PEDOT dispersion with a high power of force N

Abstract

The present invention relates to a dispersion comprising i) a dispersant; ii) at least one polythiophene dispersed in the dispersant i); and the Ostwald de l / l / ae / e relationship for the dispersion. T =Ky n The exponent n in the power law is in the range of 0.62 to 0.92. T The present invention relates to a dispersion in which is the shear stress, K is the fluid viscosity constant, Y is the shear rate dy / dt, and the dispersion has a solid content of at least 1.5% by weight based on the total weight of the dispersion. The present invention also relates to a process for preparing a dispersion, a dispersion obtained by the process, a process for preparing a laminate, a laminate obtained by the process, and the use of the dispersion for forming a solid electrolyte layer in a capacitor.

Description

[Technical Field]

[0001] The present invention relates to a dispersion comprising a dispersant and at least one polythiophene dispersed in the dispersant, a process for preparing the dispersion, a dispersion obtained by the process, a process for preparing a laminate, a laminate obtained by the process, and the use of the dispersion for forming a solid electrolyte layer in a capacitor. [Background technology]

[0002] A typical electrolytic capacitor generally consists of a porous metal electrode, an oxide layer placed on the metal surface, a generally solid conductive material introduced into the porous structure, external electrodes (contacts) such as a silver layer, and other electrical contacts and encapsulants. One frequently used electrolytic capacitor is the tantalum electrolytic capacitor, where the anode electrode is made from valve metal tantalum, and a uniform dielectric layer of tantalum pentoxide is formed (also called "formed") on top of it by anodizing. A liquid or solid electrolyte forms the cathode of the capacitor. Aluminum capacitors are also frequently used, where the anode electrode is made from valve metal aluminum, and a uniform electrically insulating aluminum oxide layer is formed as the dielectric on top of it by anodizing. Here again, a liquid or solid electrolyte forms the cathode of the capacitor. Aluminum capacitors are generally embodied as wound capacitors or stacked capacitors.

[0003] Due to their high conductivity, π-conjugated polymers are particularly suitable as solid electrolytes in the above-mentioned capacitors. π-conjugated polymers are also called conductive polymers or synthetic metals. Compared to metals, polymers have advantages in terms of processing, weight, and the selective tuning of properties by chemical modification, and therefore conjugated polymers are gaining increasing commercial importance. Examples of known π-conjugated polymers include polypyrrole, polythiophene, polyaniline, polyacetylene, polyphenylene, and poly(p-phenylene-vinylene), with poly(3,4-ethylene-dioxythiophene) (PEDOT) being a particularly important polythiophene used technically due to its very high conductivity in its oxidized form.

[0004] In the prior art, alternative methods have been developed for producing solid electrolytes based on conductive polymers in electrolytic capacitors. For example, German Patent Publication No. 102005043828(A) describes a process for producing a solid electrolyte in a capacitor in which a dispersion containing polythiophene, for example, a PEDOT / PSS dispersion known from the prior art, is applied to an oxide layer, and the dispersion medium is then removed by evaporation.

[0005] However, it has been observed that the equivalent series resistance (ESR) of electrolytic capacitors with a solid electrolyte layer prepared using conventional PEDOT / PSS dispersions is often too high for certain applications.

[0006] The present invention relates to capacitors, preferably to electrolytic capacitors, more preferably to capacitors known from the prior art that include a solid electrolyte layer based on a π-conjugated polymer such as PEDOT, and even more preferably to capacitors known from the prior art that include a solid electrolyte layer based on PEDOT / PSS, and is based on the objective of overcoming the drawbacks arising from the prior art.

[0007] In particular, the present invention was intended to provide a dispersion containing at least one polythiophene, preferably a dispersion containing a polythiophene-polyanion complex, and more preferably a dispersion containing a PEDOT / PSS complex, which is particularly useful for fabricating a solid electrolyte layer in capacitors characterized by low ESR.

[0008] Furthermore, an object of the present invention was to provide a process for preparing such advantageous dispersions. The process for preparing advantageous dispersions should be characterized by enabling the production of these dispersions in the simplest possible manner.

[0009] Furthermore, an object of the present invention is to provide a preparation process for a laminate, preferably an electrolytic capacitor, characterized in that the ESR is reduced compared to electrolytic capacitors known from the prior art. [Overview of the project]

[0010] Contributions to solving at least one, preferably two or more, of the above objectives are made by the independent claims. Dependent claims provide preferred embodiments that contribute to solving at least one of the objectives at least partially.

[0011] |1a| A contribution to solving at least one of the objectives of the present invention is, i) Dispersants (also called "dispersing agents"); ii) A dispersion comprising i) at least one polythiophene dispersed in a dispersant; Regarding dispersions, related to Ostwald de Waele.

[0012]

number

[0013]

number

number

[0014] As used in connection with the present invention, the term "dispersion" generally refers to any liquid composition in which polythiophene, for example, polythiophene as part of a complex containing polythiophene and polyanion, is distributed in some way in a homogeneous phase formed by liquid dispersant i) (dispersant i), and thus forms the liquid phase of the dispersion. Note that the transition between "dispersion" and "solution" can be fluid. Therefore, there is no distinction between the terms "dispersed" and "dissolved" below. Similarly, there is no distinction between "dispersion" and "solution" or between "dispersant" and "solvent." Rather, these terms are used synonymously.

[0015] |2a|According to a preferred embodiment of the dispersion according to the present invention, the dispersant i) comprises water. Preferably, in each case, the dispersant i) comprises water in an amount of at least 50% by weight, more preferably at least 65% by weight, even more preferably at least 70% by weight, and most preferably at least 80% by weight, based on the total weight of the dispersion. This preferred embodiment is a second embodiment of the dispersion according to the present invention, and is preferably dependent on the first embodiment.

[0016] |3a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) is an externally doped polythiophene such as a cationic polythiophene existing in the form of a polythiophene / polyanion complex, more preferably in the form of a PEDOT / PSS complex, a self-doped polythiophene such as poly(4-[(2,3-dihydrothieno-[3,4-b]-[1,4]dioxin-2-yl)methoxy]propane-1-sulfonic acid), poly(4-[(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy]butane-1-sulfonic acid)(PEDOT-S) or poly-(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid) or a mixture thereof. This preferred embodiment is a third embodiment of the dispersion according to the present invention and is preferably dependent on the first or second embodiment.

[0017] |4a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) exists in the form of particles of a complex comprising at least one polythiophene ii) and a polyanion. This preferred embodiment is a fourth embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to third embodiments.

[0018] |5a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) exists in the form of particles of a complex comprising at least one polythiophene ii) and a polyanion, where the polythiophene is poly(3,4-ethylenedioxythiophene) and the polyanion is an anion of polystyrene sulfonic acid. Therefore, the complex of polythiophene and polyanion is preferably a PEDOT / PSS complex. This preferred embodiment is a fifth embodiment of the dispersion according to the present invention and is preferably dependent on any of the first to fourth embodiments.

[0019] |6a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) exists in the form of particles of a complex comprising at least one polythiophene ii) and a polyanion, preferably in the form of particles comprising PEDOT / PSS, and the dispersion contains the polyanion and polythiophene in a polyanion:polythiophene weight ratio in the range of 0.5:1 to 30:1, preferably in the range of 0.8:1 to 15:1, more preferably in the range of 1:1 to 10:1, even more preferably in the range of 1.2:1 to 8:1, and most preferably in the range of 1.4:1 to 4:1. The weight of polythiophene in this context corresponds to the weight of the thiophene monomer used in the preparation of the polythiophene, assuming that complete conversion occurs during polymerization. This preferred embodiment is a sixth embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to fifth embodiments.

[0020] |7a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) is present in the form of particles of a complex comprising at least one polythiophene ii) and a polyanion, preferably in the form of particles comprising PEDOT / PSS, and the weight-average diameter (d) of these particles is determined by ultracentrifugation measurement. 50 The wavelength is in the range of 1 nm to 100 nm, more preferably in the range of 2 nm to 50 nm, even more preferably in the range of 3 nm to 40 nm, and most preferably in the range of 4 nm to 30 nm. This preferred embodiment is a seventh embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to sixth embodiments.

[0021] |8a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) is present in the form of particles of a composite comprising at least one polythiophene ii) and a polyanion, preferably in the form of particles comprising PEDOT / PSS, and the dispersion has a diameter distribution of these particles determined by ultracentrifugation measurement of less than 100 nm, preferably less than 80 nm, more preferably less than 60 nm, and most preferably less than 50 nm 90It has a value. This preferred embodiment is an eighth embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to seventh embodiments.

[0022] |9a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) is present in the form of particles of a composite comprising at least one polythiophene ii) and a polyanion, preferably in the form of particles comprising PEDOT / PSS, and the dispersion has a diameter distribution of these particles determined by ultracentrifugation measurement of greater than 1 nm, preferably greater than 2 nm, more preferably greater than 3 nm, and most preferably greater than 4 nm. 10 It has a value. This preferred embodiment is a ninth embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to eighth embodiments.

[0023] |10a|According to a more preferred embodiment of the dispersion according to the present invention, the dispersion has a pH value (measured at 25°C) in the range of 2.5 to 8.0, preferably in the range of 2.5 to 7, and more preferably in the range of 3 to 6. This preferred embodiment is the tenth embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to ninth embodiments.

[0024] |11a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) is present in the form of particles of a complex comprising at least one polythiophene ii) and a polyanion, preferably in the form of particles comprising PEDOT / PSS, and the dispersion in each case contains a total amount of polythiophene and polyanion (i.e., amount of polythiophene + amount of polyanion) of at least 1.5% by weight, preferably at least 1.6% by weight, more preferably at least 1.7% by weight, and most preferably at least 1.8% by weight, based on the total weight of the dispersion. This preferred embodiment is the 11th embodiment of the dispersion according to the present invention, and is preferably dependent on any of the 1st to 10th embodiments.

[0025] |12a|According to a more preferred embodiment of the dispersion according to the present invention, the dispersion is iii) further comprising at least one additive, the at least one of which is selected from the group consisting of binders, pH adjusters, crosslinking agents, adhesion promoters, conductivity enhancers, surfactants, stabilizers, and at least two combinations thereof.

[0026] This preferred embodiment is a twelfth embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to eleventh embodiments.

[0027] |13a|According to a more preferred embodiment of the dispersion according to the present invention, the dispersion has a viscosity in the range of 0.1 to 200 mPa×s, preferably in the range of 1 to 100 mPa×s, more preferably in the range of 5 to 70 mPa×s, and most preferably in the range of 10 to 50 mPa×s (at 20°C and 100°S) -1 It has a shear rate (measured with a rheometer). This preferred embodiment is a thirteenth embodiment of the dispersion according to the present invention, which preferably depends on any of the first to twelfth embodiments.

[0028] |14a|According to a more preferred embodiment of the dispersion according to the present invention, the conductive layer prepared from the dispersion has a conductivity of more than 10 S / cm, preferably more than 50 S / cm, more preferably more than 100 S / cm, even more preferably more than 200 S / cm, and most preferably more than 300 S / cm, in each case determined by the test method disclosed herein (i.e., the test method for determining the conductivity of the conductive layer for a dispersion obtained after adding 1 g of DMSO to 19 g of the dispersion according to the present invention). This preferred embodiment is a 14th embodiment of the dispersion according to the present invention, which preferably depends on any of the 1st to 13th embodiments.

[0029] |1b| A contribution to solving at least one objective of the present invention is a process 1 for preparing a dispersion, I) i) Dispersant; ii) A dispersion comprising at least one polythiophene dispersed in a dispersant i), The process involves preparing the product by polymerizing a thiophene monomer in the presence of a dispersant i) and an oxidizing agent, wherein the molar ratio of the oxidizing agent to the thiophene monomer before polymerization is in the range of 1:1 to 1.3:1. In each case, the dispersion has a solid content of at least 1.5% by weight, preferably at least 1.6% by weight, more preferably at least 1.7% by weight, and even more preferably at least 1.8% by weight, based on the total weight of the dispersion. The dispersion has an conductivity of more than 10 S / cm, preferably more than 50 S / cm, more preferably more than 100 S / cm, even more preferably more than 200 S / cm, and most preferably more than 300 S / cm, in each case determined by the test method disclosed herein, II) A step of adjusting the power law exponent n in the dispersion provided in process step I) to be in the range of 0.62 to 0.92, preferably in the range of 0.66 to 0.88, more preferably in the range of 0.70 to 0.84, and even more preferably in the range of 0.72 to 0.82, This is also done by a first embodiment of process 1 for preparing the dispersion, which includes the following:

[0030] |2b|According to a preferred embodiment of Process 1 according to the present invention, the dispersant i) comprises water. Preferably, in each case, the dispersant i) comprises water in an amount of at least 50% by weight, more preferably at least 65% by weight, even more preferably at least 70% by weight, and most preferably at least 80% by weight, based on the total weight of the dispersion. This preferred embodiment is a second embodiment of Process 1 according to the present invention, and is preferably dependent on the first embodiment.

[0031] |3b|According to a more preferred embodiment of Process 1 according to the present invention, the thiophene monomer is polymerized in the presence of a dispersant i) and a polyanion to obtain a dispersion containing a polythiophene-polyanion complex. This preferred embodiment is a third embodiment of Process 1 according to the present invention and is preferably dependent on the first or second embodiment.

[0032] |4b|According to a more preferred embodiment of Process 1 according to the present invention, a thiophene monomer is polymerized in the presence of a dispersant i) and a polyanion to obtain a dispersion containing a polythiophene-polyanion complex, wherein the thiophene monomer is 3,4-ethylenedioxythiophene and the polyanion is an anion of polystyrene sulfonic acid. Therefore, the polythiophene-polyanion complex is preferably a PEDOT / PSS complex. This preferred embodiment is a fourth embodiment of Process 1 according to the present invention and is preferably dependent on any of the first to third embodiments.

[0033] |5b|According to a more preferred embodiment of Process 1 according to the present invention, polythiophene is contained in the dispersion obtained in Process Step I) in an amount ranging from 12 to 40% by weight, based on the total weight of polythiophene and polyanions in the dispersion. This preferred embodiment is a fifth embodiment of Process 1 according to the present invention, and is preferably dependent on the fourth embodiment.

[0034] |6b|According to a more preferred embodiment of Process 1 according to the present invention, the adjustment of the power law exponent n in the dispersion provided in Process Step I) is achieved by subjecting the dispersion provided in Process Step I) to a series of high-pressure homogenization steps, more preferably high-pressure homogenization, more preferably at least 25, preferably at least 35, more preferably at least 45, more preferably at least 55, most preferably at least 65, carried out at a pressure of at least 1,000 bar, preferably at least 1,200 bar, more preferably at least 1,400 bar, even more preferably at least 1,600 bar, and most preferably at least 1,800 bar. This preferred embodiment is a sixth embodiment of Process 1 according to the present invention and is preferably dependent on any of the first to fifth embodiments.

[0035] |7b|According to a more preferred embodiment of Process 1 according to the present invention, a thiophene monomer is polymerized in the presence of a dispersant i) and a polyanion to obtain a dispersion containing a polythiophene-polyanion complex, where the thiophene monomer is 3,4-ethylenedioxythiophene and the polyanion is an anion of polystyrene sulfonic acid. - The molar ratio of oxidizing agent to thiophene monomer before polymerization is in the range of 1.09:1 to 1.13:1. -Polythiophene is present in the dispersion obtained in process step I) in an amount ranging from 27 to 30% by weight, based on the total weight of polythiophene and polyanions in the dispersion. - The adjustment of the power law exponent n in the dispersion provided in process step I) is achieved by subjecting the dispersion provided in process step I) to a series of at least 55 high-pressure homogenization steps performed at a pressure of at least 1,400 bar.

[0036] This preferred embodiment is a seventh embodiment of process 1 according to the present invention, and is preferably dependent on any of the first to sixth embodiments.

[0037] |8b|According to a more preferred embodiment of Process 1 according to the present invention, a thiophene monomer is polymerized in the presence of a dispersant i) and a polyanion to obtain a dispersion containing a polythiophene-polyanion complex, where the thiophene monomer is 3,4-ethylenedioxythiophene and the polyanion is an anion of polystyrene sulfonic acid. - The molar ratio of oxidizing agent to thiophene monomer before polymerization is in the range of 1.09:1 to 1.13:1. -Polythiophene is present in the dispersion obtained in process step I) in an amount ranging from 13 to 15% by weight, based on the total weight of polythiophene and polyanions in the dispersion. - The adjustment of the power law exponent n in the dispersion provided in process step I) is achieved by subjecting the dispersion provided in process step I) to a series of at least 55 high-pressure homogenization steps performed at a pressure of at least 1,400 bar.

[0038] This preferred embodiment is an eighth embodiment of process 1 according to the present invention, and is preferably dependent on any of the first to sixth embodiments.

[0039] |9b|According to a more preferred embodiment of Process 1 according to the present invention, a thiophene monomer is polymerized in the presence of a dispersant i) and a polyanion to obtain a dispersion containing a polythiophene-polyanion complex, where the thiophene monomer is 3,4-ethylenedioxythiophene and the polyanion is an anion of polystyrene sulfonic acid. - The molar ratio of oxidizing agent to thiophene monomer before polymerization is in the range of 1.20:1 to 1.24:1. -Polythiophene is present in the dispersion obtained in process step I) in an amount ranging from 27 to 30% by weight, based on the total weight of polythiophene and polyanions in the dispersion. - The adjustment of the power law exponent n in the dispersion provided in process step I) is achieved by subjecting the dispersion provided in process step I) to a series of at least 55 high-pressure homogenization steps performed at a pressure of at least 1,400 bar.

[0040] This preferred embodiment is a ninth embodiment of process 1 according to the present invention, and is preferably dependent on any of the first to eighth embodiments.

[0041] |1c| A contribution to solving at least one objective of the present invention is also made by a dispersion obtained by process 1 according to the present invention, preferably by process 1 according to any of the first to ninth embodiments thereof. Preferably, this dispersion has the same properties as the dispersion according to the present invention, preferably as defined in any of the first to fourteenth embodiments thereof.

[0042] |1d| A contribution to solving at least one of the objectives of the present invention is also made by a first embodiment of process 2 for the preparation of a laminate, the process comprising the following steps: A) The process of preparing the base material, B) A step of applying a dispersion according to the present invention, preferably a dispersion according to the present invention as defined in any of the first to fourteenth embodiments thereof, or a dispersion obtained by process 1 according to the present invention, preferably a dispersion obtained by process 1 as defined in any of the first to nineth embodiments thereof, to at least a portion of the surface of the substrate. C) The process includes a step of at least partially removing the dispersant i) in order to obtain a laminate including a conductive layer coated on at least a portion of the surface of the substrate.

[0043] |2d|According to a preferred embodiment of process 2 according to the present invention, the laminate is part of an electrolytic capacitor, the substrate is a porous electrode body made of an electrode material, the dielectric layer covers at least partially the surface of the electrode material, and the conductive layer is a solid electrolyte layer covering at least partially the surface of the dielectric layer. This preferred embodiment is a second embodiment of process 2 according to the present invention and is preferably dependent on the first embodiment.

[0044] |3d|According to a preferred embodiment of process 2 according to the present invention, the process is A) A step of preparing a porous electrode body made of an electrode material, wherein a dielectric layer covers at least partially the surface of the electrode material. B) A step of introducing a dispersion according to the present invention, preferably a dispersion according to the present invention as defined in any of the first to fourteenth embodiments thereof, or a dispersion obtained by process 1 according to the present invention, preferably process 1 as defined in any of the first to ninth embodiments thereof, into at least a portion of the porous electrode body prepared in process step A), thereby applying the dispersion to at least a portion of the surface of the dielectric layer. C) A step of at least partially removing the dispersant i) in order to form a solid electrolyte that at least partially covers the surface of the dielectric layer, D) The process includes optionally applying a dispersion containing a conductive polymer, preferably a dispersion containing polythiophene and a dispersant, more preferably a dispersion containing a dispersant and particles of a polythiophene and polymer anion complex, and even more preferably a PEDOT / PSS dispersion, to at least a portion of the surface of a solid electrolyte layer, and at least partially removing the dispersant in order to form a polymer outer layer that at least partially covers the surface of the solid electrolyte layer.

[0045] This preferred embodiment is a third embodiment of process 2 according to the present invention, and is preferably dependent on the first or second embodiment.

[0046] |4d|According to a more preferred embodiment of Process 2 according to the present invention, the laminate is an aluminum capacitor or a tantalum capacitor. This preferred embodiment is a fourth embodiment of Process 2 according to the present invention, preferably dependent on any of the first to third embodiments thereof.

[0047] |1e| A contribution to solving at least one of the objectives of the present invention is also made by the laminate obtained by process 2 according to the present invention, preferably by process 2 according to any of the first to fourth embodiments thereof.

[0048] |1f|A contribution to solving at least one of the objectives of the present invention is also made by the use of a dispersion according to the present invention, preferably a dispersion according to the present invention as defined in any of its first to fourteenth embodiments, or a dispersion obtained by process 1 according to the present invention, preferably a dispersion obtained by process 1 as defined in any of its first to ninth embodiments, for the formation of a solid electrolyte layer in a capacitor.

[0049] |2f|According to a preferred embodiment of use according to the present invention, the capacitor is an aluminum capacitor or a tantalum capacitor. This preferred embodiment is a second embodiment of use according to the present invention and is preferably dependent on the first embodiment. [Modes for carrying out the invention]

[0050] Polythiophene The dispersion according to the present invention comprises a dispersant and at least one polythiophene dispersed in the dispersant.

[0051] Preferred polythiophenes are those having repeating units of general formula (I), general formula (II), general formula (III), or combinations thereof:

[0052] [ka] During the ceremony, A is an arbitrarily substituted C1-C5 alkylene group, R is independently substituted with C1-C in any linear or branched chain, with H. 18 - Alkyl alkyl groups, optionally substituted C5-C 12 -Cycloalkyl groups, optionally substituted C6-C 14 -aryl group, optionally substituted C7-C 18 - Aralkyl group, optionally substituted C1-C4 hydroxyalkyl group or hydroxyl group, x is an integer between 0 and 8. If multiple R groups are bonded to A, they may be the same or different.

[0053] General formulas (I) and (II) should be understood as allowing x substituents R to bond to the alkylene group A.

[0054] Polythiophenes having repeating units of general formula (I) or (II), or repeating units of general formula (I) and (II), are particularly preferred, where A is an optionally substituted C2-C3 alkylene group and x is 0 or 1. Particularly preferred polythiophenes are optionally substituted poly(3,4-ethylenedioxythiophene) (PEDOT), such as poly(4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]propane-1-sulfonic acid), poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-1-sulfonic acid) (PEDOT-S), or poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid).

[0055] In the context of the present invention, the prefix "poly" should be understood to mean that two or more identical or different repeating units are present in the polymer or polythiophene. The polythiophene contains a total of n repeating units of general formula (I) or general formula (II) or general formula (III), or general formula (I) and (II), or general formula (I) and (III), or general formula (II) and (III), or general formula (I), (II), and (III), where n is an integer from 2 to 2000, preferably from 2 to 100. The repeating units of general formula (I) or general formula (II) or general formula (III), or the repeating units of general formula (I) and (II), or the repeating units of general formula (I) and (III), or the repeating units of general formula (II) and (III), or the repeating units of general formula (I), (II), and (III) may each be the same or different within the polythiophene. In any case, a polythiophene having the same repeating units of general formula (I) or general formula (II) or general formula (III), or in any case having the same repeating units of general formula (I) and (II) or general formula (I) and (III) or general formula (II) and (III), or in any case having the same repeating units of general formula (I), (II), and (III) is preferred. In any case, a polythiophene having the same repeating units of general formula (I) or general formula (II), or in any case having the same repeating units of general formula (I) and (II) is particularly preferred. At the terminal groups, the polythiophene preferably each has H.

[0056] In the context of the present invention, the C1-C5-alkylene group A is preferably methylene, ethylene, n-propylene, n-butylene, or n-pentylene. C1-C 18-Alkyl R is preferably a linear or branched C1-C such as methyl, ethyl, n- or iso-propyl, 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. 18 -It is an alkyl group, C5~C 12 -The cycloalkyl group R is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, C6-C 14 -The aryl group R is, for example, phenyl or naphthyl, and C7~C 18 -The aralkyl group R is, for example, benzyl, o-, m-, p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-xylyl, or mesityl. The above list is helpful in illustrating the present invention as an example and should not be considered exclusive.

[0057] In the context of the present invention, any further substituents of the A group and / or R group include a number of organic groups, such as alkyl, cycloalkyl, aryl, aralkyl, alkoxy, halogen, ether, thioether, disulfide, sulfoxide, sulfone, sulfonate, amino, aldehyde, keto, carboxylic acid ester, carboxylic acid, carbonate, carboxylate, cyano, alkylsilane and alkoxysilane groups, and carboxamide groups.

[0058] Polythiophenes may be uncharged or cationic. In preferred embodiments, they are cationic, and "cationic" refers only to the charge present in the main polythiophene chain. Due to substituents on the R group, polythiophenes can have positive and negative charges within their structural units, in which case the positive charge is on the main polythiophene chain, and the negative charge, if present, is on the R group substituted with a sulfonate or carboxylate group. The positive charge of the main polythiophene chain may be partially or completely saturated by anionic groups that may be present on the R group. Overall, polythiophenes in these cases may be cationic, uncharged, or anionic. Nevertheless, in the context of the present invention, the positive charge on the main polythiophene chain is important, so all are considered cationic polythiophenes. The positive charge is not shown in the formula because it is not possible to clearly state the exact number and location. However, the number of positive charges is at least 1 and at most n, where n is the total number of all repeating units (identical or different) in the polythiophene.

[0059] The positive charge of polythiophene can be balanced by sulfonate or carboxylate-substituted, and therefore negatively charged, R groups (so-called "self-doped polythiophene") or by counterions (so-called "foreign-doped polythiophene").

[0060] According to a first preferred embodiment of the polythiophene in dispersion according to the present invention, the polythiophene is a self-doped polythiophene containing repeating units of formula (IV) to preferably at least 50%, more preferably at least 75%, more preferably at least 95%, and most preferably at least 100%.

[0061] [ka] During the ceremony, X and Y are the same or different, O, S, NR 1Show, R 1 is aryl, C1~C 18 - Represents alkyl or hydrogen, Z is an anionic functional group, preferably SO3. - It is an organic group having a group, and Z is -(CH2) m -CR 2 R 3 -(CH2) n - is particularly preferred, R 2 is hydrogen, -(CH2) s -O-(CR 4 2) p -SO3 - M + or -(CH2) p -SO3 - M + Show, R 3 is, -(CH2) s -O-(CR 4 2) p -SO3 - M + or -(CH2) p -SO3 - M + Show, M + This indicates a cation, m and n are integers between 0 and 3, and can be the same or different. R 4 is hydrogen or C1-C 10 The alkyl group, preferably a methyl group, s represents an integer between 0 and 10. p represents an integer between 1 and 18.

[0062] The percentage values ​​above are intended to represent the numerical content of units of structural formula (IV) in the total number of monomer units in the self-doped conductive polymer in this context.

[0063] Appropriate cation M + For example, H + Li + na + , K + , Rb+ , Cs + and NH4 + A particularly suitable cation is Na. + and K + That is the case.

[0064] The most preferred monomers for structural formula (IV) are as follows: X and Y indicate O. Z is -(CH2) m -CR 2 R 3 -(CH2) n - indicates, R 2 is hydrogen or -(CH2) s -O-(CH2) p -SO3 - M + ,-(CH2) p -SO3 - M + or -(CH2) s -O-(CH2) p -CHR 4 -SO3 - M + Show, R 3 is, -(CH2) s -O-(CH2) p -SO3 - M + ,-(CH2) p -SO3 - M + or -(CH2) s -O-(CH2) p -CHR 4 -SO3 - M + Show, M + This indicates a cation, m and n are integers between 0 and 3, and can be the same or different. R 4 This represents hydrogen, a methyl group, or an ethyl group. s represents an integer between 0 and 10. p represents an integer between 1 and 18.

[0065] The highly particularly preferred monomers of Structural Formula (IV) are as follows. X and Y represent O, Z is -(CH2)-CR 2 R 3 -(CH2) n - represents, R 2 represents hydrogen, R 3 is -(CH2) s -O-(CH2) p -SO3 - M + 、-(CH2) p -SO3 - M + 、or -(CH2) s -O-(CH2) p -CH(CH3)-SO3 - M + or -(CH2) s -O-(CH2) p -CH(CH2CH3)-SO3 - M + represents, M + is Na + or K + represents, n represents 0 or 1, s represents 0 or 1, p represents 2, 3, 4, or 5.

[0066] Suitable examples of self-doped polymers are disclosed in International Publication No. WO 2014 / 048562 (A) and U.S. Patent Application Publication No. US 2015 / 0337061 (A). Specific examples of highly particularly preferred self-doped conductive polymers include poly(4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]propane-1-sulfonic acid), poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-1-sulfonic acid) (PEDOT-S), poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid), or mixtures thereof.

[0067] According to a second preferred embodiment of the polythiophene in the dispersion according to the present invention, the polythiophene is preferably an externally doped polythiophene containing a polymer counterion for balancing the positive charge, the latter also referred to hereafter as "polyanion". Thus, according to a preferred embodiment of the dispersion according to the present invention, the polythiophene is a cationic polythiophene containing a polyanion that functions as a counterion to the polythiophene.

[0068] Polyanions are preferred over monomer anions because they contribute to film formation and, due to their size, result in thermally more stable conductive films. Polyanions as used herein may be anions of polymeric carboxylic acids such as polyacrylic acid, polymethacrylic acid, or polymaleic acid, or polymeric sulfonic acids such as polystyrene sulfonic acid and polyvinyl sulfonic acid. These polycarboxylic acids and sulfonic acids may also be copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as acrylic esters and styrene.

[0069] Preferred polyanions are anions of polymeric carboxylic acids or sulfonic acids. Particularly preferred polyanions are anions of polystyrene sulfonic acid (PSS) or its derivatives.

[0070] The molecular weight of the polyacid that yields the polyanion is preferably 1,000 to 2,000,000, more preferably 2,000 to 500,000. Polyacids or their alkali metal salts, such as polystyrene sulfonic acid and polyacrylic acid, are commercially available, or can otherwise be prepared by known methods (see, for example, Houben Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], vol. E 20 Makromolekulare Stoffe [Macromolecular Substances], part 2, (1987), p. 1141ff.).

[0071] A particularly preferred example of an externally doped polythiophene is the complex of poly(3,4-ethylenedioxythiophene) with the anion of polystyrene sulfonic acid (PEDOT / PSS).

[0072] Further additives According to a preferred embodiment of the dispersion according to the present invention, the dispersion further comprises at least one additive, the at least one additive being selected from the group consisting of binders, pH adjusters, crosslinking agents, adhesion promoters, conductivity enhancers, surfactants, stabilizers, and at least two combinations thereof.

[0073] - Suitable binders include organic binders that are particularly soluble in organic solvents, such as polyolefins, polyvinyl acetate, polycarbonate, polyvinyl butyral, polyacrylic acid esters, polyacrylamides, polymethacrylates, polymethacrylates, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinylpyrrolidone, polybutadiene, polyisoprene, polyethers, polyesters, polyurethanes, polyamides, polyimides, polysulfones, polysilicones, epoxy resins, styrene-acrylates, vinyl acetate / acrylate and ethylene / vinyl acetate copolymers, polyvinyl alcohols, or cellulose derivatives, which can also be added to the composition. Copolymers of the above polymers are also suitable as binders. - Suitable pH adjusters include, for example, bases or acids described in International Publication No. 2010 / 003874(A2), page 4, lines 13-32. Additives that do not inhibit film formation of the dispersion, do not volatilize at relatively high temperatures, such as soldering temperatures, and remain in the solid electrolyte under these conditions are preferred. Compounds such as 2-dimethylaminoethanol, 2,2'-iminodiethanol, or 2,2',2''-nitrilotriethanol and polystyrene sulfonic acid are particularly suitable. - Suitable crosslinking agents include melamine compounds, capped isocyanates, functional silanes such as tetraethoxysilane, alkoxysilane hydrolysates based on tetraethoxysilane, or epoxysilanes such as 3-glycidoxypropyltrialkoxysilane. - Suitable adhesion promoters include organic functional silanes or their hydrolysates, such as 3-glycidoxypropyltrialkoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacrylicoxypropyltrimethoxysilane, vinyltrimethoxysilane, or octyltriethoxysilane. - Suitable conductivity enhancers include, for example, compounds such as tetrahydrofuran, lactone group-containing compounds such as butyrolactone and valerolactone, amide group-containing compounds or lactam group-containing compounds such as caprolactam, N-methylcaprolactam, N,N-dimethylacetamide, N-methylacetamide, N,N-dimethylformamide (DMF), N-methylformamide, N-methylformanilide, and N-methylpyrrolidone (NMP), pyrrolidone, sulfones and sulfoxides, such as sulfolane (tetramethylenesulfone) and dimethyl sulfoxide (DMSO), sugars or sugar derivatives, such as sucrose, glucose, fructose, and lactose, sugar-based surfactants, such as Tween or Span 60, sugar alcohols, such as sorbitol and mannitol, furan derivatives, such as 2-furanic acid and 3-furanic acid, and / or di- or polyalcohols, such as ethylene glycol, glycerol, or di- or triethylene glycol or polyglycerin. As conductivity enhancers, ethylene glycol, diethylene glycol, triethylene glycol, polyglycerin, dimethyl sulfoxide, or sorbitol are particularly preferred. Suitable surfactants include anionic surfactants, such as alkylbenzene sulfonic 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; and nonionic surfactants, particularly nonionic amphiphilic surfactants, such as linear or branched alcohol ethoxylates, oxo alcohol ethoxylates, alkylphenol ethoxylates or alkyl polyglucosides. Representative examples of suitable surfactants include fluorinated surfactants, such as ZONYL® surfactants, including ZONYL® FSN, ZONYL® FSO, ZONYL® FSA, ZONYL® FSH (DuPont Chemicals, Wilmington, Del.) and NOVEC® (3M, St. Paul, Minn.). Other exemplary surfactants include nonionic surfactants based on alkylphenol ethoxylates. Preferred surfactants include, for example, octylphenol ethoxylates such as TRITON®, and secondary alcohol ethoxylates such as TERGITOL® 15-S series (Dow Chemical Company, Midland Mich.). Further exemplary nonionic surfactants include acetylene-based surfactants, n-dodecyl β-D-maltoside, and alcohol ethoxylates, such as TERGITOL® TMN. - Suitable stabilizers are compounds mentioned in International Publication No. 2012 / 041507(A1), and aromatic compounds containing at least two OH groups and one further functional group having a heteroatom different from carbon are particularly preferred. Examples of preferred stabilizers include 3,4,5-trihydroxybenzoic acid and its derivatives such as 3,4,5-trihydroxybenzoic acid esters (gallic acid esters), more particularly alkyl esters, alkenyl esters, cycloalkyl esters, cycloalkenyl esters, and aryl esters, each preferably having 1 to 15 carbon atoms in the aryl or alkyl group of the ester. Particularly preferred are gallic acid and gallic acid esterified with sugars, which are often called tannins or gallotannins (see Rompp Chemie, 10th edition (1999), p. 4391). Suitable stabilizers include the "hydroxyl group-containing aromatic compounds" mentioned in paragraph

[0049] of European Patent Publication No. 1798259(A1), the "antioxidants" mentioned in paragraph

[0025] of European Patent Publication No. 1043720(A1), and the "sulfo group-excluded aromatic compounds containing at least two hydroxyl groups" mentioned on pages 10 and 11 of International Publication No. 2008 / 055834(A1).

[0074] Capacitor manufacturing process According to a preferred embodiment of the laminate preparation process of the present invention, the laminate is part of an electrolytic capacitor. In this case, the process is A) A step of preparing a porous electrode body made of an electrode material, wherein a dielectric layer covers at least partially the surface of the electrode material. B) A step of introducing a dispersion according to the present invention, preferably a dispersion according to the present invention as defined in any of the first to fourteenth embodiments thereof, or a dispersion obtained by process 1 according to the present invention, preferably process 1 as defined in any of the first to ninth embodiments thereof, into at least a portion of the porous electrode body prepared in process step A), thereby applying the dispersion to at least a portion of the surface of the dielectric layer. C) A step of at least partially removing the dispersant i) in order to form a solid electrolyte layer that at least partially covers the surface of the dielectric layer, D) A dispersion containing a conductive polymer, preferably a dispersion containing polythiophene and a dispersant, more preferably a dispersion containing a polythiophene-polymer anion complex dispersant and particles, and even more preferably a PEDOT / PSS dispersion, is optionally applied to at least a portion of the surface of the solid electrolyte layer, and the dispersant is at least partially removed in order to form a polymer outer layer that at least partially covers the surface of the solid electrolyte layer. E) optionally includes a step of filling at least a portion of the pores of the porous electrode body obtained in process step C) or process step D) (i.e., a porous electrode body in which at least a portion of the dielectric layer is covered with a solid electrolyte layer) with an impregnation solution containing at least one impregnation solvent.

[0075] Process step A): In process step A), a porous electrode body made of electrode material is provided, and a dielectric layer covers at least partially the surface of this electrode material.

[0076] In principle, a porous electrode body can be manufactured by compressing and sintering valve metal powder having a large surface area to form the porous electrode body. In this regard, an electrical contact wire, preferably made from valve metal such as tantalum, is conventionally compressed into the porous electrode body. The porous electrode body is then coated with a dielectric, i.e., an oxide layer, for example, by electrochemical oxidation. Alternatively, to obtain an anode film having porous regions, a metal film can be etched and coated with a dielectric by electrochemical oxidation. In the case of a wound capacitor, the anode film and cathode film, which have porous regions forming the electrode body, are separated by a separator and wound together.

[0077] Within the scope of this invention, metals whose oxide coatings do not allow current to flow uniformly in both directions are understood as valve metals. When a voltage is applied to the anode, the oxide layer of the valve metal blocks the flow of current, while when a voltage is applied to the cathode, a large current is generated, potentially destroying the oxide layer. Examples of valve metals include Be, Mg, Al, Ge, Si, Sn, Sb, Bi, Ti, Zr, Hf, V, Nb, Ta, and W, as well as alloys or compounds of at least one of these metals with other elements. The most well-known representative examples of valve metals are Al, Ta, and Nb. Combinations of electrical properties equivalent to valve metals are those that have the conductivity of a metal, can be oxidized, and whose oxide layer provides the above properties. For example, NbO exhibits the conductivity of a metal but is generally not considered a valve metal. However, a layer of oxidized NbO exhibits typical properties of a valve metal oxide layer, and as a result, NbO or alloys or compounds of NbO are typical examples of compounds with electrical properties equivalent to valve metals. Electrode materials made of tantalum, aluminum, and niobium or niobium oxide are preferred. Aluminum is particularly preferred as an electrode material.

[0078] To manufacture porous electrode bodies, which often have porous regions, the valve metal can be sintered, for example, in powder form to provide a generally porous electrode body, or alternatively, the porous structure can be imprinted onto the metal body. The latter can be carried out, for example, by etching a film.

[0079] For brevity, a body containing porous regions is also referred to as a porous body. For example, an electrode body containing porous regions is also referred to as a porous electrode body. On the one hand, a porous body can be permeated by multiple channels and is therefore spongy. This is often the case when tantalum is used in capacitor structures. On the other hand, pores can exist only on the surface, and regions located beneath the surface pores can be formed in a solid state. This is often observed when aluminum is used in capacitor structures.

[0080] Next, the porous electrode body thus manufactured is oxidized by applying a voltage in a suitable electrolyte, such as phosphoric acid or an aqueous solution of ammonium adipate, to form a dielectric. The magnitude of this formation voltage depends on the thickness of the oxide layer to be achieved, or correspondingly, the operating voltage of the subsequent capacitor. Preferred formation voltages are in the range of 1 to 1000 V, particularly preferably in the range of 10 to 200 V, more preferably in the range of 15 to 100 V, and more preferably in the range of 20 to 50 V.

[0081] The porous electrode body used preferably has a porosity of 10-90%, preferably 30-80%, and particularly preferably 50-80%, and an average pore diameter of 10-10000nm, preferably 50-5000nm, and particularly preferably 100-3000nm.

[0082] According to a special embodiment of the process of the present invention, the electrolytic capacitor to be manufactured is an aluminum wound capacitor. In this case, in process step A), a porous aluminum film is formed on the anode as an electrode material, thereby forming an aluminum oxide coating as a dielectric. Then, a contact wire is provided on the aluminum film thus obtained (anode film) and it is wound, and a contact wire is also provided on a further porous aluminum film (cathode film), so that these two films are separated from each other by one or more separator papers, for example, based on cellulose, or preferably based on synthetic paper. After winding, the anode body thus obtained is fixed, for example, by adhesive tape. The separator paper can be carbonized by heating in an oven. A method for manufacturing an anode body for this aluminum wound capacitor is well known from the prior art, for example, described in U.S. Patent No. 7,497,879(B2).

[0083] Process steps B) and C): In process step B) of the process according to the present invention, the dispersion according to the present invention, preferably the dispersion according to the present invention as defined in any of the first to fourteenth embodiments thereof, or the dispersion obtained by process 1 according to the present invention, preferably the dispersion obtained by process 1 as defined in any of the first to nineteenth embodiments thereof, is introduced into at least a portion of the porous electrode body provided in process step A). ​​Then, in process step C), the dispersant i) is at least partially removed in order to form a solid electrolyte layer that at least partially covers the surface of the dielectric layer.

[0084] The dispersion is introduced into the porous region using known processes, such as immersion, immersion, pouring, dropping, injection, spraying, diffusion, coating, or printing such as inkjet printing, screen printing, or pad printing. Introduction is preferably carried out by immersing the porous electrode body provided in process step A) in the dispersion, thereby impregnating it with the dispersion. Immersion or impregnation in the dispersion is preferably carried out for a duration ranging from 1 second to 120 minutes, particularly preferably from 10 seconds to 60 minutes, and most preferably from 30 seconds to 15 minutes. Introduction of the dispersion into the anode body can be facilitated, for example, by increasing or decreasing pressure, vibration, ultrasound, or heat.

[0085] After impregnating the porous electrode body with the above dispersion, the dispersant is at least partially removed in process step c) to form a solid electrolyte layer that partially or completely covers the dielectric. In this regard, the coverage of the dielectric with the solid electrolyte layer preferably reaches at least 50%, particularly preferably at least 70%, and most preferably at least 80%, enabling the measurement of the capacitance of the capacitor under dry and wet conditions at 120°C to make determinations as described in German Patent Publication No. 102005043828(A).

[0086] The removal of the dispersant is preferably carried out by removing the porous electrode body from the dispersion used in process step b) and subsequently drying, which is preferably carried out at a temperature in the range of 20°C to 200°C, particularly preferably in the range of 50°C to 180°C, and more preferably in the range of 80°C to 150°C. The drying conditions (i.e., drying time, drying pressure, and drying temperature) are preferably adjusted to ensure that at least 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, even more preferably at least 95% by weight, and most preferably at least 99% by weight of the total amount of dispersant is removed when forming the solid electrolyte layer. In a particularly preferred embodiment of the process according to the present invention, the drying conditions are adjusted to ensure that the dispersant is completely removed when forming the solid electrolyte layer.

[0087] Process step D): In process step D), a dispersion containing a conductive polymer, preferably a dispersion containing polythiophene and a dispersant, more preferably a dispersion containing the dispersant and particles of a composite of polythiophene and polymer anions, and even more preferably a PEDOT / PSS dispersion, is applied to at least a portion of the surface of the solid electrolyte layer, and then the dispersant may be at least partially removed to form a polymer outer layer that at least partially covers the surface of the solid electrolyte layer (for example, as disclosed in German Patent Application Publication No. 102004022674(A1)). As used herein, the term “polymer outer layer” preferably refers to an outer layer that contains the exact same conductive polymer as the solid electrolyte layer, but differs from the solid electrolyte layer in terms of properties such as chemical composition, conductivity, and / or hardness, surface roughness, and adhesive properties. The polymer outer layer, typically having a thickness in the range of 5 to 50 μm, functions as a mechanical buffer between the capacitor anode and cathode-side contacts, preventing the cathode-side contacts from contacting the dielectric under mechanical stresses that may occur during the manufacture of the capacitor.

[0088] Before applying the dispersion containing the conductive polymer to at least a portion of the surface of the solid electrolyte layer in process step D), it may also be advantageous to apply a crosslinking agent to at least a portion of the surface of the solid electrolyte layer in order to improve the coverage of the capacitor anode by the polymer outer layer. Suitable crosslinking agents and processes for such applications are disclosed, for example, in German Patent Application Publication No. 10 2009 007 594(A1).

[0089] Process step E): In process step E) of the process according to the present invention, at least a portion of the pores of the porous electrode body obtained in process step C) (i.e., a porous electrode body in which at least a portion of the dielectric layer is covered with a solid electrolyte layer) can be filled with an impregnation solution containing at least one impregnation solvent.

[0090] Immersion in the impregnation solution, or corresponding impregnation in the impregnation solution, is preferably carried out for a duration ranging from 1 second to 120 minutes, particularly preferably from 10 seconds to 60 minutes, and most preferably from 30 seconds to 15 minutes. Immersion is preferably carried out by at least partially immersing the porous electrode body obtained in process step C) in the impregnation solution, or by injecting the impregnation solution into the porous electrode body and impregnating it accordingly. The introduction of the impregnation solution into the porous electrode body can be facilitated, for example, by increasing or decreasing pressure, vibration, ultrasound, or heat.

[0091] In process step E), it is particularly preferable that the impregnation solution be applied immediately before carrying out process step F) described below, i.e., before sealing the porous electrode body in order to prevent the impregnation solvent from evaporating from the pores. Therefore, the impregnation solution applied in process step E) remains in the pores of the porous electrode body to some extent, preferably completely, before sealing.

[0092] Examples of impregnation solvents include sulfone compounds, lactone compounds, carbonate compounds, and polyhydric alcohols. The impregnation solvent may be used individually or in combination of two or more types.

[0093] Examples of sulfone compounds include sulfolane, dimethyl sulfoxide, and diethyl sulfoxide. Examples of lactone compounds include γ-butyrolactone and γ-valerolactone. Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, and fluoroethylene carbonate. Examples of polyhydric alcohols include glycerin compounds, sugar alcohol compounds, and glycol compounds. Examples of glycerin compounds include glycerin, polyglycerin (diglycerin, triglycerin, etc.) and their derivatives. Examples of glycol compounds include alkylene glycols (C2-4 alkylene glycols (ethylene glycol, propylene glycol, etc.)) and polyalkylene glycols (poly-C2-4 alkylene glycols (diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, etc.)).

[0094] The impregnation solution may contain a solute. Examples of solutes include acidic components such as carboxylic acids, sulfur-containing acids, boron-containing acids, and phosphorus-containing acids, as well as basic components such as ammonia, amines, quaternary ammonium compounds, and amidinium compounds.

[0095] The liquid component may contain the acid component and the base component in a free state, or in the form of a salt. The liquid component may also contain an organic salt. Examples of organic salts include those in which at least one of the acid component and the base component is organic.

[0096] The concentration of the solute in the liquid component may be, for example, 0.1% by mass or more and 25% by mass or less, or 0.5% by mass or more and 15% by mass or less.

[0097] Encapsulation in process step F): If, after process step C), at least a portion of the dispersant i) is removed, or if process steps D) and / or E) are performed, if a polymer outer layer is applied after process step D), or if, after process step E), at least a portion of the pores of the porous electrode body obtained in process step C) are filled with the impregnation solution, the electrolytic capacitor can be finished and especially sealed by processes known to those skilled in the art. In the case of a tantalum electrolytic capacitor, the capacitor body can be coated with a graphite layer and a silver layer, for example, as known from German Patent Publication No. 102005043828(A), and in the case of an aluminum wound capacitor corresponding to the teachings of U.S. Patent No. 7,497,879(B2), the capacitor body is constructed in an aluminum cup, provided with sealing rubber, and mechanically tightly closed by flanging.

[0098] Encapsulation is preferably achieved by sealing the capacitor body with a resin such as an epoxy resin or thermoplastic resin, as disclosed in European Patent Publication No. 0 447 165(A2). In the case of an aluminum electrolytic capacitor, encapsulation is preferably achieved by providing an aluminum cup to the porous electrode body obtained in process step e) and closing it with sealing rubber.

[0099] The features disclosed in the claims, specification, and drawings are likely essential, either individually or in any combination with each other, for the various embodiments of the invention described in the claims. [Brief explanation of the drawing]

[0100] The following schematic diagrams illustrate embodiments of the present invention to further enhance understanding of the invention in relation to several illustrative figures. [Figure 1] The layered structure according to the present invention, for example, the structure of a layer body 100 prepared by a general antistatic film preparation process, is shown. On the substrate surface of the substrate 101, there is a conductive layer 102 prepared with the composition according to the present invention, which is often a PE, PP, or PET layer in the case of an antistatic film. [Figure 2] This is a schematic cross-sectional view of a part of a capacitor obtained by a specific embodiment of the preparation process for a laminated structure according to the present invention. The capacitor includes a porous electrode body 101a containing pores 103, mainly made from a porous electrode material 101b such as aluminum. A dielectric layer 101c is formed as a thin layer on the surface of the electrode material 101b, forming a porous anode body including the electrode body 101a made of electrode material 101b and the dielectric layer 101c. A layer of solid electrolyte 102a (made using the dispersion of the present invention) is optionally further laminated on the dielectric layer 101c, forming a capacitor body including the electrode body 101a made of electrode material 101b, the dielectric layer 101c, and the solid electrolyte layer 102a.

[0101] Measurement method: Solids Weigh an empty measuring bottle with a cap (50 mm in diameter) using an analytical balance (weight A). Fill the empty measuring bottle with approximately 5 g of dispersion and weigh it using the cap (weight B). Transfer the opened measuring bottle and cap separately to a drying cabinet and dry at 100°C for 15-16 hours.

[0102] After drying, seal the measuring bottle directly with the cap and leave the cap on to cool to room temperature. Then, weigh the bottle using the cap. (Weight C) Repeat the second measurement with a new sample.

[0103] The solid content is calculated as follows: Weight % solids = (CA) × 100 / (BA)

[0104] The solids content is measured as two separate measurements. The two solids content measurements may differ by up to 0.03%. If the difference is greater, the measurement must be repeated.

[0105] The final value is the average of two single measurements.

[0106] conductivity To measure electrical conductivity, 19 g of the dispersion of the analyte is mixed with 1 g of DMSO in a beaker and stirred for 10 minutes. Electrical conductivity is the reciprocal of resistivity. Resistivity is calculated from the product of the surface resistance and thickness of the conductive polymer layer. Surface resistance is determined for conductive polymers according to DIN EN ISO 3915. The mixture of polymer dispersion and DMSO is applied as a homogeneous film to a completely cleaned 50 mm × 50 mm glass substrate by spin coating. The coating composition is applied to the substrate by pipette to completely cover the area and is directly spun off by spin coating. The spin conditions for the coating composition were approximately 1,000 rpm for 20 seconds in air. Subsequently, a drying process was performed on a hot plate (130°C in air for 15 minutes). A silver electrode 2.0 cm long and 2.0 cm apart is deposited onto the polymer layer via a shadow mask. Then, a square area of ​​the layer between the electrodes is electrically isolated from the rest of the layer by scratching two lines with a scalpel. Surface resistance is measured between Ag electrodes using a resistometer (Keithley 614). The thickness of the polymer layer is determined at the scraped area using a Stylus Profilometer (Dektac 150, Veeco).

[0107] Determination of the exponent n in a power law The power law exponent n is measured using a Rheometer Haake RV 1 with thermostat (supplied by Haake), a PC with Software Rheo Win Pro, and a cup and rotor for a double-gap cylinder system DG 43 (supplied by Haake).

[0108] The zero value is set once, the day before the first measurement. A dry, clean cup is placed in the rheometer and pressed into the unit using the palm of your hand. It is then secured using the locking lever. The rotor is secured to the top using the appropriate screws. The computer is started, and then the software "Rheo Win Jobmanager" is launched. The program point "Manual Use" is opened, and "Setting Zero Value" is opened. The zero value is then set automatically, and the "Manual Use" unit is closed.

[0109] The thermostat is set so that the temperature reader inside the rheometer reads 20.0°C. The temperature must be within the range of 20.0°C ± 0.2°C. The gap in the dry, clean cup is filled with 12.0 ± 0.3 mL of the dispersion of the analyte. The cylinder and rotor are fixed inside the rheometer. The program for determining the exponent n includes the following steps: 1) Rotation at 20.0℃, deviation + / -0.2℃, time 120 seconds, shear rate 20 1 / second 2) Rotating ramp at 20.0℃, from 20 1 / second to 1000 1 / second for no more than 100 seconds. 3) Regression of a rotating ramp using the Ostwald de Waele model selected in the Rheo Win job manager.

[0110] The value of the exponent n is recorded so that it is measured according to the regression using Rheo Win software.

[0111] Particle size (d 50 ) decision The particle size is determined as disclosed by HGMuller in Colloid Polym. Sci. 267, 1113-1116 (1989). The diameter distribution is d 50 The value is that 50% of the total weight of all conductive polymer particles in the dispersion is d 50 This indicates that it can be assigned to particles with a diameter less than or equal to the value.

[0112] Equivalent series resistance (ESR) The equivalent series resistance (mΩ) was determined using an LCR meter (Agilent 4284A) at 20°C and 100kHz. In each capacitor experiment, three capacitors were fabricated and the average ESR value was determined. [Examples]

[0113] Example 1 In a 3L stainless steel reactor equipped with a stirrer, vents, an upper material inlet, an internal thermometer, an UltraTurrax, a lower material outlet, and a temperature jacket connected to a thermostat, 1,711 g of deionized water and 660 g of aqueous polystyrene sulfonic acid solution (average molecular weight Mw 70,000 g / mol; solids content 3.8 wt%; total PSS solids content 25.1 g) were initially charged. The reaction temperature was maintained at 18°C. The mixture was flushed with nitrogen for 3 hours. The mixture was then evacuated to 33 hPa. 10.2 g of 3,4-ethylenedioxythiophene (71.8 mmol) was added by stirring and using Turrax. The solution was stirred for 30 minutes. Then, 0.06 g of iron(III) sulfate and 19.0 g of sodium persulfate (79.8 mmol) dissolved in 25 g of water were added, and the solution was stirred under reduced pressure for a further 23 hours.

[0114] This corresponds to an oxidizer:monomer ratio of 1.11 and a PEDOT fraction of 28.6% by weight.

[0115] After the reaction was complete, the inorganic salts were removed using 200 mL of a strongly acidic cation exchanger (Lewatit S108H, Lanxess AG) and 500 mL of a weakly basic anion exchanger (Lewatit MP62, Lanxess AG), and the solution was stirred for a further 2 hours. The ion exchanger was filtered off.

[0116] A poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate dispersion was homogenized three times at a pressure of 1000 bar using a high-pressure homogenizer. The resulting "Dispersion 1A" exhibited the following characteristics: Solid content: 1.2% by weight Dispersion 1A was concentrated, and then 200g of the concentrated dispersion was homogenized 110 times at 1500 bar using a high-pressure homogenizer. Subsequently, 150g of the dispersion was subjected to sonication for 10 minutes (Hielscher UP 200S, 100%, cycle 1). The resulting dispersion is "Dispersion 1B".

[0117] 2 g of ethylene glycol was added to 47.9 g of dispersion 1B. The pH of the mixture was adjusted to 6 using an aqueous solution of ammonium hydroxide. The resulting "dispersion 1C" (according to the present invention) exhibited the following characteristics: Solid content: 1.8% by weight Power exponent n: 0.740 Conductivity: 336S / cm

[0118] Example 2 In the reactor described in Example 1, 2,108 g of water, 153 g of polystyrene sulfonic acid (Mw 70,000 g / mol; 25% solids; 38.3 g total PSS solids), and 6.5 g of 10% iron(III) sulfate solution were added. The reaction temperature was maintained at 18°C. The mixture was flushed with nitrogen for 3 hours. The mixture was then evacuated to 33 hPa. 6.4 g of 3,4-ethylenedioxythiophene (45 mmol) was added by stirring and turrax. The solution was stirred for 30 minutes. Then, 12.5 g of sodium persulfate (52.5 mmol) dissolved in 32 g of water was added, and the solution was stirred under reduced pressure for a further 23 hours. This corresponds to an oxidizing agent:monomer ratio of 1.11 and a PEDOT fraction of 14.3%.

[0119] After the reaction was complete, the inorganic salts were removed using 188 g of a strongly acidic cation exchanger (Lewatit S108H, Lanxess AG) and 148 g of a weakly basic anion exchanger (Lewatit MP62, Lanxess AG), and the solution was stirred for a further 2 hours. The ion exchanger was filtered off.

[0120] A poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate dispersion was homogenized three times at a pressure of 1000 bar using a high-pressure homogenizer. The resulting "dispersion 2A" exhibited the following characteristics. Solid content: 1.6% by weight

[0121] Dispersion 2A was concentrated, and then 200g of the concentrated dispersion was homogenized 60 times at 1500 bar using a high-pressure homogenizer. The resulting dispersion is "Dispersion 2B".

[0122] 2 g of ethylene glycol was added to 47.9 g of dispersion 2B. The pH of the mixture was adjusted to 6 using an aqueous solution of ammonium hydroxide. The resulting "dispersion 2C" (according to the present invention) exhibited the following characteristics. Solid content: 1.8% by weight Power exponent n: 0.802 Conductivity: 148S / cm

[0123] Example 3 1,686 g of deionized water and 660 g of aqueous polystyrene sulfonic acid solution (Mw 70,000 g / mol; solids content 3.8 wt%; total PSS solids content 25.1 g) were charged into the reactor described in Example 1. The reaction temperature was maintained at 18°C. The mixture was flushed with nitrogen for 3 hours. The mixture was then evacuated to 33 hPa. 10.2 g of 3,4-ethylenedioxythiophene (71.8 mmol) was added by stirring and turrax. The solution was stirred for 30 minutes. Then, 0.06 g of iron(III) sulfate dissolved in 50 g of water and 20.9 g of sodium persulfate (87.8 mmol) were added, and the solution was stirred and dispersed under reduced pressure for a further 23 hours. This corresponds to an oxidizing agent:monomer ratio of 1.22 and a PEDOT fraction of 28.6%.

[0124] After the reaction was complete, the inorganic salts were removed using 200 mL of a strongly acidic cation exchanger (Lewatit S108H, Lanxess AG) and 500 mL of a weakly basic anion exchanger (Lewatit MP 62, Lanxess AG), and the solution was stirred for a further 2 hours. The ion exchanger was filtered off.

[0125] A poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate dispersion was homogenized three times at a pressure of 1000 bar using a high-pressure homogenizer. The resulting "dispersion 3A" exhibited the following characteristics: Solid content: 1.2% by weight

[0126] Dispersion 3A was concentrated, and then 200g of the concentrated dispersion was homogenized 100 times at 1500 bar using a high-pressure homogenizer. The resulting dispersion is "Dispersion 3B".

[0127] 2 g of ethylene glycol was added to 47.9 g of dispersion 3B. The pH of the mixture was adjusted to 6 using an aqueous solution of ammonium hydroxide. The resulting "dispersion 3C" (according to the present invention) exhibited the following characteristics. Solid content: 1.8% by weight Power exponent n: 0.776 Conductivity: 186S / cm

[0128] Example 4 100 g of dispersion 1A was placed in a glass bottle and subjected to sonication for 30 minutes (Hielscher UP 200S, 100%, cycle 1). The dispersion was then concentrated to 1.8% by weight. Subsequently, 30 g of the dispersion was further sonicated for 45 minutes (Hielscher UP 200S, 100%, cycle 1). During sonication, the glass bottle containing the dispersion was placed in a water bath and the temperature was maintained at 15°C to 45°C. The mixture was then cooled to room temperature. 1 g of ethylene glycol was added to the 23.95 g of sonicated dispersion. The pH of the mixture was adjusted to 6 using an aqueous ammonium hydroxide solution. The resulting "dispersion 4C" (not according to the present invention) exhibited the following characteristics: Solid content: 1.8% by weight Power exponent n: 0.941 Conductivity: 154S / cm

[0129] Example 5 A 400g dispersion identical to dispersion 1A was concentrated, and then the concentrated 200g dispersion was homogenized 10 times at 1,500 bar using a high-pressure homogenizer. The resulting dispersion is "Dispersion 5B".

[0130] 2 g of ethylene glycol was added to 47.9 g of dispersion 5B. The pH of the mixture was adjusted to 6 using an aqueous solution of ammonium hydroxide. The resulting "dispersion 5C" (not according to the present invention) exhibited the following properties: Solid content: 1.8% by weight Power exponent n: 0.610 Conductivity: 362S / cm

[0131] Example 6 (not based on the present invention) 100 g of the same dispersion as dispersion 1A was placed in a glass bottle and sonicated for 30 minutes (Hielscher UP 200S, 100%, cycle 1). The dispersion was then concentrated to 1.5% by weight. Subsequently, 30 g of the dispersion was sonicated for 30 minutes (Hielscher UP 200S, 100%, cycle 1). During sonication, the glass bottle containing the dispersion was cooled in a water bath, maintaining the temperature inside the container at 15°C to 40°C. 1 g of ethylene glycol was added to the 23.95 g of sonicated dispersion. The pH of the mixture was adjusted to 6 using an aqueous ammonium hydroxide solution. The resulting "dispersion 6C" (not according to the present invention) exhibited the following characteristics: Solid content: 1.5% by weight Power exponent n: 0.964 Conductivity: 175S / cm

[0132] Example 7 A 400g dispersion identical to "Dispersion 1A" was concentrated, and then the concentrated 200g dispersion was homogenized 65 times at 1,500 bar using a high-pressure homogenizer. Next, 150g of the dispersion was subjected to sonication for 10 minutes (Hielscher UP 200S, 100%, cycle 1). The resulting dispersion is "Dispersion 7B".

[0133] 2 g of ethylene glycol was added to 47.9 g of dispersion 7B. The pH of the mixture was adjusted to 6 using an aqueous solution of ammonium hydroxide. The resulting "dispersion 7C" (according to the present invention) exhibited the following characteristics.

[0134] Solid content: 1.5% by weight Power exponent n: 0.751 Conductivity: 214S / cm

[0135] Example 8 A 400g dispersion identical to dispersion 1A was concentrated, and then the concentrated 200g dispersion was homogenized 35 times at 1,500 bar using a high-pressure homogenizer. The resulting dispersion is "Dispersion 8B".

[0136] 2 g of ethylene glycol was added to 47.9 g of dispersion 8B. The pH of the mixture was adjusted to 6 using an aqueous solution of ammonium hydroxide. The resulting "dispersion 8C" (not according to the present invention) exhibited the following characteristics: Solid content: 1.5% by weight Power exponent n: 0.613 Conductivity: 305S / cm

[0137] Example 9 A 400g portion of the same dispersion as dispersion 1A was homogenized 10 times at 1,500 bar using a high-pressure homogenizer. The resulting dispersion is "Dispersion 9B".

[0138] 2 g of ethylene glycol was added to 47.9 g of dispersion 9B. The pH of the mixture was adjusted to 6 using an aqueous solution of ammonium hydroxide. The resulting "dispersion 9C" (not according to the present invention) exhibited the following properties: Solid content: 1.2% by weight Power exponent n: 0.610 Conductivity: 364S / cm

[0139] Example 10 A 400g portion of the same dispersion as dispersion 1A was homogenized 45 times at 1,500 bar using a high-pressure homogenizer. The resulting dispersion is "dispersion 10B".

[0140] 2 g of ethylene glycol was added to 47.9 g of dispersion 10B. The pH of the mixture was adjusted to 6 using an aqueous solution of ammonium hydroxide. The resulting "dispersion 10C" (not according to the present invention) exhibited the following characteristics: Solid content: 1.2% by weight Power exponent n: 0.781 Conductivity: 378S / cm

[0141] Example 11 A 400g portion of the same dispersion as dispersion 1A was homogenized 125 times at 1,500 bar using a high-pressure homogenizer. The resulting dispersion is "dispersion 11B".

[0142] 2 g of ethylene glycol was added to 47.9 g of dispersion 11B. The pH of the mixture was adjusted to 6 using an aqueous solution of ammonium hydroxide. The resulting "dispersion 11C" (not according to the present invention) exhibited the following characteristics: Solid content: 1.2% by weight Power exponent n: 0.950 Conductivity: 356S / cm

[0143] Example 12 200 g of dispersion 2B was homogenized 20 more times. The resulting dispersion was "dispersion 12B". 2 g of ethylene glycol was added to 47.9 g of dispersion 12B. The pH of the mixture was adjusted to 6 using an aqueous solution of ammonium hydroxide. The resulting "dispersion 12C" (according to the present invention) exhibited the following characteristics. Solid content: 1.8% by weight Power exponent n: 0.891 Conductivity: 146S / cm

[0144] Example 13 A 400g dispersion identical to dispersion 1A was concentrated, and then the concentrated 200g dispersion was homogenized 65 times at 1,500 bar using a high-pressure homogenizer. Next, 150g of the dispersion was subjected to sonication for 3 minutes (Hielscher UP 200S, 100%, cycle 1). The resulting dispersion is "dispersion 13B". 2g of ethylene glycol was added to 47.9g of dispersion 13B. The pH of the mixture was adjusted to 6 using an aqueous ammonium hydroxide solution. The resulting "dispersion 13C" (according to the present invention) exhibited the following characteristics. Solid content: 1.5% by weight Power exponent n: 0.652 Conductivity: 220S / cm

[0145] Table 1 summarizes the results of Examples 1 to 13.

[0146] [Table 1] i. = According to the present invention; ni = Not according to the present invention

[0147] Capacitor preparation process Process step A): A porous electrode body for a cylindrical aluminum capacitor (shown in Figure 2) with a rated voltage of 25V was fabricated by the following method. The surface of the aluminum foil was roughened by etching. Next, the aluminum foil was subjected to anodizing with an aqueous solution of ammonium adipate, thereby forming a dielectric layer on the surface of the aluminum foil. In this way, the anode foil was fabricated.

[0148] The surface of the second aluminum foil was roughened by etching. This is how the cathode foil was fabricated.

[0149] The anode lead wire and cathode lead wire were connected to the anode and cathode foils, respectively. The anode and cathode foils were wound together with two separator papers between them. Tape was applied to the outside of the wound element to prevent the foils from unwinding. The wound element was then subjected to another anodic oxidation to form a dielectric layer on the cut edge of the anode foil.

[0150] In this way, an anode body comprising an electrode body having a dielectric layer was fabricated.

[0151] Process step B): The porous electrode body from process step A) was placed in a chamber containing a bath of a liquid composition with a conductive polymer. The air pressure inside the chamber was reduced to 100 hPa. The anode body was immersed in the liquid composition for 300 seconds. Then, the anode body was removed from the liquid composition, and the chamber was ventilated to atmospheric pressure.

[0152] Process step C) The anode was dried at 120°C for 30 minutes.

[0153] Process steps B) and C) were carried out further. Thus, a capacitor body including a solid electrolyte layer based on PEDOT / PSS was obtained.

[0154] Process step F) The capacitor body from process step C) was placed inside a cylindrical aluminum housing and sealed with a rubber seal.

[0155] Example 14 A first anode body was prepared according to process step A). ​​Next, the dispersion 1C of Example 1 was used to form a solid electrolyte layer, and the anode body was treated according to process steps B) and C). Process steps B) and C) were repeated. Thus, a capacitor body was obtained. The capacitor body was sealed according to process step F) to obtain a completed capacitor. The average ESR of the capacitor (according to the present invention) is shown in Table 2.

[0156] Example 15 A capacitor was fabricated and evaluated in the same manner as in Example 14, except that dispersion 2C from Example 2 was used to form the solid electrolyte layer. The average ESR of the capacitor (according to the present invention) is shown in Table 2.

[0157] Example 16 A capacitor was fabricated and evaluated in the same manner as in Example 14, except that dispersion 3C from Example 3 was used to form the solid electrolyte layer. The average ESR of the capacitor (according to the present invention) is shown in Table 2.

[0158] Example 17 Capacitors were fabricated and evaluated in the same manner as in Example 14, except that dispersion 4C from Example 4 was used to form the solid electrolyte layer. The average ESR of the capacitors (not according to the present invention) is shown in Table 2.

[0159] Example 18 Capacitors were fabricated and evaluated in the same manner as in Example 14, except that dispersion 5C from Example 5 was used to form the solid electrolyte layer. The average ESR of the capacitors (not according to the present invention) is shown in Table 2.

[0160] Example 19 Capacitors were fabricated and evaluated in the same manner as in Example 14, except that dispersion 6C from Example 6 was used to form the solid electrolyte layer. The average ESR of the capacitors (not according to the present invention) is shown in Table 2.

[0161] Example 20 A capacitor was fabricated and evaluated in the same manner as in Example 14, except that dispersion 7C from Example 7 was used to form the solid electrolyte layer. The average ESR of the capacitor (according to the present invention) is shown in Table 2.

[0162] Example 21 Capacitors were fabricated and evaluated in the same manner as in Example 14, except that dispersion 8C from Example 8 was used to form the solid electrolyte layer. The average ESR of the capacitors (not according to the present invention) is shown in Table 2.

[0163] Example 22 Capacitors were fabricated and evaluated in the same manner as in Example 14, except that dispersion 9C from Example 9 was used to form the solid electrolyte layer. The average ESR of the capacitors (not according to the present invention) is shown in Table 2.

[0164] Example 23 Capacitors were fabricated and evaluated in the same manner as in Example 14, except that dispersion 10C from Example 10 was used to form the solid electrolyte layer. The average ESR of the capacitors (not according to the present invention) is shown in Table 2.

[0165] Example 24 Capacitors were fabricated and evaluated in the same manner as in Example 14, except that dispersion 11C from Example 11 was used to form the solid electrolyte layer. The average ESR of the capacitors (not according to the present invention) is shown in Table 2.

[0166] Example 25 A capacitor was fabricated and evaluated in the same manner as in Example 14, except that dispersion 12C from Example 12 was used to form the solid electrolyte layer. The average ESR of the capacitor (according to the present invention) is shown in Table 2.

[0167] Example 26 A capacitor was fabricated and evaluated in the same manner as in Example 14, except that dispersion 13C from Example 13 was used to form the solid electrolyte layer. The average ESR of the capacitor (according to the present invention) is shown in Table 2.

[0168] Table 2 summarizes the results of Examples 14-26.

[0169] [Table 2] i. = According to the present invention; ni = Not according to the present invention

[0170] Key for reference number 100-layer structure 101 Base material 101a Porous electrode body 101b Electrode material 101c dielectric layer 102 Conductive layer 102a Solid electrolyte layer 103 Pores

Claims

1. i) Dispersant; ii) at least one polythiophene dispersed in the dispersant i); A dispersion containing, Regarding the aforementioned dispersion, Ostwald de Waele relationship [Math 1] The exponent n in the power law is in the range of 0.62 to 0.

92. [Math 2] is the shear stress, and K is the flow viscosity constant. [Math 3] shear rate [Math 4] And, A dispersion having a solid content of at least 1.5% by weight based on the total weight of the dispersion.

2. The dispersion according to claim 1, wherein the power law exponent n is in the range of 0.66 to 0.

88.

3. The dispersion according to claim 2, wherein the power law exponent n is in the range of 0.70 to 0.

84.

4. The dispersion according to any one of claims 1 to 3, wherein the dispersion has a solid content of at least 1.7% by weight based on the total weight of the dispersion.

5. The dispersion according to any one of claims 1 to 4, wherein the dispersant i) contains water.

6. The dispersion according to any one of claims 1 to 5, wherein the polythiophene exists in the form of particles of a complex comprising the polythiophene and a polyanion.

7. The dispersion according to claim 6, wherein the polythiophene is poly(3,4-ethylenedioxythiophene) and the polyanion is an anion of polystyrene sulfonic acid.

8. The dispersion according to any one of claims 1 to 7, wherein the polythiophene exists in the form of particles of a complex containing the polythiophene and polyanions, and the solid content according to claims 1 and 4 refers to the total amount of polythiophene and polyanions in the dispersion.

9. The dispersion according to any one of claims 1 to 8, wherein the conductive layer prepared from the dispersion has an conductivity of at least 100 S / cm when determined by the test method disclosed herein.

10. The aforementioned dispersion is iii) Conductivity improver A dispersion according to any one of claims 1 to 9, further comprising the above.

11. A process for preparing a laminate (100), comprising the process steps: A) A step of preparing the base material (101), B) A step of applying the dispersion according to any one of claims 1 to 10 to at least a portion of the surface of the substrate (101), C) To obtain a laminate (100) including a conductive layer (102) coated on at least a portion of the surface of the substrate (101), the steps include removing at least a portion of the dispersant i), A process that includes this.

12. The process according to claim 11, wherein the laminate (100) is part of an electrolytic capacitor, the substrate (101) is a porous electrode body (101a) made of an electrode material (101b), the dielectric layer (101c) covers at least partially the surface of the electrode material (101b), and the conductive layer (102) is a solid electrolyte layer (101d) that covers at least partially the surface of the dielectric layer (101c).

13. The aforementioned process, A) A step of preparing a porous electrode body (101a) made of electrode material (101b), wherein a dielectric layer (101c) covers at least partially the surface of the electrode material (101b), B) A step of introducing the dispersion liquid according to any one of claims 1 to 10 into at least a portion of the porous electrode body (101a) prepared in process step A) and applying the dispersion liquid to at least a portion of the surface of the dielectric layer (101c), C) A step of at least partially removing the dispersant i) in order to form a solid electrolyte layer (101d) that at least partially covers the surface of the dielectric layer (101c), The process according to claim 12, including the process described in claim 12.

14. A laminate obtained by the process described in any one of claims 11 to 13.

15. Use of the dispersion according to any one of claims 1 to 10 for forming a solid electrolyte layer in a capacitor.

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