WO2016143658A1 - 水素排出膜 - Google Patents
水素排出膜 Download PDFInfo
- Publication number
- WO2016143658A1 WO2016143658A1 PCT/JP2016/056587 JP2016056587W WO2016143658A1 WO 2016143658 A1 WO2016143658 A1 WO 2016143658A1 JP 2016056587 W JP2016056587 W JP 2016056587W WO 2016143658 A1 WO2016143658 A1 WO 2016143658A1
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- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- hydrogen discharge
- metal layer
- film
- alloy
- Prior art date
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 169
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 169
- 239000012528 membrane Substances 0.000 title claims abstract description 68
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000002431 hydrogen Chemical class 0.000 claims description 105
- 239000010410 layer Substances 0.000 claims description 98
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 28
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/08—Housing; Encapsulation
- H01G9/12—Vents or other means allowing expansion
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/30—Arrangements for facilitating escape of gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a hydrogen discharge film provided in electrochemical elements such as batteries, capacitors, capacitors, and sensors.
- Aluminum electrolytic capacitors have been used for applications such as inverters for wind power generation and solar power generation, large power sources such as storage batteries.
- Aluminum electrolytic capacitors may generate hydrogen gas inside due to reverse voltage, overvoltage, and overcurrent, and if a large amount of hydrogen gas is generated, the outer case may burst due to an increase in internal pressure.
- a general aluminum electrolytic capacitor is provided with a safety valve equipped with a special film.
- 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.
- lithium-ion batteries are widely used as batteries for mobile phones, notebook computers, and automobiles.
- lithium-ion batteries have become increasingly interested in safety in addition to increasing capacity and improving cycle characteristics.
- a lithium ion battery generates gas in the cell, and there is a concern about expansion and rupture of the battery pack accompanying an increase in internal pressure.
- Patent Document 2 discloses an amorphous alloy (for example, 36Zr-64Ni alloy) made of an alloy of zirconium (Zr) and nickel (Ni) as a hydrogen selective permeable alloy film that selectively permeates hydrogen gas generated in a battery.
- amorphous alloy for example, 36Zr-64Ni alloy
- Zr zirconium
- Ni nickel
- the amorphous alloy forms a hydride (ZrH 2 ) and becomes brittle when exposed to hydrogen in a low temperature range (for example, 50 ° C.), so that the function as a pressure adjusting film cannot be maintained for a long time. There was a problem.
- Patent Document 3 in order to solve the above problem, a hydrogen discharge film containing a Pd—Ag alloy, in which the content of Ag in the Pd—Ag alloy is 20 mol% or more is proposed. .
- the hydrogen discharge membrane of Patent Document 3 is not easily embrittled at the use temperature of the electrochemical device, and has sufficient hydrogen discharge properties at the initial stage of use, but there is a problem that the hydrogen discharge properties gradually decrease depending on the use environment. .
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a hydrogen discharge membrane in which hydrogen discharge performance is unlikely to deteriorate even when used for a long period of time. It is another object of the present invention to provide an electrochemical element safety valve provided with the hydrogen discharge membrane and an electrochemical element provided with the safety valve.
- the present invention relates to a hydrogen exhaust film having a metal layer, wherein at least one surface of the hydrogen exhaust film has a contact angle with water of 85 ° or more.
- the present inventor has intensively studied the cause of the gradual decrease in the hydrogen discharge performance of the conventional hydrogen discharge film, not because the metal layer becomes brittle due to hydrogen, but an electrolyte solution or a component (e.g. The gas generated from the tube, electrode lead material, electrolytic paper, fixing material, tape, etc.) is applied to the membrane surface of the hydrogen discharge membrane, particularly to the hydrogen introduction side surface (the inner side surface when the hydrogen discharge membrane is provided on the electrochemical device).
- an electrolyte solution or a component e.g. The gas generated from the tube, electrode lead material, electrolytic paper, fixing material, tape, etc.
- Such a phenomenon does not pose a problem in a conventional hydrogen purification metal film used at a high temperature of 400 ° C. or higher for separating high purity hydrogen from a mixed gas, and a hydrogen discharge film using a metal film. Has not been known because it has not been put into practical use.
- the hydrogen discharge membrane has a hydrogen introduction side surface and a hydrogen discharge side surface, and the hydrogen introduction side surface preferably has a contact angle of 85 ° or more with water.
- the hydrogen discharge film may be formed by laminating the metal layer and the coat layer directly or via another layer.
- one surface of the coat layer is the hydrogen introduction side surface. If the coating layer is provided on the hydrogen introduction side of the metal layer, the hydrogen permeability of the hydrogen discharge membrane is hindered. Therefore, conventionally, no functional layer is provided on the hydrogen introduction side of the metal layer.
- by laminating a coating layer on one side of the metal layer and making one surface of the coating layer a hydrogen introduction side surface it becomes easy to adjust the contact angle with water on the hydrogen introduction side surface to 85 ° or more, and hydrogen discharge properties Can be effectively suppressed from gradually decreasing. The decrease in hydrogen permeability of the hydrogen discharge membrane due to the provision of the coating layer can be minimized by adjusting the material and thickness of the coating layer.
- the coat layer preferably contains at least one compound selected from the group consisting of a fluorine-based compound, a rubber-based polymer, and a silicone-based polymer.
- the coat layer preferably has a thickness of 0.1 to 80 ⁇ m.
- the thickness of the coat layer is less than 0.1 ⁇ m, it is difficult to obtain a uniform coating film, and gas-derived contaminants tend to adhere.
- it exceeds 80 ⁇ m the hydrogen permeability of the hydrogen discharge membrane tends to deteriorate.
- the metal layer is preferably an alloy layer containing a Pd alloy from the viewpoint of excellent hydrogen permeability, oxidation resistance, and embrittlement resistance during hydrogen storage.
- 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.
- An alloy layer containing a Pd-Group 11 element alloy dissociates hydrogen molecules into hydrogen atoms on the film surface to solidify hydrogen atoms in the film, and diffuses the dissolved hydrogen atoms from the high pressure side to the low pressure side. It has the 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 alloy tends to be insufficient or the function tends to be difficult to develop, and when it exceeds 65 mol%, the hydrogen permeation rate decreases. There is a tendency.
- the hydrogen discharge membrane of the present invention preferably has a support on one side or both sides of the metal layer.
- the support is provided to prevent the metal layer from falling into the electrochemical element when the metal layer falls off the safety valve.
- the metal layer needs to have a function as a safety valve that self-destructs when the internal pressure of the electrochemical element exceeds a predetermined value.
- the mechanical strength of the metal layer is low, so that the internal pressure of the electrochemical element may be destroyed before reaching a predetermined value, and the function as a safety valve cannot be achieved. Therefore, when a metal layer is a thin film, it is preferable to laminate
- the present invention also relates to a safety valve for an electrochemical element provided with the hydrogen discharge membrane, and an electrochemical element having the safety valve.
- 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 membrane or the electrochemical element safety valve.
- the hydrogen discharge method of the present invention it is preferable to discharge hydrogen in an environment of 150 ° C. or lower using the hydrogen discharge film or the like.
- the hydrogen discharge membrane of the present invention is less likely to deteriorate the hydrogen discharge performance even when the electrochemical device is used for a long period of time, and can discharge hydrogen stably.
- the hydrogen discharge film of the present invention can quickly discharge only hydrogen gas generated inside the electrochemical element to the outside, and can prevent impurities from entering the electrochemical element from the outside.
- the safety valve provided with the hydrogen discharge membrane of the present invention can self-destruct and reduce the internal pressure when the internal pressure of the electrochemical element suddenly increases, thereby preventing the electrochemical element itself from bursting. By these effects, the performance of the electrochemical element can be maintained for a long time, and the lifetime of the electrochemical element can be extended.
- the hydrogen discharge membrane of the present invention has at least a metal layer.
- the metal forming the metal layer is not particularly limited as long as it is a single substance or a metal having a hydrogen permeation function by alloying, for example, Pd, Nb, V, Ta, Ni, Fe, Al, Cu, Ru, Examples thereof include Re, Rh, 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, but a group 11 element is preferably used, and 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 electrochemical element.
- the Pd alloy preferably contains 20 to 65 mol% of a Group 11 element, more preferably 30 to 65 mol%, still more preferably 30 to 60 mol%, and particularly preferably 40 to 60 mol%.
- 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 alloy layer containing the Pd alloy is not limited to the alloy containing the two components containing Pd, but may be an alloy containing, for example, the three components of Pd—Au—Ag, and includes the three components of Pd—Au—Cu.
- An alloy may be used.
- an alloy containing four components of Pd—Au—Ag—Cu may be used.
- the total content of Au and the other metal in the Pd—Au alloy is preferably 55 mol% or less, more preferably 50 mol%. Or less, more preferably 45 mol% or less, and particularly preferably 40 mol% or less.
- the metal layer can be produced by, for example, a rolling method, a sputtering method, a vacuum deposition method, an ion plating method, a plating method, etc., but when producing a thick metal layer, a rolling method is used. It is preferable to use a sputtering method when a thin metal layer is manufactured.
- 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 metal 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, the Ar gas pressure is adjusted to a predetermined value, a predetermined sputtering current is applied to the metal target, and the metal is deposited on the substrate. A film is formed. Thereafter, the metal film is peeled from the substrate to obtain a metal layer.
- a target a single target or a some target can be used according to the metal 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 metal 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 metal layer, which is not preferable because of inferior cost.
- the film area of the metal 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 the safety valve.
- the film area is the area of the metal layer where hydrogen is actually discharged, and does not include the portion where a ring-shaped adhesive described later is applied.
- At least one surface of the hydrogen discharge membrane having the metal layer has a contact angle with water of 85 ° or more, preferably 90 ° or more, more preferably 95 ° or more, and further preferably 100 ° or more. It is. If the contact angle with water is 85 ° or more, contaminants derived from gas are difficult to adhere to the film surface, and the metal layer of the hydrogen discharge film is hardly corroded. As a result, even if it is used for a long period of time, the hydrogen discharging property is unlikely to decrease.
- the upper limit of the contact angle with water is not particularly limited, but is practically about 170 °.
- the hydrogen discharge membrane has a hydrogen introduction side surface and a hydrogen discharge side surface, and the contact angle between the hydrogen introduction side surface and water is preferably 85 ° or more.
- the method for making the contact angle with water on the membrane surface of the hydrogen exhaust film 85 ° or more is not particularly limited.
- a fine uneven shape is formed on the surface of the metal layer to make the contact angle with water 85 ° or more.
- a method of forming a thin film on the surface of the metal layer by a vacuum deposition method so that the contact angle with water is 85 ° or more, or a coat layer having a surface with a contact angle with water of 85 ° or more The method of laminating
- a method for forming a fine uneven shape on the surface of the metal layer is not particularly limited. For example, femtosecond laser processing using an ultra-high frequency pulse laser, anodizing treatment in H 2 SO 4 aqueous solution, NaOH aqueous solution And an FPP treatment in which hard fine particles having a particle size of several tens of ⁇ m are projected onto the surface of the metal layer at high speed.
- the method for forming a thin film on the surface of the metal layer by a vacuum deposition method is not particularly limited.
- a vapor deposition material that has been vaporized or sublimated by heating in a high vacuum to form gas molecules collides with and adheres to the metal layer.
- a deposited thin film can be formed.
- the vapor deposition material is not particularly limited as long as the contact angle of the obtained thin film with water is 85 ° or more, but an organic compound having a perfluoroalkyl derivative is suitable.
- the deposited thin film may be subjected to polymerization treatment by heating or ultraviolet irradiation.
- the raw material of the coating layer is not particularly limited as long as it can form a surface having a contact angle with water of 85 ° or more.
- fluorine compound for example, fluorine compound, rubber polymer, silicone polymer, urethane polymer, and polyester System polymers and the like.
- 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)
- rubber-based polymers examples 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 or another layer provided on the 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 coat layer is not particularly limited, but the lower limit is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, still more preferably 0.5 ⁇ m or more, and particularly preferably 1.0 ⁇ m.
- the upper limit is preferably 80 ⁇ m or less, more preferably 50 ⁇ m or less, further preferably 30 ⁇ m or less, further preferably 20 ⁇ m or less, still more preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
- the thickness of the coating layer can be adjusted by the solid content concentration of the coating layer raw material composition and the number of coatings.
- the coating layer is preferably a non-porous layer in order to prevent permeation of gas-derived contaminants.
- a support may be provided on one side or both sides of the metal layer.
- the metal layer obtained by the sputtering method is thin, it is preferable to laminate a support on one side or both sides of the metal layer in order to improve mechanical strength.
- a preferred embodiment of the hydrogen discharge membrane of the present invention is a metal layer containing a Pd alloy provided with a coating layer containing a fluorine compound, and particularly at least one selected from the group consisting of Au, Ag, and Cu.
- a Pd alloy containing a Group 11 element is preferably provided with a coat layer containing a fluorine-based compound.
- FIG. 1 and 2 are schematic sectional views showing the structure of the hydrogen discharge membrane 1 of the present invention.
- the hydrogen discharge film 1 has a hydrogen introduction side surface 6 and a hydrogen discharge side surface 7.
- a support 4 may be laminated on one or both sides of the metal layer 2 using a ring-shaped adhesive 3, and FIG. 2 (a) or (b) As shown in FIG. 3, the support 4 may be laminated on one side or both sides of the metal layer 2 using a jig 8. Further, the coat layer 5 may be provided on the metal layer 2 or may be provided on the support 4.
- the support 4 is not particularly limited as long as it is hydrogen permeable and can support the metal layer 2, and may be a non-porous body or a porous body.
- 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, so that it is difficult to form a metal layer with a uniform film thickness on the porous body when a metal layer is produced by sputtering or the like. Pinholes or cracks are likely to occur in the metal 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 metal layer 2 is produced by the sputtering method
- the metal layer 2 can be directly formed on the support body 4, and the hydrogen discharge film can be used without using the adhesive 3 or the jig 8. 1 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.
- UF membrane ultrafiltration membrane
- the shape of the hydrogen discharge membrane of the present invention 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 of the present invention is particularly useful as a component of a safety valve for an aluminum electrolytic capacitor or a lithium ion battery.
- the hydrogen discharge membrane of the present invention can be provided in the electrochemical element as a hydrogen discharge valve separately from the safety valve.
- the method for discharging the hydrogen generated inside the electrochemical device using the hydrogen discharge film of the present invention is not particularly limited.
- the hydrogen discharge film of the present invention is provided on a part of the exterior of an aluminum electrolytic capacitor or a lithium ion battery. This can be used as an outer and inner diaphragm.
- the interior and exterior of the exterior are separated by the hydrogen exhaust film, and the hydrogen exhaust film does not permeate gases other than hydrogen. Hydrogen generated inside the exterior is discharged to the outside through the hydrogen discharge film due to an increase in pressure, and the interior of the exterior does not rise above a predetermined pressure.
- the hydrogen discharge membrane of the present invention has an advantage that it can be used at a temperature of, for example, 150 ° C. or lower, and further 110 ° C. or lower because it does not become brittle at low temperatures by appropriately adjusting the alloy composition. That is, the hydrogen discharge membrane of the present invention is particularly preferably used in a hydrogen discharge method in an aluminum electrolytic capacitor or a lithium ion battery that is not used at a high temperature (for example, 400 to 500 ° C.) depending on its application.
- a high temperature for example, 400 to 500 ° C.
- 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.
- 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.
- strain inside the Pd—Au alloy caused by rolling was removed, and a Pd—Au alloy layer having a thickness of 20 ⁇ m and an Au content of 30 mol% was produced.
- Production Example 2 [Production of Pd—Ag alloy layer (Ag content 30 mol%) by rolling method] A Pd—Ag alloy layer having a thickness of 20 ⁇ m and an Ag content of 30 mol% was produced in the same manner as in Example 1 except that Pd and Ag raw materials were used so that the Ag content in the ingot was 30 mol%.
- Example 1 A coating layer raw material composition (manufactured by Harves, Durasurf DS-3302TH) was applied to one side of the Pd—Au alloy layer produced in Production Example 1 by the dip coating method, and dried to form a coating layer to form a hydrogen discharge film Was made.
- Example 2 In Example 1, a hydrogen discharge membrane was prepared in the same manner as in Example 1 except that Durasurf DS-3308TH (manufactured by Harves) was used instead of Durasurf DS-3302TH.
- Durasurf DS-3308TH manufactured by Harves
- Example 3 In Example 1, instead of Durasurf DS-3302TH, Durasurf DS-3308TH (manufactured by Harves) and Durasurf DS-3320C (manufactured by Harves) were mixed in the same amount to obtain a solid content concentration of 14 wt%. A hydrogen discharge membrane was produced in the same manner as in Example 1 except that the layer raw material composition was used.
- Example 4 In Example 1, a hydrogen discharge membrane was produced in the same manner as in Example 1 except that Durasurf DS-3320C (manufactured by Harves) was used instead of Durasurf DS-3302TH.
- Example 5 In Example 1, a hydrogen discharge membrane was produced in the same manner as in Example 1 except that Durasurf DS-3330C (manufactured by Harves) was used instead of Durasurf DS-3302TH.
- Durasurf DS-3330C manufactured by Harves
- Example 6 In the same manner as in Example 5, the coating layer raw material composition was applied and dried, and then Durasurf DS-3330C (manufactured by Harves) was further applied and dried. Was made.
- Example 7 In Example 1, a hydrogen discharge membrane was produced in the same manner as in Example 1 except that Durasurf DS-5480H (manufactured by Harves) was used instead of Durasurf DS-3302TH.
- Example 8 In Example 1, a hydrogen discharge membrane was produced in the same manner as in Example 1 except that Elep Coat LSS-520MH (manufactured by Nitto Shinko) was used instead of Durasurf DS-3302TH.
- Elep Coat LSS-520MH manufactured by Nitto Shinko
- Example 2 a hydrogen discharge membrane was produced in the same manner as in Example 1 except that G-90 (manufactured by Nikken) was used instead of Durasurf DS-3302TH.
- 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 hydrogen gas was adjusted to 0.15 MPa, and the pressure change in an environment of 105 ° C. was monitored. Since the number of moles (volume) of hydrogen permeated through the hydrogen discharge membrane was found by the pressure change, this was converted into the permeation amount per day, and the hydrogen permeation amount was calculated.
- the hydrogen permeation amount of the hydrogen discharge membrane is preferably 10 ml / day or more, more preferably 40 ml / day or more, still more preferably 70 ml / day or more, and particularly preferably 100 ml / day or more.
- the upper limit of the hydrogen permeation amount is about 1000 ml / day.
- the retention rate of the hydrogen permeation amount before and after the exposure treatment needs to be 40% or more, preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, particularly preferably. Is 80% or more.
- the hydrogen discharge membrane of the present invention is suitably used as a component of a safety valve provided in electrochemical elements such as batteries, capacitors, capacitors, and sensors.
- Hydrogen discharge membrane 2 Metal layer 3: Adhesive 4: Support 5: Coat layer 6: Hydrogen introduction side surface 7: Hydrogen discharge side surface 8: Jig
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Abstract
Description
〔圧延法によるPd-Au合金層(Au含有量30mol%)の作製〕
インゴット中のAu含有量が30mol%となるようにPd及びAu原料をそれぞれ秤量し、水冷銅坩堝を備えたアーク溶解炉に投入し、大気圧のArガス雰囲気中でアーク溶解した。得られたボタンインゴットをロール径100mmの2段圧延機を用いて厚さ5mmになるまで冷間圧延して板材を得た。その後、ガラス管の中に圧延した板材を入れ、ガラス管の両端を封止した。ガラス管内部を室温で5×10-4Paまで減圧し、その後700℃まで昇温して24時間放置し、その後室温まで冷却した。この熱処理により、合金中のPd及びAuの偏析を解消した。次に、ロール径100mmの2段圧延機を用いて板材を厚さ100μmになるまで冷間圧延し、さらにロール径20mmの2段圧延機を用いて板材を厚さ20μmになるまで冷間圧延した。その後、ガラス管の中に圧延した板材を入れ、ガラス管の両端を封止した。ガラス管内部を室温で5×10-4Paまで減圧し、その後500℃まで昇温して1時間放置し、その後室温まで冷却した。この熱処理により、圧延によって生じたPd-Au合金内部のひずみを除去し、厚さ20μm、Au含有量30mol%のPd-Au合金層を作製した。
〔圧延法によるPd-Ag合金層(Ag含有量30mol%)の作製〕
インゴット中のAg含有量が30mol%となるようにPd及びAg原料をそれぞれ使用した以外は実施例1と同様の方法で厚さ20μm、Ag含有量30mol%のPd-Ag合金層を作製した。
製造例1で作製したPd-Au合金層の片面にコート層原料組成物(ハーベス社製、デュラサーフDS-3302TH)をディップコート法で塗布し、乾燥させてコート層を形成して水素排出膜を作製した。
実施例1において、デュラサーフDS-3302THの代わりに、デュラサーフDS-3308TH(ハーベス社製)を用いた以外は実施例1と同様の方法で水素排出膜を作製した。
実施例1において、デュラサーフDS-3302THの代わりに、デュラサーフDS-3308TH(ハーベス社製)とデュラサーフDS-3320C(ハーベス社製)を同量混合し、固形分濃度を14wt%としたコート層原料組成物を用いた以外は実施例1と同様の方法で水素排出膜を作製した。
実施例1において、デュラサーフDS-3302THの代わりに、デュラサーフDS-3320C(ハーベス社製)を用いた以外は実施例1と同様の方法で水素排出膜を作製した。
実施例1において、デュラサーフDS-3302THの代わりに、デュラサーフDS-3330C(ハーベス社製)を用いた以外は実施例1と同様の方法で水素排出膜を作製した。
実施例5と同様にしてコート層原料組成物を塗布し、乾燥した後、さらにデュラサーフDS-3330C(ハーベス社製)を塗布し、乾燥した以外は実施例5と同様の方法で水素排出膜を作製した。
実施例1において、デュラサーフDS-3302THの代わりに、デュラサーフDS-5480H(ハーベス社製)を用いた以外は実施例1と同様の方法で水素排出膜を作製した。
実施例1において、デュラサーフDS-3302THの代わりに、エレップコートLSS-520MH(日東シンコー社製)を用いた以外は実施例1と同様の方法で水素排出膜を作製した。
製造例1で作製したPd-Au合金層を水素排出膜とした。
実施例1において、デュラサーフDS-3302THの代わりに、G-90(日研社製)を用いた以外は実施例1と同様の方法で水素排出膜を作製した。
製造例2で作製したPd-Ag合金層を水素排出膜とした。
(接触角の測定)
水素排出膜の水素導入側面の水との接触角は、JIS R3257(基板ガラス表面のぬれ性試験方法)に準拠して測定し、接触角測定装置(英弘精機社製、OCAシリーズ)を用いて静的接触角を測定した。具体的には、25℃の雰囲気下で、2cm角の試料に純水を8μL滴下し、液面と試料表面のなす角θ(下記図面を参照)をマイクロスコープで測定した。左右二つのθの平均値を接触角とした。
作製した水素排出膜をスウェージロック社製のVCRコネクターに取り付け、片側にSUSチューブを取り付け、密封された空間(63.5ml)を作製した。チューブ内を真空ポンプで減圧後、水素ガスの圧力が0.15MPaになるように調整し、105℃の環境下での圧力変化をモニターした。圧力変化により水素排出膜を透過した水素モル数(体積)がわかるため、これを1日当たりの透過量に換算して水素透過量を算出した。例えば、2時間で圧力が0.15MPaから0.05MPaに変化した場合(変化量0.10MPa)、水素排出膜を透過した水素体積は63.5mlになる。よって、1日当たりの水素透過量は63.5×24/2=762ml/dayとなる。水素排出膜の水素透過量は、10ml/day以上であることが好ましく、より好ましくは40ml/day以上であり、さらに好ましくは70ml/day以上であり、特に好ましくは100ml/day以上である。また、水素透過量の上限値は1000ml/day程度である。
密閉されたSUS缶内にモデル電解液として、アジピン酸二アンモニウム(和光純薬工業株式会社製)2g及びエチレングリコール18gを入れた。コート層側表面のみを汚染物質で曝露させるために、作製した水素排出膜(15mm×15mm)の合金層側表面をアルミ箔でマスクし、SUS缶の蓋から吊り下げた。その後、SUS缶を105℃に加熱して96時間放置し、前記2種の化合物から発生したガスで水素排出膜のコート層側表面を曝露処理した。その後、合金層側表面からアルミ箔を取り外し、水素排出膜の水素透過量を上記と同様の方法で測定した。曝露処理前後の水素透過量の保持率は40%以上であることが必要であり、好ましくは50%以上であり、より好ましくは60%以上であり、さらに好ましくは70%以上であり、特に好ましくは80%以上である。
2:金属層
3:接着剤
4:支持体
5:コート層
6:水素導入側面
7:水素排出側面
8:治具
Claims (15)
- 金属層を有する水素排出膜において、前記水素排出膜の少なくとも一方の面は、水との接触角が85°以上であることを特徴とする水素排出膜。
- 前記水素排出膜は、水素導入側面と水素排出側面を有しており、前記水素導入側面は、水との接触角が85°以上である請求項1記載の水素排出膜。
- 前記水素排出膜は、前記金属層とコート層とが直接又は他の層を介して積層されたものである請求項1又は2記載の水素排出膜。
- 前記コート層の一方の面が前記水素導入側面である請求項3記載の水素排出膜。
- 前記コート層は、フッ素系化合物、ゴム系ポリマー、及びシリコーン系ポリマーからなる群より選択される少なくとも1種の化合物を含む請求項3又は4記載の水素排出膜。
- 前記コート層は、厚さが0.1~80μmである請求項3~5のいずれかに記載の水素排出膜。
- 前記金属層は、Pd合金を含む合金層である請求項1~6のいずれかに記載の水素排出膜。
- 前記Pd合金は、第11族元素を20~65mol%含む請求項7記載の水素排出膜。
- 前記第11族元素は、Au、Ag、及びCuからなる群より選択される少なくとも1種である請求項8記載の水素排出膜。
- 前記金属層の片面又は両面に支持体を有する請求項1~9のいずれかに記載の水素排出膜。
- 請求項1~10のいずれかに記載の水素排出膜を備えた電気化学素子用安全弁。
- 請求項11記載の電気化学素子用安全弁を備えた電気化学素子。
- 前記電気化学素子が、アルミ電解コンデンサ又はリチウムイオン電池である請求項12記載の電気化学素子。
- 請求項1~10のいずれかに記載の水素排出膜、又は請求項11記載の電気化学素子用安全弁を用いた水素排出方法。
- 150℃以下の環境下で水素を排出させる請求項14記載の水素排出方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201680011297.9A CN107430941A (zh) | 2015-03-06 | 2016-03-03 | 氢气排出膜 |
KR1020177027693A KR20170125915A (ko) | 2015-03-06 | 2016-03-03 | 수소 배출막 |
EP16761628.3A EP3267446A1 (en) | 2015-03-06 | 2016-03-03 | Hydrogen discharge membrane |
US15/555,580 US20180053923A1 (en) | 2015-03-06 | 2016-03-03 | Hydrogen-releasing film |
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