WO1989004556A1 - Electrochemical process for manufacturing a pore-free membrane based on palladium and supported by a porous metallic element - Google Patents
Electrochemical process for manufacturing a pore-free membrane based on palladium and supported by a porous metallic element Download PDFInfo
- Publication number
- WO1989004556A1 WO1989004556A1 PCT/CH1988/000205 CH8800205W WO8904556A1 WO 1989004556 A1 WO1989004556 A1 WO 1989004556A1 CH 8800205 W CH8800205 W CH 8800205W WO 8904556 A1 WO8904556 A1 WO 8904556A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- palladium
- foil
- porous
- alloy
- electrolyte
- Prior art date
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000012528 membrane Substances 0.000 title claims abstract description 31
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000002184 metal Substances 0.000 claims abstract description 31
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 239000011888 foil Substances 0.000 claims abstract description 17
- 229910001369 Brass Inorganic materials 0.000 claims abstract description 14
- 239000010951 brass Substances 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000446 fuel Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000007772 electrode material Substances 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 6
- -1 halide ions Chemical class 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 208000031872 Body Remains Diseases 0.000 claims 2
- 241000353345 Odontesthes regia Species 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical class [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/94—Non-porous diffusion electrodes, e.g. palladium membranes, ion exchange membranes
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- semipermeable membranes are often used, which selectively let a gas pass through and retain the remaining components.
- pore-free palladium / silver foils or tubes are still of great importance for the purification of hydrogen because of their ideal selectivity, the palladium content normally being between 75 and 80% and use in the temperature range between 350 and 400 ° C. Since palladium and many of its alloys have an extraordinarily good dissolving power for hydrogen, the use of such membranes is also possible at a lower temperature, the hydrogen adsorption or desorption being substantially improved by coating the surfaces with suitable catalysts, in particular finely divided palladium or platinum can be.
- suitable catalysts in particular finely divided palladium or platinum can be.
- the selectivity for hydrogen permeation is not achieved here by the (non-non-porous) Pd layer, but by the organosilicon film.
- this membrane is particularly unsuitable for use in fuel cells because it conducts the electrical current in the extremely thin Pd / Ag layer insufficiently and because it is unstable in the presence of strong alkalis (electrolyte).
- a Pd / Ag membrane from Johnson-Matthey (European Pat. 106,523 (1984)) connected to a perforated metal support or a metal net does not have this disadvantage.
- the Pd / Ag film has to be produced conventionally by rolling, there are limits to its thickness and thus to the need for palladium, as already mentioned.
- a palladium-based membrane can be produced directly on a porous metal body.
- the electrochemical deposition of palladium or palladium alloys is preferred as the deposition method over more complex and less efficient methods such as vapor deposition.
- the electrochemical deposition of such alloys on smooth metal surfaces, especially on copper, is already known. There are various methods for this, the metal ions in the electrolyte always being present as complexes. Examples of complexing agents are glycinate (HJ Schuster and KDHeppner, Manual Off. 26 57 925 (1978)), ammonia (B. Sturzenegger and J.Cl. Puippe, Plat.Met.Rev.
- a porous metal body would, for example, be a sintered body, preferably a sintered film.
- a method is proposed, such as an initially solid, non-porous metal body in a porous one Metal body can be converted.
- foil-shaped alloy consisting of a nobler and a less noble metal.
- foils made of a copper / zinc alloy (brass), copper / tin (bronze), copper / aluminum, nickel / aluminum etc. are particularly suitable.
- Brass foils with a relatively high zinc content are particularly suitable.
- the porosity is now created by the less noble metal, in this case the zinc, being selectively and practically quantitatively extracted from the foil-like alloy without this changing its external dimensions.
- the process is known per se and is used, for example, in Raney nickel, «where the less noble aluminum is selectively extracted from an aluminum / nickel powder by concentrated lye and highly porous, catalytically active nickel remains.
- the less noble component can be extracted in this way.
- the potential measured in relation to a reference electrode is cyclically varied over a longer period between a more positive and a less positive (or a less negative and a more negative) range, the more positive (or the less negative) potential range being chosen such that the less noble and also the nobler metal dissolve, and the less positive (or the more negative) area so that only the nobler metal can separate again.
- This method can be carried out both in an acidic and in an alkaline electrolyte, in the latter case the ions of the less noble metal must be (excess) soluble, which is the case when using conc. Potash or sodium hydroxide solution is often the case.
- the ions in solution of the nobler alloy component can migrate as little as possible so that the outer shape of the foil is not impaired by the pore formation.
- This can be achieved by adding anions to the electrolyte, which selectively precipitate the more noble metal, which is also oxidized when the potential is positive, and thus convert it into an insoluble or only slightly soluble form, the precipitated or not at all dissolved solution must be reducible in the more negative potential range.
- This function can be performed when using an acidic electrolyte such as 1 molar sulfuric acid or 1 molar sulfamic acid in the case of the use of copper alloys such as brass, halide ions, preferably chloride ions, which are best added in the form of hydrogen chloride, ammonium chloride or an alkali chloride.
- an acidic electrolyte such as 1 molar sulfuric acid or 1 molar sulfamic acid
- copper alloys such as brass
- halide ions preferably chloride ions, which are best added in the form of hydrogen chloride, ammonium chloride or an alkali chloride.
- the halide ions can also affect the counterelectrode, for example by forming complexes with platinum and partially solve continuous cycling. However, if platinum gets into solution, it can deposit undesirably on the working electrode, i.e. on the foil-like alloy. This can be remedied by installing a commercially available semipermeable membrane, which keeps the electrolyte space of the counter electrode free of halide ions.
- the use of sulfuric acid, slightly chloride-containing electrolytes is recommended.
- the electrochemical cyclization at pH 0 advantageously takes place in the range between 0 mV and -200 mV compared to a KCl-saturated calomel electrode, the cycle duration being in the second range and the temperature of the electrolyte being approximately 50 ° C.
- the brass foils should be chemically polished using conventional methods before use. The duration of the entire process is based on the thickness of the foils used and is in the range of several hours.
- the zinc loss can be determined by weighing the film and / or by using conventional analysis methods such as EDAX or AAS determination.
- a foil-like alloy consisting of a nobler and a less noble metal, preferably a brass foil
- a palladium alloy preferably with a palladium / silver alloy
- in a second step is converted into the porous form by means of the electrochemical cyclization described above, the electrolyte used for the first process being held in place by a holder which is sealed at the edges of the film should be separated from the electrolyte used for the second process.
- the foil-shaped alloy can at most before the galvanic deposition of the Palladium / silver alloy can be chemically or in particular electrochemically treated by superficially removing the less noble component according to the described method, which in this case is carried out only briefly.
- a catalyst such as palladium black or platinum black can also preferably be deposited galvanically.
- a thermal sintering process can be carried out using conventional methods for stabilization after the electrochemical production, with the benefit that the linear thermal expansion coefficient of copper (16.6-10 -6 ° C -1 ) lies between that of palladium (11.7 x 10 -6 ° C -1 ) and that of silver (19.7 - 10 -6 ° C -1 ), which is only a slight stress due to the different ones occurring during heating Expansions of the porous copper carrier on the one hand and the palladium / silver layer on the other hand can be expected.
- the proposed method is of course also applicable to bodies other than flat bodies, e.g. applicable to tubes.
- Such pore-free, palladium-based membranes produced in this way and supported by a porous metal body can be used instead of rolled Pd / Ag membranes in the manner mentioned at the outset for hydrogen separation and as electrodes in fuel cells such as in electrolyzers.
- porous metal bodies without the Pd / Ag layer for example as hydrogenation catalysts, particularly for viscous liquids or solutions which are difficult to filter, or as porous electrode materials in fuel cells or in electrolyzers, the metal optionally being additionally provided with suitable catalysts.
- the water-rinsed film is then electrochemically cycled in 1 M sulfuric acid / 0.004 M HCl at 50 ° C. for 12 hours in a cell separated by a semipermeable membrane using a potentiostat and a function generator.
- the 1 M sulfuric acid in the electrolyte area of the Pt counter electrode must be free of chloride.
- An SCE with saturated potassium sulfate solution as the intermediate electrolyte is used as the reference electrode.
- the potential of the working electrode is varied cyclically in the following way: 1) 500 ms at a potential of 0 mV
- the porous copper foil is (due to chemical etching) at the end approx. 85 ⁇ m thick, the Pd / Ag membrane contains 77% by weight palladium and is approx. 1 ⁇ m thick. If necessary, it can also be electrochemically coated with catalytically active Pd black or the like.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH4326/87A CH675843A5 (enrdf_load_stackoverflow) | 1987-11-07 | 1987-11-07 | |
| CH4326/87-5 | 1987-11-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1989004556A1 true WO1989004556A1 (en) | 1989-05-18 |
Family
ID=4273985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CH1988/000205 WO1989004556A1 (en) | 1987-11-07 | 1988-11-04 | Electrochemical process for manufacturing a pore-free membrane based on palladium and supported by a porous metallic element |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0358727A1 (enrdf_load_stackoverflow) |
| JP (1) | JPH02502320A (enrdf_load_stackoverflow) |
| CH (1) | CH675843A5 (enrdf_load_stackoverflow) |
| WO (1) | WO1989004556A1 (enrdf_load_stackoverflow) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1179361A1 (de) * | 2000-08-12 | 2002-02-13 | OMG AG & Co. KG | Verfahren zur Herstellung einer Metallverbundmembran, damit hergestellte Metallverbundmembran und deren Verwendung |
| EP1180392A1 (de) * | 2000-08-12 | 2002-02-20 | OMG AG & Co. KG | Geträgerte Metallmembran, Verfahren zu ihrer Herstellung und Verwendung |
| US6379524B1 (en) * | 1997-12-24 | 2002-04-30 | Korea Research Institute Of Chemical Technology | Method for preparing composite membrane for separation of hydrogen gas |
| EP1258283A4 (en) * | 1999-11-18 | 2003-07-02 | Toyota Motor Co Ltd | DEVICE FOR THE PRODUCTION OF FUEL AND FUEL CELL AND COMPOSITE MATERIAL FOR THE SEPARATION OF HYDROGEN |
| CN114214626A (zh) * | 2022-01-12 | 2022-03-22 | 浙江花园新能源股份有限公司 | 具有表面多孔结构的铜箔的制备工艺及其产品和应用 |
| CN114369829A (zh) * | 2022-01-12 | 2022-04-19 | 浙江花园新能源股份有限公司 | 一种多孔铜箔的制备工艺及其产品和应用 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8749953B2 (en) | 2010-06-30 | 2014-06-10 | Semiconductor Energy Laboratory Co., Ltd. | Electric double layer capacitor, lithium ion capacitor and manufacturing method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3053741A (en) * | 1961-04-06 | 1962-09-11 | Leesona Corp | Deposition of metals |
| GB998925A (en) * | 1961-04-06 | 1965-07-21 | Leesona Corp | Improvements in or relating to fuel cells |
-
1987
- 1987-11-07 CH CH4326/87A patent/CH675843A5/de not_active IP Right Cessation
-
1988
- 1988-11-04 JP JP63508389A patent/JPH02502320A/ja active Pending
- 1988-11-04 WO PCT/CH1988/000205 patent/WO1989004556A1/de not_active Application Discontinuation
- 1988-11-04 EP EP88909193A patent/EP0358727A1/de not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3053741A (en) * | 1961-04-06 | 1962-09-11 | Leesona Corp | Deposition of metals |
| GB998925A (en) * | 1961-04-06 | 1965-07-21 | Leesona Corp | Improvements in or relating to fuel cells |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6379524B1 (en) * | 1997-12-24 | 2002-04-30 | Korea Research Institute Of Chemical Technology | Method for preparing composite membrane for separation of hydrogen gas |
| EP1258283A4 (en) * | 1999-11-18 | 2003-07-02 | Toyota Motor Co Ltd | DEVICE FOR THE PRODUCTION OF FUEL AND FUEL CELL AND COMPOSITE MATERIAL FOR THE SEPARATION OF HYDROGEN |
| US7255721B1 (en) | 1999-11-18 | 2007-08-14 | Toyota Jidosha Kabushiki Kaisha | Device forming fuel gas for fuel cell and composite material for hydrogen separation |
| EP1179361A1 (de) * | 2000-08-12 | 2002-02-13 | OMG AG & Co. KG | Verfahren zur Herstellung einer Metallverbundmembran, damit hergestellte Metallverbundmembran und deren Verwendung |
| EP1180392A1 (de) * | 2000-08-12 | 2002-02-20 | OMG AG & Co. KG | Geträgerte Metallmembran, Verfahren zu ihrer Herstellung und Verwendung |
| US6649559B2 (en) | 2000-08-12 | 2003-11-18 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Supported metal membrane, a process for its preparation and use |
| CN114214626A (zh) * | 2022-01-12 | 2022-03-22 | 浙江花园新能源股份有限公司 | 具有表面多孔结构的铜箔的制备工艺及其产品和应用 |
| CN114369829A (zh) * | 2022-01-12 | 2022-04-19 | 浙江花园新能源股份有限公司 | 一种多孔铜箔的制备工艺及其产品和应用 |
| CN114369829B (zh) * | 2022-01-12 | 2022-07-08 | 浙江花园新能源股份有限公司 | 一种多孔铜箔的制备工艺及其产品和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CH675843A5 (enrdf_load_stackoverflow) | 1990-11-15 |
| EP0358727A1 (de) | 1990-03-21 |
| JPH02502320A (ja) | 1990-07-26 |
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