WO2016002176A1 - 電解コンデンサの製造方法 - Google Patents
電解コンデンサの製造方法 Download PDFInfo
- Publication number
- WO2016002176A1 WO2016002176A1 PCT/JP2015/003213 JP2015003213W WO2016002176A1 WO 2016002176 A1 WO2016002176 A1 WO 2016002176A1 JP 2015003213 W JP2015003213 W JP 2015003213W WO 2016002176 A1 WO2016002176 A1 WO 2016002176A1
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- WO
- WIPO (PCT)
- Prior art keywords
- solvent
- capacitor element
- conductive polymer
- treatment liquid
- electrolytic capacitor
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
- H01G9/0032—Processes of manufacture formation of the dielectric layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
- H01G9/0036—Formation of the solid electrolyte layer
Definitions
- the present invention relates to a method for manufacturing an electrolytic capacitor, and more particularly to a method for manufacturing an electrolytic capacitor excellent in the film repairability of a dielectric layer.
- capacitors used for them are also required to be small, have a large capacity, and have a low equivalent series resistance (ESR) in the high frequency range.
- ESR equivalent series resistance
- an electrolytic capacitor using a conductive polymer such as polypyrrole, polythiophene, polyfuran, or polyaniline as a cathode material is promising.
- a conductive polymer layer is provided as a cathode material on an anode foil (anode body) on which a dielectric layer is formed.
- Patent Document 1 an element including a separator is impregnated with a dispersion of a conductive polymer to form a conductive solid layer, and then impregnated with an electrolytic solution to include the conductive solid layer and the electrolytic solution.
- a method for manufacturing an electrolytic capacitor has been proposed.
- the dielectric layer is formed by the surface treatment of the anode foil, it inherently has many defects, and such defects tend to cause leakage current.
- the film repairability for repairing defects in the dielectric layer may be insufficient depending on the conditions for forming a conductive solid layer containing a conductive polymer.
- One aspect of the present invention provides a first step of preparing a capacitor element including an anode body having a dielectric layer; A second step of impregnating the capacitor element with a first treatment liquid containing at least a conductive polymer and a first solvent; After the second step, a third step of swelling the conductive polymer by impregnating the capacitor element with a second treatment liquid containing a swelling agent in a state where at least part of the first solvent remains. And an electrolytic capacitor manufacturing method.
- FIG. 1 is a schematic cross-sectional view of an electrolytic capacitor obtained by a manufacturing method according to an embodiment of the present invention.
- FIG. 2 is a schematic diagram in which a part of the capacitor element according to the electrolytic capacitor is developed.
- an electrolytic capacitor includes a capacitor element 10 including an anode body 21 on which a dielectric layer is formed and a conductive high layer that covers (or adheres to at least a part of) the surface of at least a part of the dielectric layer. Molecule (not shown).
- the capacitor element 10 is housed in the outer case in a state where at least a part of the surface of the dielectric layer is covered with the conductive polymer.
- the exterior case includes a bottomed case 11 that houses the capacitor element 10 therein, an insulating sealing member 12 that closes the opening of the bottomed case 11, and a seat plate 13 that covers the sealing member 12. The vicinity of the open end of the bottomed case 11 is drawn inward, and the open end is curled so as to be crimped to the sealing member 12.
- the capacitor element 10 as shown in FIG. 2 is called a wound body.
- the capacitor element 10 includes an anode body 21 connected to the lead tab 15A, a cathode body 22 connected to the lead tab 15B, and a separator 23.
- the anode body 21 and the cathode body 22 are wound through a separator 23.
- the outermost periphery of the capacitor element 10 is fixed by a winding tape 24.
- FIG. 2 shows a state where a part of the capacitor element 10 is unfolded before stopping the outermost periphery.
- the anode body 21 includes a metal foil roughened so that the surface has irregularities, and a dielectric layer is formed on the metal foil having irregularities.
- the conductive polymer is attached so as to cover at least a part of the surface of the dielectric layer formed on the anode body 21.
- the present invention is not limited to this, and the anode body 21 and the cathode body 22 It may be attached at any position between.
- the conductive polymer covers at least part of the surface of the dielectric layer formed on the anode body 21, and further, at least one part of the surface of the cathode body 22 and / or the surface of the separator 23. The part may be covered.
- a conductive polymer (specifically, a film containing a conductive polymer) covering at least a part of the surface of an anode body, a cathode body, a separator, or the like is used as a conductive polymer layer. May be called.
- the electrolytic capacitor may further contain an electrolytic solution.
- the electrolytic solution is housed in the outer case (specifically, the bottomed case 11) together with the capacitor element 10 in which at least a part of the surface of the dielectric layer is covered with the conductive polymer.
- the outer case specifically, the bottomed case 11
- the capacitor element 10 in which at least a part of the surface of the dielectric layer is covered with the conductive polymer.
- the surface of the metal foil is roughened.
- a plurality of irregularities are formed on the surface of the metal foil.
- the roughening is preferably performed by etching the metal foil.
- the etching treatment may be performed by, for example, a direct current electrolytic method or an alternating current electrolytic method.
- a dielectric layer is formed on the surface of the roughened metal foil.
- the formation method of a dielectric material layer is not specifically limited, It can form by performing a chemical conversion treatment of metal foil.
- the chemical conversion treatment may be performed, for example, by immersing the metal foil in a chemical conversion solution such as an ammonium adipate solution.
- a voltage may be applied in a state where the metal foil is immersed in the chemical conversion liquid as necessary.
- a roughening treatment and a chemical conversion treatment are performed on a metal foil formed of a large valve metal or the like.
- the anode body 21 is prepared by cutting the foil after processing into a desired size.
- (I-2) Step of Preparing Cathode Body 22 As with the anode body, a metal foil may be used for the cathode body 22 as well.
- the type of metal is not particularly limited, but it is preferable to use a valve action metal such as aluminum, tantalum, or niobium or an alloy containing the valve action metal. If necessary, the surface of the metal foil may be roughened.
- the surface of the cathode body 22 may be provided with a chemical conversion film, or a metal (different metal) different from the metal constituting the cathode body or a non-metal film may be provided.
- Examples of dissimilar metals and nonmetals include metals such as titanium and nonmetals such as carbon.
- separator 23 for example, a nonwoven fabric containing fibers of cellulose, polyethylene terephthalate, vinylon, polyamide (for example, an aromatic polyamide such as aliphatic polyamide or aramid) may be used.
- polyamide for example, an aromatic polyamide such as aliphatic polyamide or aramid
- the material of the lead tabs 15A and 15B is not particularly limited as long as it is a conductive material.
- the surface of the lead tabs 15A and 15B may be subjected to chemical conversion treatment.
- the part which contacts the sealing body 12 of lead tab 15A, 15B and the connection part with lead wire 14A, 14B may be covered with the resin material.
- the material of the lead wires 14A and 14B connected to each of the lead tabs 15A and 15B is not particularly limited, and a conductive material or the like may be used.
- the end of the outer surface of the one located in the outermost layer of the wound body (the cathode body 22 in FIG. 2) is provided with a winding tape 24. Then, it is fixed with the winding tape 24.
- the anode body 21 is prepared by cutting a large-sized metal foil, in order to provide a dielectric layer on the cut surface of the anode body 21, the capacitor element in a state such as a wound body is further formed. Processing may be performed.
- Step of impregnating the capacitor element (winding body) 10 with the first treatment liquid (second step) Next, the capacitor element 10 is impregnated with the first treatment liquid.
- the impregnation of the first treatment liquid into the capacitor element 10 is not particularly limited as long as the first treatment liquid can be applied to at least the anode body (particularly, at least the dielectric layer).
- the capacitor element is immersed in the first treatment liquid.
- the first treatment liquid may be injected into the capacitor element.
- the impregnation may be performed under atmospheric pressure, but may also be performed under reduced pressure, for example, in an atmosphere of 10 to 100 kPa, preferably 40 to 100 kPa. Impregnation may be performed under ultrasonic vibration as necessary.
- the impregnation time depends on the size of the capacitor element 10, but is, for example, 1 second to 5 hours, preferably 1 minute to 30 minutes. Through this step, the first treatment liquid is applied to the capacitor element 10.
- Examples of the conductive polymer include polypyrrole, polythiophene, polyfuran, polyaniline, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, and polythiophene vinylene. These may be used alone or in combination of two or more, or may be a copolymer of two or more monomers.
- polypyrrole, polythiophene, polyfuran, polyaniline and the like mean polymers having a basic skeleton of polypyrrole, polythiophene, polyfuran, polyaniline and the like, respectively. Accordingly, polypyrrole, polythiophene, polyfuran, polyaniline and the like can also include respective derivatives.
- polythiophene includes poly (3,4-ethylenedioxythiophene) and the like.
- the conductive polymer may contain a dopant.
- a polyanion can be used as the dopant.
- Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene sulfonic acid, poly Anions such as acrylic acid can be mentioned. Of these, polyanions derived from polystyrene sulfonic acid are preferred. These may be used alone or in combination of two or more. These may be a single monomer polymer or a copolymer of two or more monomers.
- the weight average molecular weight of the polyanion is not particularly limited, but is 1,000 to 1,000,000, for example.
- Such a conductive polymer containing a polyanion is easily dispersed homogeneously in a liquid solvent containing the first solvent, and easily adheres uniformly to the surface of the dielectric layer.
- the first treatment liquid only needs to contain at least a liquid solvent containing the conductive polymer and the first solvent.
- the first treatment liquid may be either a solution in which a conductive polymer is dissolved in a liquid solvent or a dispersion in which a conductive polymer is dispersed in a liquid solvent.
- the conductive polymer is dispersed in the liquid solvent in the form of particles.
- a conductive polymer containing a dopant is obtained by polymerizing a raw material of a conductive polymer (for example, a precursor of a monomer and / or oligomer of a conductive polymer) in a liquid solvent in the presence of a dopant.
- the liquid solvent of the first treatment liquid only needs to contain at least the first solvent, and may contain a solvent other than the first solvent.
- the liquid solvent contained in the first treatment liquid may contain a plurality of different first solvents.
- the first solvent may occupy 30% by mass or more, preferably 50% by mass or more, and more preferably 70% by mass or more of the liquid solvent of the first treatment liquid.
- the first solvent is not particularly limited, and may be water or a non-aqueous solvent.
- the non-aqueous solvent is a general term for liquids excluding water and liquids containing water, and includes organic solvents and ionic liquids.
- a 1st solvent is a polar solvent.
- the polar solvent may be a protic solvent or an aprotic solvent.
- protic solvents examples include methanol, ethanol, propanol, butanol, ethylene glycol (EG), propylene glycol (PG), polyethylene glycol (PEG), diethylene glycol monobutyl ether, glycerin, 1-propanol, butanol, polyglycerin and the like.
- examples include alcohols, formaldehyde and water.
- the aprotic solvent include amides such as N-methylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, esters such as methyl acetate, methyl ethyl ketone, and ⁇ -butyrolactone ( ⁇ BL).
- Ketones, ethers such as 1,4-dioxane
- sulfur-containing compounds such as dimethyl sulfoxide and sulfolane (SL)
- carbonate compounds such as propylene carbonate.
- the first solvent is preferably a protic solvent.
- the first solvent is preferably water.
- the handleability of the first treatment liquid and the dispersibility of the conductive polymer are improved.
- water has a low viscosity, it can be expected that the contact property between the conductive polymer and the swelling agent is improved in the third step, which is a subsequent step.
- the first solvent is water
- the water preferably occupies 50% by mass or more of the liquid solvent of the first treatment liquid, more preferably 70% by mass or more, and particularly preferably 90% by mass or more.
- the particles of the conductive polymer dispersed in the dispersion are the median diameter (hereinafter simply referred to as the median diameter by the dynamic light scattering method). Is preferably 0.01 to 0.5 ⁇ m.
- the particle diameter of the conductive polymer can be adjusted by polymerization conditions, dispersion conditions, and the like.
- the concentration of the conductive polymer (including dopant or polyanion) in the first treatment liquid is preferably 0.5 to 10% by mass.
- the first treatment liquid having such a concentration is suitable for adhering an appropriate amount of the conductive polymer, and is easy to be impregnated into the capacitor element 10 and is advantageous in improving productivity.
- the liquid solvent such as the first solvent can be removed as necessary. However, at least a part of the liquid solvent remains in the capacitor element (particularly, the anode body), and the third solvent is used. This is very important.
- the liquid solvent may be removed by evaporation under heating, or may be removed under reduced pressure as necessary.
- the remaining amount of the liquid solvent is preferably 5% by mass or more (for example, 5 to 100% by mass), and more preferably 20% by mass or more (for example, 20 to 100% by mass). Alternatively, it is more preferably 50% by mass or more (for example, 50 to 100% by mass).
- the remaining amount of the liquid solvent is within such a range, the swelling agent is easily mixed in the conductive polymer and the capacitor element in the third step. It becomes easy to adhere uniformly.
- the remaining amount of the liquid solvent is the mass of the liquid solvent contained in the capacitor element used in the third step with respect to the mass of the liquid solvent contained in the first treatment liquid impregnated in the capacitor element in the second step. It is a ratio (mass%).
- the third step it is important to swell the conductive polymer by impregnating the second treatment liquid with at least a part of the first solvent remaining in the capacitor element (particularly, the anode body).
- the capacitor element including the anode body in a state where the liquid solvent remains has extremely high permeability of the second processing liquid. Therefore, when a 2nd process liquid is provided to the capacitor
- a conductive polymer film prepared from a solution or dispersion containing a conductive polymer is immersed in a room temperature (eg, 20 to 30 ° C.) for a predetermined time (eg, 24 hours) and taken out.
- a film having a swelling rate of more than 1 after the film is defined as a swelling agent.
- the swelling rate of a film is the ratio of the thickness of the film after being immersed in the swelling agent with respect to the thickness (initial thickness) of the film before being immersed in the swelling agent.
- the 2nd process liquid has a swelling action as a whole. Therefore, it is preferable that the swelling ratio of the film when immersed in the second treatment liquid is larger than 1.
- the swelling rate is more preferably 1.1 or more, and further preferably 1.5 or more.
- the initial thickness of the film is not particularly limited, and may be, for example, 20 to 40 ⁇ m.
- the boiling point of the swelling agent is preferably higher than the boiling point of the first solvent.
- the difference between the boiling point of the swelling agent and the boiling point of the first solvent may be, for example, 20 ° C. or higher, preferably 50 ° C. or higher.
- the swelling agent for example, a liquid that is miscible with the liquid solvent contained in the first treatment liquid is preferably used.
- the liquid miscible with the liquid solvent refers to a liquid that can be mixed with the liquid solvent to be in a homogeneous state.
- the swelling agent may be either protic or aprotic.
- various compounds generally referred to as a protic solvent and an aprotic solvent can be used as long as it has a swelling action, and among them, a protic organic compound (also referred to as a protic organic solvent) and / or Alternatively, an aprotic organic compound (also referred to as an aprotic organic solvent) is preferable.
- the protic organic compound those having a protic group such as a hydroxyl group and / or a carboxyl group are preferable.
- the swelling agent examples include polyols (eg, aliphatic polyols), carboxylic acids (eg, C 1-5 carboxylic acids such as formic acid and acetic acid), chain sulfones (eg, dimethyl sulfoxide), and chain amides (N-methylacetamide). N, N-dimethylformamide, etc.).
- the aliphatic polyol examples include alkylene glycols such as ethylene glycol and propylene glycol, polyethylene glycols such as diethylene glycol and triethylene glycol, and glycerins such as glycerin and polyglycerin.
- the hydroxyl value of the swelling agent is, for example, preferably 100 mgKOH / g or more, and more preferably 300 mgKOH / g or more.
- the swelling agent tends to exist stably between the particles of the conductive polymer, and the dispersion stability is improved. Therefore, since the effect of swelling the conductive polymer is increased, the film repairability of the dielectric layer can be further enhanced.
- the mass of the swelling agent impregnated in the capacitor element is preferably 2 to 100 times, more preferably 3 to 80 times the mass of the conductive polymer impregnated in the capacitor element. preferable.
- the mass ratio is in such a range, the effect of swelling the conductive polymer can be easily obtained, so that the effect of repairing the dielectric layer is further enhanced.
- the second treatment liquid may further contain a solvent and / or an additive as necessary. If the amount of the swelling agent in the second treatment liquid is too small, the swelling action by the swelling agent may be difficult to obtain. It is preferable that the second treatment liquid has a swelling action as a whole.
- the ratio of the swelling agent in the second treatment liquid may be, for example, 20 to 100% by mass, but is preferably 50 to 100% by mass, and more preferably 70 to 100% by mass.
- the solvent added to the second treatment liquid other than the swelling agent for example, among non-aqueous solvents exemplified as the first solvent of the first treatment liquid, protic solvents other than alkylene glycols such as EG and PG and polyethylene glycol , And aprotic solvents.
- the solvent include monoalkyl ethers of alkylene glycol (or polyalkylene glycol) such as diethylene glycol monobutyl ether, lactones such as ⁇ -butyrolactone, cyclic ketones such as cyclohexanone and isophorone, carbonates such as diethyl carbonate, ethylene carbonate, and vinylene carbonate.
- Step of removing the solvent component After the third step, the solvent component remaining in the capacitor element can be removed in the fourth step. In the fourth step, at least part of the solvent component may be removed, and all of the solvent component may be removed. By removing the solvent component in the fourth step, the conductive polymer can be more uniformly attached to the surface of the dielectric layer.
- the solvent component here refers to the liquid solvent contained in the first treatment liquid, the swelling agent contained in the second treatment liquid, and other solvents. Among these, it is preferable to remove at least part of the first solvent in the fourth step.
- the solvent component can be removed by evaporation under heating, may be removed under atmospheric pressure, or may be removed under reduced pressure as necessary.
- the temperature at which the solvent component is removed may be 40 to 250 ° C., for example.
- the temperature at which the solvent component is removed may be equal to or higher than the boiling point of the first solvent, and may be lower than the boiling point of the swelling agent.
- the removal of the solvent component may be performed, for example, at a plurality of stages having different temperatures (for example, two stages or three stages or more) or may be performed while raising the temperature.
- the conductive polymer adheres between the anode body 21 and the cathode body 22 (particularly the surface of the dielectric layer), and the capacitor element 10 to which the conductive polymer adheres is manufactured.
- the conductive polymer attached to the surface of the dielectric layer functions as a practical cathode material.
- the conductive polymer is preferably attached so as to cover at least part of the surface of the dielectric layer. At this time, the conductive polymer may adhere not only to the surface of the dielectric layer but also to the surfaces of the cathode body 22 and / or the separator 23.
- a process selected from these processes may be repeated twice or more as a series of processes. For example, after the second step is repeated a plurality of times, another step may be performed, and the second step, the liquid solvent removing step, and the third step may be repeated a plurality of times as a series of steps. . From the viewpoint of easily increasing the coverage of the conductive polymer with respect to the dielectric layer, it is advantageous to repeat at least the first step a plurality of times.
- All the solvent components may be removed from the capacitor element 10 obtained in the third step or the fourth step. Further, the capacitor element 10 obtained in the third step or the fourth step may be in a state where the solvent component remains. When the solvent component remains, the function of repairing the dielectric layer can be further improved. Further, since the remaining solvent component exists between the conductive polymer particles, when the capacitor element is impregnated with the electrolytic solution in the fifth step, the electrolytic solution easily permeates between the conductive polymer particles. Therefore, the function of repairing the dielectric layer by the electrolytic solution can be easily obtained. By increasing the repair function of the dielectric layer, it is possible to effectively suppress a short circuit even when the guaranteed lifetime of the electrolytic capacitor has passed.
- Step of impregnating capacitor element (winding body) 10 with electrolyte Step of impregnating capacitor element (winding body) 10 with electrolyte
- the capacitor element 10 can be further impregnated with the electrolytic solution after the third step.
- the fifth step is not particularly limited as long as it is after the third step, and may be performed subsequent to the third step.
- another step for example, the fourth step
- Five steps may be performed.
- the fifth step is not always necessary, the function of repairing the dielectric layer can be further improved by impregnating with the electrolytic solution.
- a nonaqueous solvent may be used, or a solution containing a nonaqueous solvent and an ionic substance (solute) dissolved in the nonaqueous solvent may be used.
- an organic solvent or an ionic liquid may be used.
- the non-aqueous solvent those having a high boiling point are desirable, and as the non-aqueous solvent having a high boiling point, an ionic liquid and / or an organic solvent having a high boiling point can be used.
- the boiling point of the non-aqueous solvent is, for example, higher than 100 ° C., preferably 150 ° C. or higher, and more preferably 200 ° C. or higher.
- organic solvent As an organic solvent, the organic solvent illustrated about the 1st solvent of the 1st processing liquid, the polyol illustrated as a swelling agent, the solvent illustrated about the 2nd processing liquid, etc. are mentioned, for example.
- a non-aqueous solvent can be used individually by 1 type or in combination of 2 or more types.
- alkylene glycol polyethylene glycol, glycerin, lactone, cyclic sulfone, formaldehyde, ethers, amides, esters, and ketones are preferable.
- polyethylene glycol and / or glycerins are preferable.
- an anion and a cation salt are used, and an organic salt in which at least one of the anion and cation is an organic substance is preferable.
- Organic salts include trimethylamine maleate, triethylamine borodisalicylate, ethyldimethylamine phthalate, mono 1,2,3,4-tetramethylimidazolinium phthalate, mono 1,3-dimethyl-2-ethyl imidazole phthalate Examples include linium. Solutes may be used singly or in combination of two or more.
- the impregnation of the electrolytic solution into the capacitor element 10 is not particularly limited and can be performed by a known method.
- the capacitor element 10 may be immersed in the electrolytic solution, or the electrolytic solution may be poured into a container that contains the capacitor element 10.
- the impregnation of the electrolytic solution into the capacitor element may be performed under reduced pressure (for example, 10 to 100 kPa) as necessary.
- Step of sealing the capacitor element (winding body) 10 Next, the capacitor element 10 is sealed. Specifically, first, the capacitor element 10 is accommodated in the bottomed case 11 so that the lead wires 14 ⁇ / b> A and 14 ⁇ / b> B are positioned on the upper surface where the bottomed case 11 is opened.
- a metal such as aluminum, stainless steel, copper, iron, brass, or an alloy thereof can be used.
- the sealing member 12 formed so that the lead wires 14 ⁇ / b> A and 14 ⁇ / b> B penetrate is disposed above the capacitor element 10, and the capacitor element 10 is sealed in the bottomed case 11.
- the sealing member 12 may be an insulating material.
- an elastic body is preferable, among which silicone rubber, fluorine rubber, ethylene propylene rubber, hyperon rubber, butyl rubber, isoprene rubber, and the like having high heat resistance are preferable.
- the wound type electrolytic capacitor has been described.
- the scope of the present invention is not limited to the above, and other electrolytic capacitors, for example, a chip type electrolytic capacitor using a metal sintered body as an anode body.
- the present invention can also be applied to a capacitor or a multilayer electrolytic capacitor using a metal plate as an anode body.
- Example 1 A wound type electrolytic capacitor (diameter: 6.3 mm, length: 5.8 mm) having a rated voltage of 35 V and a rated capacitance of 47 ⁇ F as shown in FIG. 1 was prepared and evaluated by the following procedure.
- Etching was performed on an aluminum foil having a thickness of 100 ⁇ m to roughen the surface of the aluminum foil.
- a dielectric layer was formed on the surface of the aluminum foil by a chemical conversion treatment using an ammonium adipate aqueous solution to prepare an anode body having the dielectric layer.
- An aluminum foil having a thickness of 50 ⁇ m was etched to roughen the surface of the aluminum foil to prepare a cathode body.
- An anode lead tab and a cathode lead tab were connected to the anode body and the cathode body, and the anode body and the cathode body were wound through a separator while winding the lead tab to obtain a capacitor element.
- An anode lead wire and a cathode lead wire were connected to the ends of each lead tab protruding from the capacitor element. Then, chemical conversion treatment was performed again on the manufactured capacitor element, and a dielectric layer was formed on the cut end portion of the anode body. Next, the end of the outer surface of the capacitor element was fixed with a winding tape. (Impregnation of the first treatment liquid) A mixed solution in which 3,4-ethylenedioxythiophene and polystyrene sulfonic acid as a dopant were dissolved in ion-exchanged water (first solvent) was prepared.
- the obtained first treatment liquid was impregnated into the capacitor element for 5 minutes.
- the capacitor element was impregnated with the second treatment liquid.
- Polyethylene glycol weight average molecular weight Mw; 300
- the mass of the swelling agent impregnated in the capacitor element was 5 times the mass of the conductive polymer impregnated in the capacitor element.
- the solvent component was removed by heating the capacitor element at 150 ° C. for 20 minutes.
- Capacitance Capacitance ( ⁇ F) was measured as an initial characteristic of the electrolytic capacitor. Specifically, the initial capacitance ( ⁇ F) at a frequency of 120 Hz was measured for the electrolytic capacitor using an LCR meter for 4-terminal measurement.
- ⁇ Comparative Example 2 Example 1 except that after the capacitor element was impregnated with the first treatment liquid, the solvent component was completely removed by heating at 150 ° C. for 30 minutes (residual amount of the solvent component in the capacitor element: 0% by mass). In the same manner as above, an electrolytic capacitor was produced and performance evaluation was performed.
- ⁇ Comparative Example 3 An electrolytic capacitor was produced and evaluated for performance in the same manner as in Example 1 except that ⁇ -butyrolactone was used instead of polyethylene glycol as the second treatment liquid.
- Example 2 An electrolytic capacitor was produced and evaluated for performance in the same manner as in Example 1 except that diethylene glycol was used instead of polyethylene glycol as the second treatment liquid.
- Example 3 An electrolytic capacitor was produced and evaluated for performance in the same manner as in Example 1 except that ethylene glycol was used instead of polyethylene glycol as the second treatment liquid.
- Example 4 An electrolytic capacitor was produced and evaluated for performance in the same manner as in Example 1 except that dimethyl sulfoxide was used instead of polyethylene glycol as the second treatment liquid.
- Example 5 An electrolytic capacitor was produced and evaluated for performance in the same manner as in Example 1 except that N, N-dimethylformamide was used instead of polyethylene glycol as the second treatment liquid.
- Example 6 The same as Example 1 except that a mixed solution containing polyethylene glycol (swelling agent) and ⁇ -butyrolactone (solvent) at a mass ratio of 75:25 was used instead of polyethylene glycol as the second treatment liquid.
- Example 7 Similar to Example 1 except that a mixed liquid containing polyethylene glycol (swelling agent) and ⁇ -butyrolactone (solvent) in a mass ratio of 50:50 was used instead of polyethylene glycol as the second treatment liquid. Thus, an electrolytic capacitor was produced and performance evaluation was performed. The mass of the swelling agent impregnated in the capacitor element was 2.5 times the mass of the conductive polymer impregnated in the capacitor element.
- Example 8 The same procedure as in Example 1 except that a mixed solution containing polyethylene glycol (swelling agent) and ⁇ -butyrolactone (solvent) at a mass ratio of 25:75 was used instead of polyethylene glycol as the second treatment solution. Thus, an electrolytic capacitor was produced and performance evaluation was performed. The mass of the swelling agent impregnated in the capacitor element was 1.25 times the mass of the conductive polymer impregnated in the capacitor element.
- Table 1 shows the results of Examples and Comparative Examples. Table 1 also shows the constituent components of the second treatment liquid.
- polyethylene glycol was a value larger than 1 when a film was prepared from a dispersion containing polyethylene dioxythiophene doped with polystyrene sulfonic acid used in this example and the swelling ratio was measured.
- the swelling ratio of each of diethylene glycol, ethylene glycol, diethyl sulfoxide, and N, N-dimethylformamide was greater than 1.
- the swelling ratio of ⁇ -butyrolactone was a value of 1 or less.
- Example 1 As shown in Table 1, in Example 1, the leakage current was small and a large capacitance was obtained. On the other hand, when the capacitor element was not impregnated with the second treatment liquid, the leakage current increased and the capacitance decreased (Comparative Example 1). Further, when the capacitor element is impregnated with the second treatment liquid, if the first solvent does not remain, even if the second treatment liquid is impregnated, the leakage current is reduced to the same level as in the first embodiment. And the electrostatic capacity was almost the same as that of Comparative Example 1 (Comparative Example 2). In Comparative Example 3 using ⁇ -butyrolactone instead of the swelling agent, although the capacitance was improved, the effect of suppressing the leakage current was insufficient.
- the present invention can be used for an electrolytic capacitor using a conductive polymer as a cathode material.
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Abstract
Description
前記コンデンサ素子に、導電性高分子と第1溶媒とを少なくとも含む第1処理液を含浸させる第2工程と、
前記第2工程の後、前記コンデンサ素子に前記第1溶媒の少なくとも一部が残存した状態で膨潤化剤を含む第2処理液を含浸させて、前記導電性高分子を膨潤化する第3工程と、を含む、電解コンデンサの製造方法に関する。
≪電解コンデンサ≫
図1は、本発明の一実施形態に係る製造方法により得られる電解コンデンサの断面模式図である。図2は、同電解コンデンサに係るコンデンサ素子の一部を展開した概略図である。
≪電解コンデンサの製造方法≫
以下に、本発明の実施形態に係る電解コンデンサの製造方法の一例について、工程ごとに説明する。
(i)コンデンサ素子10を準備する工程(第1工程)
(i-1)誘電体層を有する陽極体21を準備する工程
まず、陽極体21の原料である金属箔を準備する。金属の種類は特に限定されないが、誘電体層の形成が容易である点から、アルミニウム、タンタル、ニオブなどの弁作用金属、または弁作用金属を含む合金を用いることが好ましい。
(i-2)陰極体22を準備する工程
陰極体22にも、陽極体と同様、金属箔を用いてもよい。金属の種類は特に限定されないが、アルミニウム、タンタル、ニオブなどの弁作用金属または弁作用金属を含む合金を用いることが好ましい。必要に応じて、金属箔の表面を粗面化してもよい。
(i-3)コンデンサ素子(巻回体)10を作製する工程
次に、陽極体21および陰極体22を用いてコンデンサ素子10を作製する。コンデンサ素子は、陽極体21と陰極体22とを、セパレータ23を介して重ね合わせることにより得られる。陽極体21と陰極体22とを、セパレータを介して巻回することにより、図2に示されるような巻回体を形成してもよい。このとき、リードタブ15A,15Bを巻き込みながら巻回することにより、図2に示すように、リードタブ15A,15Bを巻回体から植立させてもよい。
(ii)コンデンサ素子(巻回体)10に第1処理液を含浸させる工程(第2工程)
次に、コンデンサ素子10に、第1処理液を含浸させる。
(iii)導電性高分子を膨潤化する工程(第3工程)
第3工程では、第1処理液が付与されたコンデンサ素子に、膨潤化剤を含む第2処理液を含浸させて、導電性高分子を膨潤化する。
(iv)溶媒成分を除去する工程(第4工程)
第3工程の後、コンデンサ素子に残存している溶媒成分を第4工程で除去することができる。第4工程では、溶媒成分の少なくとも一部を除去すればよく、溶媒成分の全てを除去してもよい。第4工程で溶媒成分を除去することにより、誘電体層の表面に導電性高分子をより均一に付着させることができる。
(v)コンデンサ素子(巻回体)10に電解液を含浸させる工程(第5工程)
第5工程では第3工程の後に、さらにコンデンサ素子10に電解液を含浸させることができる。第5工程は、第3工程の後であれば特に制限されず、第3工程に引き続いて行ってもよく、第3工程の後に他の工程(例えば、第4工程)を行い、その後に第5工程を行ってもよい。第5工程は、必ずしも必要ではないが、電解液を含浸させることで、誘電体層の修復機能をさらに向上させることができる。
(vi)コンデンサ素子(巻回体)10を封止する工程
次に、コンデンサ素子10を封止する。具体的には、まず、リード線14A,14Bが有底ケース11の開口する上面に位置するように、コンデンサ素子10を有底ケース11に収納する。有底ケース11の材料としては、アルミニウム、ステンレス鋼、銅、鉄、真鍮などの金属あるいはこれらの合金を用いることができる。
《実施例1》
下記の手順で、図1に示すような、定格電圧35V、定格静電容量47μFの巻回型の電解コンデンサ(直径6.3mm、長さ5.8mm)を作製し、評価を行った。
(1)電解コンデンサの製造
(誘電体層を有する陽極体の準備)
厚さ100μmのアルミニウム箔にエッチング処理を行い、アルミニウム箔の表面を粗面化した。その後、アルミニウム箔の表面に、アジピン酸アンモニウム水溶液を用いる化成処理により、誘電体層を形成し、誘電体層を有する陽極体を準備した。
(陰極体の準備)
厚さ50μmのアルミニウム箔にエッチング処理を行い、アルミニウム箔の表面を粗面化し、陰極体を準備した。
(コンデンサ素子(巻回体)の作製)
陽極体および陰極体に陽極リードタブおよび陰極リードタブを接続し、陽極体と陰極体とを、リードタブを巻き込みながら、セパレータを介して巻回し、コンデンサ素子を得た。コンデンサ素子から突出する各リードタブの端部には、陽極リード線および陰極リード線をそれぞれ接続した。そして、作製されたコンデンサ素子に対して、再度化成処理を行い、陽極体の切断された端部に誘電体層を形成した。次に、コンデンサ素子の外側表面の端部を巻止めテープで固定した。
(第1処理液の含浸)
3,4-エチレンジオキシチオフェンと、ドーパントとしてのポリスチレンスルホン酸とを、イオン交換水(第1溶媒)に溶かした混合溶液を調製した。得られた混合溶液を撹拌しながら、イオン交換水に溶解させた硫酸第二鉄および過硫酸ナトリウム(酸化剤)を添加し、重合反応を行った。反応後、得られた反応液を透析して、未反応モノマーおよび過剰な酸化剤を除去し、約5質量%のポリスチレンスルホン酸がドープされたポリ3,4-エチレンジオキシチオフェン(PEDOT)を含む分散液(第1処理液)を得た。
(第2処理液の含浸)
次いで、コンデンサ素子に、第2処理液を含浸させた。第2処理液に含まれる膨潤化剤として、ポリエチレングリコール(重量平均分子量Mw;300)を用いた。コンデンサ素子に含浸させた膨潤化剤の質量は、コンデンサ素子に含浸させた導電性高分子の質量の5倍であった。
(電解液の含浸)
次いで、コンデンサ素子に、減圧下で電解液を含浸させた。電解液としては、PEG:γBL:SL:フタル酸モノ(エチルジメチルアミン)(溶質)=25:25:25:25(質量比)で混合した溶液を用いた。
(コンデンサ素子の封止)
電解液を含浸させたコンデンサ素子を、図1に示すような外装ケースに収容し、封止して、電解コンデンサを作製した。同様にして、合計300個の電解コンデンサを作製した。
(2)性能評価
(a)静電容量
電解コンデンサの初期特性として、静電容量(μF)を測定した。具体的には、電解コンデンサについて4端子測定用のLCRメータを用いて、周波数120Hzにおける初期静電容量(μF)を測定した。
(b)漏れ電流
電解コンデンサに1kΩの抵抗を直列につなぎ、直流電源にて25Vの定格電圧を1分間印加した後の漏れ電流(μA)を測定した。漏れ電流の測定は、ランダムに選択した120個の電解コンデンサについて行った。
《比較例1》
コンデンサ素子に第1処理液を含浸させた後、第2処理液の含浸を行わず、150℃で30分間加熱することにより溶媒成分を除去したこと以外は、実施例1と同様にして、電解コンデンサを作製し、性能評価を行った。
《比較例2》
コンデンサ素子に第1処理液を含浸させた後、150℃で30分間加熱することにより溶媒成分を完全に除去した(コンデンサ素子の溶媒成分の残存量:0質量%)こと以外は、実施例1と同様にして、電解コンデンサを作製し、性能評価を行った。
《比較例3》
第2処理液であるポリエチレングリコールに代えて、γ-ブチロラクトンを用いたこと以外は、実施例1と同様にして、電解コンデンサを作製し、性能評価を行った。
《実施例2》
第2処理液であるポリエチレングリコールに代えて、ジエチレングリコールを用いたこと以外は、実施例1と同様にして、電解コンデンサを作製し、性能評価を行った。
《実施例3》
第2処理液であるポリエチレングリコールに代えて、エチレングリコールを用いたこと以外は、実施例1と同様にして、電解コンデンサを作製し、性能評価を行った。
《実施例4》
第2処理液であるポリエチレングリコールに代えて、ジメチルスルホキシドを用いたこと以外は、実施例1と同様にして、電解コンデンサを作製し、性能評価を行った。
《実施例5》
第2処理液であるポリエチレングリコールに代えて、N,N-ジメチルホルムアミドを用いたこと以外は、実施例1と同様にして、電解コンデンサを作製し、性能評価を行った。
《実施例6》
第2処理液であるポリエチレングリコールに代えて、ポリエチレングリコール(膨潤化剤)とγ-ブチロラクトン(溶媒)とを75:25の質量比で含む混合液を用いたこと以外は、実施例1と同様にして、電解コンデンサを作製し、性能評価を行った。コンデンサ素子に含浸させた膨潤化剤の質量は、コンデンサ素子に含浸させた導電性高分子の質量の3.75倍であった。
《実施例7》
第2処理液であるポリエチレングリコールに代えて、ポリエチレングリコール(膨潤化剤)とγ-ブチロラクトン(溶媒)とを50:50の質量比で含む混合液を用いたこと以外は、実施例1と同様にして、電解コンデンサを作製し、性能評価を行った。コンデンサ素子に含浸させた膨潤化剤の質量は、コンデンサ素子に含浸させた導電性高分子の質量の2.5倍であった。
《実施例8》
第2処理液であるポリエチレングリコールに代えて、ポリエチレングリコール(膨潤化剤)とγ-ブチロラクトン(溶媒)とを25:75の質量比で含む混合液を用いたこと以外は、実施例1と同様にして、電解コンデンサを作製し、性能評価を行った。コンデンサ素子に含浸させた膨潤化剤の質量は、コンデンサ素子に含浸させた導電性高分子の質量の1.25倍であった。
Claims (8)
- 誘電体層を有する陽極体を備えるコンデンサ素子を準備する第1工程と、
前記コンデンサ素子に、導電性高分子と第1溶媒とを少なくとも含む第1処理液を含浸させる第2工程と、
前記第2工程の後、前記コンデンサ素子に前記第1溶媒の少なくとも一部が残存した状態で膨潤化剤を含む第2処理液を含浸させて、前記導電性高分子を膨潤化する第3工程と、を含む、電解コンデンサの製造方法。 - 前記膨潤化剤の沸点は、前記第1溶媒の沸点よりも高い、請求項1に記載の電解コンデンサの製造方法。
- 前記膨潤化剤は、ポリオール、カルボン酸、鎖状スルホン、および鎖状アミドからなる群より選択される少なくとも一種である、請求項1または2に記載の電解コンデンサの製造方法。
- 前記膨潤化剤は、脂肪族ポリオールである、請求項1~3のいずれか1項に記載の電解コンデンサの製造方法。
- 前記コンデンサ素子に含浸させた前記膨潤化剤の質量は、前記コンデンサ素子に含浸させた前記導電性高分子の質量の2~100倍である、請求項1~4のいずれか1項に記載の電解コンデンサの製造方法。
- 前記第3工程の後、さらに、前記第1溶媒の少なくとも一部を除去する第4工程を含む、請求項1~5のいずれか1項に記載の電解コンデンサの製造方法。
- 前記第1溶媒は水であり、
前記第3工程において、前記コンデンサ素子に、少なくとも水が残存した状態で、前記第2処理液を含浸させて前記導電性高分子を膨潤化する、請求項1~6のいずれか1項に記載の電解コンデンサの製造方法。 - 前記第3工程の後に、電解液を前記コンデンサ素子に含浸させる第5工程を含む、請求項1~7のいずれか1項に記載の電解コンデンサの製造方法。
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