TW201729448A - Electrochemical element - Google Patents

Abstract

The purpose of the present invention is to provide an electrochemical element that suffers little damage or degradation as a result of the pressure of generated hydrogen gas even when used over a long period of time and that can withstand use over a long period of time. This electrochemical element comprises a layered body that is provided with a hydrogen discharge film and in which an anode and a cathode are layered with electrolytic paper therebetween. The hydrogen discharge film contains a metal layer. The amount of dimethyl disulfide released by the electrolytic paper when heated for twelve hours at 105 DEG C is 0.0004 [mu]g/cm2 or less.

Description

Electrochemical element

The present invention relates to electrochemical elements such as batteries, condensers, and capacitors.

In recent years, aluminum electrolytic capacitors have been used for applications such as inverters for electric power generation and solar power generation, and large power sources such as batteries. In an aluminum electrolytic capacitor, hydrogen gas is generated inside due to a reverse voltage, an overvoltage, and an overcurrent. If a large amount of hydrogen gas is generated, the outer casing may be broken due to an increase in internal pressure. Therefore, a general-purpose aluminum electrolytic capacitor is provided with a safety valve having a special film. In addition to the function of discharging the hydrogen gas inside the capacitor to the outside, the safety valve also has a function of self-destruction to lower the internal pressure and prevent the capacitor itself from being broken when the internal pressure of the capacitor rises sharply. Regarding a special film which is a constituent member of such a safety valve, for example, the following is proposed. Patent Document 1 discloses a pressure-regulating film comprising a foil tape comprising a palladium-silver (Pd-Ag) alloy containing 20 wt% (19.8 mol%) of Ag in palladium. However, the foil tape of the patent document 1 is easy to embrittle in an environment of about 50 to 60 ° C or less, and it is not possible to maintain the function as a pressure-regulating film for a long period of time, and it has not been put into practical use. On the other hand, lithium-ion batteries are widely used as batteries for mobile phones, notebook computers, and automobiles. Further, in recent years, in addition to high capacity and improved cycle characteristics, lithium ion batteries have also increased their concern for safety. In particular, lithium ion batteries are known to generate gas in the battery, and there is concern about expansion or cracking of the battery pack accompanying an increase in internal pressure. Patent Document 2 discloses that an amorphous alloy (for example, a 36Zr-64Ni alloy) film containing an alloy of zirconium (Zr) and nickel (Ni) is used as a hydrogen selective permeability alloy that selectively permeates hydrogen generated in a battery. membrane. However, the above amorphous alloy has a problem that if hydrogen gas is contacted in a low temperature region (for example, 50 ° C), a hydride (ZrH ₂ ) is formed to cause embrittlement, and thus it is impossible to maintain the function as a pressure regulating film for a long period of time. In order to solve the above problem, Patent Document 3 proposes a hydrogen gas discharge film comprising a Pd-Ag alloy and having a Ag content of 20 mol% or more in the Pd-Ag alloy. In order to solve the above problem, Patent Document 4 proposes a hydrogen gas discharge film containing a Pd—Cu alloy and having a Cu content of 30 mol% or more in the Pd—Cu alloy. However, the hydrogen gas discharge membranes of Patent Documents 3 and 4 have problems in that they are not easily embrittled at the use temperature of the electrochemical device and have sufficient hydrogen gas discharge performance at the initial stage of use, but the hydrogen gas discharge property is gradually lowered due to the use environment. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent No. 4208014 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-297325 [Patent Document 3] International Publication No. 2014/098038 [Patent Document 4 ]International Publication No. 2015/019906

[Problems to be Solved by the Invention] The present invention has been made in view of the above problems, and an object thereof is to provide a method capable of withstanding damage and deterioration due to the pressure of hydrogen gas generated even in the case of long-term use. Electrochemical components that are used for a long time. [Means for Solving the Problems] The present invention relates to an electrochemical device characterized in that it has a hydrogen gas discharge film and has a laminate in which an anode and a cathode are interposed with electrolytic paper, and the hydrogen gas discharge film is provided. The metal layer is contained, and when the electrolyzed paper is heated at 105 ° C for 12 hours, the amount of dimethyl disulfide released is 0.0004 μg / cm ² or less. The present inventors have made an effort to study the reason why the hydrogen gas discharge property of the hydrogen gas discharge film containing the metal layer is gradually lowered, and as a result, it has been found that not hydrogen gas causes embrittlement of the metal layer, but is generated from electrolytic paper which is a constituent member of the electrochemical element. Dimethyl disulfide, which corrodes (oxidizes or vulcanizes, etc.) a metal layer, causes deterioration of the metal layer, and as a result, hydrogen gas discharge property is gradually lowered. That is, in the method of producing kraft pulp as a raw material of electrolytic paper, sodium sulphide is used in the step of extracting fibers from wood chips using a medicinal liquid, but the sodium sulfide is bonded to hydrocarbons in cellulose. It produces various sulfur-based components. Further, it has been found that among various sulfur-based components, especially dimethyl disulfide, the metal layer is deteriorated. The present inventors conducted an effort to study the solution based on the above findings, and as a result, found that electrolytic paper having a release amount of dimethyl disulfide of 0.0004 μg/cm ² or less by heating at 105 ° C for 12 hours was used. The metal layer is not easily deteriorated by corrosion, and as a result, even in the case of long-term use, the hydrogen gas discharge property of the hydrogen gas discharge film is not easily lowered. The metal layer is preferably an alloy layer containing a Pd alloy from the viewpoint of excellent hydrogen permeation resistance, oxidation resistance, and excellent embrittlement resistance when hydrogen is stored. The Pd alloy preferably contains 20 to 65 mol% of a Group 11 element from the viewpoint of excellent hydrogen permeation resistance, oxidation resistance, and excellent embrittlement resistance when hydrogen is absorbed. Further, the Group 11 element is preferably at least one selected from the group consisting of Au, Ag, and Cu. The Pd alloy layer containing the Pd-Group 11 element alloy has the following functions: dissociating the hydrogen molecules into hydrogen atoms on the surface of the film and solid-dissolving the hydrogen atoms in the film, so that the solid-dissolved hydrogen atoms diffuse from the high pressure side to the low pressure side, Hydrogen atoms are again converted into hydrogen molecules on the surface of the membrane on the low pressure side and discharged. When the content of the element of the 11th group is less than 20 mol%, the strength of the Pd alloy is insufficient or the function is not easily exhibited, and when it exceeds 65 mol%, the hydrogen permeation rate tends to decrease. The hydrogen gas discharge film preferably has a support on one side or both sides of the metal layer. The support system is provided to prevent the metal layer from falling into the electrochemical component when it is detached from the safety valve or the hydrogen discharge valve. Further, when the metal layer has a function as a safety valve, the safety valve self-destructs when the internal pressure of the electrochemical element becomes a specific value or more, and when the metal layer is a film, the mechanical strength of the metal layer is low. Therefore, the internal pressure of the electrochemical element is self-destructive before it becomes a specific value, and it cannot function as a safety valve. Therefore, in the case where the metal layer is a film, in order to improve the mechanical strength, a single-sided or double-area layer support of the metal layer is preferred. The above electrolytic paper is preferably an electrolytic paper using non-wood pulp, and more preferably contains hemp paper. Examples of the electrochemical device include an aluminum electrolytic capacitor and a lithium ion battery. [Effect of the Invention] When the electrochemical device of the present invention is used for a long period of time, the hydrogen gas discharge property of the hydrogen gas discharge film is not easily lowered, and only the hydrogen gas generated inside the electrochemical device can be quickly discharged to the outside. Thereby, it is possible to effectively prevent the electrochemical element from being damaged by the pressure of the hydrogen gas generated inside the electrochemical element. Further, the hydrogen gas discharge film prevents impurities from entering the inside of the electrochemical device from the outside. Further, the hydrogen gas discharge film may have a function of self-destructing when the internal pressure of the electrochemical element rises rapidly to lower the internal pressure, thereby preventing the electrochemical element itself from being broken. By these effects, the initial performance of the electrochemical device can be maintained for a long period of time, and the life of the electrochemical device can be extended.

Hereinafter, embodiments of the present invention will be described. The electrochemical device of the present invention includes a hydrogen gas discharge film that discharges hydrogen gas generated inside the electrochemical device to the outside and has a laminate in which an anode and a cathode are interposed with electrolytic paper. Examples of the electrochemical device include a battery, a capacitor, a capacitor, and the like, and an aluminum electrolytic capacitor or a lithium ion battery is particularly preferable. The constituent members other than the hydrogen gas discharge film and the electrolytic paper can be used without any particular limitation. Further, the electrochemical device of the present invention can be produced by a conventional method in addition to the following hydrogen gas discharge film and electrolytic paper. Hereinafter, the hydrogen gas discharge film and the electrolytic paper will be described in detail. The above hydrogen gas discharge film system includes a metal layer. The metal layer needs to be a non-porous body which can discharge only hydrogen gas generated inside the electrochemical element to the outside and can prevent the substance from intruding into the electrochemical element from the outside, for example, a through hole having substantially no fineness. The metal forming the metal layer is not particularly limited as long as it has a hydrogen gas permeation function or a hydrogen gas permeation function by alloying, and examples thereof include Pd, Nb, V, Ta, Ni, Fe, Al, Cu, and Ru. Re, R h, Au, Pt, Ag, Cr, Co, Sn, Zr, Y, Ce, Ti, Ir, Mo, and an alloy containing two or more of these metals. The metal layer is preferably an alloy layer containing a Pd alloy. The other metal forming the Pd alloy is not particularly limited, and it is preferred to use a Group 11 element, and more preferably at least one selected from the group consisting of Au, Ag, and Cu. In particular, the Pd-Au alloy is preferred because it is excellent in corrosion resistance from an electrolyte solution or a gas component generated in a constituent member of the electrochemical device. The Pd alloy preferably contains 20 to 65 mol% of the Group 11 element, more preferably 30 to 65 mol%, still more preferably 30 to 60 mol%. Further, the Pd alloy layer is preferably hardly embrittled by hydrogen even in a low temperature region of about 50 to 60 ° C or less. Therefore, the Pd alloy layer contains a Pd-Ag alloy having an Ag content of 20 mol% or more, Cu. A Pd-Cu alloy having a content of 30 mol% or more or a Pd-Au alloy having an Au content of 20 mol% or more. Further, the Pd alloy may also contain a Group IB and/or Group IIIA metal within the range not impairing the effects of the present invention. The Pd alloy may be not only a binary alloy containing Pd, but also a ternary alloy of Pd-Au-Ag, or a ternary alloy of Pd-Au-Cu. Further, it may be a quaternary alloy of Pd-Au-Ag-Cu. For example, in the case of a multi-component alloy containing Pd, Au, and other metals, the total content of Au and other metals in the Pd-Au alloy is preferably 55 mol% or less, more preferably 50 mol% or less, and further preferably It is 45 mol% or less, and particularly preferably 40 mol% or less. The metal layer can be produced, for example, by a roll method, a sputtering method, a vacuum deposition method, an ion plating method, a plating method, or the like. In the case of producing a metal layer having a thick film thickness, it is preferable to use a roll. In the case of producing a metal layer having a thin film thickness, sputtering is preferably used. The rolling method can be either hot rolling or cold rolling. The rolling method is a method in which a pair of or a plurality of rollers are rotated, and a metal as a raw material is passed through a pressure between the rolls to form a film. The film thickness of the metal layer obtained by the rolling method is preferably from 5 to 50 μm, more preferably from 10 to 30 μm. When the film thickness is less than 5 μm, it is easy to cause pinholes or cracks during production, or it is easily deformed if hydrogen is absorbed. On the other hand, when the film thickness exceeds 50 μm, it takes a long time for the hydrogen gas to permeate, so that the hydrogen gas permeability is lowered or the cost is poor, which is not preferable. The sputtering method is not particularly limited, and can be carried out using a sputtering apparatus such as a parallel plate type, a monolithic type, a pass type, a DC sputtering, or an RF sputtering. For example, after mounting a substrate on a sputtering device provided with a metal target, vacuum evacuation in the sputtering device and adjusting the argon gas pressure to a specific value, a specific sputtering current is flowed into the metal target, and a metal film is formed on the substrate. . Thereafter, the metal film is peeled off from the substrate to obtain a metal layer. Further, as the target, a single or a plurality of targets may be used depending on the metal layer to be produced. Examples of the substrate include a glass plate, a ceramic plate, a tantalum wafer, and a metal plate such as aluminum or stainless steel. The film thickness of the metal layer obtained by the sputtering method is preferably from 0.01 to 5 μm, more preferably from 0.05 to 2 μm. When the film thickness is less than 0.01 μm, not only the possibility of pinhole formation but also the required mechanical strength is not easily obtained. Moreover, it is easy to break when peeling from a board|substrate, and it is difficult to operate after peeling. On the other hand, if the film thickness exceeds 5 μm, it takes time to manufacture the metal layer, which is inferior in cost and is therefore unsatisfactory. The film area of the metal layer can be appropriately adjusted in consideration of the amount of hydrogen permeation and the thickness of the film, but it is about 0.01 to 100 mm ² when used as a constituent member of the safety valve. Further, in the present invention, the area of the portion of the metal layer in which the hydrogen gas is substantially discharged in the film area is not included in the ring-shaped portion to which the adhesive is applied. A coating other than the metal layer may also be provided on the surface of the metal layer. By providing a coating layer, it is possible to prevent a contaminant other than dimethyl disulfide (for example, an electrolytic solution) generated from the electrolytic paper from adhering to the surface of the metal layer of the hydrogen discharge film to corrode it. The material of the coating layer is preferably a surface having a contact angle with water of 85° or more, and examples thereof include a fluorine-based compound, a rubber-based polymer, a polyoxymethylene-based polymer, and a urethane-based polymer. Polyester polymer, etc. Among these, it is preferable to use a fluorine-based compound, a rubber-based polymer, and a polyfluorene-based polymer from the viewpoint that the contact angle with water is large and the hydrogen gas permeability of the hydrogen gas-releasing film is hardly hindered. At least one compound of the group consisting of. Examples of the fluorine-based compound include a fluorine-containing alkyl compound such as a fluoroalkyl carboxylate, a fluoroalkyl quaternary ammonium salt, and a fluoroalkyl ethylene oxide adduct; a perfluoroalkyl carboxylate; a perfluoroalkyl-containing compound such as a perfluoroalkyl quaternary ammonium salt and a perfluoroalkyl ethylene oxide adduct; a tetrafluoroethylene/hexafluoropropylene copolymer and a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer a fluorine-containing carbon-based compound; a tetrafluoroethylene polymer; a copolymer of vinylidene fluoride and tetrafluoroethylene; a copolymer of vinylidene fluoride and hexafluoropropylene; a fluorine-containing (meth) acrylate; (Meth) acrylate polymer; fluorine-containing (meth) acrylate alkyl ester polymer; copolymer of fluorine-containing (meth) acrylate and other monomers. In addition, the "DURASURF" series manufactured by HARVES, the "OPTOOL" series manufactured by DAIKIN Industries, and the "KY-100" series manufactured by Shin-Etsu Chemical Co., Ltd., etc. can be used for the fluorine-based compound. Examples of the rubber-based polymer include natural rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, chloroprene rubber, polyisoprene rubber, polybutadiene rubber, and ethylene propylene rubber. Ethylene-propylene-diene terpolymer rubber, chlorosulfonated polyethylene rubber, and ethylene-vinyl acetate copolymer rubber. In addition, as the rubber-based polymer which is a raw material of the coating, an "ELEP COAT" series manufactured by Nitto Shinko Co., Ltd., or the like can be used. Examples of the polyoxymethylene-based polymer include polydimethyl siloxane, alkyl-modified polydimethyl siloxane, carboxyl-modified polydimethyl siloxane, and amine-modified polydimethylene. Alkoxyoxane, epoxy-modified polydimethyloxane, fluorine-modified polydimethyloxane, and (meth)acrylate-modified polydimethyloxane. The coating can be formed, for example, by coating and hardening the coating material composition on the metal layer or other layer disposed on the metal layer. 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 inkjet method, and a gravure method. Coating method, etc. The solvent may be appropriately selected depending on the raw material of the coating. When a fluorine-based compound is used as a raw material of the coating layer, for example, a fluorine-based solvent, an alcohol-based solvent, an ether-based solvent, an ester-based solvent, or a hydrocarbon-based solvent may be used alone or in combination. Among these, it is preferred to use a fluorine-based solvent which is pyrogen free and rapidly volatilized, or to mix it with another solvent. Examples of the fluorine-based solvent include hydrofluoroether, perfluoropolyether, perfluoroalkane, hydrofluoropolyether, hydrofluorocarbon, perfluorocycloether, perfluorocycloalkane, hydrofluorocycloalkane, and hexafluoroxylene. , hydrochlorofluorocarbon and perfluorocarbon. The thickness of the coating layer is not particularly limited, but is preferably 0.1 to 20 μm, more preferably 0.2 to 10 μm, still more preferably 0.3 to 5 μm. The support may also be provided on one or both sides of the metal layer. In particular, since the metal layer obtained by the sputtering method has a thin film thickness, it is preferably a single-sided or double-area layer support layer of the metal layer in order to improve mechanical strength. 1 and 2 are schematic cross-sectional views showing the structure of the hydrogen gas discharge film 1. The support 4 may be laminated on the one or both sides of the metal layer 2 as shown in Fig. 1 (a) or (b), or as shown in Fig. 2 (a) or (b). The support 4 is used for the single-sided or double-area layer of the metal layer 2 using the jig 5. The support 4 is not particularly limited as long as it has hydrogen gas permeability and can support the metal layer 2, and may be a non-porous body or a porous body. Further, the support 4 may be a woven fabric or a non-woven fabric. Examples of the material for forming the support 4 include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polyethylene naphthalate, and polyarylene ethers such as polyfluorene and polyether oxime. Fluorine resins such as ruthenium, polytetrafluoroethylene and polyvinylidene fluoride, epoxy resins, polyamines, polyimines, polyamidiamines, and the like. Among these, it is preferred to use a chemically stable and thermally stable polyfluorene, polytetrafluoroethylene, polyamine, polyimine, and polyamidimide. The support 4 is preferably a porous body having an average pore diameter of 100 μm or less. When the average pore diameter exceeds 100 μm, the surface smoothness of the porous body is lowered. Therefore, when a metal layer is produced by a sputtering method or the like, it is not easy to form a metal layer having a uniform film thickness on the porous body, or it is easy to produce a metal layer. Pinhole or crack. The thickness of the support 4 is not particularly limited, but is usually about 5 to 1000 μm, preferably 10 to 300 μm. When the metal layer 2 is produced by the sputtering method, when the support 4 is used as the substrate, the metal layer 2 can be directly formed on the support 4, and the hydrogen gas discharge film 1 can be produced without using the adhesive 3 or the jig 5. Therefore, it is preferable from the viewpoint of physical properties and production efficiency of the hydrogen gas discharge film 1. In this case, as the support 4, it is preferred to use a porous body having an average pore diameter of 100 μm or less, more preferably a porous body having an average pore diameter of 5 μm or less, and particularly preferably an ultrafiltration membrane (UF membrane, Ultrafiltration membrane). ). The shape of the hydrogen gas discharge film may be substantially circular, and may be a polygonal shape such as a triangle, a quadrangle or a pentagon. Any shape suitable for the following purposes can be produced. The above hydrogen gas discharge film is useful as a constituent member of a safety valve of an electrochemical element. Further, the hydrogen gas discharge film may be disposed on the electrochemical element as a hydrogen gas discharge valve unlike the safety valve. Since the hydrogen gas discharge film does not become brittle at a low temperature, it can be used, for example, at a temperature of 150 ° C or lower and further at a temperature of 110 ° C or lower. That is, it can be preferably used as a safety valve or a hydrogen discharge valve of an aluminum electrolytic capacitor or a lithium ion battery which is not used at a high temperature (for example, 400 to 500 ° C). As the above-mentioned electrolytic paper, the amount of release of dimethyl disulfide when heated at 105 ° C for 12 hours was 0.0004 μg / cm ² or less. The release amount of dimethyl disulfide is preferably 0.0002 μg/cm ² or less, more preferably 0.0001 μg/cm ² or less. When an electrolytic paper having a release amount of dimethyl disulfide of more than 0.0004 μg/cm ² is used, the metal layer of the hydrogen gas discharge film is easily corroded by dimethyl disulfide, and the metal layer is easily deteriorated. Therefore, the hydrogen gas discharge property of the hydrogen gas discharge film is liable to lower. The electrolyzed paper is not particularly limited as long as the amount of release of dimethyl disulfide is within the above range, and examples thereof include non-wood pulp electrolyzed paper such as hemp paper, manila hemp paper, kiln paper, and needle paper. An electrolytic paper mixed with hemp pulp or Manila hemp pulp and kraft pulp, and an electrolytic paper obtained by laminating hemp paper and kraft paper. It is especially suitable for non-wood pulp electrolytic paper such as hemp paper, manila hemp paper, kiln paper and needle paper, and more preferably hemp paper. The above electrolytic paper preferably has a density of 0.25 to 1.00 g/cm ³ and a thickness of 20 to 100 μm. When the density of the electrolytic paper is less than 0.25 g/cm ³ , the tensile strength is insufficient, and the strength required for producing the capacitor cannot be ensured. Further, the shielding property of the electrolytic paper is lowered, and the short circuit failure of the capacitor is increased. On the other hand, when it exceeds 1.00 g/cm ³ , the ion permeability is deteriorated and the characteristics of the capacitor are lowered. Further, when the thickness of the electrolytic paper is less than 20 μm, it is difficult to ensure the denseness, and the short circuit failure of the capacitor is increased. On the other hand, when it exceeds 100 μm, the ion permeability is deteriorated and the capacitor characteristics are lowered. Fig. 3 is a perspective view showing an example of the structure of an aluminum electrolytic capacitor of the present invention. The capacitor element 6 is formed by interposing an electrolytic paper (separator) 9 between an anode foil 7 made of an aluminum foil and a cathode foil 8, and winding a joint portion including a rod shape on each of the electrodes 7 and 8. And leads 10 of the solderable external lead. The capacitor element 6 is impregnated with a driving electrolyte solution (not shown), and is housed in a case 12 made of aluminum having a bottomed cylindrical shape, and the opening of the case 12 is sealed by the sealing body 11. As shown in FIG. 4, the hydrogen gas discharge film 1 is usually provided in the sealing body 11. The outer circumference of the casing 12 is covered by an exterior member (not shown). [Examples] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by the examples. Production Example 1 [Preparation of Pd-Au alloy layer by roll method (Au content: 30 mol%)] Pd and Au raw materials were weighed so as to have an Au content of 30 mol% in the ingot, and put into In an arc melting furnace equipped with a water-cooled copper crucible, arc melting is performed in an argon atmosphere at atmospheric pressure. For the obtained button ingot, cold rolling was performed using a two-roll mill having a roll diameter of 100 mm until the thickness became 5 mm, and the sheet was obtained. Thereafter, the rolled sheet was placed in a glass plate tube, and both ends of the glass tube were sealed. The inside of the glass plate tube was depressurized to 5 × 10 ^-4 Pa at room temperature, and then heated to 700 ° C for 24 hours, and then cooled to room temperature. By this heat treatment, segregation of Pd and Au in the alloy is eliminated. Then, the sheet was cold-rolled using a two-roll mill having a roll diameter of 100 mm until the thickness became 100 μm, and the sheet was cold-rolled using a two-roll mill having a roll diameter of 20 mm until the thickness became 20 μm. Thereafter, the rolled sheet was placed in a glass plate tube, and both ends of the glass tube were sealed. The inside of the glass plate tube was depressurized to 5 × 10 ^-4 Pa at room temperature, and then heated to 500 ° C for 1 hour, and then cooled to room temperature. By this heat treatment, the strain inside the Pd-Au alloy generated by the rolling was removed, and a hydrogen discharge film containing a Pd-Au alloy layer having a thickness of 20 μm and an Au content of 30 mol% was produced. Example 1 An aluminum electrolytic capacitor was produced by using a hydrogen gas discharge film produced in Production Example 1 and a hemp paper having a release amount of dimethyl disulfide of 0 μg/cm ² . Example 2 An aluminum electrolytic capacitor was produced by using the hydrogen discharge film produced in Production Example 1 and an electrolytic paper obtained by laminating kraft paper and hemp paper with a release amount of dimethyl disulfide of 0.00034 μg/cm ² . Example 3 An electrolytic paper prepared by mixing a kraft pulp and a manila hemp pulp with a hydrogen gas discharge film produced in Production Example 1 and a release amount of dimethyl disulfide of 0.00038 μg/cm ² was used to prepare an aluminum electrolytic solution. Capacitor. Comparative Example 1 An aluminum electrolytic capacitor was produced by using a hydrogen gas discharge film produced in Production Example 1 and a kraft paper having a release amount of dimethyl disulfide of 0.00045 μg/cm ² . [Measurement and Evaluation Method] (Measurement of Release of Dimethyl Disulfide) 200 cm ² of electrolytic paper was placed in a 20 ml vial and sealed. Then, using a headspace sampler (HSS, manufactured by Agilent Technologies, G1888), heating at 105 ° C for 12 hours, and injecting 1 ml of the generated gas into a GC (Gas chromatography) The measurement was carried out in a MS (mass spectrometry) / FPD (flame photometric detector) (manufactured by Agilent Technologies, 7890A/5975C). The conditions of each device are as follows. HSS oven temperature: 105 °C Heating time: 12 h GC/MS/FPD ・GC Column: HP-5MS UI 30 m × inner diameter 0.25 mm × film thickness 0.25 μm Column temperature: 40 ° C (3 min) → +20 ° C /min→300°C (4 min) Carrier gas: He (3.0 ml/min) Injection inlet: Split ratio 5:1 Injection temperature: 250°C Detector: MS/FPD ・MS ionization method: EI method electron energy: 70 eV EM voltage: 1776 V ion source temperature: 230 ° C interface temperature: 300 ° C mass range: m / z = 35 ~ 800 · FPD ... sulfur compound selection detection temperature: 200 ° C hydrogen flow: 70 ml / min air flow : 100 ml/min (Evaluation of Hydrogen Permeability) The hydrogen discharge film produced in Production Example 1 was attached to a VCR connector manufactured by Swagelok Company, and a SUS tube was mounted on one side to produce a sealed space. (63.5 ml). After the inside of the tube was depressurized by a vacuum pump, the pressure of the hydrogen gas was adjusted to 0.15 MPa, and the pressure change in an environment of 105 ° C was monitored. The number of hydrogen moles (volume) of the membrane discharged through the hydrogen gas due to the pressure change was known, so that the amount of hydrogen permeation was calculated by converting the amount of hydrogen gas per one day. For example, when the pressure is changed from 0.15 MPa to 0.05 MPa in 2 hours (the amount of change is 0.10 MPa), the volume of hydrogen gas discharged through the hydrogen gas discharge membrane is 63.5 ml. Thus, the hydrogen permeation amount per day became 63.5 × 24 / 2 = 762 ml / day. The hydrogen permeation amount of the hydrogen gas discharge membrane is preferably 10 ml/day or more, more preferably 100 ml/day or more. (Evaluation of Corrosion Resistance) In a sealed SUS can, a sample in which 50 g of the electrolytic paper used in the examples and the comparative examples was impregnated with ethylene glycol was placed and suspended from the lid of the SUS can. The hydrogen discharge film (15 mm × 15 mm) produced in 1. The heat treatment was carried out at 105 ° C for 12 hours to expose the gas generated from the sample to the surface of the hydrogen discharge film. Thereafter, the evaluation of hydrogen gas permeability was carried out in the same manner as above. (Evaluation of Aluminum Electrolytic Capacitor) The aluminum electrolytic capacitors produced in the examples and the comparative examples were subjected to voltage application at 400 V for 500 hours at an ambient temperature of 105 °C. Thereafter, the deformation of the aluminum casing of the aluminum electrolytic capacitor was visually confirmed. 〇: The aluminum shell has no shape change ×: The aluminum shell has a bulge [Table 1] As is clear from Table 1, in Comparative Example 1 in which an electrolytic paper having a release amount of dimethyl disulfide of 0.00045 μg/cm ² was used, the hydrogen permeability of the hydrogen gas discharge film was lost due to corrosion, and hydrogen gas could not be discharged to the outside. Therefore, the bulging of the aluminum casing occurs. On the other hand, in Examples 1 to 3, since electrolytic paper having a release amount of dimethyl disulfide of 0.0004 μg/cm ² or less was used, hydrogen gas permeating through the hydrogen gas discharge film even in the coexistence of electrolytic paper The properties are also good, and the internal pressure of the aluminum electrolytic capacitor can be prevented from rising, so that the deformation of the aluminum casing does not occur. [Industrial Applicability] The electrochemical device of the present invention is suitably used for various power sources and the like.

1‧‧‧Hydrogen discharge membrane
2‧‧‧metal layer
3‧‧‧Binder
4‧‧‧Support
5‧‧‧ fixture
6‧‧‧Capacitive components
7‧‧‧Anode foil
8‧‧‧Cathode foil
9‧‧‧ Electrolytic paper (separator)
10‧‧‧ lead
11‧‧‧ Sealing body
12‧‧‧ housing

Fig. 1 (a) and (b) are schematic cross-sectional views showing the structure of a hydrogen gas discharge film of the present invention. 2(a) and 2(b) are schematic cross-sectional views showing another configuration of the hydrogen gas discharge film of the present invention. Fig. 3 is a perspective view showing an example of the structure of an aluminum electrolytic capacitor of the present invention. Fig. 4 is a perspective view showing an example of a structure of a sealing body provided with a hydrogen gas discharge film.

1‧‧‧Hydrogen discharge membrane

2‧‧‧metal layer

3‧‧‧Binder

4‧‧‧Support

Claims (8)

An electrochemical device comprising a hydrogen gas discharge film and a laminate in which an anode and a cathode are interposed with electrolytic paper, and the hydrogen gas discharge film comprises a metal layer, and the electrolyte paper is at 105 ° C. The release amount of dimethyl disulfide at the time of heating for 12 hours was 0.0004 μg/cm ² or less. The electrochemical component of claim 1, wherein the metal layer comprises an alloy layer of a Pd alloy. The electrochemical device of claim 2, wherein the Pd alloy comprises 20 to 65 mol% of the Group 11 element. The electrochemical device according to claim 3, wherein the Group 11 element is at least one selected from the group consisting of Au, Ag, and Cu. The electrochemical element according to claim 1, wherein the hydrogen gas discharge film has a support on one side or both sides of the metal layer. The electrochemical component of claim 1, wherein the electrolyzed paper is an electrolytic paper of non-wood pulp. The electrochemical component of claim 6, wherein the non-wood pulp is a hemp paper. The electrochemical component according to any one of claims 1 to 7, wherein the electrochemical component is an aluminum electrolytic capacitor or a lithium ion battery.