WO2015194470A1 - 水素排出膜 - Google Patents
水素排出膜 Download PDFInfo
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- WO2015194470A1 WO2015194470A1 PCT/JP2015/067000 JP2015067000W WO2015194470A1 WO 2015194470 A1 WO2015194470 A1 WO 2015194470A1 JP 2015067000 W JP2015067000 W JP 2015067000W WO 2015194470 A1 WO2015194470 A1 WO 2015194470A1
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- Prior art keywords
- hydrogen discharge
- hydrogen
- film
- alloy
- mol
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 292
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 292
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910001020 Au alloy Inorganic materials 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 150000002431 hydrogen Chemical class 0.000 claims description 214
- 238000000034 method Methods 0.000 claims description 48
- 239000012528 membrane Substances 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 239000003990 capacitor Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
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- 230000007613 environmental effect Effects 0.000 abstract 1
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- 229910052763 palladium Inorganic materials 0.000 description 12
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- 239000002994 raw material Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
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- 239000010949 copper Substances 0.000 description 6
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 2
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- 241001391944 Commicarpus scandens Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
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- 108700031620 S-acetylthiorphan Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- ZRSKSQHEOZFGLJ-UHFFFAOYSA-N ammonium adipate Chemical compound [NH4+].[NH4+].[O-]C(=O)CCCCC([O-])=O ZRSKSQHEOZFGLJ-UHFFFAOYSA-N 0.000 description 1
- 235000019293 ammonium adipate Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- H01M50/394—Gas-pervious parts or elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D69/10—Supported membranes; Membrane supports
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- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/02—Inorganic material
- B01D71/0213—Silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/022—Metals
- B01D71/0223—Group 8, 9 or 10 metals
- B01D71/02231—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
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- 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
- 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
- H01G11/18—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors against thermal overloads, e.g. heating, cooling or ventilating
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- 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
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
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- 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
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
-
- 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
- H01M50/342—Non-re-sealable arrangements
- H01M50/3425—Non-re-sealable arrangements in the form of rupturable membranes or weakened parts, e.g. pierced with the aid of a sharp member
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
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- 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
- H01G11/78—Cases; Housings; Encapsulations; Mountings
- H01G11/80—Gaskets; Sealings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/20—Pressure-sensitive devices
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- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a hydrogen discharge membrane provided in electrochemical elements such as batteries, capacitors, capacitors, and sensors. More specifically, the present invention relates to a hydrogen discharge membrane having a function of discharging generated hydrogen to the outside under an environment of use of about 150 ° C. or lower in an electrochemical element in which hydrogen gas is generated and the internal pressure is increased during use.
- 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.
- the foil strip of Patent Document 1 has a problem that it tends to become brittle in an environment of about 50 to 60 ° C. or less, and the function as a pressure adjusting film cannot be maintained for a long time.
- the pressure adjustment film is deteriorated by the gas released from a part of the organic material used as the exterior case part and accessory of the electrochemical element, and the hydrogen discharge function is reduced. A new problem was also identified.
- 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.
- 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 film, a composite hydrogen discharge film, and a hydrogen discharge laminated film that are not easily embrittled at the use environment temperature of the electrochemical element. Another object of the present invention is to provide a hydrogen discharge film, a composite hydrogen discharge film, and a hydrogen discharge laminated film that are not easily deteriorated by a gas released from an organic material in addition to the above characteristics. Moreover, it aims at providing the electrochemical element provided with the safety valve for electrochemical elements provided with the said hydrogen discharge film
- the present invention relates to a hydrogen discharge film including an alloy, wherein the alloy is a Pd—Au alloy, and the Au content in the Pd—Au alloy is 15 mol% or more.
- a hydrogen permeable membrane containing a Pd—Ag alloy dissociates hydrogen molecules into hydrogen atoms on the membrane surface, so that the hydrogen atoms are dissolved in the membrane, and the dissolved hydrogen atoms are diffused from the high pressure side to the low pressure side.
- the film surface has a function of converting hydrogen atoms into hydrogen molecules and discharging them again. Further, it is known that the Pd—Ag alloy has a hydrogen separation function in a temperature range of 400 to 600 ° C.
- the reason why the Pd-20 wt% Ag alloy of Patent Document 1 is likely to become brittle in an environment of about 50 to 60 ° C. or less is considered as follows.
- the ⁇ lattice phase hardly changes even when hydrogen atoms are dissolved in the high temperature range, but in the low temperature range of about 50 to 60 ° C. or less, the ⁇ lattice phase It is considered that a part of the phase changes to the ⁇ lattice phase, and when dehydrogenated, the ⁇ lattice phase has the characteristic of changing again to the ⁇ lattice phase.
- the lattice constant of the ⁇ lattice phase is larger than the lattice constant of the ⁇ lattice phase, distortion occurs in a region where the ⁇ lattice phase and the ⁇ lattice phase coexist ( ⁇ + ⁇ lattice phase). Therefore, it is considered that when hydrogen solution-dehydrogenation is repeated, fracture due to strain occurs in the ⁇ + ⁇ lattice phase, and the Pd-20 wt% Ag alloy becomes brittle.
- the present inventors have formed a hydrogen discharge film using a Pd—Au alloy having an Au content of 15 mol% or more instead of a Pd—Ag alloy, thereby achieving a low temperature range of about 50 to 60 ° C. or less.
- a Pd—Au alloy having an Au content of 15 mol% or more is unlikely to change from an ⁇ lattice phase to a ⁇ lattice phase even when hydrogen atoms are dissolved in a low temperature range of about 50 to 60 ° C., that is, an ⁇ + ⁇ lattice phase. Is considered difficult to form.
- the Pd—Au alloy of the present invention does not easily embrittle even if hydrogen solution-dehydrogenation is repeated.
- the present inventors have found that a hydrogen discharge film containing a Pd—Au alloy having an Au content of 15 mol% or more is caused by a gas released from an organic material used as an exterior case part or accessory of an electrochemical element. We found that it is hard to deteriorate.
- the hydrogen discharge film preferably has an Au content in the Pd—Au alloy of 15 to 55 mol%, and the film thickness t (m) and the film area s (m 2 ) satisfy the following formula 1.
- the hydrogen discharge membrane provided in the electrochemical device has a hydrogen permeation amount of 10 ml / day or more (4.03 ⁇ 10 ⁇ 4 mol / day or more) at a square root of pressure of 76.81 Pa 1/2 (0.059 bar): according to SATP. (The volume of 1 mol ideal gas at a temperature of 25 ° C. and a pressure of 1 bar is 24.8 L)).
- the hydrogen discharge membrane having an Au content of 15 to 55 mol% in the Pd—Au alloy of the present invention has a hydrogen permeability coefficient at 50 ° C. of 3.6 ⁇ 10 ⁇ 12 to 2.5 ⁇ 10 ⁇ 9 (mol ⁇ m ⁇ 1 ⁇ sec ⁇ 1 ⁇ Pa ⁇ 1/2 ).
- the hydrogen permeation coefficient is obtained by the following equation 2.
- Hydrogen permeability coefficient (number of moles of hydrogen ⁇ film thickness t) / (membrane area s ⁇ time ⁇ square root of pressure)
- the hydrogen permeation rate is 10 ml / day (4.03 ⁇ 10 ⁇ 4 mol / day) and the hydrogen permeation coefficient is 2.5 ⁇ 10 ⁇ 9 (mol ⁇ m ⁇ 1 ⁇ sec ⁇ 1 ⁇ Pa ⁇ 1/2 )
- the condition for the hydrogen permeation amount to be 10 ml / day or more (4.03 ⁇ 10 ⁇ 4 mol / day or more) is film thickness t / film area s ⁇ 41.1 m ⁇ 1 .
- the Pd—Au alloy may further contain a group IB and / or group IIIA metal.
- the total content of Au and the metal in the Pd—Au alloy is preferably 55 mol% or less.
- the composite hydrogen discharge membrane of the present invention has the hydrogen discharge membrane on one side or both sides of the metal layer.
- the hydrogen discharge laminated film of the present invention has a support on one side or both sides of the hydrogen discharge film or the composite hydrogen discharge film.
- the support is provided in order to prevent the hydrogen discharge membrane or the like from falling into the electrochemical element when it falls off the safety valve.
- the hydrogen discharge membrane or the like needs to have a function as a safety valve that self-destructs when the internal pressure of the electrochemical element becomes a predetermined value or more. If the hydrogen discharge membrane etc. is a thin film, the mechanical strength of the hydrogen discharge membrane etc. is low, so there is a risk of self-destruction before the internal pressure of the electrochemical element reaches a predetermined value, and it cannot function as a safety valve . Therefore, when the hydrogen discharge membrane or the like is a thin film, it is preferable to laminate a support on one side or both sides of the hydrogen discharge membrane or the like in order to improve mechanical strength.
- the support is preferably a porous body having an average pore diameter of 100 ⁇ m or less. If the average pore diameter exceeds 100 ⁇ m, the surface smoothness of the porous body will decrease, so when a hydrogen discharge film or the like is produced by sputtering or the like, a hydrogen discharge film or the like having a uniform film thickness is formed on the porous body. It becomes difficult to generate a pinhole or a crack in the hydrogen discharge film or the like.
- the support is preferably formed of at least one polymer selected from the group consisting of polytetrafluoroethylene, polysulfone, polyimide, polyamideimide, and aramid from the viewpoint of being chemically and thermally stable.
- the present invention also relates to a safety valve for an electrochemical element provided with the hydrogen discharge film, the composite hydrogen discharge film, or the hydrogen discharge laminated film, 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 film, the composite hydrogen discharge film, the hydrogen discharge laminated film, 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 film, the composite hydrogen discharge film, and the hydrogen discharge laminated film of the present invention are characterized in that they are not easily embrittled at the environment temperature in which the electrochemical element is used and are not easily deteriorated by the gas released from the organic material.
- the hydrogen discharge film, composite hydrogen discharge film, and hydrogen discharge laminated film of the present invention can not only quickly discharge only hydrogen gas generated inside the electrochemical element to the outside, but also the inside of the electrochemical element from the outside. Impurity can be prevented from entering the substrate.
- the safety valve provided with the hydrogen discharge membrane, composite hydrogen discharge membrane, or hydrogen discharge laminated film of the present invention self-destructs when the internal pressure of the electrochemical element suddenly increases, lowers the internal pressure, and electrochemical The element itself can be prevented 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.
- FIG. 2 is a photograph after an evaluation test of a hydrogen discharge film produced in Example 1.
- FIG. 6 is a photograph after an evaluation test of a hydrogen discharge film produced in Example 3.
- 6 is a photograph after an evaluation test of a hydrogen discharge film produced in Example 5.
- FIG. 7 is the photograph after the evaluation test of the hydrogen discharge laminated film produced in Example 7.
- FIG. 6 is a photograph after an evaluation test of a hydrogen discharge laminated film produced in Comparative Example 3.
- the Au content is preferably 25 mol% or more, and more preferably 30 mol% or more. Further, when the content of Au is 15 mol% or more, it is possible to suppress the deterioration of the hydrogen discharge film due to the gas released from the organic material. On the other hand, since the hydrogen permeation rate tends to decrease when the Au content becomes too large, the Au content is preferably 55 mol% or less, more preferably 50 mol% or less, and even more preferably 45 mol. % Or less, and particularly preferably 40 mol% or less.
- the Pd—Au alloy may contain a group IB and / or group IIIA metal within a range not impairing the effect of the present invention, and may contain, for example, Ag and / or Cu. That is, an alloy containing three components of Pd—Au—Ag or an alloy containing three components of Pd—Au—Cu may be used. Further, an alloy containing four components of Pd—Au—Ag—Cu may be used.
- the total content of Au and other metals in the Pd—Au alloy is preferably 55 mol% or less, more preferably It is 50 mol% or less, More preferably, it is 45 mol% or less, Most preferably, it is 40 mol% or less.
- the hydrogen discharge film of the present invention can be produced by, for example, a rolling method, a sputtering method, a vacuum evaporation method, an ion plating method, a plating method, etc. It is preferable to use a rolling method, and when manufacturing a thin hydrogen discharge film, it is preferable to use a sputtering method.
- the rolling method may be hot rolling or any method of cold rolling.
- the rolling method is a method in which a pair or a plurality of pairs of rolls (rollers) are rotated, and a Pd—Au alloy as a raw material is passed between the rolls while applying pressure to form a film.
- the film thickness of the hydrogen discharge film 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 permeate, so that the hydrogen discharge performance 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, and a predetermined sputtering current is supplied to the Pd—Au alloy target.
- a Pd—Au alloy film is formed on the substrate.
- the Pd—Au alloy film is peeled from the substrate to obtain a hydrogen discharge film.
- a target a single target or a plurality of targets can be used depending on a hydrogen discharge film 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 hydrogen discharge film 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 a hydrogen discharge film, which is not preferable because of inferior cost.
- the membrane area of the hydrogen discharge membrane can be appropriately adjusted in consideration of the amount of hydrogen permeation and the thickness, but is about 0.01 to 100 mm 2 when used as a constituent member of a safety valve.
- the film area is an area of a hydrogen discharge film where hydrogen is actually discharged, and does not include a portion where a ring-shaped adhesive described later is applied.
- 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 Ag and Cu.
- the Pd alloy preferably contains a Group 11 element in an amount of 20 to 65 mol%, more preferably 30 to 65 mol%, and still more preferably 30 to 60 mol%.
- an alloy layer containing a Pd—Ag alloy having an Ag content of 20 mol% or more or a Pd—Cu alloy having a Cu content of 30 mol% or more has a hydrogen content even in a low temperature range of about 50 to 60 ° C. or less. Is preferable because it is difficult to embrittle.
- 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 metal layer can be produced by the same method as the hydrogen exhaust film. Moreover, it is preferable that the film thickness of the said metal layer is comparable as the film thickness of the said hydrogen exhaust film.
- the method for providing the hydrogen discharge film on one or both surfaces of the metal layer is not particularly limited, and examples thereof include a sputtering method, a vacuum deposition method, an ion plating method, and a plating method. Moreover, you may use a ring-shaped adhesive agent.
- a support may be provided on one or both sides of the hydrogen discharge film or the composite hydrogen discharge film to form a hydrogen discharge laminated film.
- the hydrogen discharge film obtained by sputtering is thin, it is preferable to laminate a support on one or both sides of the hydrogen discharge film in order to improve the mechanical strength.
- FIG. 1 and 2 are schematic cross-sectional views showing the structure of the hydrogen discharge laminated film 1 of the present invention.
- a support 4 may be laminated on one or both sides of the hydrogen discharge membrane 2 using a ring-shaped adhesive 3, and FIG. 2 (a) or (b ), The support 4 may be laminated on one side or both sides of the hydrogen discharge film 2 using the jig 5.
- the support 4 is not particularly limited as long as it is hydrogen permeable and can support the hydrogen discharge membrane 2, and may be a non-porous material or a porous material. When a porous body is used as the support 4, a sponge structure or a finger void structure is preferable.
- 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, polyaryl ether sulfones such as polysulfone and polyethersulfone, polytetrafluoroethylene, and polyvinylidene fluoride.
- Fluorine resin, epoxy resin, polyamide, polyimide, polyamideimide, aramid and the like can be mentioned.
- at least one selected from the group consisting of chemically and thermally stable polytetrafluoroethylene, polysulfone, polyimide, polyamideimide, and aramid is preferably used.
- the thickness of the support 4 is not particularly limited, but is usually about 5 to 1000 ⁇ m, preferably 10 to 300 ⁇ m.
- the hydrogen discharge film 2 When the hydrogen discharge film 2 is manufactured by the sputtering method, if the support 4 is used as a substrate, the hydrogen discharge film 2 can be directly formed on the support 4, and the hydrogen discharge film 2 can be formed without using the adhesive 3 or the jig 5. Since the discharge
- 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 film, composite hydrogen discharge film, and hydrogen discharge laminated film of the present invention may be substantially circular, or may be 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 film, composite hydrogen discharge film, and hydrogen discharge laminated film of the present invention are particularly useful as components for safety valves of aluminum electrolytic capacitors or lithium ion batteries.
- the hydrogen discharge film, the composite hydrogen discharge film, and the hydrogen discharge laminated film 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, composite hydrogen discharge film or hydrogen discharge laminated film of the present invention is not particularly limited, but for example, one of the exterior parts of an aluminum electrolytic capacitor or a lithium ion battery.
- the part can be provided with the hydrogen discharge film, composite hydrogen discharge film or hydrogen discharge laminated film of the present invention, and this can be used as a diaphragm inside and outside the exterior.
- the interior and exterior of the exterior are separated by a hydrogen exhaust film or the like, and the hydrogen exhaust film or the like does not transmit gas other than hydrogen.
- Hydrogen generated inside the exterior is discharged to the outside through a hydrogen discharge film or the like 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 does not become brittle at a low temperature, there is an advantage that it can be used at a temperature of 150 ° C. or lower, for example, 110 ° C. or lower. 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.
- Example 1 [Production of hydrogen discharge film by rolling method (Au content: 15 mol%)] Pd and Au raw materials were weighed so that the Au content in the ingot was 15 mol%, and charged into an arc melting furnace equipped with a water-cooled copper crucible, and arc melted in an Ar gas atmosphere at atmospheric pressure.
- the obtained button ingot was cold-rolled to a thickness of 5 mm using a two-high rolling mill having a roll diameter of 100 mm to obtain a plate material. Then, the rolled plate material was put in the glass tube, and both ends of the glass tube were sealed. The inside of the glass tube was depressurized to 5 ⁇ 10 ⁇ 4 Pa at room temperature, then heated to 700 ° C.
- the plate material is cold-rolled to a thickness of 100 ⁇ m using a two-high rolling mill with a roll diameter of 100 mm, and further, the plate material is cold-rolled to a thickness of 25 ⁇ m using a two-high rolling mill with a roll diameter of 20 mm did. Then, the rolled plate material was put in the glass tube, and both ends of the glass tube were sealed. The inside of the glass tube was depressurized to 5 ⁇ 10 ⁇ 4 Pa at room temperature, then heated to 500 ° C. and allowed to stand for 1 hour, and then cooled to room temperature.
- Example 2 [Production of hydrogen discharge film by rolling method (Au content: 20 mol%)] A Pd—Au hydrogen discharge film having a thickness of 25 ⁇ m and an Au content of 20 mol% was prepared in the same manner as in Example 1 except that Pd and Au materials were used so that the Au content in the ingot was 20 mol%. . When the hydrogen embrittlement of the hydrogen discharge film was evaluated by the following method, no change in appearance such as strain was observed.
- Example 3 [Production of hydrogen discharge film by rolling method (Au content: 30 mol%)] A Pd—Au hydrogen discharge film having a thickness of 25 ⁇ m and an Au content of 30 mol% was prepared in the same manner as in Example 1 except that Pd and Au raw materials were used so that the Au content in the ingot was 30 mol%. . When the hydrogen embrittlement of the hydrogen discharge film was evaluated by the following method, no change in appearance such as strain was observed (see FIG. 4).
- Example 4 [Production of hydrogen discharge film by rolling method (Au content 40 mol%)] A Pd—Au hydrogen discharge film having a thickness of 25 ⁇ m and an Au content of 40 mol% was prepared in the same manner as in Example 1 except that Pd and Au raw materials were used so that the Au content in the ingot was 40 mol%. . When the hydrogen embrittlement of the hydrogen discharge film was evaluated by the following method, no change in appearance such as strain was observed.
- Example 5 [Production of hydrogen discharge film by rolling method (Au content 50 mol%)] A Pd—Au hydrogen discharge film having a thickness of 25 ⁇ m and an Au content of 50 mol% was prepared in the same manner as in Example 1 except that Pd and Au raw materials were used so that the Au content in the ingot was 50 mol%. . When the hydrogen embrittlement of the hydrogen discharge film was evaluated by the following method, no change in appearance such as strain was observed (see FIG. 5).
- Example 6 [Production of hydrogen discharge film by rolling method (Au content 15 mol%, Ag content 15 mol%)] The thickness was 25 ⁇ m, the Au content was 15 mol%, and the Ag content was 15 mol, except that Pd, Au, and Ag raw materials were used so that the Au and Ag contents in the ingot were 15 mol% each. % Pd—Au—Ag hydrogen discharge membrane was prepared. When the hydrogen embrittlement of the hydrogen discharge film was evaluated by the following method, no change in appearance such as strain was observed (see FIG. 6).
- Comparative Example 1 [Production of hydrogen discharge film by rolling method (Au content: 10 mol%)] A Pd—Au hydrogen discharge film having a thickness of 25 ⁇ m and an Au content of 10 mol% was prepared in the same manner as in Example 1 except that Pd and Au raw materials were used so that the Au content in the ingot was 10 mol%. .
- the hydrogen embrittlement of the hydrogen discharge film was evaluated by the following method, the hydrogen discharge film was distorted and became unusable for practical use (see FIG. 7).
- Comparative Example 2 [Production of hydrogen discharge film by rolling method (Ag content: 19.8 mol%)] Pd and Ag raw materials were weighed so that the Ag content in the ingot would be 19.8 mol%, put into an arc melting furnace equipped with a water-cooled copper crucible, and arc melted in an atmospheric pressure Ar gas atmosphere.
- the obtained button ingot was cold-rolled to a thickness of 5 mm using a two-high rolling mill having a roll diameter of 100 mm to obtain a plate material. Then, the rolled plate material was put in the glass tube, and both ends of the glass tube were sealed. The inside of the glass tube was depressurized to 5 ⁇ 10 ⁇ 4 Pa at room temperature, then heated to 700 ° C.
- the plate material is cold-rolled to a thickness of 100 ⁇ m using a two-high rolling mill with a roll diameter of 100 mm, and further, the plate material is cold-rolled to a thickness of 25 ⁇ m using a two-high rolling mill with a roll diameter of 20 mm did. Then, the rolled plate material was put in the glass tube, and both ends of the glass tube were sealed. The inside of the glass tube was depressurized to 5 ⁇ 10 ⁇ 4 Pa at room temperature, then heated to 700 ° C. and allowed to stand for 1 hour, and then cooled to room temperature.
- Example 7 [Fabrication of hydrogen discharge laminated film by sputtering method (Au content 15 mol%)]
- a polysulfone porous sheet (manufactured by Nitto Denko Corporation, pore size: 0.001 to 0.02 ⁇ m) is mounted on an RF magnetron sputtering apparatus (manufactured by Sanyu Electronics Co., Ltd.) equipped with a Pd—Au alloy target having an Au content of 15 mol%. ) was attached.
- the inside of the sputtering apparatus is evacuated to 1 ⁇ 10 ⁇ 5 Pa or less, and a sputtering current of 4.8 A is applied to the Pd—Au alloy target at an Ar gas pressure of 1.0 Pa to form a thick film on the polysulfone porous sheet.
- a 400-nm thick Pd—Au alloy film (Au content: 15 mol%) was formed to produce a hydrogen discharge laminated film.
- Example 8 [Fabrication of hydrogen discharge laminated film by sputtering method (Au content 20 mol%)] A 400-nm-thick Pd—Au alloy film (Au content 20 mol%) was formed by the same method as in Example 7 except that a Pd—Au alloy target having an Au content of 20 mol% was used, and a hydrogen discharge laminated film Was made. When the hydrogen embrittlement of the hydrogen discharge laminated film was evaluated by the following method, no cracks were generated on the surface.
- Example 9 [Production of hydrogen-discharge laminated film by sputtering method (Au content: 30 mol%)] A 400-nm-thick Pd—Au alloy film (Au content 30 mol%) was formed by the same method as in Example 7 except that a Pd—Au alloy target having an Au content of 30 mol% was used, and a hydrogen-discharge laminated film Was made. When the hydrogen embrittlement of the hydrogen discharge laminated film was evaluated by the following method, no cracks were generated on the surface (see FIG. 9).
- Example 10 [Fabrication of hydrogen discharge laminated film by sputtering method (Au content 40 mol%)] A 400-nm-thick Pd—Au alloy film (Au content 40 mol%) was formed in the same manner as in Example 7 except that a Pd—Au alloy target having an Au content of 40 mol% was used, and a hydrogen-discharge laminated film was made. When the hydrogen embrittlement of the hydrogen discharge laminated film was evaluated by the following method, no cracks were generated on the surface.
- Example 11 [Fabrication of hydrogen discharge laminated film by sputtering method (Au content 50 mol%)] A 400-nm-thick Pd—Au alloy film (Au content 50 mol%) was formed in the same manner as in Example 7 except that a Pd—Au alloy target having an Au content of 50 mol% was used, and a hydrogen-discharge laminated film Was made. When the hydrogen embrittlement of the hydrogen discharge laminated film was evaluated by the following method, no cracks were generated on the surface (see FIG. 10).
- Example 12 [Fabrication of hydrogen discharge laminated film by sputtering method (Au content 15 mol%, Ag content 15 mol%)] A Pd—Au—Ag alloy film having a thickness of 400 nm (Au and Ag contents: each), except that a Pd—Au—Ag alloy target having an Au and Ag content of 15 mol% each was used. 15 mol%) to form a hydrogen discharge laminated film.
- a Pd—Au—Ag alloy target having an Au and Ag content of 15 mol% each was used. 15 mol%) to form a hydrogen discharge laminated film.
- Comparative Example 4 [Fabrication of hydrogen discharge laminated film by sputtering method (Ag content: 19.8 mol%)] A 400 nm thick Pd—Ag alloy film (Ag content 19.8 mol%) was formed in the same manner as in Example 7 except that a Pd—Ag alloy target having an Ag content of 19.8 mol% was used. A hydrogen discharge laminated film was prepared. When the hydrogen embrittlement of the hydrogen discharge laminated film was evaluated by the following method, cracks were generated on the surface. It is thought that hydrogen embrittlement occurred.
- the effective film area s of the hydrogen discharge film used for the measurement is 3.85 ⁇ 10 ⁇ 5 m 2
- the effective film area s of the hydrogen discharge stacked film is 7.07 ⁇ 10 ⁇ 6 m 2 .
- Hydrogen permeability coefficient (number of moles of hydrogen ⁇ film thickness t) / (membrane area s ⁇ time ⁇ square root of pressure)
- the produced hydrogen discharge film or hydrogen discharge laminated film 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 hydrogen moles (volume) permeated through the hydrogen discharge membrane or the hydrogen discharge laminated film can be determined by the pressure change, the hydrogen permeation amount was converted to the permeation amount per day.
- the effective film area s of the hydrogen discharge film used for the measurement is 3.85 ⁇ 10 ⁇ 5 m 2
- the effective film area s of the hydrogen discharge stacked film is 7.07 ⁇ 10 ⁇ 6 m 2 .
- hydrogen permeability was evaluated according to the following criteria. ⁇ : 100 mL / day or more ⁇ : 10 mL / day or more and less than 100 mL / day ⁇ : less than 10 mL / day
- the produced hydrogen discharge membrane was put in a glass tube, and both ends of the glass tube were sealed.
- the inside of the glass tube was depressurized to 5 ⁇ 10 ⁇ 3 Pa at 50 ° C., and then heated to 400 ° C. Thereafter, hydrogen gas was introduced into the glass tube and left for 1 hour in an atmosphere of 105 kPa. Thereafter, the inside of the glass tube was cooled to room temperature, and the inside of the glass tube was evacuated to 5 ⁇ 10 ⁇ 3 Pa (30 minutes). Thereafter, hydrogen gas was again introduced into the glass tube and left for 1 hour in an atmosphere of 105 kPa. After the above operation was repeated three times, the hydrogen discharge film was taken out from the glass tube, and the appearance of the hydrogen discharge film was visually observed.
- the hydrogen discharge film, composite hydrogen discharge film, and hydrogen discharge laminated film of the present invention are suitably used as components for safety valves provided in electrochemical elements such as batteries, capacitors, capacitors, and sensors.
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Abstract
Description
〈式1〉t/s<41.1m-1
電気化学素子に設けられる水素排出膜は、圧力の平方根が76.81Pa1/2(0.059bar)における水素透過量が10ml/day以上(4.03×10-4mol/day以上:SATPに従い計算(温度25℃、気圧1barにおける1molの理想気体の体積は24.8L))であることが求められる。本発明のPd-Au合金中のAuの含有量が15~55mol%である水素排出膜は、50℃における水素透過係数が3.6×10-12~2.5×10-9(mol・m-1・sec-1・Pa-1/2)である。ここで、水素透過係数は下記式2により求められる。
〈式2〉水素透過係数=(水素モル数×膜厚t)/(膜面積s×時間×圧力の平方根)
水素透過量が10ml/day(4.03×10-4mol/day)かつ水素透過係数が2.5×10-9(mol・m-1・sec-1・Pa-1/2)の場合、式2に各数値を代入すると以下のとおりである。
2.5×10-9=(4.03×10-4×膜厚t)/(膜面積s×86400×76.81)
2.5×10-9=6.08×10-11×膜厚t/膜面積s
膜厚t/膜面積s=41.1m-1
したがって、50℃における水素透過係数が3.6×10-12~2.5×10-9(mol・m-1・sec-1・Pa-1/2)の水素透過膜を用いる場合において、水素透過量が10ml/day以上(4.03×10-4mol/day以上)となる条件は、膜厚t/膜面積s<41.1m-1である。
〔圧延法による水素排出膜(Au含有量15mol%)の作製〕
インゴット中のAu含有量が15mol%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25μm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25μm、Au含有量15mol%のPd-Au水素排出膜を作製した。下記方法で水素排出膜の水素脆性を評価したところ、実用上問題ない程度の外観上の僅かな歪みが見られただけであった(図3参照)。
〔圧延法による水素排出膜(Au含有量20mol%)の作製〕
インゴット中のAu含有量が20mol%となるようにPd及びAu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25μm、Au含有量20mol%のPd-Au水素排出膜を作製した。下記方法で水素排出膜の水素脆性を評価したところ、歪などの外観変化は見られなかった。
〔圧延法による水素排出膜(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原料をそれぞれ使用した以外は実施例1と同様の方法で厚さ25μm、Au含有量30mol%のPd-Au水素排出膜を作製した。下記方法で水素排出膜の水素脆性を評価したところ、歪などの外観変化は見られなかった(図4参照)。
〔圧延法による水素排出膜(Au含有量40mol%)の作製〕
インゴット中のAu含有量が40mol%となるようにPd及びAu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25μm、Au含有量40mol%のPd-Au水素排出膜を作製した。下記方法で水素排出膜の水素脆性を評価したところ、歪などの外観変化は見られなかった。
〔圧延法による水素排出膜(Au含有量50mol%)の作製〕
インゴット中のAu含有量が50mol%となるようにPd及びAu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25μm、Au含有量50mol%のPd-Au水素排出膜を作製した。下記方法で水素排出膜の水素脆性を評価したところ、歪などの外観変化は見られなかった(図5参照)。
〔圧延法による水素排出膜(Au含有量15mol%、Ag含有量15mol%)の作製〕
インゴット中のAu及びAg含有量が各15mol%となるようにPd、Au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25μm、Au含有量15mol%及びAg含有量15mol%のPd-Au-Ag水素排出膜を作製した。下記方法で水素排出膜の水素脆性を評価したところ、歪などの外観変化は見られなかった(図6参照)。
〔圧延法による水素排出膜(Au含有量10mol%)の作製〕
インゴット中のAu含有量が10mol%となるようにPd及びAu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25μm、Au含有量10mol%のPd-Au水素排出膜を作製した。下記方法で水素排出膜の水素脆性を評価したところ、水素排出膜に歪が発生し実用上使用できない状態になった(図7参照)。
〔圧延法による水素排出膜(Ag含有量19.8mol%)の作製〕
インゴット中のAg含有量が19.8mol%となるようにPd及びAg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Ag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25μm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700℃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-Ag合金内部のひずみを除去し、厚さ25μm、Ag含有量19.8mol%のPd-Ag水素排出膜を作製した。下記方法で水素排出膜の水素脆性を評価したところ、水素排出膜に歪が発生し実用上使用できない状態になった。
〔スパッタリング法による水素排出積層膜(Au含有量15mol%)の作製〕
Au含有量が15mol%であるPd-Au合金ターゲットを装着したRFマグネトロンスパッタリング装置(サンユー電子社製)に、支持体であるポリスルホン多孔質シート(日東電工社製、孔径0.001~0.02μm)を取り付けた。その後、スパッタリング装置内を1×10-5Pa以下に真空排気し、Arガス圧1.0Paにおいて、Pd-Au合金ターゲットに4.8Aのスパッタ電流を投入して、ポリスルホン多孔質シート上に厚さ400nmのPd-Au合金膜(Au含有量15mol%)を形成して水素排出積層膜を作製した。下記方法で水素排出積層膜の水素脆性を評価したところ、表面にクラックは生じていなかった(図8参照)。
〔スパッタリング法による水素排出積層膜(Au含有量20mol%)の作製〕
Au含有量が20mol%であるPd-Au合金ターゲットを用いた以外は実施例7と同様の方法で厚さ400nmのPd-Au合金膜(Au含有量20mol%)を形成して水素排出積層膜を作製した。下記方法で水素排出積層膜の水素脆性を評価したところ、表面にクラックは生じていなかった。
〔スパッタリング法による水素排出積層膜(Au含有量30mol%)の作製〕
Au含有量が30mol%であるPd-Au合金ターゲットを用いた以外は実施例7と同様の方法で厚さ400nmのPd-Au合金膜(Au含有量30mol%)を形成して水素排出積層膜を作製した。下記方法で水素排出積層膜の水素脆性を評価したところ、表面にクラックは生じていなかった(図9参照)。
〔スパッタリング法による水素排出積層膜(Au含有量40mol%)の作製〕
Au含有量が40mol%であるPd-Au合金ターゲットを用いた以外は実施例7と同様の方法で厚さ400nmのPd-Au合金膜(Au含有量40mol%)を形成して水素排出積層膜を作製した。下記方法で水素排出積層膜の水素脆性を評価したところ、表面にクラックは生じていなかった。
〔スパッタリング法による水素排出積層膜(Au含有量50mol%)の作製〕
Au含有量が50mol%であるPd-Au合金ターゲットを用いた以外は実施例7と同様の方法で厚さ400nmのPd-Au合金膜(Au含有量50mol%)を形成して水素排出積層膜を作製した。下記方法で水素排出積層膜の水素脆性を評価したところ、表面にクラックは生じていなかった(図10参照)。
〔スパッタリング法による水素排出積層膜(Au含有量15mol%、Ag含有量15mol%)の作製〕
Au及びAg含有量が各15mol%であるPd-Au-Ag合金ターゲットを用いた以外は実施例7と同様の方法で厚さ400nmのPd-Au-Ag合金膜(Au及びAg含有量:各15mol%)を形成して水素排出積層膜を作製した。下記方法で水素排出積層膜の水素脆性を評価したところ、表面にクラックは生じていなかった(図11参照)。
〔スパッタリング法による水素排出積層膜(Au含有量10mol%)の作製〕
Au含有量が10mol%であるPd-Au合金ターゲットを用いた以外は実施例7と同様の方法で厚さ400nmのPd-Au合金膜(Au含有量10mol%)を形成して水素排出積層膜を作製した。下記方法で水素排出積層膜の水素脆性を評価したところ、表面にクラックが生じていた。水素脆化が起こったと考えられる(図12参照)。
〔スパッタリング法による水素排出積層膜(Ag含有量19.8mol%)の作製〕
Ag含有量が19.8mol%であるPd-Ag合金ターゲットを用いた以外は実施例7と同様の方法で厚さ400nmのPd-Ag合金膜(Ag含有量19.8mol%)を形成して水素排出積層膜を作製した。下記方法で水素排出積層膜の水素脆性を評価したところ、表面にクラックが生じていた。水素脆化が起こったと考えられる。
(水素透過係数の測定)
作製した水素排出膜又は水素排出積層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、50℃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又は水素排出積層膜を透過した水素モル数がわかるため、これを下記式2に代入して水素透過係数を算出した。なお、測定に用いた水素排出膜の有効膜面積sは3.85×10-5m2であり、水素排出積層膜の有効膜面積sは7.07×10-6m2である。
〈式2〉水素透過係数=(水素モル数×膜厚t)/(膜面積s×時間×圧力の平方根)
作製した水素排出膜又は水素排出積層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又は水素排出積層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たものを水素透過量とした。なお、測定に用いた水素排出膜の有効膜面積sは3.85×10-5m2であり、水素排出積層膜の有効膜面積sは7.07×10-6m2である。
(例)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。
また、下記基準で水素透過性を評価した。
〇:100mL/day以上
△:10mL/day以上100mL/day未満
×:10mL/day未満
ガラス管の中に作製した水素排出膜を入れ、ガラス管の両端を封止した。ガラス管内部を50℃で5×10-3Paまで減圧し、その後、400℃まで昇温した。その後、ガラス管内に水素ガスを導入し、105kPaの雰囲気下で1時間放置した。その後、ガラス管内を室温まで冷却し、ガラス管内を5×10-3Paまで真空排気(30分)した。その後、再びガラス管内に水素ガスを導入し、105kPaの雰囲気下で1時間放置した。上記操作を3回繰り返した後、水素排出膜をガラス管内から取り出し、水素排出膜の外観を目視にて観察した。
ガラス管の中に作製した水素排出積層膜を入れ、ガラス管の両端を封止した。ガラス管内部を50℃で5×10-3Paまで減圧した後、ガラス管内に水素ガスを導入し、105kPaの雰囲気下で1時間放置した。その後、水素排出積層膜をガラス管内から取り出し、膜表面をSEMにて観察した。
密閉されたSUS缶の中にPVC切片(積水成型工業株式会社製、エスビロンシートA-370)1gと作製した水素排出膜又は水素排出積層膜(15mm×15mm)を入れて、125℃で12時間熱処理を行い、PVCから発生したガスを水素排出膜又は水素排出積層膜の表面に曝露させた。その後、水素排出膜又は水素排出積層膜の水素透過量を上記と同様の方法で測定し、下記基準で耐腐食性Aを評価した。
〇:腐食試験前後の水素透過量の保持率が50%以上
×:腐食試験前後の水素透過量の保持率が50%未満
300mLのセパラブルフラスコに和光純薬工業株式会社製のアジピン酸二アンモニウム2gとエチレングリコール18gを入れ、作製した水素排出膜又は水素排出積層膜(15mm×15mm)をセパラブルフラスコの蓋から吊り下げた。105℃で12時間熱処理を行い、2種の化合物から発生したガスを水素排出膜又は水素排出積層膜の表面に曝露させた。その後、水素排出膜又は水素排出積層膜の水素透過量を上記と同様の方法で測定し、下記基準で耐腐食性Bを評価した。
〇:腐食試験前後の水素透過量の保持率が50%以上
×:腐食試験前後の水素透過量の保持率が50%未満
2:水素排出膜
3:接着剤
4:支持体
5:治具
Claims (12)
- 合金を含む水素排出膜において、前記合金がPd-Au合金であり、Pd-Au合金中のAuの含有量が15mol%以上であることを特徴とする水素排出膜。
- Pd-Au合金中のAuの含有量が15~55mol%であり、膜厚tと膜面積sが下記式1を満たす請求項1記載の水素排出膜。
〈式1〉
t/s<41.1m-1 - Pd-Au合金は、さらにIB族及び/又はIIIA族の金属を含み、Pd-Au合金中のAuと前記金属との合計含有量が55mol%以下である請求項1又は2に記載の水素排出膜。
- 金属層の片面又は両面に請求項1~3のいずれかに記載の水素排出膜を有する複合水素排出膜。
- 請求項1~3のいずれかに記載の水素排出膜、又は請求項4記載の複合水素排出膜の片面又は両面に支持体を有する水素排出積層膜。
- 前記支持体は、平均孔径100μm以下の多孔質体である請求項5記載の水素排出積層膜。
- 前記支持体の原料が、ポリテトラフルオロエチレン、ポリスルホン、ポリイミド、ポリアミドイミド、及びアラミド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5又は6記載の水素排出積層膜。
- 請求項1~3のいずれかに記載の水素排出膜、請求項4記載の複合水素排出膜、又は請求項5~7のいずれかに記載の水素排出積層膜を備えた電気化学素子用安全弁。
- 請求項8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9記載の電気化学素子。
- 請求項1~3のいずれかに記載の水素排出膜、請求項4記載の複合水素排出膜、請求項5~7のいずれかに記載の水素排出積層膜、又は請求項8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11記載の水素排出方法。
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- 2015-06-12 WO PCT/JP2015/067000 patent/WO2015194470A1/ja active Application Filing
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- 2015-06-12 EP EP15809679.2A patent/EP3156120A4/en not_active Withdrawn
- 2015-06-12 KR KR1020177000825A patent/KR20170018029A/ko not_active Application Discontinuation
- 2015-06-16 TW TW104119456A patent/TW201605102A/zh unknown
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2017
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Also Published As
Publication number | Publication date |
---|---|
TW201605102A (zh) | 2016-02-01 |
JPWO2015194470A1 (ja) | 2017-04-20 |
JP6867829B2 (ja) | 2021-05-12 |
EP3156120A1 (en) | 2017-04-19 |
JP2017164738A (ja) | 2017-09-21 |
KR20170018029A (ko) | 2017-02-15 |
CN106714947A (zh) | 2017-05-24 |
US10439185B2 (en) | 2019-10-08 |
CN106714947B (zh) | 2019-11-26 |
JP2017143068A (ja) | 2017-08-17 |
US20170133648A1 (en) | 2017-05-11 |
EP3156120A4 (en) | 2018-02-14 |
JP6106343B2 (ja) | 2017-03-29 |
JP6688245B2 (ja) | 2020-04-28 |
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