Solid electrolytic capacitor and manufacturing method

Abstract

To provide a manufacturing method for enhancing the capacitance appearance rate of a solid electrolytic capacitor and a solid electrolytic capacitor with an enhanced capacitance appearance rate.SOLUTION: A wound body 1 made by winding an anode foil and a cathode foil with a dielectric film formed facing each other is wound and fastened with a hydrophobic adhesive tape 2. A conductive polymer is formed using a conductive polymer solution, having a viscosity greater or equal to 10 mPa s and less than or equal to 60 mPa s, in which the conductive polymer is dispersed or dissolved. That is, by immersing the wound body 1, which is wound and fastened with the adhesive tape 2, in the conductive polymer solution with a viscosity of greater than or equal to 10 mPa s and less than or equal to 60 mPa s, the conductive polymer is made to adhere to the wound body 1.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present invention relates to a wound solid electrolytic capacitor containing a conductive polymer as an electrolyte, and a method for manufacturing the same. [Background technology]

[0002] Electrolytic capacitors have anode and cathode foils made of valve metals such as tantalum or aluminum. The anode foil is enlarged by shaping the valve metal into a sintered or etched foil, and the enlarged surface is coated with a dielectric film. An electrolyte is interposed between the anode and cathode foils. The electrolyte is in close contact with the irregular surface of the anode foil and functions as the true cathode.

[0003] A wound type electrolytic capacitor is known. A wound type electrolytic capacitor has a wound body consisting of an anode foil, a cathode foil, and a separator. The anode foil and the cathode foil are strip-shaped foils. The cathode foil and the anode foil are arranged opposite each other with the separator interposed between them. The strip is then wound so that the short side of the strip is aligned with the winding axis and the long side of the strip is curved. A strip-shaped adhesive tape is wound around the outer periphery of the wound body to prevent the wound body from unwinding (see, for example, Patent Document 1).

[0004] In recent years, solid electrolytic capacitors, in which the wound body is filled with a conductive polymer as an electrolyte, have rapidly become popular. Conductive polymers are derived from monomers with π-conjugated double bonds. An example of a conductive polymer is poly(3,4-ethylenedioxythiophene) (PEDOT), which has excellent adhesion to dielectric films. Conductive polymers exhibit high conductivity when polyanions such as organic sulfonic acids are used as dopants during chemical oxidative polymerization or electrolytic oxidative polymerization.

[0005] In addition to low equivalent series resistance, solid electrolytic capacitors have the advantage of being long-lived, as there is no risk of the electrolyte drying up due to evaporation over time. However, so-called hybrid-type solid electrolytic capacitors that use both a conductive polymer and an electrolyte to repair defects in the dielectric film and reduce leakage current in solid electrolytic capacitors are also becoming popular (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Unexamined Patent Publication No. 1-201911 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-114540 Summary of the Invention [Problem to be solved by the invention]

[0007] The conductive polymer is attached to the inside of the wound body by immersing the wound body in a conductive polymer liquid. The conductive polymer liquid is a dispersion or solution prepared by dispersing or dissolving a conductive polymer in water, with water as the main solvent. Compared to electropolymerization and oxidative polymerization, in which the wound body is immersed in a polymerization liquid to cause a polymerization reaction, the method of impregnating the wound body with a conductive polymer liquid does not expose the wound body to high heat and does not leave impurities in the wound body.

[0008] However, because water is often used in the manufacturing process of solid electrolytic capacitors, the adhesive tape used to secure the outer periphery of the wound body has a hydrophobic base material such as polypropylene. The hydrophobic adhesive tape repels the conductive polymer liquid, preventing it from penetrating into the wound body. Therefore, there is room for further improvement in the adhesion between the conductive polymer and the dielectric film, thereby improving the characteristics of the solid electrolytic capacitor, such as increasing the capacitance.

[0009] The present invention has been proposed to solve the above-mentioned problems, and an object of the present invention is to provide a manufacturing method for increasing the capacitance appearance rate of a solid electrolytic capacitor, and a solid electrolytic capacitor with an increased capacitance appearance rate. [Means for solving the problem]

[0010] In order to solve the above-described problems, the method for manufacturing a solid electrolytic capacitor of this embodiment includes a winding step of winding an anode foil and a cathode foil, each having a dielectric coating, facing each other to form a wound body; a winding stop step of fastening the circumferential surface of the wound body with a hydrophobic adhesive tape; and a solid electrolyte formation step of immersing the wound body secured with the adhesive tape in a conductive polymer solution in which a conductive polymer is dispersed or dissolved, thereby adhering the conductive polymer to the inside of the wound body, wherein in the solid electrolyte formation step, the wound body is immersed in the conductive polymer solution having a viscosity of 10 mPa s or more and 60 mPa s or less.

[0011] In order to solve the above-mentioned problems, the solid electrolytic capacitor of this embodiment includes a wound body formed by winding an anode foil and a cathode foil, each having a dielectric coating, facing each other; a hydrophobic adhesive tape that fastens the circumferential surface of the wound body; and a conductive polymer that adheres to at least the dielectric coating, wherein the conductive polymer is formed using a conductive polymer solution in which the conductive polymer is dispersed or dissolved and has a viscosity of 10 mPa s or more and 60 mPa s or less.

[0012] The conductive polymer may be attached by impregnating the wound body with the conductive polymer solution. The conductive polymer solution may contain water as a solvent. The conductive polymer solution may further contain a high-boiling point solvent. The method may further include an electrolyte impregnation step of impregnating the wound body with an electrolyte solution. The wound body may further contain an electrolyte solution to be impregnated therein.

[0013] In the winding step, a separator having an air resistance of 5.5 [s / 100 mL] or less may be interposed between the anode foil and the cathode foil and wound. A separator having an air resistance of 5.5 [s / 100 mL] or less may be interposed between the anode foil and the cathode foil in the wound body.

[0014] A lead terminal, which includes a flat portion, a round bar portion, and a lead wire connected to the flat portion of each of the anode foil and the cathode foil, is connected to the flat portion, and the round bar portion protrudes from one end face of the wound body, and the lead wire is drawn out. In the solid electrolyte forming step, the wound body may be immersed in the conductive polymer liquid to a height at least equal to or higher than the height of one end face of the wound body.

[0015] The winding body may have a flat portion, a round bar portion, and a lead wire that are connected to one another in a continuous manner, the flat portion being connected to the anode foil and the cathode foil, the round bar portion protruding from one end face of the winding body, and a lead terminal from which the lead wire is drawn out, and the conductive polymer may be attached to a height equal to or higher than the height of the one end face of the winding. [Effects of the Invention]

[0016] According to the present invention, the capacitance occurrence rate of the solid electrolytic capacitor is increased. [Brief explanation of the drawings]

[0017] [Figure 1] 2 is a schematic diagram of a wound body included in the solid electrolytic capacitor according to the embodiment. FIG. [Figure 2] 2 is a schematic diagram of a lead terminal included in the solid electrolytic capacitor according to the embodiment. FIG. [Figure 3] 3A and 3B are schematic diagrams showing the liquid level position of the conductive polymer liquid or the adhesion position of the conductive polymer. [Figure 4] FIG. 1 is a scatter diagram showing the relationship between the viscosity of a conductive polymer liquid and the ESR and capacitance appearance rate. [Figure 5] 1 is a graph showing the relationship between the height of the immersion liquid surface of the conductive polymer liquid and the amount of the conductive polymer adhered. [Figure 6]1 is a graph showing the relationship between the height of the immersion liquid surface of the conductive polymer liquid and tan δ of the solid electrolytic capacitor. [Figure 7] 1 is a graph showing the relationship between the height of the immersion liquid surface of the conductive polymer liquid and the capacitance appearance rate of the solid electrolytic capacitor. [Figure 8] FIG. 1 is a scatter diagram showing the relationship between the viscosity of a conductive polymer liquid and the ESR and capacitance appearance rate. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, a solid electrolytic capacitor and a manufacturing method thereof according to an embodiment of the present invention will be described. Note that the present invention is not limited to the embodiments described below. In addition, in each drawing, thickness, dimensions, positional relationships, ratios, numbers, shapes, etc. may be emphasized for ease of understanding, but the present invention is not limited to such emphasis.

[0019] (Overall structure and manufacturing method) A solid electrolytic capacitor is a passive device that obtains capacitance through the dielectric polarization of a dielectric film and stores and discharges electric charge. This solid electrolytic capacitor includes an anode foil and a cathode foil, each of which has a dielectric film formed on its surface. The anode foil and the cathode foil are arranged opposite each other. A separator is interposed between the anode foil and the cathode foil to prevent short-circuiting between them.

[0020] A conductive polymer is attached to the dielectric film of the anode foil. The conductive polymer is the electrolyte of the solid electrolytic capacitor, and is arranged in a continuous manner between the dielectric film and the cathode body to create a conductive path, making it the true cathode. A liquid electrolyte can also be used in solid electrolytic capacitors. The liquid electrolyte fills the gaps between the dielectric film and the conductive polymer.

[0021] FIG. 1 is a schematic diagram of a wound body included in a solid electrolytic capacitor. The solid electrolytic capacitor is wound. That is, the solid electrolytic capacitor includes a wound body 1. The wound body 1 is formed by spirally winding a laminate of an anode foil, a cathode foil, and a separator multiple times, and has a cylindrical shape. The anode foil and the cathode foil are strip-shaped foils. The strip is wound so that its short side coincides with the central axis of the wound body 1 and its long side is rounded. The process of winding the anode foil, the cathode foil, and the separator to form the wound body 1 is called the winding process.

[0022] Prior to the winding process, lead terminals 3 are connected to the anode foil and the cathode foil, respectively. The lead terminals 3 are electrically and mechanically connected to the anode foil and the cathode foil by cold welding, ultrasonic welding, laser welding, or the like. The lead terminals 3 protrude from one lead-out end surface 1a of the wound body 1 and are conductors that electrically connect the solid electrolytic capacitor to the mounting board.

[0023] After the winding process, a strip-shaped adhesive tape 2 is wound around the outer periphery of the wound body 1. At least the outer end of the strip of the adhesive tape 2 is secured to prevent the wound body 1 from unraveling. The process of securing the periphery of the wound body 1 with the adhesive tape 2 is called the winding securing process. The adhesive tape 2 has a hydrophobic base material such as polypropylene to provide water resistance against moisture during the manufacturing process of the solid electrolytic capacitor. An adhesive layer is laminated on this hydrophobic base material, making the adhesive tape 2 hydrophobic.

[0024] The width of this adhesive tape 2 in the band short direction is the same as or approximately the same as the axial length of the roll 1. The adhesive tape 2 is wound around the roll 1 so as to cover at least the outer end of the roll 1. The adhesive tape 2 is also wound around the roll 1 so that the edges of the adhesive tape 2 in the band long direction are flush or approximately flush with the lead-out end face 1a and the opposite end face 1b of the roll 1.

[0025] After the winding process, the process moves to the solid electrolyte forming process. However, instead of immediately moving to the solid electrolyte forming process after the winding process, for example, a chemical conversion treatment to repair damage to the dielectric film caused by the winding process and other treatments may be performed in between. In the solid electrolyte forming process, a conductive polymer is applied to the inside of the wound body 1. The conductive polymer covers at least a portion of the dielectric film.

[0026] The conductive polymer is formed in the wound body 1 using a conductive polymer liquid. The conductive polymer liquid is a dispersion or solution in which a conductive polymer is dispersed or dissolved. The main solvent of the conductive polymer liquid is water, and conductive polymer powder or particles are dispersed or dissolved in the water. In the solid electrolyte formation process, the wound body 1 is immersed in the conductive polymer liquid to impregnate the wound body 1 with the conductive polymer liquid. The wound body 1 may be immersed in the conductive polymer liquid once or multiple times. The wound body 1 may also be impregnated with the conductive polymer liquid in a reduced pressure environment.

[0027] After the wound body 1 is impregnated with the conductive polymer solution, the solvent in the conductive polymer solution is removed by drying. The temperature environment is, for example, 40°C or higher and 200°C or lower, and the drying time is, for example, in the range of 3 minutes or higher and 180 minutes or lower. The drying process may be repeated multiple times. Drying may also be performed in a reduced pressure environment, for example, by reducing the pressure to 5 kPa or higher and 100 kPa or lower.

[0028] When impregnating with an electrolyte solution, the solid electrolyte formation step is followed by an impregnation step in which the electrolyte solution is impregnated. The wound body 1 with the conductive polymer attached is impregnated with the electrolyte solution once or multiple times in an atmospheric pressure environment or a reduced pressure environment. Then, after the solid electrolyte formation step or the electrolyte impregnation step, the wound body 1 filled with the conductive polymer or both the conductive polymer and the electrolyte solution, i.e., the capacitor element, is inserted into a cylindrical outer case 41 with a bottom and sealed with a sealing member 42.

[0029] The sealing material 42 is an elastic body that seals the capacitor element within the exterior case, and has insertion holes 43 through which the lead terminals 3 pass. The lead terminals 3 are press-fitted into the insertion holes 43 and pulled out from the sealing material 42. The manufacture of the solid electrolytic capacitor is completed after an aging process. In the aging process, a DC voltage is applied to the solid electrolytic capacitor to repair defects in the dielectric coating layer, etc.

[0030] The capacitor element may be covered with a laminate film instead of an exterior case. The capacitor element may also be molded with a resin such as a heat-resistant resin or an insulating resin. The capacitor element may be sealed by forming the resin into a thin film by a method such as dip coating or printing.

[0031] (Detailed composition and manufacturing method) (electrode foil) The anode foil is a long foil made of a valve metal. Valve metals include aluminum, tantalum, niobium, niobium oxide, titanium, hafnium, zirconium, zinc, tungsten, bismuth, and antimony. The cathode foil is a long foil made of the same valve metal as the anode foil or other metals such as silver. The cathode foil may also be a layered foil made by laminating a carbon layer on a silver layer. The purity of the anode foil is preferably 99.9% or higher, and that of the cathode foil is preferably 99% or higher, but may also contain silicon, iron, copper, magnesium, zinc, and the like.

[0032] The long foil may be formed by stretching a valve metal or the like, or by sintering a valve metal powder. A surface-expanding layer is formed on one or both sides of the anode foil. The surface-expanding layer may be an etched layer formed by etching the foil, a sintered layer formed by sintering valve metal powder, or a vapor-deposited layer formed by vapor-depositing valve metal particles onto the foil. That is, the surface-expanding layer has a porous structure consisting of tunnel-like pits, spongy pits, or voids between densely packed powder or particles.

[0033] The tunnel-shaped etching pits are holes dug in the foil thickness direction. These tunnel-shaped etching pits are typically formed by passing a direct current in an acidic aqueous solution containing halogen ions, such as hydrochloric acid. The tunnel-shaped etching pits are further expanded by passing a direct current in an acidic aqueous solution, such as nitric acid. The spongy etching pits turn the surface-expanding layer into a sponge-like layer with fine, interconnected voids. These spongy etching pits are formed by passing an alternating current in an acidic aqueous solution containing halogen ions, such as hydrochloric acid.

[0034] The sintered layer is produced by obtaining a powder of a valve action metal of the same or different type as the foil body by a milling method, atomization method, melt spinning method, rotating disk method, rotating electrode method, etc., forming a paste with a binder or solvent, applying it to the foil body, drying it, and heating and sintering it in a vacuum or reducing atmosphere, etc. The atomization method may be any of water atomization method, gas atomization method, and water gas atomization method. The vapor deposition layer is produced by, for example, resistance heating vapor deposition method or electron beam heating vapor deposition method. This vapor deposition layer is formed by heating and vaporizing a valve action metal of the same or different type as the foil body by resistance heat or electron beam energy, and depositing the vapor of valve action metal particles on the surface of the foil body.

[0035] The dielectric coating is formed on the uneven surface of the surface-expanding layer. The dielectric coating is typically an oxide coating formed on the uneven surface of the surface-expanding layer. If the anode foil is made of aluminum, it is an aluminum oxide layer formed by oxidizing the uneven surface of the surface-expanding layer. In the chemical conversion treatment to form the dielectric coating, a voltage is applied to the anode foil in a chemical conversion solution until the desired withstand voltage is achieved. The chemical conversion solution is a solution that does not contain halogen ions, and examples of such solutions include phosphoric acid-based chemical conversion solutions such as ammonium dihydrogen phosphate, boric acid-based chemical conversion solutions such as ammonium borate, and adipic acid-based chemical conversion solutions such as ammonium adipate.

[0036] A surface enlarging layer may be formed on the cathode foil as needed, just like on the anode foil. Plain foil without a surface enlarging layer may also be used as the cathode foil. The cathode foil may also have a dielectric coating formed thereon, just like the anode foil. The dielectric coating may be a natural oxide coating or a thin oxide coating (about 1 to 10 V) formed by chemical conversion treatment. The natural oxide coating is formed when the cathode body reacts with oxygen in the air.

[0037] The cathode foil may have a conductive layer laminated on its surface. The conductive layer may be a layer containing, for example, a metal nitride such as titanium, zirconium, tantalum, or niobium, a metal carbide, a metal carbonitride, or carbon. The metal nitride, metal carbide, metal carbonitride, and carbon are formed by vapor deposition, slurry coating, or the like.

[0038] (Lead terminal) 2 is a schematic diagram of a lead terminal 3. The lead terminal 3 is drawn out through a sealing member 4 and is composed of a lead wire 31, a round bar portion 32, and a flat portion 33 arranged in series. The sealing member 42 is an elastic body for sealing the capacitor element in the exterior case and has an insertion hole 43 through which the lead terminal 3 passes. The lead wire 31 is an electric wire that extends outward beyond the sealing member 42 and electrically connects the solid electrolytic capacitor to the mounting board. This lead wire 31 is generally a copper-coated steel wire called a CP wire, and its surface is plated with solder such as lead or tin.

[0039] The round bar portion 32 is typically made of aluminum and is a generally cylindrical round bar. However, the cross-sectional shape of the round bar portion 32 is not limited to a perfect circle, and may be an ellipse, a polygonal shape such as a triangle or a rectangle, or another shape. The lead wire 31 and the round bar portion 32 are connected by arc welding or the like, and a welded connection portion 34 is interposed between the lead wire 31 and the round bar portion 32. Alternatively, the lead wire 31 may be formed from a portion of the round bar portion 32. The round bar portion 32 is set to be slightly larger than the insertion hole 43 of the sealing member 42. The round bar portion 32 is press-fitted into the insertion hole 43, and the increased internal pressure of the sealing member 4 after crimping causes the round bar portion 32 to adhere closely to the inner wall of the insertion hole 43.

[0040] The flat portion 33 is formed by crushing the side of the round bar portion 32 opposite to the lead wire 31 by press working or the like into a flat plate. The boundary between the round bar portion 32 and the flat portion 33 is an inclined portion whose thickness linearly decreases to the thickness of the flat portion 33. This inclined portion is included in the round bar portion 32.

[0041] The flat portion 33 is electrically and mechanically connected to each electrode foil 5, which is a collective term for anode foil and cathode foil, using one of various connection methods such as stitch connection, cold pressure welding, ultrasonic welding, or laser welding. The flat portion 33 is brought into contact with one surface and one long side of the electrode foil 5, and the round bar portion 32 and lead wire 31 are allowed to protrude from the electrode foil 5 so as to be perpendicular to the long side of the electrode foil 5, connecting the flat portion 33 and the electrode foil 5. The winding process is performed after the lead terminals 3 are connected to each electrode foil 5.

[0042] (separator) The separator prevents short-circuiting between the anode foil and the cathode foil and holds the conductive polymer and the electrolyte. The separator may be made of cellulose paper such as kraft, Manila hemp, esparto, hemp, or rayon, or a mixture thereof; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and derivatives thereof; polytetrafluoroethylene resins, polyvinylidene fluoride resins, vinylon resins; polyamide resins such as aliphatic polyamides, semi-aromatic polyamides, and fully aromatic polyamides; polyimide resins; polyethylene resins; polypropylene resins; trimethylpentene resins; polyphenylene sulfide resins; acrylic resins; or polyvinyl alcohol resins, which may be used alone or in combination.

[0043] The separator may be fibrillated by generating thin fibers that branch out from the surface of the original fiber, such as fibrillated cellulose. The fibrillation can be achieved, for example, by beating. The fibrillated fibers are entangled with each other using the fibrillated thin fibers, improving the strength of the separator. This allows the separator to be made thinner.

[0044] It is also preferable to use a separator with an air resistance of 5.5 [s / 100 mL] or less for the wound body 1. If the separator has an air resistance of 5.5 [s / 100 mL] or less, the conductive polymer liquid will easily permeate into the wound body 1 during the solid electrolyte formation process. This increases the amount of conductive polymer liquid impregnated into the wound body 1 and the amount of conductive polymer attached to the wound body 1, improving the rate of production of solid electrolytic capacitors.

[0045] Here, the air resistance is also called the Gurley value, and is the time required for 100 mL of air to permeate the separator. The air resistance is measured by the Gurley method in accordance with JIS P8117:2009. A gasket with an inner diameter of 28.6 mm is used for the measurement. However, for those with an air resistance of 1 s / 100 mL or less, the measurement is made using a gasket with an inner diameter of 6 mm and converted to the value measured with an inner diameter of 28.6 mm. Specifically, the value obtained with an inner diameter of 6 mm is multiplied by 28.6. 2 / 6 2 Use the conversion formula to multiply by.

[0046] (conductive polymer) Conductive polymers are self-doped conjugated polymers doped with an intramolecular dopant, or conjugated polymers doped with external dopant molecules. Conjugated polymers are obtained by chemical oxidative polymerization or electrolytic oxidative polymerization of monomers or their derivatives having π-conjugated double bonds. The dopant or external dopant molecule acts as an acceptor that readily accepts electrons into the conjugated polymer, or as a donor that readily donates electrons, which allows the conductive polymer to exhibit high conductivity.

[0047] As the conjugated polymer, any known polymer can be used without any particular limitation. Examples include polypyrrole, polythiophene, polyfuran, polyaniline, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polythiophene vinylene, etc. These conjugated polymers may be used alone or in combination of two or more types, or may even be a copolymer of two or more types of monomers.

[0048] Among the above conjugated polymers, preferred are conjugated polymers obtained by polymerizing thiophene or its derivatives, and preferred are conjugated polymers obtained by polymerizing 3,4-ethylenedioxythiophene (i.e., 2,3-dihydrothieno[3,4-b][1,4]dioxin), 3-alkylthiophene, 3-alkoxythiophene, 3-alkyl-4-alkoxythiophene, 3,4-alkylthiophene, 3,4-alkoxythiophene, or derivatives thereof. The thiophene derivative is preferably a compound selected from thiophenes having substituents at the 3rd and 4th positions, and the substituents at the 3rd and 4th positions of the thiophene ring may form a ring together with the carbon atoms at the 3rd and 4th positions. The alkyl group or alkoxy group preferably has 1 to 16 carbon atoms.

[0049] In particular, a polymer of 3,4-ethylenedioxythiophene, also known as EDOT, i.e., poly(3,4-ethylenedioxythiophene), also known as PEDOT, is preferred. A substituent may be added to 3,4-ethylenedioxythiophene. For example, alkylated ethylenedioxythiophene, in which an alkyl group having 1 to 5 carbon atoms is added as a substituent, may be used. Examples of alkylated ethylenedioxythiophene include methylated ethylenedioxythiophene (i.e., 2-methyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin), ethylated ethylenedioxythiophene (i.e., 2-ethyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin), butylated ethylenedioxythiophene (i.e., 2-butyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin), and 2-alkyl-3,4-ethylenedioxythiophene.

[0050] Any known dopant can be used without any particular limitation. A single dopant may be used, or two or more dopants may be used in combination. Furthermore, a polymer or a monomer may be used. Examples of dopants include inorganic acids such as polyanions, boric acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid, oxalic acid, citric acid, tartaric acid, squaric acid, rhodizonic acid, croconic acid, salicylic acid, p-toluenesulfonic acid, 1,2-dihydroxy-3,5-benzenedisulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, borodisalicylic acid, bisoxalateborate acid, sulfonylimide acid, dodecylbenzenesulfonic acid, propylnaphthalenesulfonic acid, and butylnaphthalenesulfonic acid.

[0051] Examples of polyanions include substituted or unsubstituted polyalkylenes, substituted or unsubstituted polyalkenylenes, substituted or unsubstituted polyimides, substituted or unsubstituted polyamides, and substituted or unsubstituted polyesters, and include polymers consisting only of structural units having anionic groups, and polymers consisting of structural units having anionic groups and structural units not having anionic groups.Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallylsulfonic acid, polyacrylic sulfonic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, polyacrylic acid, polymethacrylic acid, and polymaleic acid.

[0052] An example of such a conductive polymer is poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonic acid, and hereinafter this conductive polymer is referred to as PEDOT / PSS.

[0053] In the solid electrolyte formation process, the wound body 1 is immersed in a conductive polymer solution to adhere the conductive polymer to the inside of the wound body 1. The conductive polymer solution is a dispersion or solution in which a conductive polymer is dispersed. The conductive polymer solution is prepared by purifying the solution after electrolytic polymerization or chemical polymerization by ultrafiltration, cation exchange, anion exchange, or the like to remove residual monomers and impurities, and dispersing or dissolving the resultant in a solvent, or by adding particles or powder of the conductive polymer to a solvent and dispersing or dissolving the resultant in the solvent.

[0054] The main solvent of the conductive polymer liquid is water. The viscosity of the conductive polymer liquid is adjusted to 10 mPa·s or more and 60 mPa·s or less by adjusting the processing time using a dispersion method such as an ultrasonic homogenizer or jet mixing, the type and amount of dispersion medium, the type and amount of additives, the degree of polymerization of the polymer, and the polymer concentration. A viscosity within this range allows the conductive polymer liquid to easily permeate the wound body 1 while maintaining a good ESR of the solid electrolytic capacitor, thereby improving the capacitance appearance rate of the solid electrolytic capacitor. However, if the viscosity is less than 10 mPa·s, the ESR will increase rapidly. Furthermore, if the viscosity exceeds 60 mPa·s, the capacitance appearance rate will decrease rapidly.

[0055] The capacitance appearance rate is the ratio of the capacitance of the solid electrolytic capacitor to the combined capacitance of the anode foil and cathode foil, and is a percentage obtained by dividing the capacitance of the solid electrolytic capacitor by the combined capacitance of the anode foil and cathode foil. The combined capacitance of the anode foil and cathode foil is the combined capacitance when the solid electrolytic capacitor is regarded as a capacitor with an anode side and a cathode side connected in series. If the cathode foil has a conductive layer or if the capacitance of the cathode body can be said to converge to infinity, the combined capacitance of the anode foil and cathode foil is the capacitance of the anode foil.

[0056] The solvent for the conductive polymer dispersion may be a mixture of water and an organic solvent, as long as the conductive polymer particles or powder can be dispersed or dissolved in the mixture. Suitable examples of the organic solvent include polar solvents, alcohols, esters, hydrocarbons, carbonate compounds, ether compounds, chain ethers, heterocyclic compounds, and nitrile compounds.

[0057] Examples of polar solvents include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. Examples of alcohols include methanol, ethanol, propanol, and butanol. Examples of esters include ethyl acetate, propyl acetate, and butyl acetate. Examples of hydrocarbons include hexane, heptane, benzene, toluene, and xylene. Examples of carbonate compounds include ethylene carbonate and propylene carbonate. Examples of ether compounds include dioxane and diethyl ether. Examples of linear ethers include ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, and polypropylene glycol dialkyl ether. Examples of heterocyclic compounds include 3-methyl-2-oxazolidinone. Examples of nitrile compounds include acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, and benzonitrile.

[0058] The pH of the conductive polymer liquid may be adjusted, and polyhydric alcohols and various additives may be added as needed. Examples of pH adjusters include aqueous ammonia, sodium hydroxide, primary amines, secondary amines, and tertiary amines. Examples of polyhydric alcohols include sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, polyglycerin, polyoxyethyleneglycerin, xylitol, erythritol, mannitol, dipentaerythritol, pentaerythritol, and combinations of two or more of these. Polyhydric alcohols are high-boiling point solvents and remain in the wound body 1 even after the wound body 1 is impregnated with the conductive polymer liquid and dried. The polyhydric alcohols are effective in reducing the ESR and improving the withstand voltage of the solid electrolytic capacitor. Examples of additives include organic binders, surfactants, dispersants, antifoaming agents, coupling agents, antioxidants, and UV absorbers.

[0059] In the solid electrolyte formation process, the wound body 1 is immersed in a conductive polymer liquid with the opposite end surface 1b of the wound body 1 facing downward. FIG. 3 is a schematic diagram showing the liquid level of the conductive polymer liquid or the position where the conductive polymer is attached. As shown in FIG. 3, the boundary position between the lead wire 31 of the lead terminal 3 and the upper end of the connection portion 34 is defined as the upper end A1 of the connection portion. The boundary position between the lower end of the connection portion 34 of the lead terminal 3 and the round bar portion 32 is defined as the lower end A2 of the connection portion. A3 is defined as a position halfway along the length of the round bar portion 32 or a position 1 mm or more from the lead end surface 1a of the wound body 1. The lead end surface 1a of the wound body 1 is defined as the end surface position A4.

[0060] At this time, the wound body 1 is preferably immersed in the conductive polymer liquid so that the liquid level is at least on the lead-out end surface 1a of the wound body 1. Furthermore, it is also preferable to immerse the wound body 1 in the conductive polymer liquid so that the liquid level is located between the halfway point of the round bar or a position A3 1 mm from the lead-out end surface 1a of the wound body 1 and the upper end A1 of the connection portion. In other words, it is preferable to apply the conductive polymer not only to the inside of the wound body 1 but also to the lead terminal 3 in the range from the position A3 to the upper end A1 of the connection portion. Because the contact angle between the hydrophobic adhesive tape and the conductive polymer liquid is large, a meniscus is formed. Therefore, it is necessary to immerse the wound body 1 in the conductive polymer liquid beyond the upper edge of the hydrophobic adhesive tape 2.

[0061] The conductive polymer liquid is absorbed from the opposite end surface 1b and drips down from the outlet end surface 1a. By using a separator with an air resistance of 5.5 [s / 100 mL] or less, the conductive polymer liquid that has entered from the outlet end surface 1a and the opposite end surface 1b permeates through the separator and into the wound body 1.

[0062] Therefore, in the solid electrolyte formation process, the round bar portion 32 is immersed in the conductive polymer liquid at least to a height above position A3, and in addition to the wound body 1, the conductive polymer is attached to the round bar portion 32 at least to a height above position A3, thereby increasing the capacitance appearance rate of the solid electrolytic capacitor and reducing the dielectric loss tangent (tanδ).

[0063] The impregnation time for the conductive polymer liquid can be set appropriately depending on the size of the wound body 1. Longer impregnation times do not adversely affect the properties. When impregnating the wound body 1, reduced pressure or pressurization may be performed as needed to promote impregnation. The solid electrolyte formation process may be repeated multiple times. The solvent in the conductive polymer liquid is evaporated and removed by drying as needed. Heat drying or reduced pressure drying may be performed as needed to remove the solvent.

[0064] Between the winding step and the solid electrolyte formation step, a repair chemical treatment may be performed to repair defects in the dielectric film, such as voids, cracks, or scratches, that are caused by insufficient formation of the dielectric film or bending stress due to winding. The chemical solution used for the repair chemical treatment is an aqueous solution prepared by dissolving a phosphoric acid-based solution, such as ammonium dihydrogen phosphate or diammonium hydrogen phosphate, a boric acid-based solution, such as ammonium borate, or an adipic acid-based solution, such as ammonium adipate, in water. The voltage is preferably set to, for example, 0.1 to 1.2 times the chemical voltage. Thereafter, to remove the chemical solution from the wound body 1, the wound body 1, which has been immersed in the chemical solution, is washed with a chemical solution cleaning solution, such as pure water.

[0065] (electrolyte) When an electrolyte solution is used in a solid electrolytic capacitor, the solid electrolyte formation process is followed by the electrolyte impregnation process. The electrolyte solution is a mixed solution in which a solute is dissolved in a solvent and, if necessary, an additive is added. The electrolyte solution does not need to dissolve a solute, and may be a solvent only, or may contain a solvent and an additive. Solvents for the electrolyte solution include protic organic polar solvents and aprotic organic polar solvents, which may be used alone or in combination of two or more. The solutes for the electrolyte solution include anionic components and cationic components. The solutes are typically salts of organic acids, salts of inorganic acids, or salts of complex compounds of organic acids and inorganic acids, which may be used alone or in combination of two or more. An acid that becomes an anion and a base that becomes a cation may be added separately to the solvent.

[0066] Examples of protic organic polar solvents include monohydric alcohols, polyhydric alcohols, and oxyalcohol compounds. Examples of monohydric alcohols include ethanol, propanol, butanol, pentanol, hexanol, cyclobutanol, cyclopentanol, cyclohexanol, and benzyl alcohol. Examples of polyhydric alcohols and oxyalcohol compounds include ethylene glycol, propylene glycol, glycerin, polyglycerin, methyl cellosolve, ethyl cellosolve, methoxypropylene glycol, dimethoxypropanol, and alkylene oxide adducts of polyhydric alcohols such as polyethylene glycol and polyoxyethylene glycerin. Among these, polyhydric alcohols are preferred, with ethylene glycol and glycerin being particularly preferred. Ethylene glycol and glycerin cause changes in the higher-order structure of the conductive polymer, resulting in improved initial ESR characteristics and improved high-temperature characteristics. It is even better if the ethylene glycol content in the solvent is 30 wt% or more.

[0067] Representative examples of aprotic organic polar solvents include sulfones, amides, lactones, cyclic amides, nitriles, and sulfoxides. Examples of sulfones include dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, sulfolane, 3-methyl sulfolane, and 2,4-dimethyl sulfolane. Examples of amides include N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, and hexamethylphosphoric amide. Examples of lactones and cyclic amides include γ-butyrolactone, γ-valerolactone, δ-valerolactone, N-methyl-2-pyrrolidone, ethylene carbonate, propylene carbonate, butylene carbonate, and isobutylene carbonate. Examples of nitriles include acetonitrile, 3-methoxypropionitrile, glutaronitrile, etc. Examples of sulfoxides include dimethyl sulfoxide, etc.

[0068] Examples of organic acids that serve as anionic solutes include oxalic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, benzoic acid, toluic acid, enanthic acid, malonic acid, 1,6-decanedicarboxylic acid, 1,7-octanedioic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, t-butyl adipic acid, 11-vinyl-8-octadecenedioic acid, resorcylic acid, phloroglucinic acid, gallic acid, gentisic acid, protocatechuic acid, pyrocatechuic acid, trimellitic acid, and pyromellitic acid, as well as carboxylic acids such as pyromellitic acid, phenols, and sulfonic acids.

[0069] Examples of inorganic acids include boric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, carbonic acid, silicic acid, etc. Examples of composite compounds of organic acids and inorganic acids include borodisalicylic acid, borodioxalic acid, borodiglycolic acid, borodimalonic acid, borodisuccinic acid, borodiadipic acid, borodiazelaic acid, borodibenzoic acid, borodimaleic acid, borodilactic acid, borodimalic acid, boroditartaric acid, borodicitric acid, borodiphthalic acid, borodi(2-hydroxy)isobutyric acid, borodiresorcylic acid, borodimethylsalicylic acid, borodinaphthoic acid, borodimandelic acid, and borodi(3-hydroxy)propionic acid, etc.

[0070] Furthermore, examples of at least one salt of an organic acid, an inorganic acid, or a composite compound of an organic acid and an inorganic acid include ammonium salts, quaternary ammonium salts, quaternized amidinium salts, amine salts, sodium salts, and potassium salts. Examples of quaternary ammonium ions of quaternary ammonium salts include tetramethylammonium, triethylmethylammonium, and tetraethylammonium. Examples of quaternized amidinium salts include ethyldimethylimidazolinium and tetramethylimidazolinium. Examples of amine salts include salts of primary amines, secondary amines, and tertiary amines. Examples of primary amines include methylamine, ethylamine, and propylamine. Examples of secondary amines include dimethylamine, diethylamine, ethylmethylamine, and dibutylamine. Examples of tertiary amines include trimethylamine, triethylamine, tributylamine, ethyldimethylamine, and ethyldiisopropylamine.

[0071] Other additives may also be added to the electrolyte. Examples of additives include complex compounds of boric acid and polysaccharides (e.g., mannitol, sorbitol), complex compounds of boric acid and polyhydric alcohols, boric acid esters, nitro compounds (e.g., o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, o-nitrophenol, m-nitrophenol, p-nitrophenol, p-nitrobenzyl alcohol), and phosphate esters. These may be used alone or in combination of two or more. The amount of additive added is not particularly limited, but it is preferable to add it to an amount that does not deteriorate the characteristics of the solid electrolytic capacitor, for example, 60 wt % or less of the electrolyte. [Example]

[0072] The solid electrolytic capacitor and the manufacturing method of the present invention will be described in more detail below based on examples, but the present invention is not limited to the following examples.

[0073] (Examples 1-7) As described below, solid electrolytic capacitors of Examples 1 to 7 and Comparative Examples 1 and 2 were fabricated. The solid electrolytic capacitors of Examples 1 to 7 and Comparative Examples 1 and 2 are common except for the viscosity of the conductive polymer solution used in the fabrication.

[0074] First, the anode and cathode foils were strip-shaped aluminum foils stretched to a long length. The anode and cathode foils were then subjected to DC etching to enlarge the surface area. After enlarging the surface area, the anode foils were subjected to a chemical conversion treatment to form a dielectric coating.

[0075] A lead terminal 3 was attached to each of the anode foil and the cathode foil by stitch connection. A separator made of fibrillated cellulose was interposed between the anode foil and the cathode foil to which the lead terminal 3 was connected, and the foil was wound so that the strip was curled in the longitudinal direction to form a wound body 1. In the solid electrolytic capacitor of Example 1, a separator made of fibrillated cellulose and having an air resistance of 5.48 [s / 100 mL] was used.

[0076] An adhesive tape 2 having the same width as the entire axial length of the wound body 1 was prepared, and the outer periphery of the wound body 1 was wound and secured with this adhesive tape 2. A voltage of 57 V was applied to the wound body 1 in the chemical conversion solution, and repair chemical conversion was performed.

[0077] The wound body 1 was impregnated with a conductive polymer liquid. The conductive polymer liquid was prepared by dispersing poly(3,4-ethylenedioxythiophene) (PEDOT / PSS) doped with polystyrene sulfonic acid (PSS) in water. PEDOT / PSS was added at a ratio of 1.2 wt% to the total conductive polymer liquid. Ethylene glycol was also added to the conductive polymer liquid at a ratio of 10 wt% to the conductive polymer liquid. In the solid electrolytic capacitor of Example 1, the viscosity of the conductive polymer liquid was adjusted by dispersing it with an ultrasonic homogenizer.

[0078] The wound body 1 was impregnated with the conductive polymer liquid for 10 minutes at room temperature in a reduced pressure environment of 80 kPa or less. The wound body 1 was immersed in the conductive polymer liquid so that the liquid level was located at the lower end A2 of the connection part as shown in Figure 3, and the conductive polymer adhered up to the height of the lower end A2 of the connection part. After each impregnation step, the wound body 1 was left to stand at room temperature for 10 minutes, and then left to stand in a temperature environment of 110°C for 30 minutes to dry.

[0079] After being impregnated with the conductive polymer and dried, the wound body 1 was housed in an outer case 41, and the outer case 41 was sealed with a sealing member 42. The sealing member 42 and the outer case 41 were tightly attached by crimping. The lead terminal 3 was press-fitted into the insertion hole 43 of the sealing member 42, and the outer surface of the round bar portion 32 was tightly attached to the inner surface of the insertion hole 43. The completed solid electrolytic capacitor was subjected to an aging treatment in which a voltage of 40 V was applied for 1 hour. As a result, an electrolytic capacitor of Example 1 was produced, having a diameter of 10 mm, a height of 10 mm, a rated voltage of 35 WV, and a rated capacitance of 270 μF.

[0080] (Capacitor characteristics) The equivalent series resistance (ESR) and capacitance appearance rate (%) of the solid electrolytic capacitors of Examples 1 to 7 and Comparative Examples 1 and 2 were measured. The ESR was expressed with Comparative Example 2 as the reference (100%). The results are shown in Table 1 together with the viscosities of the conductive polymer solutions used in Examples 1 to 7 and Comparative Examples 1 and 2. The relationship between the viscosity of the conductive polymer solution and the ESR and capacitance appearance rate is shown in the scatter diagram of FIG. 4. In FIG. 4, the white plots represent the capacitance appearance rate, and the black plots represent the ESR.

[0081] The equivalent series resistance (ESR) was measured at room temperature using an LCR meter at a frequency of 100 kHz and an AC amplitude of 0.5 Vms.

[0082] Regarding the capacitance appearance rate, the capacitance of the anode foil or cathode foil was measured by cutting out a test piece of a specified area from the anode foil or cathode foil, immersing it in a capacitance measurement solution in a glass measurement tank with a platinum plate as the counter electrode, and using a capacitance meter. The specified area was 1 cm. 2The capacitance measurement liquid was an aqueous solution of ammonium adipate at 30°C, the capacitance meter was an LCR meter, and the measurement conditions were an AC amplitude of 0.5 Vms.

[0083] (Table 1) TIFF0007768445000001.tif106161

[0084] As shown in Table 1 and FIG. 4, the solid electrolytic capacitors of Comparative Example 1 and Examples 1 to 7 were formed using a conductive polymer solution with a viscosity of 60 mPa·s or less. The solid electrolytic capacitors of Comparative Example 1 and Examples 1 to 7 exhibited a good capacitance appearance ratio. However, Comparative Example 1, in which the conductive polymer was formed using a conductive polymer solution with a viscosity of less than 10 mPa·s, exhibited a high ESR. On the other hand, Examples 1 to 7, in which the conductive polymer was formed using a conductive polymer solution with a viscosity of 10 mPa·s or more and 60 mPa·s or less, exhibited a good capacitance appearance ratio and a good ESR.

[0085] This confirmed that even when the capacitor is wound with hydrophobic adhesive tape 2, by setting the viscosity of the conductive polymer liquid to 10 mPa·s or more and 60 mPa·s or less, the capacitance appearance rate is improved and the ESR is also reduced.

[0086] Example 8 A solid electrolytic capacitor of Example 8 was fabricated. Example 8 shared the following characteristics with Example 4. Specifically, for the solid electrolytic capacitor of Example 8, a wound body 1 was impregnated with a conductive polymer liquid having a viscosity of 30 mPa·s, as in Example 4. The wound body 1 was immersed in the conductive polymer liquid so that the liquid level was located at the lower end A2 of the connection portion shown in FIG. 3 and the conductive polymer adhered up to the height of the lower end A2 of the connection portion. The lower end A2 of the connection portion was located 2 mm from the lead-out end surface 1a of the wound body 1. However, unlike Example 4, Example 8 used a separator with an air resistance of 5.76 [s / 100 mL]. In all other respects, Example 8 had the same configuration as Example 4 and was fabricated using the same manufacturing method and conditions.

[0087] (Capacity appearance rate) The capacitance appearance rate (%) was measured for the solid electrolytic capacitors of Examples 4 and 8. The results are shown in Table 2 below. (Table 2) TIFF0007768445000002.tif36163

[0088] As shown in Table 2, the capacitance appearance rate of Example 8, in which the separator air resistance was 5.76 [s / 100 mL], was good, unlike Comparative Example 2, but was lower than that of Example 4. In other words, it was confirmed that when the viscosity of the conductive polymer liquid was 10 mPa s or more and 60 mPa s or less and the separator air resistance was 5.5 [s / 100 mL] or less, which falls within the range of Examples 1 to 8, the capacitance appearance rate of the solid electrolytic capacitor was further improved.

[0089] Example 9 A solid electrolytic capacitor of Example 9 was fabricated. Example 9 shared the following characteristics with Example 4. Specifically, the solid electrolytic capacitor of Example 9 used a separator made of filtrated cellulose with an air resistance of 5.48 [s / 100 mL], as in Example 4. A conductive polymer liquid with a viscosity of 30 mPa·s was impregnated into the wound body 1. However, unlike Example 4, the wound body 1 of Example 9 was immersed in the conductive polymer liquid so that the liquid level was located at the upper end A1 of the connection portion shown in FIG. 3 and the conductive polymer adhered up to the height of the upper end A1 of the connection portion. In other respects, Example 9 had the same configuration as Example 4 and was fabricated using the same manufacturing method and conditions. The upper end A1 of the connection portion was located 2.7 mm from the lead-out end surface 1a of the wound body 1.

[0090] Example 10 A solid electrolytic capacitor according to Example 10 was fabricated. Example 11 shares the following features with Example 4. Specifically, the solid electrolytic capacitor according to Example 11 used a separator made of filtrated cellulose with an air resistance of 5.48 [s / 100 mL], as in Example 4. A conductive polymer liquid with a viscosity of 30 mPa·s was impregnated into the wound body 1. However, unlike Example 4, the wound body 1 according to Example 11 was immersed in the conductive polymer liquid so that the liquid level was positioned at position A3 shown in FIG. 3 and the conductive polymer adhered up to the height of the upper end A1 of the connection portion. Otherwise, Example 11 had the same configuration as Example 4 and was fabricated using the same manufacturing method and conditions. Position A3 was 1 mm from the lead-out end surface 1a of the wound body 1.

[0091] Example 11 A solid electrolytic capacitor of Example 11 was fabricated. Example 11 shared the following features with Example 4. Specifically, the solid electrolytic capacitor of Example 12 used a separator made of filtrated cellulose with an air resistance of 5.48 [s / 100 mL], as in Example 4. A conductive polymer liquid with a viscosity of 30 mPa·s was impregnated into the wound body 1. However, unlike Example 4, the wound body 1 of Example 11 was immersed in the conductive polymer liquid so that the liquid level of the conductive polymer liquid was located at end surface position A4 shown in FIG. 3 and the conductive polymer adhered up to the height of end surface position A4. In other respects, Example 11 had the same configuration as Example 4 and was fabricated using the same manufacturing method and conditions.

[0092] (Adhesion test) The amounts of the conductive polymer solution impregnated into the wound body 1 of Example 4 and Examples 9 to 11 were measured. The adhesion amounts were calculated from the change in weight of the wound body 1 before and after the solid electrolyte formation step. The adhesion amounts of Example 4 and Examples 9 to 10 are shown with the adhesion amount of Example 11 as the reference (100%).

[0093] FIG. 5 shows the relationship between the weight of the conductive polymer liquid attached to the wound body 1 of Example 4 and Examples 9 to 11 and the height of the immersion liquid surface of the conductive polymer liquid.

[0094] As shown in Figure 5, it was confirmed that the amount of conductive polymer liquid adhered was significantly improved at A3, which is half the height in the longitudinal direction of the round bar portion 32, compared to when the immersion liquid level of the conductive polymer liquid and the conductive polymer adhesion height were set at end surface position A4.

[0095] Furthermore, it was confirmed that at the lower end A2 and upper end A1 of the connection portion, which are in the height range of the connection portion 34 between the round bar portion 32 and the lead wire 31, the amount of conductive polymer liquid adhered was further improved compared to when the immersion liquid level of the conductive polymer liquid and the conductive polymer adhesion height were set at the end face position A4.

[0096] (Capacitor characteristics) The dielectric loss tangent (tanδ) and capacitance appearance ratio (%) of the solid electrolytic capacitors of Example 4 and Examples 9 to 11 were measured. The results are shown in Figures 6 and 7. The measurement results of the capacitance appearance ratio (%) are shown in Table 3 below, and the measurement results of the dielectric loss tangent (tanδ) are shown in Table 4 below. The dielectric loss tangent (tanδ) was measured at room temperature using an LCR meter. The measurement frequency for tanδ was 120 Hz, and the AC amplitude was a sine wave of 0.5 Vms.

[0097] (Table 3) TIFF0007768445000003.tif56167

[0098] (Table 4) TIFF0007768445000004.tif56167

[0099] As shown in Tables 3 and 4 and FIGS. 6 and 7, it can be confirmed that tan δ and the capacitance appearance rate are improved in accordance with the amount of conductive polymer attached in FIG.

[0100] That is, when the wound body 1 is secured with hydrophobic adhesive tape 2, the viscosity of the conductive polymer liquid is set to 10 mPa·s or more and 60 mPa·s or less, making it easier to spread the conductive polymer throughout the wound body 1. The immersion liquid surface of the conductive polymer liquid is positioned at the halfway point of the round bar portion 32, which is halfway along the length of the round bar portion 32, or at or above A3, which is 1 mm from the lead-out end surface 1a of the wound body 1, and the amount of conductive polymer liquid adhered is increased. It has been confirmed that this further improves the capacitance appearance rate of the solid electrolytic capacitor and also improves tan δ.

[0101] (Examples 12 to 14) Solid electrolytic capacitors of Examples 12 to 14 were fabricated. Examples 12 to 14 were common to Example 1 in the following respects. That is, for the solid electrolytic capacitors of Examples 12 to 14, as in Example 1, a wound body 1 was impregnated with a conductive polymer liquid having a viscosity of 13 mPa s. The wound body 1 was immersed in the conductive polymer liquid so that the liquid level was located at the lower end A2 of the connection portion shown in FIG. 3, and the conductive polymer adhered up to the height of the lower end A2 of the connection portion. The lower end A2 of the connection portion is located 2 mm from the lead-out end surface 1a of the wound body 1.

[0102] However, unlike Example 1, the solid electrolytic capacitors of Examples 12 to 14 used a separator made of natural cellulose with an air resistance of 0.03 [s / 100 mL]. Examples 12 to 14 differed from each other in the viscosity of the conductive polymer liquid impregnated into the wound body 1. In Example 12, like Example 1, the wound body 1 was impregnated with a conductive polymer liquid having a viscosity of 13 mPa s. In Example 13, unlike Example 12, the wound body 1 was impregnated with a conductive polymer liquid having a viscosity of 25 mPa s. In Example 14, unlike Example 12, the wound body 1 was impregnated with a conductive polymer liquid having a viscosity of 60 mPa s.

[0103] In other respects, Examples 12 to 14 have the same configuration as Example 1, and were produced using the same manufacturing method and conditions.

[0104] Furthermore, a solid electrolytic capacitor was produced according to Comparative Example 3. The solid electrolytic capacitor according to Comparative Example 3 had the same configuration as Examples 12 to 14, except that the wound body 1 was impregnated with a conductive polymer liquid having a viscosity of 125 mPa s, and was produced according to the same production method and conditions.

[0105] (Capacitor characteristics) The equivalent series resistance (ESR) and capacitance appearance rate (%) of the solid electrolytic capacitors of Examples 12 to 14 and Comparative Example 3 were measured. The measurement methods and conditions for ESR and capacitance appearance rate were the same as those of Examples 1 to 8. The results are shown in Table 5 below, along with the viscosities of the conductive polymer solutions used in Examples 12 to 14 and Comparative Example 3. ESR is expressed with Comparative Example 3 as the reference (100%).

[0106] (Table 5) TIFF0007768445000005.tif57164

[0107] Based on Table 5, the relationship between the viscosity of the conductive polymer liquid and the ESR and the capacitance appearance rate is shown in the scatter diagram of Figure 8. In Figure 8, the white plots represent the capacitance appearance rate, and the black plots represent the ESR.

[0108] As shown in Table 5 and FIG. 8, even when natural cellulose with an air resistance value of 0.03 [s / 100 mL] was used, Examples 12 to 14, in which conductive polymers were formed using conductive polymer solutions with viscosities of 10 mPa s or more and 60 mPa s or less, showed good capacitance appearance rates and good ESR. [Explanation of symbols]

[0109] 1 wound body 1a Lead-out end face 1b Opposite end face 2 adhesive tapes 3 Lead terminal 31 Leader 32 Round bar section 33 Flat area 34 Welded section 41 Outer case 42 Sealing member 43 Insertion hole 5 Electrode foil

Claims

1. a connecting step of connecting a lead terminal, which includes a flat portion, a round bar portion, and a lead wire, to the anode foil and the cathode foil on which the dielectric coating is formed, at the flat portion; a winding step of winding the anode foil and the cathode foil so that they face each other, causing the round bar portion to protrude from one end surface of a wound body, and drawing out the lead wires to form the wound body; a winding step of winding a circumferential surface of the wound body with a hydrophobic adhesive tape; a solid electrolyte forming step of immersing the wound body secured by the adhesive tape in a conductive polymer solution in which a conductive polymer is dispersed or dissolved, thereby causing the conductive polymer to adhere to the inside of the wound body; Including, In the solid electrolyte forming step, the wound body is immersed in the conductive polymer liquid having a viscosity of 10 mPa·s or more and 60 mPa·s or less to a height equal to or greater than the height of one end surface of the wound body; A method for manufacturing a solid electrolytic capacitor, comprising:

2. the conductive polymer liquid contains water as a solvent; 2. The method for producing a solid electrolytic capacitor according to claim 1,

3. further comprising an electrolyte impregnation step of impregnating the wound body with an electrolyte; 2. The method for producing a solid electrolytic capacitor according to claim 1,

4. a wound body in which an anode foil and a cathode foil, each having a dielectric film formed thereon, are wound facing each other; a lead terminal having a flat portion, a round bar portion, and a lead wire connected to one another, the flat portion being connected to the anode foil and the cathode foil, the round bar portion protruding from one end surface of the wound body, and the lead wire being drawn out; a hydrophobic adhesive tape that fastens the circumferential surface of the wound body; a conductive polymer attached to at least the dielectric film; Equipped with the conductive polymer is formed using a conductive polymer liquid in which the conductive polymer is dispersed or dissolved and has a viscosity of 10 mPa·s or more and 60 mPa·s or less, and is attached to a height equal to or higher than the one end surface of the wound body; A solid electrolytic capacitor characterized by:

5. further comprising an electrolyte impregnated in the wound body; 5. The solid electrolytic capacitor according to claim 4, wherein

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