TW201729448A - Electrochemical element - Google Patents
Electrochemical element Download PDFInfo
- Publication number
- TW201729448A TW201729448A TW105134710A TW105134710A TW201729448A TW 201729448 A TW201729448 A TW 201729448A TW 105134710 A TW105134710 A TW 105134710A TW 105134710 A TW105134710 A TW 105134710A TW 201729448 A TW201729448 A TW 201729448A
- Authority
- TW
- Taiwan
- Prior art keywords
- hydrogen gas
- metal layer
- paper
- gas discharge
- alloy
- Prior art date
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 claims abstract description 65
- 239000002184 metal Substances 0.000 claims abstract description 65
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003990 capacitor Substances 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 244000025254 Cannabis sativa Species 0.000 claims description 9
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 9
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 9
- 235000009120 camo Nutrition 0.000 claims description 9
- 235000005607 chanvre indien Nutrition 0.000 claims description 9
- 239000011487 hemp Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 229920001131 Pulp (paper) Polymers 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 31
- 150000002431 hydrogen Chemical class 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 65
- 239000010410 layer Substances 0.000 description 61
- 239000000123 paper Substances 0.000 description 45
- -1 polyoxymethylene Polymers 0.000 description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 229910052731 fluorine Inorganic materials 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000004544 sputter deposition Methods 0.000 description 12
- 239000012528 membrane Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 229910001020 Au alloy Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000002655 kraft paper Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 240000000907 Musa textilis Species 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910002668 Pd-Cu Inorganic materials 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920002098 polyfluorene Polymers 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XXZOEDQFGXTEAD-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1C(F)(F)F XXZOEDQFGXTEAD-UHFFFAOYSA-N 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 229910002708 Au–Cu Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
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- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002510 pyrogen Substances 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- H01G9/02—Diaphragms; Separators
-
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- 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
- H01G11/52—Separators
-
- 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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Gas Exhaust Devices For Batteries (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Separators (AREA)
Abstract
Description
本發明係關於電池、電容器(condenser)及電容(capacitor)等電化學元件。The present invention relates to electrochemical elements such as batteries, condensers, and capacitors.
近年來,鋁電解電容器被使用於風力發電及太陽能發電等之反相器、蓄電池等大型電源等用途。鋁電解電容器存在因反向電壓、過電壓及過電流而於內部產生氫氣之情形,若大量產生氫氣,則有因內部壓力之上升而致包裝外殼破裂之虞。 因此,一般之鋁電解電容器中設置有具備特殊膜之安全閥。安全閥除了具有將電容器內部之氫氣排出至外部之功能以外,亦具有於電容器之內部壓力急遽上升之情形時自我破壞使內部壓力降低而防止電容器本身破裂之功能。關於作為此種安全閥之構成構件的特殊膜,例如提出有以下者。 專利文獻1中揭示有具備如下箔帶之壓力調節膜,該箔帶係由使鈀中含有20 wt%(19.8 mol%)之Ag之鈀銀(Pd-Ag)合金所構成。 但是,專利文獻1之箔帶存在於50~60℃左右以下之環境下容易脆化而無法長時間維持作為壓力調節膜之功能之問題,而未實現實用化。 另一方面,作為行動電話、筆記型電腦及汽車等之電池,現廣泛使用鋰離子電池。又,近年來,對於鋰離子電池,除了高容量化及提昇循環特性以外,對其安全性之關注亦提高。尤其是,已知有鋰離子電池會於電池內產生氣體之情況,而擔憂內壓上升所伴隨之電池組之膨脹或破裂。 專利文獻2中揭示有,使用包含鋯(Zr)與鎳(Ni)之合金的非晶合金(例如,36Zr-64Ni合金)膜作為選擇性地透過電池內所發生之氫氣的氫氣選擇透過性合金膜。 但是,上述非晶合金存在如下問題:若於低溫區域(例如50℃)接觸氫氣,則會形成氫化物(ZrH2 )而導致脆化,因此無法長時間維持作為壓力調節膜之功能。 為了解決上述問題,專利文獻3中提出有包含Pd-Ag合金且Pd-Ag合金中之Ag之含量為20 mol%以上之氫氣排出膜。 為了解決上述問題,專利文獻4中提出有包含Pd-Cu合金且Pd-Cu合金中之Cu之含量為30 mol%以上之氫氣排出膜。 但是,專利文獻3及4之氫氣排出膜存在如下問題:雖然於電化學元件之使用溫度下不易脆化且使用初期具有充分之氫氣排出性,但氫氣排出性會因使用環境而逐漸降低。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利第4280014號說明書 [專利文獻2]日本專利特開2003-297325號公報 [專利文獻3]國際公開第2014/098038號 [專利文獻4]國際公開第2015/019906號In recent years, aluminum electrolytic capacitors have been used for applications such as inverters for electric power generation and solar power generation, and large power sources such as batteries. In an aluminum electrolytic capacitor, hydrogen gas is generated inside due to a reverse voltage, an overvoltage, and an overcurrent. If a large amount of hydrogen gas is generated, the outer casing may be broken due to an increase in internal pressure. Therefore, a general-purpose aluminum electrolytic capacitor is provided with a safety valve having a special film. In addition to the function of discharging the hydrogen gas inside the capacitor to the outside, the safety valve also has a function of self-destruction to lower the internal pressure and prevent the capacitor itself from being broken when the internal pressure of the capacitor rises sharply. Regarding a special film which is a constituent member of such a safety valve, for example, the following is proposed. Patent Document 1 discloses a pressure-regulating film comprising a foil tape comprising a palladium-silver (Pd-Ag) alloy containing 20 wt% (19.8 mol%) of Ag in palladium. However, the foil tape of the patent document 1 is easy to embrittle in an environment of about 50 to 60 ° C or less, and it is not possible to maintain the function as a pressure-regulating film for a long period of time, and it has not been put into practical use. On the other hand, lithium-ion batteries are widely used as batteries for mobile phones, notebook computers, and automobiles. Further, in recent years, in addition to high capacity and improved cycle characteristics, lithium ion batteries have also increased their concern for safety. In particular, lithium ion batteries are known to generate gas in the battery, and there is concern about expansion or cracking of the battery pack accompanying an increase in internal pressure. Patent Document 2 discloses that an amorphous alloy (for example, a 36Zr-64Ni alloy) film containing an alloy of zirconium (Zr) and nickel (Ni) is used as a hydrogen selective permeability alloy that selectively permeates hydrogen generated in a battery. membrane. However, the above amorphous alloy has a problem that if hydrogen gas is contacted in a low temperature region (for example, 50 ° C), a hydride (ZrH 2 ) is formed to cause embrittlement, and thus it is impossible to maintain the function as a pressure regulating film for a long period of time. In order to solve the above problem, Patent Document 3 proposes a hydrogen gas discharge film comprising a Pd-Ag alloy and having a Ag content of 20 mol% or more in the Pd-Ag alloy. In order to solve the above problem, Patent Document 4 proposes a hydrogen gas discharge film containing a Pd—Cu alloy and having a Cu content of 30 mol% or more in the Pd—Cu alloy. However, the hydrogen gas discharge membranes of Patent Documents 3 and 4 have problems in that they are not easily embrittled at the use temperature of the electrochemical device and have sufficient hydrogen gas discharge performance at the initial stage of use, but the hydrogen gas discharge property is gradually lowered due to the use environment. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent No. 4208014 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-297325 [Patent Document 3] International Publication No. 2014/098038 [Patent Document 4 ]International Publication No. 2015/019906
[發明所欲解決之問題] 本發明係鑒於上述問題而成者,其目的在於提供一種即便於長期使用之情形時,因所發生之氫氣之壓力引起之破損及劣化亦較少,而能夠耐受長期使用之電化學元件。 [解決問題之技術手段] 本發明係關於一種電化學元件,其特徵在於: 其係具備氫氣排出膜且具有將陽極與陰極介隔電解紙進行積層而成之積層體者,並且 上述氫氣排出膜包含金屬層, 上述電解紙於105℃下加熱12小時之時之二甲基二硫醚之釋出量為0.0004 μg/cm2 以下。 本發明者對包含金屬層之氫氣排出膜之氫氣排出性逐漸降低之原因進行了努力研究,結果發現:並非氫氣導致金屬層脆化,而是由於自作為電化學元件之構成構件的電解紙產生二甲基二硫醚,其會腐蝕(氧化或硫化等)金屬層,而導致金屬層劣化,結果氫氣排出性逐漸降低。即,認為於作為電解紙之原料的牛皮紙漿之製法中,於使用藥液自木材片提取纖維之脫木質素步驟時係使用硫化鈉,但該硫化鈉會與纖維素中之烴鍵結,而產生各種硫系成分。並且發現,各種硫系成分中尤其是二甲基二硫醚會使金屬層劣化。 本發明者基於上述見解對解決方案進行了努力研究,結果發現:藉由使用於105℃下加熱12小時之時之二甲基二硫醚之釋出量為0.0004 μg/cm2 以下之電解紙,金屬層不易因腐蝕而劣化,結果即便於長期使用之情形時,氫氣排出膜之氫氣排出性亦不易降低。 就氫氣透過性、耐氧化性及吸藏氫氣時之耐脆化優異之觀點而言,上述金屬層較佳為包含Pd合金之合金層。 就氫氣透過性、耐氧化性及吸藏氫氣時之耐脆化優異之觀點而言,上述Pd合金較佳為包含20~65 mol%之第11族元素。又,上述第11族元素較佳為選自由Au、Ag及Cu所組成之群之至少一種。 包含Pd-第11族元素合金之Pd合金層具有如下功能:於膜表面將氫氣分子解離為氫原子並使氫原子固溶於膜內,使固溶之氫原子自高壓側擴散至低壓側,於低壓側之膜表面再次將氫原子轉換為氫氣分子並排出。於第11族元素之含量未達20 mol%之情形時,有Pd合金之強度不充分,或不易表現出上述功能之傾向,於超過65 mol%之情形時,有氫氣透過速度降低之傾向。 上述氫氣排出膜較佳為於金屬層之單面或雙面具有支持體。支持體係為了於金屬層自安全閥或氫氣排出閥脫落之情形時防止其掉落至電化學元件內而設置。又,於金屬層具有作為安全閥之功能之情形時,該安全閥於電化學元件之內部壓力成為特定值以上時自我破壞,於金屬層為薄膜之情形時,有金屬層之機械強度較低,因此於電化學元件之內部壓力成為特定值前自我破壞之虞,而無法發揮作為安全閥之功能。因此,於金屬層為薄膜之情形時,為了提昇機械強度,較佳為於金屬層之單面或雙面積層支持體。 上述電解紙較佳為使用非木材系紙漿之電解紙,更佳為包含麻紙。 作為電化學元件,例如可列舉鋁電解電容器及鋰離子電池等。 [發明之效果] 本發明之電化學元件即便於長期使用之情形時,氫氣排出膜之氫氣排出性亦不易降低,可僅將電化學元件內部所發生之氫氣迅速地排出至外部。藉此,可有效地防止電化學元件因電化學元件內部所發生之氫氣之壓力而破損。又,上述氫氣排出膜可防止雜質自外部向電化學元件內部侵入。又,上述氫氣排出膜亦可具有如下功能:於電化學元件之內部壓力急遽上升之情形時自我破壞而使內部壓力降低,從而防止電化學元件本身破裂。藉由該等效果,可長時間維持電化學元件之初始性能,而可實現電化學元件之長壽命化。[Problems to be Solved by the Invention] The present invention has been made in view of the above problems, and an object thereof is to provide a method capable of withstanding damage and deterioration due to the pressure of hydrogen gas generated even in the case of long-term use. Electrochemical components that are used for a long time. [Means for Solving the Problems] The present invention relates to an electrochemical device characterized in that it has a hydrogen gas discharge film and has a laminate in which an anode and a cathode are interposed with electrolytic paper, and the hydrogen gas discharge film is provided. The metal layer is contained, and when the electrolyzed paper is heated at 105 ° C for 12 hours, the amount of dimethyl disulfide released is 0.0004 μg / cm 2 or less. The present inventors have made an effort to study the reason why the hydrogen gas discharge property of the hydrogen gas discharge film containing the metal layer is gradually lowered, and as a result, it has been found that not hydrogen gas causes embrittlement of the metal layer, but is generated from electrolytic paper which is a constituent member of the electrochemical element. Dimethyl disulfide, which corrodes (oxidizes or vulcanizes, etc.) a metal layer, causes deterioration of the metal layer, and as a result, hydrogen gas discharge property is gradually lowered. That is, in the method of producing kraft pulp as a raw material of electrolytic paper, sodium sulphide is used in the step of extracting fibers from wood chips using a medicinal liquid, but the sodium sulfide is bonded to hydrocarbons in cellulose. It produces various sulfur-based components. Further, it has been found that among various sulfur-based components, especially dimethyl disulfide, the metal layer is deteriorated. The present inventors conducted an effort to study the solution based on the above findings, and as a result, found that electrolytic paper having a release amount of dimethyl disulfide of 0.0004 μg/cm 2 or less by heating at 105 ° C for 12 hours was used. The metal layer is not easily deteriorated by corrosion, and as a result, even in the case of long-term use, the hydrogen gas discharge property of the hydrogen gas discharge film is not easily lowered. The metal layer is preferably an alloy layer containing a Pd alloy from the viewpoint of excellent hydrogen permeation resistance, oxidation resistance, and excellent embrittlement resistance when hydrogen is stored. The Pd alloy preferably contains 20 to 65 mol% of a Group 11 element from the viewpoint of excellent hydrogen permeation resistance, oxidation resistance, and excellent embrittlement resistance when hydrogen is absorbed. Further, the Group 11 element is preferably at least one selected from the group consisting of Au, Ag, and Cu. The Pd alloy layer containing the Pd-Group 11 element alloy has the following functions: dissociating the hydrogen molecules into hydrogen atoms on the surface of the film and solid-dissolving the hydrogen atoms in the film, so that the solid-dissolved hydrogen atoms diffuse from the high pressure side to the low pressure side, Hydrogen atoms are again converted into hydrogen molecules on the surface of the membrane on the low pressure side and discharged. When the content of the element of the 11th group is less than 20 mol%, the strength of the Pd alloy is insufficient or the function is not easily exhibited, and when it exceeds 65 mol%, the hydrogen permeation rate tends to decrease. The hydrogen gas discharge film preferably has a support on one side or both sides of the metal layer. The support system is provided to prevent the metal layer from falling into the electrochemical component when it is detached from the safety valve or the hydrogen discharge valve. Further, when the metal layer has a function as a safety valve, the safety valve self-destructs when the internal pressure of the electrochemical element becomes a specific value or more, and when the metal layer is a film, the mechanical strength of the metal layer is low. Therefore, the internal pressure of the electrochemical element is self-destructive before it becomes a specific value, and it cannot function as a safety valve. Therefore, in the case where the metal layer is a film, in order to improve the mechanical strength, a single-sided or double-area layer support of the metal layer is preferred. The above electrolytic paper is preferably an electrolytic paper using non-wood pulp, and more preferably contains hemp paper. Examples of the electrochemical device include an aluminum electrolytic capacitor and a lithium ion battery. [Effect of the Invention] When the electrochemical device of the present invention is used for a long period of time, the hydrogen gas discharge property of the hydrogen gas discharge film is not easily lowered, and only the hydrogen gas generated inside the electrochemical device can be quickly discharged to the outside. Thereby, it is possible to effectively prevent the electrochemical element from being damaged by the pressure of the hydrogen gas generated inside the electrochemical element. Further, the hydrogen gas discharge film prevents impurities from entering the inside of the electrochemical device from the outside. Further, the hydrogen gas discharge film may have a function of self-destructing when the internal pressure of the electrochemical element rises rapidly to lower the internal pressure, thereby preventing the electrochemical element itself from being broken. By these effects, the initial performance of the electrochemical device can be maintained for a long period of time, and the life of the electrochemical device can be extended.
以下,對本發明之實施形態進行說明。 本發明之電化學元件係具備將電化學元件內部所發生之氫氣排出至外部之氫氣排出膜且具有將陽極與陰極介隔電解紙進行積層而成之積層體者。作為該電化學元件,例如可列舉電池、電容器及電容等,尤佳為鋁電解電容器或鋰離子電池。氫氣排出膜及電解紙以外之構成構件可無特別限制地使用先前者。又,本發明之電化學元件除了使用下述氫氣排出膜及電解紙以外,可藉由先前之方法而製造。以下,對氫氣排出膜及電解紙進行詳細說明。 上述氫氣排出膜係包含金屬層者。金屬層需為可僅將電化學元件內部所發生之氫氣排出至外部且可防止物質自外部侵入至電化學元件內部者,例如實質上無微細之貫通孔之無孔體。 形成金屬層之金屬只要為單質具有氫氣透過功能或藉由合金化而具有氫氣透過功能之金屬,則無特別限制,例如可列舉Pd、Nb、V、Ta、Ni、Fe、Al、Cu、Ru、Re、R h、Au、Pt、Ag、Cr、Co、Sn、Zr、Y、Ce、Ti、Ir、Mo及包含2種以上該等金屬之合金等。 上述金屬層較佳為包含Pd合金之合金層。形成Pd合金之其他金屬並無特別限制,較佳為使用第11族元素,更佳為選自由Au、Ag及Cu所組成之群之至少一種。尤其是,Pd-Au合金對於自電化學元件內部之電解液或構成構件所產生之氣體成分之耐腐蝕性優異,故而較佳。Pd合金較佳為包含20~65 mol%之第11族元素,更佳為包含30~65 mol%,進而較佳為包含30~60 mol%。又,如下之Pd合金層即便於50~60℃左右以下之低溫區域內亦不易由於氫而脆化,故而較佳,該Pd合金層包含Ag含量為20 mol%以上之Pd-Ag合金、Cu含量為30 mol%以上之Pd-Cu合金或Au含量為20 mol%以上之Pd-Au合金。又,Pd合金亦可於無損本發明之效果之範圍內包含IB族及/或IIIA族金屬。 Pd合金不僅可為包含Pd之二元合金,例如亦可為Pd-Au-Ag之三元合金,亦可為Pd-Au-Cu之三元合金。進而,亦可為Pd-Au-Ag-Cu之四元合金。例如,於包含Pd、Au及其他金屬之多元系合金之情形時,Pd-Au合金中之Au與其他金屬之合計含量較佳為55 mol%以下,更佳為50 mol%以下,進而較佳為45 mol%以下,尤佳為40 mol%以下。 金屬層例如可藉由輥軋法、濺鍍法、真空蒸鍍法、離子鍍覆法及鍍覆法等而製造,於製造膜厚度較厚之金屬層之情形時,較佳為使用輥軋法,於製造膜厚度較薄之金屬層之情形時,較佳為使用濺鍍法。 輥軋法可為熱軋、冷軋之任一方法。輥軋法係藉由使一對或複數對輥(roller)旋轉,並於輥間一面施加壓力一面使作為原料之金屬通過而將其加工為膜狀之方法。 藉由輥軋法而獲得之金屬層之膜厚度較佳為5~50 μm,更佳為10~30 μm。於膜厚度未達5 μm之情形時,容易於製造時產生針孔或龜裂,或若吸藏氫氣則容易變形。另一方面,若膜厚度超過50 μm,則使氫氣透過需要時間,因此氫氣透過性降低,或於成本方面較差,故而欠佳。 濺鍍法並無特別限定,可使用平行板型、單片型、通過型、DC濺鍍及RF濺鍍等之濺鍍裝置而進行。例如於設置有金屬靶之濺鍍裝置上安裝基板後,對濺鍍裝置內真空排氣並將氬氣氣壓調整為特定值,對金屬靶流入特定之濺鍍電流,而於基板上形成金屬膜。其後,自基板剝離金屬膜而獲得金屬層。再者,作為靶,可根據所製造之金屬層而使用單一或複數個靶。 作為基板,例如可列舉玻璃板、陶瓷板、矽晶圓、鋁及不鏽鋼等之金屬板。 藉由濺鍍法而獲得之金屬層之膜厚度較佳為0.01~5 μm,更佳為0.05~2 μm。於膜厚度未達0.01 μm之情形時,不僅有形成針孔之可能性,亦不易獲得所要求之機械強度。又,自基板剝離時容易破損,剝離後之操作亦較困難。另一方面,若膜厚度超過5 μm,則製造金屬層需要時間,於成本方面較差,故而欠佳。 金屬層之膜面積可考慮氫氣透過量及膜厚度而適當調整,但於用作安全閥之構成構件之情形時,為0.01~100 mm2
左右。再者,於本發明中,膜面積係金屬層中實質上排出氫氣之部分之面積,不包括下述之環狀之塗佈有接著劑之部分。 亦可於金屬層之表面設置金屬層以外之塗層。藉由設置塗層,可防止自電解紙所產生之二甲基二硫醚以外之污染物(例如電解液)附著於氫氣排出膜之金屬層之表面而將其腐蝕之情況。 塗層之原料較佳為可形成與水之接觸角為85°以上之表面者,例如可列舉氟系化合物、橡膠系聚合物、聚矽氧系聚合物、胺基甲酸酯系聚合物及聚酯系聚合物等。該等之中,就與水之接觸角較大且不易阻礙氫氣排出膜之氫氣透過性之觀點而言,較佳為使用選自由氟系化合物、橡膠系聚合物及聚矽氧系聚合物所組成之群之至少一種化合物。 作為氟系化合物,例如可列舉:氟烷基羧酸鹽、氟烷基四級銨鹽及氟烷基環氧乙烷加成物等含氟烷基之化合物;全氟烷基羧酸鹽、全氟烷基四級銨鹽及全氟烷基環氧乙烷加成物等含全氟烷基之化合物;四氟乙烯/六氟丙烯共聚物及四氟乙烯/全氟烷基乙烯醚共聚物等含氟碳基之化合物;四氟乙烯聚合物;偏二氟乙烯與四氟乙烯之共聚物;偏二氟乙烯與六氟丙烯之共聚物;含氟(甲基)丙烯酸酯;含氟(甲基)丙烯酸酯聚合物;含氟(甲基)丙烯酸烷基酯聚合物;含氟(甲基)丙烯酸酯與其他單體之共聚物等。 又,關於作為塗層之原料的氟系化合物,亦可使用HARVES公司製造之「DURASURF」系列、DAIKIN工業公司製造之「OPTOOL」系列及信越化學工業公司製造之「KY-100」系列等。 作為橡膠系聚合物,例如可列舉:天然橡膠、苯乙烯丁二烯橡膠、丙烯腈丁二烯橡膠、氯丁二烯橡膠、聚異戊二烯橡膠、聚丁二烯橡膠、乙烯丙烯橡膠、乙烯-丙烯-二烯三元聚合物橡膠、氯磺化聚乙烯橡膠及乙烯-乙酸乙烯酯共聚物橡膠等。 又,關於作為塗層之原料的橡膠系聚合物,亦可使用Nitto Shinko公司製造之「ELEP COAT」系列等。 作為聚矽氧系聚合物,例如可列舉:聚二甲基矽氧烷、烷基改性聚二甲基矽氧烷、羧基改性聚二甲基矽氧烷、胺基改性聚二甲基矽氧烷、環氧改性聚二甲基矽氧烷、氟改性聚二甲基矽氧烷及(甲基)丙烯酸酯改性聚二甲基矽氧烷等。 塗層例如可藉由在金屬層上或設置於金屬層上之其他層上塗佈塗層原料組合物並使之硬化而形成。 塗佈方法並無特別限制,例如可列舉:輥塗法、旋轉塗佈法、浸漬塗佈法、噴塗法、棒式塗佈法、刮塗法、模嘴塗佈法、噴墨法及凹版塗佈法等。 溶劑根據塗層之原料適當選擇即可。於使用氟系化合物作為塗層之原料之情形時,例如可單獨使用氟系溶劑、醇系溶劑、醚系溶劑、酯系溶劑及烴系溶劑等溶劑,或將該等混合而使用。該等之中,較佳為單獨使用無引火性且迅速揮發之氟系溶劑,或將其與其他溶劑混合而使用。 作為氟系溶劑,例如可列舉:氫氟醚、全氟聚醚、全氟烷烴、氫氟聚醚、氫氟碳、全氟環醚、全氟環烷烴、氫氟環烷烴、六氟二甲苯、氫氟氯碳及全氟碳等。 塗層之厚度並無特別限制,較佳為0.1~20 μm,更佳為0.2~10 μm,進而較佳為0.3~5 μm。 亦可於金屬層之單面或雙面設置支持體。尤其是藉由濺鍍法而獲得之金屬層由於膜厚度薄,故而較佳為為了提昇機械強度,而於金屬層之單面或雙面積層支持體。 圖1及2係表示氫氣排出膜1之結構的概略剖視圖。可如圖1(a)或(b)所示於金屬層2之單面或雙面使用環狀之接著劑3而積層支持體4,亦可如圖2(a)或(b)所示使用治具5而於金屬層2之單面或雙面積層支持體4。 支持體4只要為具有氫氣透過性且可支持金屬層2者,則無特別限定,可為無孔體,亦可為多孔體。又,支持體4亦可為織布、不織布。作為支持體4之形成材料,例如可列舉聚乙烯及聚丙烯等聚烯烴、聚對苯二甲酸乙二酯及聚萘二甲酸乙二酯等聚酯、聚碸及聚醚碸等聚芳醚碸、聚四氟乙烯及聚偏二氟乙烯等氟樹脂、環氧樹脂、聚醯胺、聚醯亞胺、聚醯胺醯亞胺等。該等之中,較佳為使用化學穩定及熱穩定之聚碸、聚四氟乙烯、聚醯胺、聚醯亞胺及聚醯胺醯亞胺。 支持體4較佳為平均孔徑為100 μm以下之多孔體。若平均孔徑超過100 μm,則多孔體之表面平滑性降低,因此於藉由濺鍍法等製造金屬層之情形時,不易於多孔體上形成膜厚度均勻之金屬層,或容易於金屬層產生針孔或龜裂。 支持體4之厚度並無特別限定,通常為5~1000 μm左右,較佳為10~300 μm。 於藉由濺鍍法製造金屬層2之情形時,若使用支持體4作為基板,則可於支持體4上直接形成金屬層2,可不使用接著劑3或治具5而製造氫氣排出膜1,因此就氫氣排出膜1之物性及製造效率之觀點而言較佳。於該情形時,作為支持體4,較佳為使用平均孔徑為100 μm以下之多孔體,更佳為平均孔徑為5 μm以下之多孔體,尤佳為使用超過濾膜(UF膜,Ultrafiltration membrane)。 上述氫氣排出膜之形狀可為大致圓形,亦可為三角形、四角形、五角形等多角形。可製成適於下述用途之任意之形狀。 上述氫氣排出膜作為電化學元件之安全閥之構成構件有用。又,氫氣排出膜亦可不同於安全閥而作為氫氣排出閥設置於電化學元件上。 上述氫氣排出膜於低溫下不會脆化,因此有例如可於150℃以下之溫度、進而110℃以下之溫度使用之優勢。即,可較佳地用作不於高溫(例如400~500℃)下使用之鋁電解電容器或鋰離子電池之安全閥或氫氣排出閥。 作為上述電解紙,使用於105℃下加熱12小時之時之二甲基二硫醚之釋出量為0.0004 μg/cm2
以下者。二甲基二硫醚之釋出量較佳為0.0002 μg/cm2
以下,更佳為0.0001 μg/cm2
以下。若使用二甲基二硫醚之釋出量超過0.0004 μg/cm2
之電解紙,則氫氣排出膜之金屬層容易因二甲基二硫醚而腐蝕,金屬層容易劣化。因此,氫氣排出膜之氫氣排出性容易降低。 作為上述電解紙,只要二甲基二硫醚之釋出量為上述範圍者,則無特別限定,例如可列舉麻紙、馬尼拉麻紙、瓊麻紙及針茅紙等非木材系紙漿之電解紙、將麻紙漿或馬尼拉麻紙漿與牛皮紙漿混合之電解紙及將麻紙與牛皮紙積層而成之電解紙等。尤佳為麻紙、馬尼拉麻紙、瓊麻紙及針茅紙等非木材系紙漿之電解紙,更佳為麻紙。 上述電解紙較佳為密度為0.25~1.00 g/cm3
,厚度為20~100 μm。於電解紙之密度未達0.25 g/cm3
之情形時,拉伸強度不足,無法確保製作電容器時所需之強度。又,電解紙之遮蔽性降低,電容器之短路不良增加。另一方面,若超過1.00 g/cm3
,則離子透過性惡化而電容器之特性降低。又,於電解紙之厚度未達20 μm之情形時,難以確保緻密性,電容器之短路不良增加。另一方面,若超過100 μm,則離子透過性惡化,電容器特性降低。 圖3係表示本發明之鋁電解電容器之結構之一例的立體圖。電容元件6係使電解紙(隔離件)9介存於由鋁箔構成之陽極箔7與陰極箔8之間並加以捲繞而構成,於各電極7、8上接合有包括棒狀之接合部及可焊接之外部引出部之引線10。電容元件6含浸有驅動用電解液(未圖示),收納於有底筒狀之由鋁構成之殼體12中,殼體12之開口部利用封口體11而進行密封。如圖4所示,氫氣排出膜1通常設置於封口體11。殼體12之外周被外裝構件(未圖示)所被覆。 [實施例] 以下,列舉實施例對本發明進行說明,但本發明不受該等實施例之任何限定。 製造例1 [藉由輥軋法之Pd-Au合金層(Au含量為30 mol%)之製作] 以鑄錠中之Au含量成為30 mol%之方式分別稱取Pd及Au原料,並投入至具備水冷銅坩堝之電弧熔解爐中,於大氣壓之氬氣氛圍中進行電弧熔解。對所獲得之紐扣鑄錠,使用輥直徑為100 mm之二輥軋機進行冷軋,直至厚度成為5 mm,而獲得板材。其後,於玻璃板管中放入經輥軋之板材,並將玻璃板管之兩端密封。於室溫下將玻璃板管內部減壓至5×10-4
Pa,其後升溫至700℃並放置24小時,其後冷卻至室溫。藉由該熱處理,而消除合金中之Pd及Au之偏析。繼而,使用輥直徑為100 mm之二輥軋機對板材進行冷軋直至厚度成為100 μm,進而使用輥直徑為20 mm之二輥軋機對板材進行冷軋直至厚度成為20 μm。其後,於玻璃板管中放入經輥軋之板材,並將玻璃板管之兩端密封。於室溫下將玻璃板管內部減壓至5×10-4
Pa,其後升溫至500℃並放置1小時,其後冷卻至室溫。藉由該熱處理,而消除因輥軋而產生之Pd-Au合金內部之應變,而製作包含厚度為20 μm且Au含量為30 mol%之Pd-Au合金層的氫氣排出膜。 實施例1 使用製造例1中所製作之氫氣排出膜及二甲基二硫醚之釋出量為0 μg/cm2
之麻紙,而製作鋁電解電容器。 實施例2 使用製造例1中所製作之氫氣排出膜及二甲基二硫醚之釋出量為0.00034 μg/cm2
之將牛皮紙與麻紙積層而成之電解紙,而製作鋁電解電容器。 實施例3 使用製造例1中所製作之氫氣排出膜及二甲基二硫醚之釋出量為0.00038 μg/cm2
之將牛皮紙漿與馬尼拉麻紙漿混合而製作之電解紙,而製作鋁電解電容器。 比較例1 使用製造例1中所製作之氫氣排出膜及二甲基二硫醚之釋出量為0.00045 μg/cm2
之牛皮紙,而製作鋁電解電容器。 [測定及評價方法] (二甲基二硫醚之釋出量之測定) 將200 c m2
之電解紙放入至20 ml之小瓶中並蓋嚴。繼而,使用頂空進樣器(HSS,headspace sampler)(Agilent Technologies製造,G1888)於105℃下加熱12小時,將所產生之氣體1 ml注入至GC(Gas chromatography,氣相層析儀)/MS(mass spectrometry,質譜儀)/FPD(flame photometric detector,火焰光度檢測器)(Agilent Technologies製造,7890A/5975C)中進行測定。各裝置之條件如下。 HSS 烘箱溫度:105℃ 加熱時間:12 h GC/MS/FPD ・GC 管柱:HP-5MS UI 30 m×內徑0.25 mm×膜厚0.25 μm 管柱溫度:40℃(3 min)→+20℃/min→300℃(4 min) 載氣:He(3.0 ml/min) 注入口:分流比5:1 注入口溫度:250℃ 檢測器:MS/FPD ・MS 離子化法:EI法 電子能:70 eV E.M.電壓:1776 V 離子源溫度:230℃ 接口溫度:300℃ 質量範圍:m/z=35~800 ・FPD…硫系化合物之選擇檢測 溫度:200℃ 氫氣流量:70 ml/min 空氣流量:100 ml/min (氫氣透過性之評價) 將製造例1中所製作之氫氣排出膜安裝於Swagelok公司(Swagelok Company)製造之VCR連接器,於單側安裝SUS管,而製作經密封之空間(63.5 ml)。將管內利用真空泵進行減壓後,以氫氣之壓力成為0.15 MPa之方式進行調整,對105℃之環境下之壓力變化進行監控。得知因壓力變化而透過氫氣排出膜之氫氣莫耳數(體積),因此將其換算為每1天之透過量而算出氫氣透過量。例如,於壓力以2小時自0.15 MPa變化為0.05 MPa之情形時(變化量為0.10 MPa),透過氫氣排出膜之氫氣體積為63.5 ml。由此,每1天之氫氣透過量成為63.5×24/2=762 ml/day。氫氣排出膜之氫氣透過量較佳為10 ml/day以上,更佳為100 ml/day以上。 (耐腐蝕性之評價) 於經密閉之SUS罐內,分別放入使50 g實施例及比較例中使用之電解紙中含浸有乙二醇之試樣,並自SUS罐之蓋懸掛製造例1中所製作之氫氣排出膜(15 mm×15 mm)。於105℃下進行12小時之熱處理,使自試樣產生之氣體暴露於氫氣排出膜之表面。其後,以與上述相同之方法進行氫氣透過性之評價。 (鋁電解電容器之評價) 對實施例及比較例中所製作之鋁電解電容器,於105℃之環境溫度下進行500小時之400V之電壓施加。其後,目視確認鋁電解電容器之鋁殼體之變形。 〇:鋁殼體無形狀變化 ×:鋁殼體有鼓出 [表1]
1‧‧‧氫氣排出膜
2‧‧‧金屬層
3‧‧‧接著劑
4‧‧‧支持體
5‧‧‧治具
6‧‧‧電容元件
7‧‧‧陽極箔
8‧‧‧陰極箔
9‧‧‧電解紙(隔離件)
10‧‧‧引線
11‧‧‧封口體
12‧‧‧殼體1‧‧‧Hydrogen discharge membrane
2‧‧‧metal layer
3‧‧‧Binder
4‧‧‧Support
5‧‧‧ fixture
6‧‧‧Capacitive components
7‧‧‧Anode foil
8‧‧‧Cathode foil
9‧‧‧ Electrolytic paper (separator)
10‧‧‧ lead
11‧‧‧ Sealing body
12‧‧‧ housing
圖1(a)、(b)係表示本發明之氫氣排出膜之結構的概略剖視圖。 圖2(a)、(b)係表示本發明之氫氣排出膜之另一結構的概略剖視圖。 圖3係表示本發明之鋁電解電容器之結構之一例的立體圖。 圖4係表示設置有氫氣排出膜之封口體之結構之一例的立體圖。Fig. 1 (a) and (b) are schematic cross-sectional views showing the structure of a hydrogen gas discharge film of the present invention. 2(a) and 2(b) are schematic cross-sectional views showing another configuration of the hydrogen gas discharge film of the present invention. Fig. 3 is a perspective view showing an example of the structure of an aluminum electrolytic capacitor of the present invention. Fig. 4 is a perspective view showing an example of a structure of a sealing body provided with a hydrogen gas discharge film.
1‧‧‧氫氣排出膜 1‧‧‧Hydrogen discharge membrane
2‧‧‧金屬層 2‧‧‧metal layer
3‧‧‧接著劑 3‧‧‧Binder
4‧‧‧支持體 4‧‧‧Support
Claims (8)
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CN104870080A (en) * | 2012-12-17 | 2015-08-26 | 日东电工株式会社 | Hydrogen-releasing film |
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WO2017073403A1 (en) | 2017-05-04 |
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