiophene conductive polymer is preferably prepared by oxidative polymerization of the above-mentioned thiophene monomers. More preferably, the conductive polymer is prepared by oxidative polymerization of the above-mentioned thiophene monomers in an aqueous medium.

[0087] The oxidative polymerization is preferably carried out in the presence of the polyanions described above.

[0088] The concentration of the thiophene monomer in the aqueous phase medium is preferably in the range of 0.1 to 25% by weight, preferably in the range of 0.5 to 10% by weight, all based on the total weight of the aqueous reaction medium.

[0089] Suitable oxidizing agents are iron(III) salts, such as FeCl3, and iron(III) salts of aromatic and aliphatic sulfonic acids; H2O2; K2Cr2O7; KMnO4, alkali metal perborates; alkali metal or ammonium persulfates; and mixtures thereof.

[0090] Further suitable oxidizing agents are described, for example, in the Handbook of Conducting Polymers (Ed. Skotheim, TA, Marcel Dekker: New York, 1986, Vol. 1, pages 46-57).

[0091] Particularly suitable oxidizing agents are peroxodisulfates, especially K2S2O8, Na2S2O8; iron(III) salts, especially iron(III) chloride; or combinations thereof.

[0092] Particularly suitable are mixtures of peroxodisulfate with at least one further compound which catalyzes the cleavage of the peroxodisulfate, such as an Fe(III) salt.

[0093] According to a particularly preferred embodiment, the oxidizing agent is a mixture of Fe2(SO4)3 and Na2S2O8.

[0094] The aqueous reaction medium can be prepared in a variety of ways. The thiophene monomer can be dissolved or dispersed in the aqueous reaction medium, followed by the addition of the oxidizing agent(s), which can also be dissolved or dispersed in the aqueous phase. Alternatively, the oxidizing agent(s) can be first dissolved or dispersed in the aqueous reaction medium, followed by the addition of the thiophene monomer, which can also be dissolved or dispersed in the aqueous phase.

[0095] When more than one oxidizing agent is used, for example, a mixture of Fe2(SO4)3 and Na2S2O8, it is further possible to first mix one of these components with the thiophene monomer in the aqueous reaction medium, followed by the addition of the second oxidizing agent.

[0096] The oxidative polymerization is preferably carried out under an inert atmosphere, as disclosed in EP-11453877 (Agfa Gevaert). The oxygen content of the reaction medium, when an oxidizing agent such as peroxodisulfate is added thereto, is preferably less than 3 mg / liter, more preferably less than 1.5 mg / liter, and most preferably less than 0.5 mg / liter.

[0097] The oxygen concentration in the reaction medium can be controlled by any means, such as freeze-thaw techniques, bubbling an inert gas (such as argon, nitrogen, or helium) through the reaction medium for an extended period of time, consuming oxygen by a sacrificial reaction under an inert gas atmosphere, etc. The inert gas is preferably bubbling through the reaction medium until polymerization is complete, thereby maintaining the oxygen concentration below 3 mg / L.

[0098] The oxidative polymerization is preferably carried out at low pH, as disclosed in EP-A 1384739 (Heraeus). The pH is preferably below 1.5, more preferably below 1.00.

[0099] An acid can be used to adjust the pH, and the acid is preferably selected from the group consisting of water-soluble inorganic acids and water-soluble organic acids. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of organic acids include p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid.

[0100] The temperature of the reaction mixture is preferably 0 to 100°C, more preferably 0 to 50°C, and most preferably 5 to 30°C.

[0101] The amounts of thiophene monomer and polyanion in the reaction mixture are selected so that a stable polythiophene / polyanion dispersion is obtained, the solids content of which is preferably 0.05 to 25 wt %, more preferably 0.1 to 10 wt %, and most preferably 0.8 to 2 wt %.

[0102] After the polymerization reaction is complete, the liquid composition can be further purified, for example, by filtration, especially ultrafiltration, and / or treatment with ion exchangers, especially anion and cation exchangers.

[0103] After the purification step, the conductive polymer dispersion can be further optimized for its intended use. For example, when used to prepare an antistatic layer, the liquid formulations described below can be prepared from the conductive polymer dispersion.

[0104] During the preparation of the conductive polymer, various homogenization techniques can be used. The homogenization techniques can be selected from: -Ultrasonic homogenization technique; -pressure homogenization technique; and -Mechanical homogenization techniques.

[0105] Suitable mechanical homogenizers are rotor-stator homogenizers and blade homogenizers. Another mechanical homogenization technique is the use of a spinning disc reactor.

[0106] Suitable high pressure homogenizers, such as a Gaulin homogenizer or an Ariete homogenizer, force the dispersion through very narrow channels or orifices under pressure. Another suitable high pressure homogenizer is a microfluidizer.

[0107] Two or more homogenizers can be used in combination, preferably in a sequential manner.

[0108] Homogenization techniques can be used before, during, and after the polymerization reaction. Such homogenization techniques can also be used during the preparation of the liquid formulations described below.

[0109] Conductive Polymer Compounds Depending on the application for which the conductive polymer dispersion is to be used, additional components can be added to the conductive polymer dispersion to form a conductive polymer formulation optimized for the application.

[0110] For example, when used in preparing a polymer capacitor, such a formulation may be referred to as a conductive polymer capacitor formulation.

[0111] In addition to the conductive polymer and polyanion, the formulation may contain further additives, such as surfactants, adhesion promoters, crosslinking agents, binders, conductivity-enhancing compounds, heat and moisture stability improving compounds, acidic compounds, and alkaline compounds.

[0112] The surfactant compound can be: anionic surfactants, such as alkylbenzenesulfonic acids and salts, paraffin sulfonates, alcohol sulfonates, ether sulfonates, sulfosuccinates, phosphate esters, alkyl ether carboxylic acids or carboxylates; cationic surfactants, such as quaternary alkylammonium salts; nonionic surfactants, such as linear alcohol ethoxylates, oxoalcohol ethoxylates, alkylphenol ethoxylates, or alkylpolyglucosides; and - zwitterionic surfactants, for example, compounds having both a carboxylic acid group and a quaternary ammonium group (e.g., lauryl-N,N-(dimethyl-ammonio) butyrate and lauryl-N,N-(dimethyl)-glycine betaine, etc.), compounds having both a sulfate group and a quaternary ammonium group (e.g., 3-[(3-cholamido-propyl)dimethylammonio]-1-propanesulfonate, 3-(4-tert-butyl-1-pyridinio)-1-propanesulfonate, 3-(1- compounds with both a phosphate group and a quaternary ammonium group (e.g., those with hexadecylphosphocholine); compounds with a quaternary ammonium group attached to a hydroxy group (e.g., lauryldimethylamine N-oxide); and phospholipids consisting of a quaternary ammonium head coupled to two hydrophobic fatty acids via a phosphate group and glycerol.

[0113] Particularly suitable surfactants are commercially available surfactants available under the Dynol® and Zonyl® trademarks.

[0114] Suitable adhesion promoters are organofunctional silanes or their hydrolyzates, such as 3-glycidoxypropyltrialkoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, or octyltriethoxysilane.

[0115] Suitable crosslinking agents include melamine compounds, blocked isocyanates, functional silanes such as tetraethoxysilane, alkoxysilane hydrolysates such as tetraethoxysilane, and epoxy silanes such as 3-glycidoxypropyltrialkoxysilane.

[0116] Suitable binders are polyurethanes, polyacrylates, or polyolefins.

[0117] Suitable conductivity enhancing compounds are: - compounds containing ether groups, such as tetrahydrofuran; -lactone group-containing compounds, such as γ-butyrolactone or γ-valerolactone; - compounds containing an amide or lactam group, such as caprolactam, N-methylcaprolactam, N,N-dimethylacetamide, N-methylacetamide, formamide, N,N-dimethylformamide (DMF), N-methylformamide, N-methylformanilide, N-methyl-2-pyrrolidone (NMP), N-octylpyrrolidone, 2-pyrrolidone, N-butylpyrrolidone, and N-hydroxyethylpyrrolidon; sulfones and sulfoxides, such as, for example, sulfolane (tetramethylene sulfone) or dimethyl sulfoxide (DMSO); sugars or sugar derivatives, such as arabinose, saccharose, glucose, fructose or lactose; Di- or polyalcohols, for example, sorbitol, xylitol, mannitol, mannose, galactose, sorbose, gluconic acid or ethylene glycol, di- or tri(ethylene glycol), 1,1,1-trimethylolpropane, 1,3-propanediol, 1-,2-propanediol, 1,5-pentanediol, 1,2,3-propanetriol, 1,2,4-butanetriol, or 1,2,6-hexanetriol, aromatic di- or polyalcohols such as resorcinol.

[0118] Particularly suitable conductivity enhancing compounds are selected from the group consisting of N-methylpyrrolidinone, N-butylpyrrolidone, N-hydroxyethylpyrrolidone, DMSO, ethylene glycol, and diethylene glycol.

[0119] Preferred stability improving compounds are gallic acid derivatives.

[0120] The polymer capacitor formulation may have a pH of 1 to 14, more preferably a pH of 1 to 8. In the case of corrosion-sensitive dielectrics such as aluminum oxide or niobium oxide, the polymer capacitor formulation preferably has a pH of 2.5 to 8 in order not to damage the dielectric.

[0121] To adjust the pH, bases or acids as described in WO2010 / 003874, page 4, lines 13-32, are preferably used. These compounds do not impair the film formation of the polymer capacitor formulation and do not volatilize at high temperatures, such as soldering temperatures. Suitable compounds are 2-dimethylaminoethanol, 2,2'-iminodiethanol, or 2,2',2''-nitrilotriethanol as bases, and polystyrene sulfonic acid as acids.

[0122] The viscosity of polymer capacitor formulations is typically optimized as a function of the application method, ranging from 1 to 1000 mPa·s (using a rheometer at 20°C and a shear rate of 100 s -1 The viscosity can be (measured by). Preferably, the viscosity is 5 to 500 mPa·s, more preferably 10 to 250 mPa·s. In the case of producing an aluminum wound capacitor, the viscosity is preferably 1 to 200 mPa·s, while in the case of producing a tantalum electrolytic capacitor or an aluminum multilayer capacitor, the viscosity is preferably 1 to 50 mPa·s.

[0123] Viscosity adjustment can be achieved, for example, by adding suitable rheology modifiers as further additives.

[0124] The solids content of the polymer capacitor formulation is preferably 0.01 to 20 wt %, more preferably 0.1 to 15 wt %, most preferably 0.25 to 10 wt %, in each case based on the total weight of the formulation. [Example]

[0125] material All materials used in the following examples were readily available from standard sources, e.g., ALDRICH CHEMICAL Co. (Belgium) and ACROS (Belgium), unless otherwise stated. Water used was deionized water.

[0126] 4-Vinylbenzenesulfonic acid, sodium salt is sold by TCI Europe (Belgium).

[0127] EDOT is 3,4-ethylenedioxythiophene, sold by Heraeus.

[0128] INI-01 is 2,2'-azobis[2-methyl-N-2-hydroxyethyl)propionamide], sold by Fujifilm (Belgium).

[0129] PSS-1 is an aqueous solution of polystyrene sulfonic acid with a molecular weight of 300 kDa, prepared according to the method disclosed in Houben-Weyl, Methoden der organischen Chemie, Vol. E 20, Makromolekulaire Stoffe, Teil 2 (1987), page 1141.

[0130] Lewatit® MonoPlus M600 is a basic gel-like anion exchange resin, sold by Lanxess AG.

[0131] Lewatit® MonoPlus S 108 H is an acidic gel-like anion exchange resin, sold by Lanxess AG.

[0132] method Molecular weight measurement Polymer molecular weights were determined by gel permeation chromatography (GPC) using a Waters e2695 coupled to a 2998A PDA detector, calibrated with polystyrene sulfonate standards. Molecular weight distributions (polydispersity D) were calculated using Waters Empower 3.

[0133] Viscosity measurement The viscosity was measured with a glass capillary viscometer.

[0134] Surface resistance measurement The surface resistance SER was measured at room temperature using a two-terminal method.

[0135] Particle size measurement The median particle size (Φ) was determined by liquid-phase centrifugal sedimentation particle size analysis using a CPS instruments Model MOD DC24000 UHR Disc centrifuge.

[0136] Capacitance Measurement The capacitance of the capacitor was measured at room temperature and 120 Hz using a constant potential electrolysis device.

[0137] ESR measurement The equivalent series resistance (ESR) was measured at room temperature and 100 kHz using a potentiostatic electrolysis apparatus.

[0138] Example 1: Preparation of Polyanion-01(a) to Polyanion-01(e) Preparation of catalyst / ligand complex solution 0.055 g of CuCl was dissolved in 50 mL of water. This was degassed with nitrogen for 45 minutes. 0.25 g of 2,2-bipyridine was added as a smelt. The solution was further degassed with nitrogen for 30 minutes.

[0139] Polyanion-01(a) 8.80 g of 4-vinylbenzenesulfonic acid, sodium salt, was dissolved in 57.86 mL of water and 41.09 mL of methanol. A 1 wt% solution of NaCl was prepared and added (0.06 mL) to this solution. 4-(Bromomethyl)benzoic acid (41.4 mg) was added, and the pH was adjusted to 12 with NaOH. The reaction mixture was degassed by bubbling nitrogen for 60 minutes. 9.09 g of CuCl / 2,2-bipyridine catalyst / ligand complex solution was added. The reaction mixture was stirred at 55°C for 3 hours. The catalyst / ligand complex was then separated from the reaction mixture by filtration through silica (washing with 20 / 80% v / v MeOH / water). The filtrate was dialyzed using dialysis tubing under a running water stream with a 1000 Da cutoff. The resulting product was treated twice with an ion exchanger (123 g of Lewatit® MonoPlus S 108 H, filtered and washed twice with 40 mL). This procedure gave a clear to slightly yellow aqueous solution of Polyanion-01(a).

[0140] Polyanion-01(b) Polymerization was carried out in the same manner as described for Polyanion-01(a), except that a catalyst / ligand complex solution using 79 mg of CuBr was used. 15.0 g of 4-vinylbenzenesulfonic acid, sodium salt, was dissolved in 49.3 mL of water and 35.0 mL of methanol. 0.1 mL of 1 wt% NaCl solution and 70.5 mg of 4-(bromomethyl)benzoic acid were added. 16.71 g of CuBr / 2,2-bipyridine catalyst / ligand complex solution was added. The reaction was stirred at room temperature for 24 hours. 121 g of Lewatit® MonoPlus S 108 H was used, and the ion exchanger was washed twice with 40 mL of water.

[0141] Polyanion-01(c) The polymerization was carried out in the same manner as described for Polyanion-01(b), except that 169 mL of water was used as the solvent. 115 g of Lewatit® MonoPlus S 108 H was used, and the ion exchanger was washed twice with 40 mL of water.

[0142] Polyanion-01(d) The polymerization was carried out in the same manner as described for polyanion-01(b), except that 4.00 g of 4-vinylbenzenesulfonic acid, sodium salt, 52.9 mg of 4-(bromomethyl)benzoic acid, and 0.07 mL of 1 wt % NaCl solution were used. 70 g of Lewatit® MonoPlus S 108 H was used, and the ion exchanger was washed twice with 30 mL of water.

[0143] Polyanion-01(e) Polymerization was carried out in the same manner as described for polyanion-01(d), except that 35.2 mg of 4-(bromomethyl)benzoic acid, 0.05 mL of 1 wt % NaCl solution, and 8.36 g of CuBr / 2,2-bipyridine catalyst / ligand complex solution were used. 80 g of Lewatit® MonoPlus S 108 H was used, and the ion exchanger was washed twice with 30 mL of water.

[0144] Example 2 Synthesis of Monomer IV ((4-Vinylphenyl)methanesulfonate, Sodium Salt) [ka] Under a nitrogen atmosphere, sodium sulfite (22.72 g, 180 mmol) and 2,6-di-tert-butyl-4-methylphenol (0.79 g, 4 mmol) were dissolved in 144 mL of water. A solution of 1-(chloromethyl)-4-vinylbenzene (20.35 g, 120 mmol) in acetone (114 mL) was added to the stirred reaction mixture. The reaction mixture was then refluxed for 6 hours. The reaction mixture was then cooled to room temperature. The resulting precipitate was filtered and washed with ethanol. The filtrate was concentrated under reduced pressure.

[0145] Both fractions were recrystallized from water / isopropanol (0.75 / 0.25), filtered, and washed with acetone to give (4-vinylphenyl)methanesulfonate, sodium salt (23.4 g, 88.6%) as a white powder.

[0146] Example 3: Preparation of Polyanion-02(a) to Polyanion-02(b) Polyanion-02(a) Dissolve 0.20 g of CuCl in 49 mL of water and degas with nitrogen for 45 minutes. Add 0.95 g of 2,2-bipyridine. Heat the mixture to 50°C to dissolve the product. The solution was further degassed with nitrogen for 30 minutes.

[0147] Dissolve 10.0 g of 4-vinylbenzenesulfonic acid, sodium salt, in 122.36 mL of water and 37.49 mL of methanol. Prepare a 1 wt% solution of NaCl and add (0.14 mL) to this solution. Add 4-(bromomethyl)benzoic acid (41.6 mg). Degas the reaction mixture by bubbling nitrogen for 60 minutes. Add 6.64 g of the CuCl / 2,2-bipyridine catalyst / ligand complex solution. Stir the reaction mixture at 22.5°C for 4 hours. Then, with stirring, add aqueous sulfuric acid (6N, 15.1 mL). Dialyze the product in a dialysis tubing under a running water stream with a cutoff of 1000 Da. This procedure yielded a clear to slightly yellow aqueous solution of polyanion-02(a).

[0148] Polyanion-02(b) 0.21 g of CuCl was dissolved in 200 mL of water and degassed with nitrogen for 45 minutes. 1.0 g of a 1.4 wt % 2,2-bipyridine aqueous solution was added. The solution was further degassed with nitrogen for 30 minutes.

[0149] Dissolve 8.80 g of 4-vinylbenzenesulfonic acid, sodium salt in 99 mL of water. Prepare a 1 wt% solution of NaCl and add (0.05 mL) to this solution. Add 42.2 mg of 4-(bromomethyl)benzoic acid and adjust the pH to 6 with HCl. Degas the reaction mixture by bubbling with nitrogen for 60 minutes. Add 8.51 g of CuCl / 2,2-bipyridine catalyst / ligand complex solution. Stir the reaction mixture at room temperature for 3 hours. Then, filter the catalyst / ligand complex from the reaction mixture through alumina (wash with 20 / 80% v / v MeOH / water). Dialyze the filtrate in a dialysis tubing under a running water stream with a cutoff of 1000 Da. The product is lyophilized and redissolved in 100 mL of water. The resulting product was treated twice with an ion exchanger (115 g of Lewatit® MonoPlus S 108 HH, filtered and washed twice with 50 mL). This procedure gave a clear to slightly yellow aqueous solution of Polyanion-01(b).

[0150] Comparative Example 1: Free Radical Polymerization of Monomer IV In 77.73 mL of water was dissolved 5.22 g of monomer IV (4-vinylphenyl) methanesulfonate, sodium salt) obtained in Example 1. The reaction mixture was stirred and heated to 90°C.

[0151] A 2.00 wt% aqueous solution of INI-01 was prepared and degassed with nitrogen for 1 hour. The initiator solution was rapidly added to the reaction mixture in an amount that resulted in an initiator concentration of 3.33 mol%. The solution was stirred at 90°C for 20 hours.

[0152] The reaction mixture was then treated twice with an ion exchanger (30 g of Lewatit® MonoPlus S 108 H, filtered and washed twice with 20 mL of water).

[0153] This procedure yielded a clear to slightly yellow solution of polyanion-02(c).

[0154] Example 4 The molecular weights (Mw) in kDa of polyanion-01(a) to polyanion-01(e) and PSS-1 and their polydispersities D were determined as described above. The results are shown in Table 2. [Table 2]

[0155] Example 5: Preparation of PEDOT / Polyanion-01(a) In a reaction vessel, 216.8 g of Polyanion-01(a) obtained in Example 1, deionized water (132 mL), and nitric acid (3.80 g) were mixed. Iron(III) sulfate (0.14 g) and sodium persulfate (2.77 g) were added. The reaction mixture was stirred under a nitrogen flow for 90 minutes and cooled to 5°C. The oxygen level was less than 30 ppb. 3,4-ethylenedioxythiophene (EDOT) (1.50 g) was added to the reaction mixture, which was then stirred at 5°C under nitrogen for 20 hours. The reaction mixture was treated with an ion exchanger (100 g of Lewatit® MonoPlus M600 + 50 g of Lewatit® MonoPlus S 108 H, filtered, and washed three times with 50 mL of water, repeating this process). The resulting viscous mixture was subjected to high-shear homogenization (Lab Gaulin, 4 times at 600 bar). The dispersion was concentrated under reduced pressure. This procedure resulted in a blue PEDOT / polyanion-01(a) aqueous dispersion (1.50 wt %).

[0156] Example 6: Preparation of PEDOT / Polyanion-01(b) The polymerization was carried out in the same manner as in Example 5, except that 204.9 g of Polyanion-01(b) obtained in Example 1 and 144 mL of deionized water were used. The reaction mixture was treated with an ion exchanger (95 g of Lewatit® MonoPlus M600 + 50 g of Lewatit® MonoPlus S 108 H, filtered and washed three times with 50 mL of water, and the procedure was repeated). This procedure resulted in a blue PEDOT / Polyanion-01(b) aqueous dispersion (1.37 wt %).

[0157] Example 7: Preparation of PEDOT / Polyanion-01(c) The polymerization was carried out in the same manner as in Example 6, except that 231.5 g of Polyanion-01(c) obtained in Example 1 and 117 mL of deionized water were used. This procedure resulted in a blue PEDOT / Polyanion-01(c) aqueous dispersion (1.38 wt %).

[0158] Example 8: Preparation of PEDOT / Polyanion-01(d) The polymerization was carried out in the same manner as in Example 6, except that 255.1 g of Polyanion-01(d) obtained in Example 1 and 93.4 mL of deionized water were used. This procedure resulted in a blue PEDOT / Polyanion-01(d) aqueous dispersion (1.31 wt %).

[0159] Example 9: Preparation of PEDOT / Polyanion-01(e) The polymerization was carried out in the same manner as in Example 6, except that 232.9 g of Polyanion-01(e) obtained in Example 1 and 115.6 mL of deionized water were used. This procedure resulted in a blue PEDOT / Polyanion-01(e) aqueous dispersion (1.26 wt %).

[0160] Example 10: Preparation of PEDOT / Polyanion-02(a) Polymerization was carried out in the same manner as in Example 5, except that 126.3 g of polyanion-02(a) from Example 3, 152.6 mL of deionized water, 2.9 g of nitric acid, 0.10 g of iron(III) sulfate, 2.11 g of sodium persulfate, and 1.14 g of EDOT were used. The reaction mixture was treated with an ion exchanger (75 g of Lewatit® MonoPlus M600 + 40 g of Lewatit® MonoPlus S 108 H, filtered, washed twice with 50 mL of water, and repeated). This procedure yielded a blue PEDOT / polyanion-02(a) aqueous dispersion (1.26 wt %).

[0161] Example 11: Preparation of PEDOT / Polyanion-02(b) Polymerization was carried out in the same manner as in Example 5, except that 279.8 g of polyanion-02(b) obtained in Example 3, 18.9 mL of deionized water, 3.11 g of nitric acid, 0.11 g of iron(III) sulfate, 2.26 g of sodium persulfate, and 1.23 g of EDOT were used. The reaction mixture was treated with an ion exchanger (80 g of Lewatit® MonoPlus M600 + 45 g of Lewatit® MonoPlus S 108 H, filtered, washed twice with 70 mL of water, and repeated). This procedure yielded a blue PEDOT / polyanion-02(b) aqueous dispersion (1.41 wt %).

[0162] Comparative Example 2: Polymerization of PEDOT:Polyanion-02(c) Polymerization was carried out in the same manner as in Example 6, except that 172.8 g of Polyanion-02(c) obtained in Example 3, 206 mL of deionized water, 3.9 g of nitric acid, 0.14 g of iron(III) sulfate, 2.86 g of sodium persulfate, and 1.55 g of EDOT were used. The reaction mixture was treated with an ion exchanger (100 g of Lewatit® MonoPlus M600 + 55 g of Lewatit® MonoPlus S 108 H, filtered, washed twice with 50 mL of water, and repeated). This procedure yielded a blue PEDOT / Polyanion-02(c) aqueous dispersion (1.28 wt %).

[0163] Comparative Example 3: Polymerization of PEDOT:PSS In a reaction vessel, 88.7 g of PSS-1, deionized water (389 mL), and nitric acid (14.3 g) were mixed.

[0164] Iron(III) sulfate (0.094 g) and sodium persulfate (3.48 g) were added. The reaction mixture was stirred and cooled to 5°C under a nitrogen flow. The oxygen level was less than 30 ppb. EDOT (2.06 g) was added to the reaction mixture and stirred at 5°C for 20 hours. The reaction mixture was then treated with an ion exchanger (130 g of Lewatit® MonoPlus M600 + 70 g of Lewatit® MonoPlus S 108 H, filtered and washed twice with 50 mL of water, and this process was repeated). The resulting viscous mixture was subjected to high-shear homogenization (Lab Gaulin, 4 times at 600 bar). After a vacuum concentration step, a blue 1.15 wt% PEDOT / PSS-1(a) aqueous dispersion was obtained.

[0165] Example 12 The median particle size (Φ) and viscosity of the conductive PEDOT / PSS dispersions and the SER of the films bar-coated onto PET are shown in Table 3, along with the weight-average molecular weight (Mw) and polydispersity (D) of the PSS used. [Table 3]

[0166] As is clear from the results in Table 3, the dispersion using the polyanion according to the present invention can have a smaller median particle size and a lower SER value.

[0167] Example 13: Preparation of capacitors A chemically converted aluminum foil with an etching layer on its surface was prepared as a valve metal substrate. A dielectric layer was formed to cover the aluminum foil. The resulting chemically converted aluminum foil was used as an anode component. The rated voltage of the alumina layer was 90 V, and the capacitance was 6.4 μF / cm. 2 A 20 μm thick solder mask was printed on Al foil with multiple 10 mm × 10 mm openings. The patterned foil was cut into 30 mm × 105 mm strips with five openings each.

[0168] The conductive polymer dispersion used to fabricate the capacitors was formulated using water, diethylene glycol, and DYNOL™ 604 and subjected to an ultrasonic homogenization process before being coated onto aluminum foil.

[0169] The strips were dip-coated with the PEDOT / polyanion-01(a) dispersion and dried at 150°C for 5 minutes. The dip-coating and curing steps were repeated multiple times. Carbon paste and silver paste were then screen-printed, in sequence, onto the PEDOT layer and cured. Capacitance and equivalent series resistance (ESR) were measured as described above.

[0170] Additional capacitors were prepared and measured as above, but using PEDOT / polyanion-01(b), PEDOT / polyanion-01(c), PEDOT / polyanion-01(d), PEDOT / polyanion-01(e), and PEDOT / PSS-1 as the conductive polymer dispersion.

[0171] Table 4 summarizes the results of the capacitor evaluation. [Table 4]

[0172] As is clear from the results in Table 4, the dispersion using the polyanion according to the present invention increases the capacitance of the capacitor while lowering the ESR.

Claims

1. 1. A method for preparing a polymer capacitor having a porous anode body, comprising the steps of: introducing a conductive polymer formulation into at least a portion of the porous anode body; The conductive polymer formulation comprises: (a) at least one oligothiophene or polythiophene obtained by polymerization of at least one monomer according to formula I; 【Chemical 1】 During the ceremony, A is a substituted or unsubstituted C １ -C ５ represents an alkylene bridge; R is selected from the group consisting of linear or branched, substituted or unsubstituted C1-C18-alkyl groups, substituted or unsubstituted C5-C12-cycloalkyl groups, substituted or unsubstituted C6-C14-aryl groups, substituted or unsubstituted C7-C18-aralkyl groups, and hydroxyl groups; s represents an integer from 0 to 8; (b) a polymeric polyanion comprising at least one monomeric unit according to Formula II 【Chemistry 2】 During the ceremony R １ ~R ５ are selected from the group consisting of hydrogen, halogen, ether, and substituted or unsubstituted alkyl groups, with the proviso that R １ ~R ５ at least one of which is represented by a substituent according to formula III; 【Chemistry 3】 During the ceremony n represents 0 or 1; R ６ and R ７ are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted alkaryl groups, and substituted or unsubstituted aryl or heteroaryl groups; R ６ and R ７ may also represent the atoms necessary to form a five- to eight-membered ring, B represents a functional group selected from the group consisting of sulfonic acid or a salt thereof, sulfuric acid ester or a salt thereof, and carboxylic acid or a salt thereof; The dashed line represents a covalent bond to the styrene ring, and Including, The polymeric polyanion is characterized in that it has a polydispersity of 3 or less and a weight average molecular weight (Mw) of 25 to 175 kDa. Said preparation method.

2. 2. The method for preparing a polymer capacitor according to claim 1, wherein the polydispersity of the polyanion is 2 or less.

3. 3. The method for preparing a polymer capacitor according to claim 1 or 2, wherein the weight average molecular weight (Mw) of the polyanion is 40 to 90 kDa.

4. 10. A method for preparing a polymer capacitor according to any one of the preceding claims, wherein the polymeric polyanion is poly(4-styrenesulfonic acid) or a salt thereof.

5. The oligothiophene or polythiophene and the polyanion have a median particle size (d ５０ 10. A method for preparing a polymer capacitor according to any one of the preceding claims, wherein the polymer is present as polythiophene / polyanion particles having a size of 5-40 nm.

6. A method for preparing a polymer capacitor according to any one of the preceding claims, wherein the formulation has a pH of 2 to 8.

5.

7. The viscosity of the dispersion was measured using a rheometer at 20°C and a shear rate of 100 s －１ 10. A method for preparing a polymer capacitor according to any one of the preceding claims, wherein the polymer capacitor has a viscosity of 1 to 250 mPa·s as measured by .

8. 10. The method for preparing a polymer capacitor according to any one of the preceding claims, wherein the formulation further comprises a conductivity enhancing compound selected from the group consisting of N-methylpyrrolidinone, N-butylpyrrolidone, N-ethylpyrrolidone, N-hydroxyethylpyrrolidone, DMSO, ethylene glycol, and diethylene glycol.

9. 10. A method for preparing a polymer capacitor according to any one of the preceding claims, wherein the polyanion is prepared by atom transfer radical polymerization (ATRP).

10. 1. A conductive polymer composition for a polymer capacitor, comprising: (a) at least one oligothiophene or polythiophene obtained by polymerization of at least one monomer according to formula I; 【Chemistry 4】 During the ceremony, A represents a substituted or unsubstituted C1-C5 alkylene bridge; R is selected from the group consisting of linear or branched, substituted or unsubstituted C1-C18-alkyl groups, substituted or unsubstituted C5-C12-cycloalkyl groups, substituted or unsubstituted C6-C14-aryl groups, substituted or unsubstituted C7-C18-aralkyl groups, and hydroxyl groups; s represents an integer from 0 to 8; (b) a polymeric polyanion comprising at least one monomeric unit according to Formula II 【Chemistry 5】 During the ceremony R １ ~R ５ are selected from the group consisting of hydrogen, halogen, ether, and substituted or unsubstituted alkyl groups, with the proviso that R １ ~R ５ at least one of which is represented by a substituent according to formula III; 【Chemistry 6】 During the ceremony n represents 0 or 1; R ６ and R ７ are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted alkaryl groups, and substituted or unsubstituted aryl or heteroaryl groups; R ６ and R ７ may also represent the atoms necessary to form a five- to eight-membered ring, B represents a functional group selected from the group consisting of sulfonic acid or a salt thereof, sulfuric acid ester or a salt thereof, and carboxylic acid or a salt thereof; The dashed line represents a covalent bond to the styrene ring, and Including, The polymeric polyanion is characterized in that it has a polydispersity of 3 or less and a weight average molecular weight (Mw) of 25 to 90 kDa. The conductive polymer composition.

11. 11. The conductive polymer composition of claim 10, wherein the polydispersity of the polyanion is 2 or less.

12. 12. The conductive polymer composition according to claim 10 or 11, wherein the weight average molecular weight (Mw) of the polyanion is 50 to 80 kDa.

13. The conductive polymer composition according to any one of claims 10 to 12, wherein the polyanion is prepared by atom transfer radical polymerization (ATRP).

14. Use of the conductive polymer composition according to any one of claims 10 to 13 for preparing a conductive layer in an electronic device.

15. 15. The use according to claim 14, wherein the electronic device is selected from photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes, IR detectors, photovoltaic devices, solar cells, coating materials for memory storage devices, field effect resistive devices, antistatic films, biosensors, electrochromic devices, solid electrolyte capacitors, hybrid capacitors, supercapacitors, energy storage devices, batteries, and electromagnetic shielding.

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