WO2017208723A1 - Condensateur électrolytique - Google Patents

Condensateur électrolytique Download PDF

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Publication number
WO2017208723A1
WO2017208723A1 PCT/JP2017/017155 JP2017017155W WO2017208723A1 WO 2017208723 A1 WO2017208723 A1 WO 2017208723A1 JP 2017017155 W JP2017017155 W JP 2017017155W WO 2017208723 A1 WO2017208723 A1 WO 2017208723A1
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Prior art keywords
electrolytic capacitor
hydrogen
film
hydrogen gas
alloy
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PCT/JP2017/017155
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English (en)
Japanese (ja)
Inventor
知洋 中村
福岡　孝博
圭子 藤原
原田　憲章
恭子 石井
俊輔 正木
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日東電工株式会社
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Priority claimed from JP2017078155A external-priority patent/JP7020792B2/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2017208723A1 publication Critical patent/WO2017208723A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • H01G9/08—Housing; Encapsulation
    • H01G9/12—Vents or other means allowing expansion

Definitions

  • the present invention relates to an electrolytic capacitor provided with a hydrogen discharge film.
  • electrolytic capacitors such as aluminum electrolytic capacitors have been used for applications such as inverters for wind power generation and solar power generation, and large power supplies such as storage batteries.
  • the anode of an aluminum electrolytic capacitor has an aluminum oxide film generated electrochemically on the surface of an aluminum electrode.
  • an aluminum electrolytic capacitor uses an electrolytic solution excellent in film repairability, and an aluminum oxide film is quickly formed by the reaction between the electrolytic solution and aluminum of the anode, and the defective portion is repaired.
  • oxidation occurs on the anode side and reduction occurs on the cathode side, generating hydrogen gas. If a large number of defective portions occur in the aluminum oxide film, a large amount of hydrogen gas is generated due to the film repairing action, and the outer case may expand or rupture due to an increase in the internal pressure of the aluminum electrolytic capacitor.
  • a general electrolytic capacitor is provided with a safety valve with a special membrane.
  • the safety valve has a function to prevent the capacitor itself from bursting by self-destructing and reducing the internal pressure when the internal pressure of the capacitor suddenly increases. is there.
  • the following has been proposed as a special membrane that is a component of such a safety valve.
  • Patent Document 1 proposes a pressure adjusting film including a foil strip made of an alloy of paradium silver (Pd—Ag) containing 20 wt% (19.8 mol%) Ag in paradium.
  • Patent Document 1 is easily embrittled in an environment of about 50 to 60 ° C. or less, and has a problem that the function as a pressure adjusting film cannot be maintained for a long period of time.
  • Patent Document 2 proposes a hydrogen discharge film containing a Pd—Ag alloy, wherein the content of Ag in the Pd—Ag alloy is 20 mol% or more.
  • Patent Document 3 proposes a hydrogen discharge film containing a Pd—Cu alloy and having a Cu content of 30 mol% or more in the Pd—Cu alloy.
  • the thickness of the oxide film is increased in order to suppress the occurrence of a defective portion in the oxide film.
  • increasing the film thickness of the oxide film has a demerit that much energy and manufacturing time are required.
  • increasing the thickness of the oxide film reduces the capacitance of the capacitor, so it is necessary to increase the surface area of the oxide film to compensate for the decrease in capacitance, making it difficult to reduce the size of the electrolytic capacitor. was there.
  • An object of the present invention is to provide an electrolytic capacitor capable of performing
  • the present invention is an electrolytic capacitor comprising a hydrogen discharge membrane,
  • the hydrogen discharge membrane includes a hydrogen gas permeable layer that selectively permeates 99% by mole or more of hydrogen gas when contacting a mixed gas containing equimolar amounts of hydrogen gas and nitrogen gas,
  • the present invention relates to an electrolytic capacitor characterized in that the ratio (average thickness / rated voltage) between the average thickness of the oxide film on the anode and the rated voltage of the capacitor is 1.2 to 2.9 (nm / V).
  • the electrolytic capacitor of the present invention has a ratio (average thickness / rated voltage) of the average thickness of the oxide film of the anode to the rated voltage of the capacitor of 1.2 to 2.9 (nm / V), and the conventional electrolytic capacitor The value of the ratio is smaller than that of (that is, the average thickness of the oxide film is thinner than that of a conventional electrolytic capacitor).
  • the electrolytic capacitor of the present invention includes a hydrogen discharge membrane including a hydrogen gas permeable layer that selectively permeates hydrogen gas by 99 mol% or more when contacting a mixed gas containing equimolar amounts of hydrogen gas and nitrogen gas. Therefore, even if a large amount of hydrogen gas is generated inside the electrolytic capacitor, only the hydrogen gas can be quickly discharged to the outside, and the outer case can be effectively prevented from expanding or bursting.
  • the ratio between the average thickness of the oxide film on the anode and the rated voltage of the capacitor is less than 1.2 (nm / V)
  • a large amount of hydrogen gas exceeding the hydrogen discharge capacity of the hydrogen discharge film can be quickly removed from the electrolytic capacitor.
  • it exceeds 2.9 (nm / V) it will be difficult to increase the capacitance of the electrolytic capacitor, and it will be difficult to reduce the size of the electrolytic capacitor.
  • the hydrogen gas permeable layer is preferably a metal layer, and more preferably a Pd alloy layer.
  • the Pd alloy which is a material for forming the Pd alloy layer, preferably contains 20 to 65 mol% of a Group 11 element from the viewpoint of excellent hydrogen permeability, oxidation resistance, and embrittlement resistance during hydrogen storage.
  • the Group 11 element is preferably at least one selected from the group consisting of Au, Ag, and Cu, and Au is particularly preferable from the viewpoint of excellent chemical resistance.
  • a Pd alloy layer containing a Pd-Group 11 element alloy dissociates hydrogen molecules into hydrogen atoms on the film surface, so that the hydrogen atoms are dissolved in the film, and the dissolved hydrogen atoms are diffused from the high pressure side to the low pressure side. In addition, it has a function of converting hydrogen atoms into hydrogen molecules again and discharging them on the low pressure side film surface.
  • the content of the Group 11 element is less than 20 mol%, the strength of the Pd alloy tends to be insufficient, or the function tends to be hardly exhibited.
  • the content exceeds 65 mol% the hydrogen permeation rate decreases. Tend to.
  • the metal layer preferably has a support on one side or both sides.
  • the support is provided to prevent the metal layer from falling into the electrolytic capacitor when the metal layer falls off the safety valve or the hydrogen discharge valve.
  • the metal layer has a function as a safety valve that self-destructs when the internal pressure of the electrolytic capacitor becomes a predetermined value or more
  • the metal layer is a thin film, the mechanical strength of the metal layer is low, There is a risk of self-destruction before the internal pressure of the electrolytic capacitor reaches a predetermined value, and the function as a safety valve cannot be performed. Therefore, when a metal layer is a thin film, it is preferable to laminate
  • Examples of the electrolytic capacitor include an aluminum electrolytic capacitor, a tantalum electrolytic capacitor, and a niobium electrolytic capacitor.
  • the average thickness of the oxide film is thinner than that of the conventional electrolytic capacitor. Therefore, the electrolytic capacitor of the present invention has an advantage that the capacitance is large while being the same size as the conventional electrolytic capacitor. In addition, the electrolytic capacitor of the present invention has an advantage that it can be downsized or have a high withstand voltage while having the same capacitance as a conventional electrolytic capacitor. In addition, the electrolytic capacitor of the present invention has an average oxide film thickness that is smaller than that of a conventional electrolytic capacitor, so that it can be manufactured with less energy and manufacturing time than the conventional electrolytic capacitor, and is excellent in terms of cost.
  • the electrolytic capacitor of the present invention is provided with a hydrogen discharge membrane that can hardly discharge hydrogen even when used for a long period of time and can discharge hydrogen stably.
  • the hydrogen discharge film can quickly discharge only the hydrogen gas generated inside the electrolytic capacitor to the outside, and can prevent impurities from entering the electrolytic capacitor from the outside.
  • the hydrogen discharge membrane may have a function of preventing destruction of the electrolytic capacitor itself by self-destructing and lowering the internal pressure when the internal pressure of the electrolytic capacitor suddenly increases.
  • the electrolytic capacitor of the present invention includes a hydrogen discharge membrane, and the hydrogen discharge membrane selectively permeates hydrogen gas by 99 mol% or more when contacting a mixed gas containing equimolar amounts of hydrogen gas and nitrogen gas.
  • a hydrogen gas permeable layer A hydrogen gas permeable layer.
  • the electrolytic capacitor of the present invention is characterized in that the ratio (average thickness / rated voltage) of the average thickness of the oxide film on the anode to the rated voltage of the capacitor is 1.2 to 2.9 (nm / V).
  • the electrolytic capacitor examples include an aluminum electrolytic capacitor, a tantalum electrolytic capacitor, and a niobium electrolytic capacitor, and an aluminum electrolytic capacitor is particularly preferable.
  • Conventional components other than the hydrogen discharge membrane and the anode can be used without particular limitation.
  • the electrolytic capacitor of the present invention can be manufactured by a conventional method except that the following hydrogen discharge membrane and anode are used. Hereinafter, the hydrogen discharge film and the anode will be described in detail.
  • the hydrogen discharge membrane includes a hydrogen gas permeable layer that selectively permeates hydrogen gas by 99 mol% or more when contacting a mixed gas containing equimolar amounts of hydrogen gas and nitrogen gas.
  • a hydrogen gas permeable layer that selectively transmits 99.9 mol% or more of hydrogen gas.
  • the hydrogen discharge membrane has a hydrogen permeation amount of 10 ml / day or more (4.03 ⁇ 10 ⁇ 4 mol / day or more: calculated according to SATP (temperature) when the square root of pressure is 76.81 Pa 1/2 (0.059 bar).
  • the volume of 1 mol ideal gas at 25 ° C. and 1 bar pressure is preferably 24.8 L)).
  • the hydrogen discharge membrane preferably has a hydrogen permeability coefficient at 50 ° C. of 1 ⁇ 10 ⁇ 12 (mol ⁇ m ⁇ 1 ⁇ sec ⁇ 1 ⁇ Pa ⁇ 1/2 ) or more, more preferably 1 ⁇ 10 10.
  • Examples of the layer having the characteristics include a metal layer such as a Pd alloy layer.
  • the other metal forming the Pd alloy that is the material of the Pd alloy layer is not particularly limited.
  • Nb, V, Ta, Ni, Fe, Al, Cu, Ru, Re, Rh, Au, Pt, Ag examples thereof include Cr, Co, Sn, Zr, Y, Ce, Ti, Ir, and Mo.
  • a Group 11 element more preferably at least one selected from the group consisting of Au, Ag, and Cu.
  • a Pd—Au alloy is preferable because it is excellent in corrosion resistance against gas components generated from the electrolyte solution or constituent members inside the electrolytic capacitor.
  • the Pd alloy preferably contains a Group 11 element in an amount of 20 to 65 mol%, more preferably 30 to 65 mol%, and still more preferably 30 to 60 mol%. Further, a Pd-Ag alloy having an Ag content of 20 mol% or more, a Pd-Cu alloy having a Cu content of 30 mol% or more, or a Pd alloy layer containing a Pd-Au alloy having an Au content of 20 mol% or more is provided. Even in a low temperature range of about 50 to 60 ° C. or less, it is preferable because it is difficult to be embrittled by hydrogen.
  • the Pd alloy may contain a group IB and / or group IIIA metal as long as the effects of the present invention are not impaired.
  • the Pd alloy is not limited to a two-component alloy containing Pd, but may be, for example, a three-component alloy of Pd—Au—Ag or a three-component alloy of Pd—Au—Cu. Further, a Pd—Au—Ag—Cu four-component alloy may be used.
  • the total content of Au and other metals in the Pd alloy is preferably 55 mol% or less, more preferably 50 mol% or less. Yes, more preferably 45 mol% or less, particularly preferably 40 mol% or less.
  • the Pd alloy layer can be manufactured, for example, by a rolling method, a sputtering method, a vacuum deposition method, an ion plating method, a plating method, or the like.
  • a rolling method is used. It is preferable to use a sputtering method when manufacturing a thin Pd alloy layer.
  • the rolling method may be hot rolling or any method of cold rolling.
  • the rolling method is a method of processing a film by rotating a pair or a plurality of pairs of rollers (rollers) and passing a metal as a raw material between the rolls while applying pressure.
  • the film thickness of the Pd alloy layer obtained by the rolling method is preferably 5 to 50 ⁇ m, more preferably 10 to 30 ⁇ m.
  • the film thickness is less than 5 ⁇ m, pinholes or cracks are likely to occur during production, or deformation occurs when hydrogen is occluded.
  • the film thickness exceeds 50 ⁇ m, it takes time to allow hydrogen to pass therethrough, so that the hydrogen permeability is lowered or the cost is inferior.
  • the sputtering method is not particularly limited, and can be performed using a sputtering apparatus such as a parallel plate type, a single wafer type, a passing type, DC sputtering, and RF sputtering.
  • a sputtering apparatus such as a parallel plate type, a single wafer type, a passing type, DC sputtering, and RF sputtering.
  • the inside of the sputtering apparatus is evacuated, an Ar gas pressure is adjusted to a predetermined value, a predetermined sputtering current is supplied to the metal target, and Pd is formed on the substrate.
  • An alloy film is formed. Thereafter, the Pd alloy film is peeled from the substrate to obtain a Pd alloy layer.
  • a target a single target or a some target can be used according to the Pd alloy layer to manufacture.
  • Examples of the substrate include glass plates, ceramic plates, silicon wafers, metal plates such as aluminum and stainless steel.
  • the film thickness of the Pd alloy layer obtained by sputtering is preferably 0.01 to 5 ⁇ m, more preferably 0.05 to 2 ⁇ m.
  • the film thickness is less than 0.01 ⁇ m, not only pinholes may be formed, but it is difficult to obtain the required mechanical strength. Moreover, it is easy to break when peeling from the substrate, and handling after peeling becomes difficult.
  • the film thickness exceeds 5 ⁇ m, it takes time to produce the Pd alloy layer, which is not preferable because of inferior cost.
  • the film area of the Pd alloy layer can be appropriately adjusted in consideration of the hydrogen permeation amount and the film thickness, but is about 0.01 to 100 mm 2 when used as a component of a safety valve.
  • the film area is the area of the portion where hydrogen is actually discharged in the Pd alloy layer, and does not include the portion where a ring-shaped adhesive described later is applied.
  • the metal layer preferably has a coating layer on one side or both sides.
  • a coating layer on one or both sides of the metal layer, pinholes or cracks existing in the metal layer can be closed. Thereby, it can suppress that the required components (electrolyte etc.) inside an electrochemical element leak outside.
  • the raw material of the coating layer is not particularly limited, and examples thereof include fluorine compounds, rubber polymers, silicone polymers, urethane polymers, and polyester polymers. Among these, it is preferable to use at least one compound selected from the group consisting of a fluorine-based compound, a rubber-based polymer, and a silicone-based polymer from the viewpoint that it is difficult to inhibit the hydrogen permeability of the hydrogen discharge membrane.
  • fluorine-based compound examples include a fluoroalkyl carboxylate, a fluoroalkyl quaternary ammonium salt, and a fluoroalkyl group-containing compound such as a fluoroalkylethylene oxide adduct; a perfluoroalkyl carboxylate, a perfluoroalkyl quaternary ammonium salt, And perfluoroalkyl group-containing compounds such as perfluoroalkylethylene oxide adducts; fluorocarbon group-containing compounds such as tetrafluoroethylene / hexafluoropropylene copolymers and tetrafluoroethylene / perfluoroalkyl vinyl ether copolymers; tetrafluoroethylene polymers; Copolymer of vinylidene fluoride and tetrafluoroethylene; copolymer of vinylidene fluoride and hexafluoropropylene; fluorine-containing (meth)
  • Examples of rubber polymers include natural rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, chloroprene rubber, polyisoprene rubber, polybutadiene rubber, ethylene propylene rubber, ethylene-propylene-diene terpolymer rubber, chlorosulfonated polyethylene rubber, And ethylene-vinyl acetate copolymer rubber.
  • Rubber-based polymer that is a raw material for the coating layer
  • “Elep Coat” series manufactured by Nitto Shinko Co., Ltd. may be used as a rubber-based polymer that is a raw material for the coating layer.
  • silicone polymer examples include polydimethylsiloxane, alkyl-modified polydimethylsiloxane, carboxyl-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, fluorine-modified polydimethylsiloxane, and (meth) acrylate-modified polydimethyl.
  • silicone polymer examples include siloxane.
  • the coating layer can be formed, for example, by applying a coating layer raw material composition on a metal layer and curing it.
  • the coating method is not particularly limited, and examples thereof include a roll coating method, a spin coating method, a dip coating method, a spray coating method, a bar coating method, a knife coating method, a die coating method, an ink jet method, and a gravure coating method.
  • the solvent may be appropriately selected according to the raw material of the coat layer.
  • solvents such as a fluorine-type solvent, an alcohol solvent, an ether solvent, an ester solvent, and a hydrocarbon solvent, can be used individually or in mixture, for example.
  • a fluorine-based solvent which is not flammable and volatilizes rapidly, either alone or mixed with another solvent.
  • fluorine-based solvent examples include hydrofluoroether, perfluoropolyether, perfluoroalkane, hydrofluoropolyether, hydrofluorocarbon, perfluorocycloether, perfluorocycloalkane, hydrofluorocycloalkane, xylene hexafluoride, hydro Examples thereof include fluorochlorocarbon and perfluorocarbon.
  • the thickness of the coating layer is not particularly limited, but is preferably 0.1 to 40 ⁇ m, more preferably 0.2 to 10 ⁇ m, and further preferably 0.3 to 5 ⁇ m.
  • a support may be provided on one side or both sides of the metal layer.
  • the Pd alloy layer obtained by sputtering is thin, it is preferable to laminate a support on one side or both sides of the Pd alloy layer in order to improve mechanical strength.
  • FIG. 1 and 2 are schematic cross-sectional views showing the structure of the hydrogen discharge membrane 1.
  • a support 4 may be laminated on one or both sides of the Pd alloy layer 2 using a ring-shaped adhesive 3, and FIG. 2 (a) or (b ), The support 4 may be laminated on one side or both sides of the Pd alloy layer 2 using the jig 5.
  • the support 4 is not particularly limited as long as it is hydrogen permeable and can support the Pd alloy layer 2, and may be a non-porous material or a porous material.
  • the support 4 may be a woven fabric or a non-woven fabric.
  • the material for forming the support 4 include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyaryl ether sulfones such as polysulfone and polyethersulfone, polytetrafluoroethylene, and polyvinylidene fluoride. Fluorine resin, epoxy resin, polyamide, polyimide and the like can be mentioned. Of these, polysulfone or polytetrafluoroethylene which is chemically and thermally stable is preferably used.
  • the support 4 is preferably a porous body having an average pore diameter of 100 ⁇ m or less.
  • the average pore diameter exceeds 100 ⁇ m, the surface smoothness of the porous body is lowered. Therefore, when a Pd alloy layer is produced by sputtering or the like, it is difficult to form a Pd alloy layer having a uniform thickness on the porous body. Or pinholes or cracks are likely to occur in the Pd alloy layer.
  • the thickness of the support 4 is not particularly limited, but is usually about 5 to 1000 ⁇ m, preferably 10 to 300 ⁇ m.
  • the support body 4 is used as a substrate, the Pd alloy layer 2 can be directly formed on the support body 4 without using the adhesive 3 or the jig 5. Since the exhaust film 1 can be manufactured, it is preferable from the viewpoint of physical properties and manufacturing efficiency of the hydrogen exhaust film 1.
  • the support 4 is preferably a porous body having an average pore diameter of 100 ⁇ m or less, more preferably a porous body having an average pore diameter of 5 ⁇ m or less, and particularly an ultrafiltration membrane (UF membrane). preferable.
  • the shape of the hydrogen discharge membrane may be a substantially circular shape or a polygon such as a triangle, a quadrangle, or a pentagon. It can be made into arbitrary shapes according to the use mentioned later.
  • the hydrogen discharge membrane is useful as a component for a safety valve of an electrolytic capacitor. Further, the hydrogen discharge membrane can be provided in the electrolytic capacitor as a hydrogen discharge valve separately from the safety valve.
  • the hydrogen discharge membrane does not become brittle at a low temperature, there is an advantage that it can be used at a temperature of, for example, 150 ° C. or lower, further 110 ° C. or lower. That is, it is preferably used as a safety valve or hydrogen discharge valve for electrolytic capacitors that are not used at high temperatures (eg, 400 to 500 ° C.).
  • the anode used in the electrolytic capacitor of the present invention has a ratio (average thickness / rated voltage) of the average thickness of the oxide film to the rated voltage of the capacitor of 1.2 to 2.9 (nm / V), preferably It is 1.3 to 2.4 (nm / V), more preferably 1.4 to 2.0 (nm / V).
  • the average thickness of the aluminum oxide film is about 1200 nm, and the average thickness / rated voltage is about 3 (nm / V). Therefore, when the rated voltage is the same, the average thickness of the oxide film of the anode used in the electrolytic capacitor of the present invention is only 40 to 95% of the average thickness of the conventional oxide film and is very thin.
  • an anode having such a very thin oxide film is used as the anode of a conventional electrolytic capacitor, many defects occur in the oxide film due to mechanical stress or electrical stress, and a large amount of hydrogen gas is generated due to the film repairing action.
  • the outer case expands or bursts due to an increase in the internal pressure of the electrolytic capacitor.
  • the outer case since the hydrogen discharge film is provided in the electrolytic capacitor, the outer case does not expand or rupture even when such an anode having a very thin oxide film is used.
  • the average thickness of the oxide film can be adjusted to a desired thickness by arbitrarily adjusting the formation voltage in the formation process (oxide film formation process).
  • the sheet material is cold-rolled to a thickness of 100 ⁇ m using a two-stage rolling mill with a roll diameter of 100 mm, and further the sheet material is cold-rolled to a thickness of 20 ⁇ m using a two-stage rolling mill with a roll diameter of 20 mm. did. Then, the rolled plate material was put in the glass tube, and both ends of the glass tube were sealed. The inside of the glass tube was depressurized to 5 ⁇ 10 ⁇ 4 Pa at room temperature, then heated to 500 ° C. and allowed to stand for 1 hour, and then cooled to room temperature.
  • Production Example 2 [Preparation of Pd—Au alloy layer by sputtering method (Au content 50 mol%)]
  • a polysulfone porous sheet (manufactured by Nitto Denko Corporation, pore size: 0.001 to 0.02 ⁇ m) is mounted on an RF magnetron sputtering apparatus (manufactured by Sanyu Electronics Co., Ltd.) equipped with a Pd—Au alloy target having an Au content of 50 mol%. ) was attached.
  • the inside of the sputtering apparatus is evacuated to 1 ⁇ 10 ⁇ 5 Pa or less, and a sputtering current of 4.8 A is applied to the Pd—Au alloy target at an Ar gas pressure of 1.0 Pa to form a thick film on the polysulfone porous sheet.
  • a 100 nm thick Pd—Au alloy layer (Au content 50 mol%) was formed.
  • a coating layer raw material composition (manufactured by Harves, Durasurf DS-3302TH) was applied on the Pd—Au alloy layer by a dip coating method and dried to form a coating layer having a thickness of 0.3 ⁇ m.
  • a discharge membrane was prepared.
  • Example 1 [Production of aluminum electrolytic capacitors] Thickness of 30 ⁇ m with a 90 ⁇ m rated 200-450V rated high-voltage chemical foil (manufactured by Nihon Denki Kogyo Kogyo Co., Ltd.) slit into a square (45 x 45mm) with protrusions for drawing out the electrodes Of cathode foil (manufactured by Nippon Denshi Kogyo Kogyo Co., Ltd.) slit into a square (45 x 45 mm) provided with a protruding part for electrode lead-out, and a hemp paper with a thickness of 70 ⁇ m (manufactured by Nippon Kogyo Paper Industries Co., Ltd.) Was slit into a square (50 ⁇ 50 mm) that was slightly larger than the electrode foil to obtain electrolytic paper.
  • cathode foil manufactured by Nippon Denshi Kogyo Kogyo Co., Ltd.
  • the exterior case that houses the elements is formed by laminating a nylon resin film with a thickness of 40 ⁇ m, an aluminum foil with a thickness of about 50 ⁇ m, and a heat-sealable polypropylene resin film with a thickness of 30 ⁇ m in this order.
  • Two aluminum laminate films (Dai Nippon Printing Co., Ltd.) slit into squares (65 ⁇ 130 mm) were used.
  • an opening of ⁇ 10 was provided at the center of one aluminum laminate film, and the hydrogen discharge film of ⁇ 20 produced in Production Example 1 was attached with an adhesive from the polypropylene resin film surface so as to cover the opening.
  • These two aluminum laminate films were overlapped so that the polypropylene resin surfaces of the respective films were aligned, and the three sides were heat-sealed (200 ° C.) with a width of 10 mm to prepare an outer case.
  • Example 2 [Production of aluminum electrolytic capacitors]
  • an aluminum electrolytic capacitor was obtained in the same manner as in Example 1 except that instead of the ⁇ 20 hydrogen discharge film produced in Production Example 1, the ⁇ 20 hydrogen discharge film produced in Production Example 2 was used. .
  • Example 3 [Production of aluminum electrolytic capacitors]
  • an aluminum electrolytic capacitor was obtained in the same manner as in Example 1 except that the sizes of the anode and the cathode were changed to 39 ⁇ 39 mm.
  • Example 4 [Production of aluminum electrolytic capacitors]
  • an aluminum electrolytic capacitor was obtained in the same manner as in Example 3 except that instead of the ⁇ 20 hydrogen discharge film produced in Production Example 1, the ⁇ 20 hydrogen discharge film produced in Production Example 2 was used. .
  • Example 1 An aluminum electrolytic capacitor was obtained in the same manner as in Example 1 except that the opening of ⁇ 10 was not provided in the center of the aluminum laminate film and the hydrogen discharge film of ⁇ 20 produced in Production Example 1 was not used. It was.
  • Example 3 An aluminum electrolytic capacitor was obtained in the same manner as in Example 3 except that the opening of ⁇ 10 was not provided in the center of the aluminum laminate film and the hydrogen discharge film of ⁇ 20 produced in Production Example 1 was not used. It was.
  • the hydrogen permeation amount of the hydrogen discharge membrane is preferably 10 ml / day or more, and more preferably 100 ml / day or more.
  • the hydrogen permeation amount of the hydrogen discharge membrane of Production Example 1 was 600 ml / day, and the hydrogen permeation amount of the hydrogen discharge membrane of Production Example 2 was 250 ml / day.
  • the produced hydrogen discharge membrane was attached to a VCR connector manufactured by Swagelok, and a SUS tube was attached to one side to produce a sealed space (63.5 ml). After depressurizing the inside of the tube with a vacuum pump, the pressure of nitrogen gas was adjusted to 150 kPa, and the pressure change under an environment of 105 ° C. was monitored. Since the number of moles (volume) of nitrogen that permeated through the hydrogen discharge membrane was found due to the pressure change, this was converted into the permeation amount per day, and the nitrogen permeation amount was calculated.
  • the nitrogen permeation amount of the hydrogen discharge membrane of Production Example 1 was 0 ml / day, and the nitrogen permeation amount of the hydrogen discharge membrane of Production Example 2 was 0 ml / day. Therefore, the hydrogen gas selective permeability of the hydrogen discharge membrane of Production Example 1 is 100%, and the hydrogen gas selective permeability of the hydrogen discharge membrane of Production Example 2 is 100%.
  • the aluminum electrolytic capacitors of Comparative Examples 1 and 2 do not have a special hydrogen discharge film, so that the hydrogen gas generated inside the capacitor cannot be discharged quickly and the internal pressure of the capacitor is reduced. This is thought to be due to a large increase.
  • the aluminum electrolytic capacitor produced with the anode foil of the rated voltage 200V of Examples 1 and 2 has a higher capacitance than the aluminum electrolytic capacitor produced with the anode foil of the rated voltage 250V when a voltage exceeding 200V is applied. Therefore, it can be seen that by using a special hydrogen discharge film, it is possible to increase the withstand voltage and the capacitance of the aluminum electrolytic capacitor without changing the appearance.
  • the aluminum electrolytic capacitors of Examples 3 and 4 are provided with a special hydrogen discharge film, and the hydrogen gas generated inside the capacitor is quickly discharged to the outside by this hydrogen discharge film, and the internal pressure of the capacitor is reduced. This is probably because the rise was effectively suppressed.
  • the aluminum electrolytic capacitor produced with the anode foil of the rated voltage 200V of Examples 3 and 4 is equivalent to the capacitor produced with the anode foil of the rated voltage 250V of Examples 1 and 2 when a voltage exceeding 200V is applied. Therefore, it can be seen that by using a special hydrogen discharge film, the aluminum electrolytic capacitor can be miniaturized without any change in appearance.
  • the electrolytic capacitor of the present invention is suitably used for various power sources.

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  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

La présente invention a pour objet de réaliser un condensateur électrolytique qui ne pose aucun problème concernant le gonflement ou la rupture d'une enveloppe extérieure même dans des cas où une grande quantité de gaz hydrogène est générée, qui présente une grande capacitance et peut permettre une réduction de taille et une augmentation de la tension de tenue. Ce condensateur électrolytique est muni d'un film de dégagement d'hydrogène, le film de dégagement d'hydrogène comprenant une couche perméable au gaz hydrogène qui permet sélectivement la perméation de 99% en moles de gaz hydrogène lorsqu'elle est en contact avec un gaz mixte contenant des quantités équimolaires de gaz hydrogène et de gaz azote, et le condensateur électrolytique est caractérisé en ce que le rapport de l'épaisseur moyenne d'un film d'oxyde sur une anode à la tension nominale du condensateur (épaisseur moyenne/tension nominale) est de 1,2 à 2,9 (nm/V).
PCT/JP2017/017155 2016-05-30 2017-05-01 Condensateur électrolytique WO2017208723A1 (fr)

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JP2016107677 2016-05-30
JP2016-107677 2016-05-30
JP2017078155A JP7020792B2 (ja) 2016-05-30 2017-04-11 電解コンデンサ
JP2017-078155 2017-04-11

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WO2017208723A1 true WO2017208723A1 (fr) 2017-12-07

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Publication number Priority date Publication date Assignee Title
CN113517138A (zh) * 2021-06-29 2021-10-19 西安交通大学 一种采用储氢合金减小铝电解电容器工作内压的方法
CN113517139A (zh) * 2021-06-29 2021-10-19 西安交通大学 一种减小铝电解电容器工作内压的方法

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Publication number Priority date Publication date Assignee Title
JP2007038095A (ja) * 2005-08-02 2007-02-15 National Institute Of Advanced Industrial & Technology 水素分離膜及びその製造方法
JP2011512664A (ja) * 2008-02-14 2011-04-21 バッツキャップ 超コンデンサの過圧を防ぐための装置
WO2014098038A1 (fr) * 2012-12-17 2014-06-26 日東電工株式会社 Membrane de décharge d'hydrogène
JP2016082126A (ja) * 2014-10-20 2016-05-16 Ｎｅｃトーキン株式会社 固体電解コンデンサ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007038095A (ja) * 2005-08-02 2007-02-15 National Institute Of Advanced Industrial & Technology 水素分離膜及びその製造方法
JP2011512664A (ja) * 2008-02-14 2011-04-21 バッツキャップ 超コンデンサの過圧を防ぐための装置
WO2014098038A1 (fr) * 2012-12-17 2014-06-26 日東電工株式会社 Membrane de décharge d'hydrogène
JP2016082126A (ja) * 2014-10-20 2016-05-16 Ｎｅｃトーキン株式会社 固体電解コンデンサ

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113517138A (zh) * 2021-06-29 2021-10-19 西安交通大学 一种采用储氢合金减小铝电解电容器工作内压的方法
CN113517139A (zh) * 2021-06-29 2021-10-19 西安交通大学 一种减小铝电解电容器工作内压的方法

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