TW201816812A - Hydrogen discharge component - Google Patents

Abstract

The purpose of the present invention is to provide a hydrogen discharge component which is not susceptible to decrease in the hydrogen permeability even if used for a long period of time. A hydrogen discharge component according to the present invention is provided with a hydrogen discharge film having a metal layer, and is additionally provided with an adsorbent on at least the hydrogen introduction surface side of the hydrogen discharge film, said adsorbent adsorbing a sulfur compound.

Description

Hydrogen discharge parts

The present invention relates to a hydrogen discharge component provided in an electrochemical element such as a battery, a capacitor, a capacitor, and a sensor.

In recent years, aluminum electrolytic capacitors have been used in applications such as inverters for wind power generation and solar power generation, and large power sources such as batteries. Aluminum electrolytic capacitors may generate hydrogen internally due to reverse voltage, overvoltage, and overcurrent. If a large amount of hydrogen is generated, the packaging case may be broken due to an increase in internal pressure. In addition, lithium-ion batteries are widely used as batteries for mobile phones, notebook computers, and automobiles. In recent years, in addition to increasing the capacity and improving the cycle characteristics of lithium-ion batteries, concerns about safety have been increasing. In particular, lithium-ion batteries are known to generate gas in the battery cells, and there is a concern that the battery pack may expand or rupture as the internal pressure rises. Therefore, a general aluminum electrolytic capacitor or a lithium ion battery is provided with a safety valve having a gas-permeable membrane. In addition to the function of venting hydrogen inside the capacitor or battery to the outside, the safety valve also has the function of self-destructing to reduce the internal pressure and prevent the capacitor or battery from rupturing when the internal pressure of the capacitor or battery rises rapidly. As such a safety valve, for example, Patent Document 1 discloses a gas-permeable member that includes a gas-permeable sheet that allows gas to pass therethrough, and a holder that holds the gas-permeable sheet, and is mounted on a surface as follows: The container body of the through-hole communicating with the internal space: ventilation is performed between the internal space and the external space of the container body by inserting from the opening through the gas permeation sheet. In addition, as a gas-permeable membrane provided in a safety valve, for example, Patent Document 2 proposes a pressure-regulating membrane having a foil tape made of 20 wt% (19.8 mol%) of Ag in palladium. Made of palladium-silver (Pd-Ag) alloy. However, the foil tape of Patent Document 2 has a problem that it is easily embrittlement in an environment of about 50 to 60 ° C. or lower, and cannot maintain the function as a pressure regulating film for a long time, and has not been put into practical use. In order to solve the above-mentioned problems, Patent Document 3 proposes a hydrogen discharge film including a Pd-Ag alloy and an Ag content in the Pd-Ag alloy of 20 mol% or more. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2015-181153 [Patent Document 2] Japanese Patent No. 4280014 Specification [Patent Document 3] International Publication No. 2014/098038

[Problems to be Solved by the Invention] However, the conventional hydrogen discharge film formed of a metal, especially a hydrogen discharge film formed of a Pd alloy, has a problem that hydrogen permeability gradually decreases depending on a use environment. The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a hydrogen exhaust component that is hardly reduced in hydrogen permeability even when it is used for a long time. It is another object of the present invention to provide an electrochemical device including the hydrogen discharge component. [Technical means for solving the problem] The present invention relates to a hydrogen discharge part, which is characterized in that it is provided with a hydrogen discharge film having a metal layer, and at least a hydrogen introduction surface side of the hydrogen discharge film is provided with an adsorbing sulfur compound Adsorption material. The present inventors made diligent research on the reason why the hydrogen permeability of the previous hydrogen discharge film provided on the hydrogen discharge part was gradually reduced, and found that the metal layer was not embrittled by hydrogen, but a constituent member from inside the electrochemical element ( For example, the gas containing sulfur compounds produced by tubes, electrode lead materials, electrolytic paper, fixing materials, and tapes etc. corrode (sulfurize, etc.) the metal layer of the hydrogen discharge film, causing the metal layer to deteriorate, thereby causing the hydrogen permeability to gradually decrease . This phenomenon has not become a problem in the conventional metal film for hydrogen purification used at a high temperature of 400 ° C or higher in order to separate high-purity hydrogen from a mixed gas, and a hydrogen discharge film using a metal film has not been put into practical use. Therefore, the industry does not know so far. In addition, the present inventors have worked hard on a solution based on the above findings, and have found that by providing an adsorbent for adsorbing a sulfur compound contained in a gas in a hydrogen exhaust part, the sulfur compound is prevented from contacting the metal layer of the hydrogen exhaust film. The metal layer of the hydrogen discharge film is less likely to be corroded. As a result, even when used for a long period of time, the hydrogen permeability is not easily reduced. The adsorbent preferably contains at least one selected from the group consisting of silica, alumina, silica-alumina, zeolite, titanium dioxide, zirconia, magnesia, zinc oxide, white clay, clay, diatomaceous earth, and activated carbon. 1 species. Moreover, it is preferable that the said adsorbent is a metal containing ceramic. By using such an adsorbent, the sulfur compounds contained in the gas can be efficiently adsorbed. From the viewpoint of excellent hydrogen permeability, oxidation resistance, and embrittlement resistance during storage of hydrogen, the metal layer is preferably an alloy layer containing a Pd alloy. The Pd alloy preferably contains 20 to 65 mol% of a Group 11 element. The Group 11 element is preferably at least one selected from the group consisting of Au, Ag, and Cu. The alloy layer containing Pd-group 11 element alloy has the following functions: dissociating hydrogen molecules into hydrogen atoms on the surface of the film and dissolving the hydrogen atoms in the film so that the dissolved hydrogen atoms diffuse from the high-pressure side to the low-pressure side, and The film surface on the low pressure side converts hydrogen atoms into hydrogen molecules again and discharges them. When the content of the Group 11 element is less than 20 mol%, the strength of the alloy may be insufficient, or the above-mentioned function may not be easily exhibited. When it exceeds 65 mol%, the hydrogen transmission rate tends to decrease. The hydrogen discharge film preferably has a support on one or both sides of the metal layer. The support system is provided to prevent the metal layer from falling into the electrochemical element when the metal layer falls off the safety valve. In addition, the metal layer must have a function as a safety valve that self-destructs when the internal pressure of the electrochemical device becomes a certain value or more. In the case where the metal layer is a thin film, the mechanical strength of the metal layer is low, so that the internal pressure of the electrochemical element may self-destruct before it becomes a specific value, and it cannot function as a safety valve. Therefore, when the metal layer is a thin film, in order to improve the mechanical strength, it is preferably on a single-sided or double-area layer support of the metal layer. Moreover, this invention relates to the electrochemical element provided with the said hydrogen discharge part. Examples of the electrochemical element include an aluminum electrolytic capacitor and a lithium ion battery. The present invention also relates to a hydrogen discharge method using the hydrogen discharge part. In the hydrogen discharge method of the present invention, it is preferable to use the above-mentioned hydrogen discharge part to discharge hydrogen under an environment of 150 ° C or lower. [Effects of the Invention] Even when the hydrogen discharge part of the present invention is used for a long period of time, the hydrogen permeability is not easily reduced, and the hydrogen can be stably discharged. In addition, the hydrogen discharge part of the present invention can not only quickly discharge hydrogen generated inside the electrochemical element to the outside, but also prevent impurities from entering the inside of the electrochemical element from the outside. In addition, the hydrogen discharge component of the present invention can self-destruct and reduce the internal pressure when the internal pressure of the electrochemical element sharply rises, thereby preventing the electrochemical element itself from being broken. By these effects, the performance of the electrochemical device can be maintained for a long period of time, and the longevity of the electrochemical device can be achieved.

Hereinafter, embodiments of the present invention will be described. The hydrogen discharge part of the present invention has at least a hydrogen discharge film having a metal layer and an adsorbent for adsorbing a sulfur compound on at least the hydrogen introduction surface side of the hydrogen discharge film, and other constituent members are not particularly limited. The hydrogen discharge film includes at least a metal layer. The metal layer needs to be able to discharge only the hydrogen generated inside the electrochemical element to the outside and prevent substances from entering the inside of the electrochemical element from the outside. For example, the metal layer is a non-porous body without substantially fine through holes. The metal forming the metal layer is not particularly limited as long as it is a metal having a hydrogen permeation function in a simple substance form or by alloying, and examples thereof include Pd, Nb, V, Ta, Ni, Fe, Al, Cu, and Ru , Re, Rh, Au, Pt, Ag, Cr, Co, Sn, Zr, Y, Ce, Ti, Ir, Mo, and alloys containing two or more of these metals. The metal layer is preferably an alloy layer containing a Pd alloy. The other metals forming the Pd alloy are 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, Pd-Au alloy is preferable because it has excellent corrosion resistance to the electrolytic solution inside the electrochemical element or the gas component generated by the constituent member. 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%, and even more preferably 40 to 60 mol%. In addition, the alloy layer containing Pd-Ag alloy with an Ag content of 20 mol% or more, Pd-Cu alloy with a Cu content of 30 mol% or more, or Pd-Au alloy with an Au content of 20 mol% or more is even about 50 to In the low temperature range below 60 ° C, it is also not easily embrittled by hydrogen, so it is preferable. In addition, the Pd alloy may contain a group IB and / or group IIIA metal within a range that does not impair the effects of the present invention. The Pd alloy may be not only an alloy containing two components including Pd, but also an alloy containing three components such as Pd-Au-Ag, and an alloy containing three components including Pd-Au-Cu. . Furthermore, Pd-Au-Ag-Cu may be an alloy containing four components. 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, and more preferably 50 mol% or less. It is preferably 45 mol% or less, and particularly preferably 40 mol% or less. The above-mentioned metal layer can be produced by, for example, a rolling method, a sputtering method, a vacuum evaporation method, an ion plating method, and a plating method, and is preferably used in the case of manufacturing a thick metal layer. The roll method is preferably a sputtering method when manufacturing a thin metal layer. The rolling method may be any of hot rolling and cold rolling. The rolling method is a method in which a pair or a plurality of pairs of rollers are rotated, and a metal as a raw material is passed through while applying pressure between the rollers to process the film into a film. The film thickness of the metal layer obtained by the rolling method is preferably 5 to 50 μm, and more preferably 10 to 30 μm. When the film thickness is less than 5 μm, pinholes or cracks are likely to occur during manufacture, or if hydrogen is stored, it is liable to deform. On the other hand, if the film thickness exceeds 50 μm, it takes time for hydrogen to pass through, so hydrogen permeability is lowered or the cost is poor, which is not good. The sputtering method is not particularly limited, and can be performed using sputtering devices such as a parallel plate type, a monolithic type, a through type, a DC (direct current) sputtering, and an RF (radio frequency) sputtering. For example, after a substrate is mounted on a sputtering device provided with a metal target, the inside of the sputtering device is evacuated, and the argon (Ar) gas pressure is adjusted to a specific value, and a specific sputtering current is passed to the metal target. A metal film is formed on the substrate. Thereafter, the metal film was peeled from the substrate to obtain a metal layer. As the target, a single or a plurality of targets may be used depending on the metal layer to be manufactured. Examples of the substrate include glass plates, ceramic plates, silicon wafers, metal plates such as aluminum and stainless steel. The film thickness of the metal layer obtained by the sputtering method is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm. When the film thickness is less than 0.01 μm, it is not only possible to form pinholes, but it is also difficult to obtain the required mechanical strength. In addition, it is easy to break when peeled from the substrate, and the operation after peeling is also difficult. On the other hand, if the film thickness exceeds 5 μm, it takes time to manufacture the metal layer, which is inferior in terms of cost, which is not preferable. The film area of the metal layer can be appropriately adjusted in consideration of the hydrogen permeation amount and film thickness, but when it is used as a constituent member of a hydrogen discharge part, it is about 0.01 to 100 mm ² . In addition, in the present invention, the film area refers to the area of the portion of the metal layer that substantially emits hydrogen, and does not include the ring-shaped portion coated with the adhesive described below. A coating can also be provided on the surface of the metal layer. By providing the coating layer, it is possible to prevent contaminants (for example, an electrolytic solution) from being attached to the surface of the metal layer of the hydrogen discharge film and corroding it. The raw material of the coating layer is preferably one that can form a surface with a contact angle of 85 ° or more with water. Examples include fluorine-based compounds, rubber-based polymers, polysiloxane-based polymers, and urethane-based polymers. And polyester polymers. Among these, it is preferable to use a material selected from the group consisting of a fluorine-based compound, a rubber-based polymer, and a polysiloxane-based polymer from the viewpoint that the contact angle with water is large and the hydrogen permeability of the hydrogen discharge film is not easily hindered. At least one compound in the group. 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 , Perfluoroalkyl quaternary ammonium salts, perfluoroalkyl ethylene oxide adducts and other compounds containing perfluoroalkyl groups; tetrafluoroethylene / hexafluoropropylene copolymers, and tetrafluoroethylene / perfluoroalkyl Fluorocarbon-based compounds such as vinyl ether copolymers; Tetrafluoroethylene polymers; Copolymers of vinylidene fluoride and tetrafluoroethylene; Copolymers of vinylidene fluoride and hexafluoropropylene; Fluorinated (meth) acrylates ; Fluorine-containing (meth) acrylate polymers; fluorine-containing (meth) acrylate alkyl ester polymers; copolymers of fluorine-containing (meth) acrylates and other monomers, and the like. These may be used singly or in combination of two or more kinds. As for the fluorine-based compound used as a raw material of the coating layer, "DURASURF" series manufactured by HARVES Corporation, "OPTOOL" series manufactured by Daikin Industries, and "KY-100" series manufactured by Shin-Etsu Chemical Industry Co., Ltd. can also be used. Examples of the rubber-based polymer 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. These may be used singly or in combination of two or more kinds. As for the rubber-based polymer used as a raw material for the coating layer, the "ELEP COAT" series manufactured by Nitto Shinko can also be used. Examples of the polysiloxane polymer include polydimethylsiloxane, alkyl-modified polydimethylsiloxane, carboxy-modified polydimethylsiloxane, and amino-modified polydimethylsiloxane. Siloxane, epoxy-modified polydimethylsiloxane, fluorine-modified polydimethylsiloxane, and (meth) acrylate-modified polydimethylsiloxane. These may be used singly or in combination of two or more kinds. The coating layer can be formed, for example, by applying and curing a coating raw material composition on a metal layer or another layer provided 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 blade coating method, a die coating method, an inkjet method, and Gravure coating method and the like. The solvent may be appropriately selected according to the coating material. 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, and a hydrocarbon-based solvent may be used alone, or a mixture of these may be used. Among these, it is preferable to use a non-pyrogenic fluorinated solvent alone or to mix it with other solvents. Examples of the fluorine-based solvent include hydrofluoroether, perfluoropolyether, perfluoroalkane, hydrofluoropolyether, hydrofluorocarbon, perfluorocyclic ether, perfluorocycloalkane, hydrofluorocycloalkane, and hexafluoroxylene. , Hydrochlorofluorocarbons, and perfluorocarbons. These may be used singly or in combination of two or more kinds. The thickness of the coating layer is not particularly limited, and the lower limit value is preferably 0.1 μm or more, more preferably 0.3 μm or more, still more preferably 0.5 μm or more, particularly preferably 1.0 μm or more, and the upper limit value is preferably 80 μm or less. It is more preferably 50 μm or less, still more preferably 30 μm or less, still more preferably 20 μm or less, still more preferably 10 μm or less, and even more preferably 5 μm or less. The thickness of the coating layer can be adjusted by the concentration of the solid content of the coating raw material composition or the number of coating times. In order to prevent permeation from gaseous pollutants, the coating is preferably a non-porous layer. A support can 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 on the metal layer in order to improve the mechanical strength. 1 and 2 are schematic cross-sectional views showing the structure of the hydrogen discharge film 1 of the present invention. The hydrogen discharge film 1 includes a hydrogen introduction surface 6 and a hydrogen discharge surface 7. As shown in Fig. 1 (a) or (b), a ring-shaped adhesive 3 is used on the single-sided or double-area-layer support 4 of the metal layer 2, or as shown in Fig. 2 (a) or (b) The holder 8 is used on the single-sided or double-area-layer support 4 of the metal layer 2. The coating 5 may be provided on the metal layer 2 or on the support 4. The support 4 is not particularly limited as long as it has hydrogen permeability and can support the metal layer 2, and may be a non-porous body or a porous body. The support 4 may be woven or non-woven. Examples of the forming material of the support 4 include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polyethylene naphthalate, and polyaromatics such as polyfluorene and polyetherfluorene. Fluorine resins such as ether fluorene, polytetrafluoroethylene and polyvinylidene fluoride, epoxy resins, polyfluorene, polyfluorine, polyfluorene and so on. Among these, it is preferred to use chemically and thermally stable polyfluorene, polytetrafluoroethylene, polyfluorene, polyimide, and polyimide. The support 4 is preferably a porous body having an average pore diameter of 100 μm or less. If the average pore diameter exceeds 100 μm, the surface smoothness of the porous body is reduced. Therefore, when a metal layer is manufactured by a sputtering method or the like, it is not easy to form a metal layer with a uniform film thickness on the porous body, or it is easy to form a metal layer on the porous body. The layer has pinholes or cracks. The thickness of the support 4 is not particularly limited, but is usually about 5 to 1000 μm, and preferably 10 to 300 μm. When the metal layer 2 is manufactured by sputtering, if the support 4 is used as the substrate, the metal layer 2 can be directly formed on the support 4, and the hydrogen discharge film 1 can be manufactured without using the adhesive 3 or the jig 8. Therefore, it is preferable from the viewpoint of the physical properties and production efficiency of the hydrogen discharge film 1. In this case, as the support 4, it is preferable 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 it is particularly preferable to use an ultrafiltration membrane (UF membrane, Ultrafiltration membrane). ). The shape of the hydrogen discharge film may be substantially circular, or may be a polygon such as a triangle, a quadrangle, or a pentagon. It can be made into any shape suitable for the application described below. The hydrogen discharge film does not become brittle at a low temperature, and therefore has an advantage that it can be used at a temperature of 150 ° C. or lower, and further, a temperature of 110 ° C. or lower. That is, it can be preferably used as a safety valve or a hydrogen discharge valve for an aluminum electrolytic capacitor or a lithium ion battery that is not used at a high temperature (for example, 400 to 500 ° C). The raw material of the adsorption material is not particularly limited as long as it adsorbs sulfur compounds, and examples thereof include silicon dioxide, aluminum oxide, silicon aluminum, zeolite, titanium dioxide, zirconia, magnesium oxide, zinc oxide, white clay, clay, and diatoms. Soil, and activated carbon. These may be used singly or in combination of two or more kinds. Further, a metal-supported ceramic may be used as a raw material of the adsorbent. The metal-supporting ceramic is not particularly limited as long as it adsorbs sulfur compounds. Examples of the metal to be supported include silver, copper, platinum, iron, nickel, tin, and zinc. As a carrier ceramic, for example, Examples: silicon dioxide, aluminum oxide, silicon aluminum, zeolite, titanium dioxide, zirconia, magnesium oxide, and zinc oxide. These may be used singly or in combination of two or more kinds. Examples of the method for forming the adsorbent include a method of firing the raw material, a method of compacting the raw material under high pressure, a method of filling the raw material into a gas-permeable container, and processing into a fiber containing the raw material. A method, and a method of forming the fiber sheet. The form of the adsorbent is not particularly limited, and any form may be adopted. In order to make it easy to mount on a holder or the like, a form of a cartridge containing the adsorbent is preferred. 3 to 5 are a schematic cross-sectional perspective view or a schematic cross-sectional view showing an example of the structure of the hydrogen discharge part of the present invention. However, the embodiment of the hydrogen discharge part of the present invention is not limited in any way by the embodiments of FIGS. 3 to 5, and all known embodiments of the hydrogen discharge part can be used except for the above-mentioned adsorbent. Hereinafter, the structure of the hydrogen discharge part will be described with reference to FIG. 3. The hydrogen discharge part 9 includes a fixing member 10, a hydrogen discharge film 1, a holder (A) 11 holding the hydrogen discharge film 1, a gas permeable film 12, a holder (B) 13 holding the gas permeable film 12, and provided in the above. An adsorption material 14 and an elastic member 15 inside the holding body (B) 13. In addition, the hydrogen discharge part 9 is installed in the recessed part 17 provided in the sealing body 16 of the electrochemical element, and a part of the holding body (B) 13 is embedded in the through hole 18 provided in the recessed part 17 and connected to the inside of the electrochemical element. That is, the conventional hydrogen discharge part has a form in which the adsorbent 14 is not provided in the hydrogen discharge part 9, and the hydrogen discharge part of the present invention has a form in which the adsorbent 14 is provided in the previous hydrogen discharge part. The forming materials of the fixing member 10, the holder (A) 11, and the holder (B) 13 are not particularly limited, and examples thereof include metals such as aluminum and stainless steel; phenol-based resins, polybutylene terephthalate (PBT) Resin such as butyl formate) resin, PP (polypropylene) resin, and PPS (polyphenylene sulfide) resin. In addition, these shapes are not particularly limited, and known shapes can be used. In order to permeate only the gas generated inside the electrochemical element and to prevent the surface of the hydrogen discharge film 1 from being damaged by the contact between the adsorbent 14 and the hydrogen discharge film 1, the gas transmission film 12 is preferably provided on the holder (B) 13. The material for forming the gas-permeable membrane 12 is not particularly limited, and examples thereof include metals, ceramics, and resins. In terms of water repellency, heat resistance, and chemical resistance, fluororesins are preferred. The elastic member 15 is formed of an elastic material such as rubber, and is provided to provide sealing properties and the like. In order to prevent the gas containing sulfur compounds generated from the inside of the electrochemical element from coming into contact with the metal layer of the hydrogen discharge film 1, it is provided on at least the hydrogen introduction surface side of the hydrogen discharge film 1 (between the inside of the electrochemical element and the hydrogen discharge film 1). Sorption material 14. The adsorption material 14 may be provided below or inside the holding body (B) 13 or may be laminated on the hydrogen introduction surface side of the hydrogen discharge film 1 directly or via another member. In addition, in order to prevent the sulfur compounds contained in the atmosphere from coming into contact with the metal layer of the hydrogen discharge film 1, an adsorption material 14 may also be provided on the hydrogen discharge surface side of the hydrogen discharge film 1. The hydrogen discharge component of the present invention is useful as a safety valve for an aluminum electrolytic capacitor or a lithium ion battery. In addition, the hydrogen discharge part of the present invention may be provided on the electrochemical element as a hydrogen discharge valve separately from the safety valve. The method of using the hydrogen discharge part of the present invention to discharge hydrogen generated inside the electrochemical element is not particularly limited. For example, the hydrogen discharge part of the present invention may be provided in a part of an external part of an aluminum electrolytic capacitor or a lithium ion battery, and the hydrogen discharge part may be used. It is used as an isolation member for exterior and interior. In this case, the interior of the exterior is separated from the exterior by a hydrogen exhaust membrane of a hydrogen exhaust component, and the hydrogen exhaust membrane does not allow gases other than hydrogen to pass through. The hydrogen generated inside the exterior is discharged to the outside through the hydrogen discharge membrane by the increase in pressure, and the interior of the exterior will not rise above a certain pressure. The hydrogen discharge film of the present invention has an advantage that it can be used at a temperature of 150 ° C. or lower, and further at a temperature of 110 ° C. or lower, by not adjusting the alloy composition by appropriately adjusting the alloy composition. That is, depending on the application, in the hydrogen discharge method of an aluminum electrolytic capacitor or a lithium ion battery that is not used at a high temperature (for example, 400 to 500 ° C.), the hydrogen discharge component of the present invention can be particularly preferably used. [Examples] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Manufacturing Example 1 [Production of a hydrogen discharge film by sputtering method (Au content: 50 mol%)] An RF magnetron sputtering device (manufactured by Sanyu Electron) equipped with a Pd-Au alloy target having an Au content of 50 mol% A porous polyimide / aromatic polyimide sheet (manufactured by Nitto Denko Corporation, having a pore diameter of 0.001 to 0.1 μm) was mounted as a support. After that, the vacuum exhaust in the sputtering device was 1 × 10 ^-5 Pa or less, and a Pd-Au alloy target was passed with a sputtering current of 4.8 A under an argon (Ar) gas pressure of 1.0 Pa to form on the support. Pd-Au alloy layer (Au content 50 mol%) with a thickness of 400 nm. Then, an antifouling layer raw material composition (DURASURF DS-3302TH, manufactured by HARVES Co., Ltd.) was coated on the Pd-Au alloy layer by a dip coating method, and dried to form an antifouling layer, thereby producing a hydrogen emission film. Example 1 Using the hydrogen emission film produced in Production Example 1, a hydrogen emission part in the form described in FIG. 3 was produced. As the adsorbent, a filter cartridge prepared by filling zeolite Ag (manufactured by Tosoh Corporation, HSZ-941, powder) into a case made of PP resin was used. Then, an aluminum electrolytic capacitor is produced using the produced hydrogen discharge parts, and hemp paper as a separator. Example 2 Using the hydrogen emission film produced in Production Example 1, a hydrogen emission part in the form described in FIG. 3 was produced. As the adsorbent, a filter cartridge produced by filling zeolite Ag (manufactured by Tosoh Corporation, HSZ-941, pellets) in a case made of PP resin was used. Then, an aluminum electrolytic capacitor is produced using the produced hydrogen discharge parts, and hemp paper as a separator. Example 3 Using the hydrogen emission film produced in Production Example 1, a hydrogen emission part in the form described in FIG. 3 was produced. As the adsorbent, a filter cartridge was used in which alumina Cu (manufactured by UNION SHOWA, GB217, powder) was filled in a case made of PP resin. Then, an aluminum electrolytic capacitor is produced using the produced hydrogen discharge parts, and hemp paper as a separator. Example 4 Using the hydrogen emission film produced in Production Example 1, a hydrogen emission part in the form described in FIG. 3 was produced. As the adsorbent, a filter cartridge was used in which alumina Cu (manufactured by UNION SHOWA Co., Ltd., GB217, pellet B) was filled in a case made of PP resin. Then, an aluminum electrolytic capacitor is produced using the produced hydrogen discharge parts, and hemp paper as a separator. Example 5 Using the hydrogen emission film produced in Production Example 1, a hydrogen emission part in the form described in FIG. 3 was produced. As the adsorbent, a filter cartridge was used in which alumina Cu (manufactured by UNION SHOWA Co., Ltd., GB217, particle G) was filled in a case made of PP resin. Then, an aluminum electrolytic capacitor is produced using the produced hydrogen discharge parts, and hemp paper as a separator. Example 6 Using the hydrogen emission film produced in Production Example 1, a hydrogen emission part in the form described in FIG. 3 was produced. As the adsorbent, a filter cartridge prepared by filling zeolite Cu (manufactured by Tosoh Corporation, HSZ-840CUA1, powder) in a case made of PP resin was used. Then, an aluminum electrolytic capacitor is produced using the produced hydrogen discharge parts, and hemp paper as a separator. Example 7 Using the hydrogen emission film produced in Production Example 1, a hydrogen emission part 9 in the form described in FIG. 4 was produced. As the adsorbent, alumina Cu (manufactured by UNION SHOWA, GB217, powder) was used to fill a case 13 (retainer (B)) made of PP resin, and a gas-permeable membrane 12 was used (Nitto Denko Corporation) (Manufactured, TEMISH, fluorine porous membrane) is a filter cartridge manufactured by covering the upper part of the casing 13. In order to ensure air tightness, a polysilicon square ring 19 is provided between the filter cartridge and the hydrogen discharge membrane 1, and a polysilicon product is provided between the filter cartridge and the sealing body (refer to the sealing body 16 in FIG. 3). Flexible member 15 (O-ring). Then, an aluminum electrolytic capacitor is produced using the produced hydrogen discharge parts, and hemp paper as a separator. Example 8 Using the hydrogen emission film produced in Production Example 1, a hydrogen emission part 9 in the form described in FIG. 5 was produced. As the adsorbent, a filter cartridge produced by the following method was used. Alumina Cu (manufactured by UNION SHOWA Co., Ltd., GB217, granule G) was placed in a case 13 (retainer (B)) made of PP resin, and a silicone sealant was filled in the gap between the alumina Cu and the case 13 (Made by Shin-Etsu Chemical Co., KE-1833). After the polysiloxane sealant was cured at 125 ° C. for 1 hour, a pin vise was used to form a 0.5 mm diameter through hole from the bottom of the case 13 to the alumina Cu, and a gas inlet 20 was provided. In addition, a needle hole pliers was used to form a through hole having a diameter of 0.5 mm from the upper portion of the casing 13 to the alumina Cu, and a gas exhaust port 21 was provided. Then, in order to prevent the alumina Cu from scattering from the case 13, a gas transmission membrane 12 (manufactured by Nitto Denko Corporation, TEMISH, fluorine porous membrane) was welded to the gas inflow port 20 and the gas discharge port 21 to produce a filter cartridge. In order to ensure air tightness, a polysilicon square ring 19 is provided between the filter cartridge and the hydrogen discharge membrane 1, and a polysilicon product is provided between the filter cartridge and the sealing body (refer to the sealing body 16 in FIG. 3). Flexible member 15 (O-ring). Then, an aluminum electrolytic capacitor is produced using the produced hydrogen discharge parts, and hemp paper as a separator. Example 9 In Example 8, except that the diameter of the above-mentioned through hole was changed from 0.5 mm to 0.8 mm, an aluminum electrolytic capacitor was manufactured by the same method as in Example 8. Comparative Example 1 Using the hydrogen emission film produced in Production Example 1, a hydrogen emission part having the form described in FIG. 3 was produced. However, no adsorbent is provided. Then, an aluminum electrolytic capacitor is produced using the produced hydrogen discharge parts, and hemp paper as a separator. [Measurement and evaluation method] (Measurement of hydrogen permeation amount of hydrogen discharge film before voltage application) The hydrogen discharge film produced in Production Example 1 was mounted on a Vacuum Coupling Radius Seal (VCR) manufactured by Swagelok Company, and vacuum-connected radial seal ) Connector, install a SUS tube on one side to make a sealed space (63.5 ml). After the pressure in the tube was reduced by a vacuum pump, the pressure was adjusted so that the pressure of hydrogen became 0.15 MPa, and the pressure change under the environment of 105 ° C was monitored. The mole number (volume) of hydrogen permeating through the hydrogen discharge membrane is known from the pressure change. Therefore, it is converted into the permeation amount per day to calculate the hydrogen permeation amount. For example, when the pressure changes from 0.15 MPa to 0.05 MPa (change amount of 0.10 MPa) within 2 hours, the volume of hydrogen passing through the hydrogen discharge membrane is 63.5 ml. Therefore, the hydrogen permeation amount per day becomes 63.5 × 24/2 = 762 ml / day. The hydrogen permeation amount of the hydrogen discharge membrane is preferably 10 ml / day or more, more preferably 40 ml / day or more, even more preferably 70 ml / day or more, and even more preferably 100 ml / day or more. (Evaluation of Aluminum Electrolytic Capacitor) The aluminum electrolytic capacitors produced in the examples and comparative examples were subjected to a voltage of 400 V for 96 hours at an ambient temperature of 105 ° C. Thereafter, the deformation of the aluminum case of the aluminum electrolytic capacitor was visually confirmed, and evaluation was performed according to the following criteria. 〇: No change in the shape of the aluminum case ×: The aluminum case has a bulge (measurement of the hydrogen transmission amount of the hydrogen discharge film after the voltage is applied) Take out the hydrogen discharge film from the above aluminum electrolytic capacitor after the voltage is applied for 96 hours, and borrow The hydrogen permeation amount of the hydrogen discharge film was measured by the same method as described above. [Table 1] [Industrial Applicability] The hydrogen discharge component of the present invention can be suitably used as a safety valve or a hydrogen discharge valve provided in an electrochemical element such as a battery, a capacitor, a capacitor, and a sensor.

1‧‧‧hydrogen exhaust membrane

2‧‧‧ metal layer

3‧‧‧ Adhesive

4‧‧‧ support

5‧‧‧ Coating

6‧‧‧ hydrogen introduction surface

7‧‧‧Hydrogen discharge surface

8‧‧‧ Fixture

9‧‧‧ Hydrogen discharge parts

10‧‧‧Fixed components

11‧‧‧ Retainer (A)

12‧‧‧Gas transmission membrane

13‧‧‧ holding body (B)

14‧‧‧ Adsorbent

15‧‧‧ Elastic member

16‧‧‧Sealing body

17‧‧‧ recess

18‧‧‧through hole

19‧‧‧ square ring

20‧‧‧Gas inlet

21‧‧‧Gas exhaust port

1 (a) and 1 (b) are schematic cross-sectional views showing the structure of a hydrogen discharge film of the present invention. 2 (a) and 2 (b) are schematic cross-sectional views showing another structure of the hydrogen discharge film of the present invention. Fig. 3 is a schematic cross-sectional perspective view showing an example of the structure of a hydrogen discharge part of the present invention. Fig. 4 is a schematic cross-sectional view showing an example of the structure of a hydrogen discharge part of the present invention. Fig. 5 is a schematic cross-sectional view showing an example of the structure of a hydrogen discharge part of the present invention.

Claims (11)

A hydrogen discharge component is characterized by comprising a hydrogen discharge film having a metal layer, and an adsorption material that adsorbs sulfur compounds is provided on at least a hydrogen introduction surface side of the hydrogen discharge film. The hydrogen discharge part according to claim 1, wherein the adsorbent contains a material selected from the group consisting of silica, alumina, silica-alumina, zeolite, titania, zirconia, magnesia, zinc oxide, clay, clay, diatomaceous earth, and activated carbon At least one of the groups formed. The hydrogen discharge part according to claim 1, wherein the adsorbent contains a metal-supported ceramic. The hydrogen discharge part according to any one of claims 1 to 3, wherein the metal layer is an alloy layer containing a Pd alloy. The hydrogen discharge part according to claim 4, wherein the Pd alloy contains 20 to 65 mol% of a Group 11 element. For example, the hydrogen exhausting part of claim 5, wherein the group 11 element is at least one selected from the group consisting of Au, Ag, and Cu. The hydrogen discharge part according to any one of claims 1 to 6, which has a support on one side or both sides of the metal layer. An electrochemical element provided with the hydrogen discharge part according to any one of claims 1 to 7. The electrochemical element according to claim 8, wherein the electrochemical element is an aluminum electrolytic capacitor or a lithium ion battery. A hydrogen discharge method using a hydrogen discharge part according to any one of claims 1 to 7. If the hydrogen exhaust method of claim 10 is used, the hydrogen is exhausted in an environment below 150 ° C.