EP3642391A1 - Gasdiffusionselektrode zur reduktion von kohlendioxid - Google Patents
Gasdiffusionselektrode zur reduktion von kohlendioxidInfo
- Publication number
- EP3642391A1 EP3642391A1 EP18735210.9A EP18735210A EP3642391A1 EP 3642391 A1 EP3642391 A1 EP 3642391A1 EP 18735210 A EP18735210 A EP 18735210A EP 3642391 A1 EP3642391 A1 EP 3642391A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas diffusion
- diffusion electrode
- silver
- electrode according
- electrocatalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000009792 diffusion process Methods 0.000 title claims abstract description 55
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 claims abstract description 41
- 239000004332 silver Substances 0.000 claims abstract description 41
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 60
- 239000000843 powder Substances 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 39
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 26
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 25
- 239000010411 electrocatalyst Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 21
- 238000002156 mixing Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 238000003825 pressing Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- 239000002759 woven fabric Substances 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 229940038773 trisodium citrate Drugs 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 102100035182 Plastin-2 Human genes 0.000 description 2
- 101710081231 Plastin-2 Proteins 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
- C25B11/032—Gas diffusion electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
Definitions
- the invention relates to a gas diffusion electrode (GDE) for the reduction of carbon dioxide (CO 2 ) based on porous silver powder as an electrocatalyst and their use for the electrochemical reduction of carbon dioxide to CO.
- GDE gas diffusion electrode
- the invention is based on known per se gas diffusion electrodes, which usually comprise an electrically conductive support, a gas diffusion layer and a catalytically active component and are used in the chlor-alkali electrolysis.
- the known electrodes are used for cathodic oxygen reduction.
- Gas diffusion electrodes are electrodes in which the three states of matter - solid, liquid and gaseous - are in contact with each other and the solid, electron-conducting catalyst catalyzes an electrochemical reaction between the liquid and the gaseous phase.
- the carbon dioxide GDE must fulfill a number of basic requirements in order to be usable in technical electrolysers.
- the catalyst and all other materials used must be chemically stable.
- a high degree of mechanical stability is required because the electrodes are installed and operated in electrolyzers of a size of usually more than 2 m 2 surface (technical size). Further properties are: a high electrical conductivity, a small layer thickness, a high internal surface and a high electrochemical activity of the electrocatalyst. Suitable hydrophobic and hydrophilic pores and a corresponding pore structure for the conduction of gas and electrolyte are just as necessary as a tightness, so that gas and liquid space remain separated.
- the long-term stability and low production costs are further special requirements for a technically usable oxygen-consuming electrode.
- Another important property is a low potential at high current density as large as possible 4kA / m 2 and a high selectivity to carbon monoxide.
- different silver morphologies and gold and carbon based catalysts are known for the electrochemical reduction of carbon dioxide to carbon monoxide.
- Hori et al. describes that a polycrystalline gold catalyst with a current strength of 5mA / cm 2 achieves a selectivity of 87% carbon monoxide.
- Chen, Y. et al. (JACS (2012) 19969) developed gold nanoparticles that have a selectivity of 98% at a current density of 6mA / cm 2 and a potential of -0.4 volts.
- silver is also known as a catalyst for carbon dioxide to carbon monoxide reduction.
- Lu et al. showed that nanoporous silver as an electrocatalyst for carbon dioxide to carbon monoxide production has a selectivity of 90% at a current density of 20 mA / cm 2 and - 0.6 volts. (Nat. Com. 5 (2014))
- nanoporous silver systems are described. All with a similar performance (selectivity of 90% at a current density of 20 mA / cm 2 ).
- the preparation of these nanoporous systems is very expensive, difficult to transfer to industrial scale and it is difficult to increase the porosity.
- Porous silver materials can be generated via a colloidal approach, e.g. monodisperse polystyrene particles are crystallized, the interstices between the particles are filled with silver and then the polystyrene particles are dissolved out. This process is very complicated and not suitable for industrial use (Chem. Mater. 2002, 14, 2199-2208).
- a polymer gel is used as a template (Chem. Mater. 2001, 13, 1114-1123), which is similarly expensive.
- all of these processes also require high sintering temperatures of up to 800 ° C in order to represent multistage processes.
- an AlAg or CuAg alloy is first elaborately prepared to dissolve the copper or aluminum, and high temperatures are required to produce the alloy (Nanoenergy 2016).
- monoliths i. get very large particles that are not suitable for further processing in a GDE.
- the porous particles consist of agglomerated nanoparticles.
- the size of the nanoparticles and thus also the porosity can be controlled by the type of addition, the mixing and the concentration of the starting materials.
- the primary particles preferably have a diameter of less than 100 nm.
- silver nitrate and trisodium citrate are dissolved in water.
- a solution consisting of a reducing agent such as NaBH4, KBH4 or formaldehyde dissolved in water is added with stirring.
- the porous particles are formed in a particle size greater than 1 ⁇ , are then filtered off, washed and dried.
- selective GDEs are obtained by mixing these porous particles with a fluoropolymer according to the present inventive method and then pressing the resulting powder mixture onto a carrier element.
- the invention relates to a gas diffusion electrode for the reduction of carbon dioxide, wherein the gas diffusion electrode comprises at least one planar, electrically conductive carrier and a gas diffusion layer applied to the carrier and applied electrocatalyst, wherein the gas diffusion layer consists of at least a mixture of electrocatalyst and a hydrophobic polymer, and wherein the silver acts as an electrocatalyst, characterized in that the electrocatalyst contains silver in the form of highly porous agglomerated nanoparticles and the nanoparticles have a BET surface area of at least 2 m 2 / g.
- the thickness of the catalytically active coating consisting of PTFE and silver gas diffusion electrode is preferably from 20 to ⁇ , more preferably from 100 to 800 ⁇ , most preferably 200 to 600 ⁇ .
- the proportion of electrocatalyst is preferably from 80 to 97 wt .-%, particularly preferably from 90 to 95 wt .-% based on the total weight of electrocatalyst and hydrophobic polymer.
- the proportion of hydrophobic polymer is preferably from 20 to 3 wt .-%, particularly preferably from 10 to 5 wt .-% based on the total weight of electrocatalyst and hydrophobic polymer.
- the hydrophobic polymer is a fluorine-substituted polymer, more preferably polytetrafluoroethylene (PTFE).
- a further preferred embodiment of the gas diffusion electrode is characterized in that the electrode has a total loading of catalytically active component in a range from 5 mg / cm 2 to 300 mg / cm 2 , preferably from 10 mg / cm 2 to 250 mg / cm 2 .
- the gas diffusion electrode which is characterized in that the silver particles are present as an agglomerate of silver nanoparticles with a mean agglomerate diameter (dso measured by laser diffraction) in the range of 1 to 100 ⁇ preferably in the range of 2 to 90 ⁇ .
- gas diffusion electrode in which the silver nanoparticles have a mean diameter in the range of 50 to 150 nm, which were determined by scanning electron microscopy with image analysis.
- the new gas diffusion electrode preferably comprises a support consisting of a material selected from the group consisting of silver, nickel, coated nickel, e.g. with silver, plastic, nickel-copper alloys or coated nickel-copper alloys, e.g. Silver-plated nickel-copper alloys were made from the flat textile structures.
- the electrically conductive carrier may in principle be a net, fleece, foam, woven fabric, braid, expanded metal.
- the support is preferably made of metal, more preferably nickel, silver or silver-plated nickel.
- the carrier may be single-layered or multi-layered.
- a multilayer carrier may be constructed of two or more superposed nets, nonwovens, foams, woven fabrics, braids, expanded metals.
- the nets, nonwovens, foams, fabrics, braids, expanded metals can be different. They may, for example, be different thicknesses or different porosity or have a different mesh size.
- Two or more nets, nonwovens, foams, fabrics, braids, expanded metals can be connected to one another, for example, by sintering or welding.
- a network of nickel or silver with a wire diameter of 0.04 to 0.4 mm and a mesh width of 0.2 to 1.2 mm is used.
- the carrier of the gas diffusion electrode is based on nickel, silver or a combination of nickel and silver.
- the carrier is in the form of a net, woven fabric, knitted fabric, knitted fabric, fleece, expanded metal or foam, preferably a woven fabric.
- the different forms of carbon dioxide electrolysis can be distinguished by how the GDE is incorporated and how this establishes the distance between the ion exchange membrane and the GDE.
- Many cell designs allow a gap between the ion exchange membrane and the GDE, the so-called finite-gap arrangement.
- the gap can be 1 to 3 mm, the gap is of e.g. KHC03 flows through.
- the flow may be from top to bottom in an upright position of the electrode (principle of the falling film cell see, for example, WO 2001 / 057290A2) or from bottom to top (gas pocket principle, see, for example, DE 4,444,114A2).
- a particular embodiment of the invention are plastic-bonded electrodes, wherein the gas diffusion electrode are provided with both hydrophilic and hydrophobic areas. These gas diffusion electrodes are chemically very resistant, especially when PTFE (polytetrafluoroethylene) is used.
- PTFE polytetrafluoroethylene
- PTFE catalyst mixtures take place in principle, for example, by using dispersions of water, PTFE and catalyst.
- emulsifiers are added in particular, and thickeners are preferably used to process the dispersion.
- thickeners are preferably used to process the dispersion.
- Alternative to this wet production process is the production by dry mixing of PTFE powder and catalyst powder.
- the gas diffusion electrodes according to the invention can be prepared as described above, by wet or dispersion and drying process. Particularly preferred is the dry production process. Dispersion methods are chosen mainly for electrodes with polymeric electrolyte - such. B. successfully introduced in the PEM (polymer electrolyte membrane) fuel cell or the HCl-GDE membrane electrolysis (WO2002 / 18675). When using the GDE in liquid electrolytes, the dry process provides more suitable GDEn. When wet / resp. Dispersion process can be dispensed by strong evaporation of the water and sintering of the PTFE at 340 ° C on a strong mechanical pressing. These electrodes are usually very porous. On the other hand, in the wrong drying conditions, cracks can quickly form in the electrode, through which liquid electrolyte can penetrate. Therefore, for liquid electrolyte applications such as the zinc-air battery or the alkaline fuel cell, the dry process has become established.
- the catalyst is intensively mixed with a polymer component (preferably PTFE).
- a polymer component preferably PTFE
- the powder mixture may be formed into a sheet-like structure by pressing, preferably by compression by rolling, which is then applied to the support (see, for example, DE 3,710,168 A2, EP 144,002 A2).
- a likewise applicable preferred alternative is described in DE 102005023615 A2; In this case, the powder mixture is sprinkled on a support and pressed together with this.
- the electrode is made of a powder mixture consisting of silver and / or its oxides and PTFE. It is likewise possible to use doped silver and / or its oxides or mixtures of silver and / or its oxides with silver and PTFE.
- the catalysts and PTFE are treated, for example, as described in US Pat. No. 6,838,408 in a dry mixing process, and the powder is compacted into a hide. The coat is then pressed together with a mechanical support. Both the fur-forming process and the compression of the skin and the wearer can take place, for example, by a rolling process.
- the pressing force has an influence on the pore diameter and the porosity of the GDE. Pore diameter and porosity influence the performance of the GDE.
- the preparation of the GDE according to the invention can be carried out analogously to DE 10.148.599A1 in that the catalyst-powder mixture is applied directly to a carrier.
- the powder mixture is produced in a particularly preferred embodiment by mixing the catalyst powder and the binder and optionally other components.
- the mixing is preferably done in a mixing device which has fast rotating mixing elements, such as beater knives.
- the mixing elements rotate preferably at a speed of 10 to 30 m / s or at a speed of 4000 to 8000 U / min.
- the powder mixture is preferably sieved.
- the sieving is preferably carried out with a sieve device or the like with nets. equipped, whose mesh size 0.04 to 2 mm.
- the temperature during the mixing process is preferably 35 to 80 ° C.
- This can be done by cooling during mixing, for example by adding a coolant, for example liquid nitrogen or other inert heat-absorbing substances.
- Another way of controlling the temperature may be that the mixing is interrupted to allow the powder mixture to cool or by selecting suitable mixing units or changing the filling level in the mixer.
- the application of the powder mixture to the electrically conductive carrier takes place, for example, by scattering.
- the spreading of the powder mixture on the carrier can be done for example by a sieve.
- a frame-shaped template is placed on the carrier, wherein the template is preferably chosen so that it just covers the carrier.
- the template can also be chosen smaller than the surface of the carrier. In this case remains after sprinkling the powder mixture and the pressing with the carrier an uncoated edge of the carrier free of electrochemically active coating.
- the thickness of the template can be selected according to the amount of powder mixture to be applied to the carrier.
- the template is filled with the powder mixture. Excess powder can be removed by means of a scraper. Then the template is removed.
- the powder mixture is pressed in a particularly preferred embodiment with the carrier.
- the pressing can be done in particular by means of rollers. Preferably, a pair of rollers is used. However, it is also possible to use a roller on a substantially flat base, wherein either the roller or the base is moved. Furthermore, the pressing can be done by a ram.
- the forces during pressing are in particular 0.01 to 7 kN / cm.
- a GDE according to the invention can basically be constructed as a single layer or as a multilayer.
- powder mixtures having different compositions and different properties are applied to the carrier in layers.
- the layers of different powder mixtures are preferably not pressed individually with the carrier, but first applied successively and then pressed together in one step together with the carrier.
- a layer of a powder mixture can be applied, which has a higher content of the binder, in particular a higher content of PTFE, than the electrochemically active layer.
- a layer with a high PTFE content of 6 to 100%. can act as a gas diffusion layer.
- a gas diffusion layer made of PTFE can also be applied.
- a layer with a high content of PTFE can be applied directly to the support as the lowest layer.
- Other layers of different composition can be applied for the preparation of the gas diffusion electrode.
- the desired physical and / or chemical properties can be specifically adjusted. These include the hydrophobicity or hydrophilicity of the layer, the electrical conductivity, the gas permeability.
- a gradient of a property can be built up by increasing or decreasing the measure of the property from layer to layer.
- the thickness of the individual layers of the GDE can be adjusted by the amount of powder mixture applied to the carrier and by the pressing forces during pressing.
- the amount of the applied powder mixture can be adjusted, for example, by the thickness of the template which is placed on the carrier to spread the powder mixture on the carrier.
- a coat is produced from the powder mixture.
- the thickness or density of the coat can not be set independently of one another, since the parameters of the rolls, such as roll diameter, roll spacing, roll material, tensile holding force and peripheral speed, have a decisive influence on these sizes.
- the pressing force when pressing the powder mixture or layers of different powder mixtures with the carrier takes place e.g. by roll pressing with a line pressing force in the range of 0.01 to 7 kN / cm.
- the carbon dioxide GDE is preferably connected as a cathode, in particular in an electrolytic cell for the electrolysis of alkali metal chlorides, preferably of sodium chloride or potassium chloride, more preferably of sodium chloride, or of hydrochloric acid.
- the carbon dioxide GDE is particularly preferably used as a cathode in the chlorine electrolysis or 02 electrolysis. Another object of the invention is therefore the use of the new gas diffusion electrode for the electrolysis of carbon dioxide to carbon monoxide, especially in the chloralkali electrolysis,
- the invention also provides a process for the electrochemical conversion of carbon dioxide to carbon monoxide, characterized in that the carbon dioxide is converted cathodically to carbon monoxide at a new gas diffusion electrode as described above and chlorine or oxygen is simultaneously produced at the anode side.
- the current density in the reaction is at least 2 kA / m 2, preferably at least 4 kA / m 2 .
- the invention is also an electrolysis device having a new gas diffusion electrode as a carbon dioxide consuming cathode.
- the invention furthermore relates to a gas diffusion electrode, characterized in that the gas diffusion electrode has at least one planar electrically conductive carrier element and a gas diffusion layer applied to the carrier element and an electrocatalyst, characterized in that the gas diffusion layer consists of a mixture of silver particles and PTFE, wherein the silver particles and the fluoropolymer is applied and compacted in powder form on the carrier element, the silver particles forming the electrocatalyst.
- a gas diffusion electrode obtained from a manufacturing method of the invention described above.
- the GDEn prepared according to the following examples were used in the oxygen electrolysis.
- a laboratory cell was used, which consisted of an anode compartment and separated by an ion exchange membrane, a cathode compartment.
- a KHCO 3 solution with a concentration of 300 g / 1 was used in which oxygen was produced on a commercially available DSA with iridium-coated titanium electrode.
- the cathode compartment was separated from the anode compartment by a commercial cation exchange membrane of Asahi Glass, Fl 33 type. Between GDE and the cation exchange membrane there was an electrolyte gap in which a NaHCO 3 solution of the concentration of 300 g 1 was pumped.
- the GDE was supplied via a gas space with carbon dioxide whose concentration was greater than 99.5 vol%. Anodes, membrane and gas diffusion electrode area were 3 cm 2 each. The temperature of the electrolytes was 25 ° C. The current density of the electrolysis was 4 kA / m 2 in all experiments.
- the GDEn were prepared as follows: 3.5 kg of a powder mixture consisting of 7% by weight of PTFE powder, 93% by weight of silver powder (eg type 331 from Ferro) were mixed in an Ika mill AI 1 basic, that the temperature of the powder mixture did not exceed 55 ° C. This was achieved by stopping the mixing and cooling the powder mixture. Overall, mixing was performed three times with a mixing time of 10 seconds. After mixing, the powder mixture was screened with a 1.0 mm mesh screen. The sieved powder mixture was subsequently applied to an electrically conductive carrier element.
- the support element was a nickel mesh with a wire thickness of 0.14 mm and a mesh width of 0.5 mm.
- the application was carried out using a 1 mm thick template, wherein the powder was applied with a sieve with a mesh width of 1.0 mm. Excess powder extending beyond the thickness of the stencil was removed by means of a wiper. After removing the template, the carrier with the applied powder mixture is pressed by means of a roller press with a pressing force of 0.4 to 1.7 kN / cm. The roller press was removed from the gas diffusion electrode.
- Example 1 Preparation of porous silver catalyst (according to the invention) 400 ml of a 0.1 molar AgNO 3 solution (6.796 g of AgNCb) were admixed with 0.8 g of trisodium citrate. 400 ml of 0.2 molar sodium borohydride (3.024 g NaBH t) were added rapidly with stirring to the first solution (about 15 seconds, Re> 10000) and allowed to stir for 1 hour. The precipitate was filtered off, washed with water and dried overnight at 50 ° C.
- a molar AgNO 3 solution 6.96 g of AgNCb
- 400 ml of 0.2 molar sodium borohydride (3.024 g NaBH t) were added rapidly with stirring to the first solution (about 15 seconds, Re> 10000) and allowed to stir for 1 hour. The precipitate was filtered off, washed with water and dried overnight at 50 ° C.
- the powder was characterized by BET, laser diffraction and scanning electron microscopy. Particle size is about 145 nm in diameter and the BET surface area is 2.23 m 2 / g (N 2 adsorption).
- Example 2 Preparation of less porous silver catalyst 400 ml of a 0.1 molar AgNC solution (6.796 g of AgNC) are mixed with 0.8 g of trisodium citrate. 400 ml of 0.2 molar sodium borohydride (3.024 g of NaBEL) are slowly added dropwise with stirring to the first solution (about 1 h) and allowed to stir for 1 h. The precipitate was filtered off, washed with water and dried overnight at 50 ° C. The powder is characterized by BET, laser diffraction and scanning electron microscopy.
- Particle size is about 290 nm in diameter and the BET surface area is 0.99 m 2 / g (N 2 adsorption).
- the GDE was prepared by the dry process, wherein 93 wt .-% silver powder according to Example 1 and 2 and silver LCP-1 Arnes Goldsmith, 7 wt .-% PTFE from DYNEON TF2053 mixed in a fka mill Al l basic and was then pressed with roller press at a force of 0.5 kN / cm.
- the electrode was used in the above electrolytic cell and operated at 2 and 4 kA / m 2 .
- the Faraday efficiency for CO is shown in the table below.
- the physisorption of gases at cryogenic temperature conditions is used to increase the specific surface area (SSA) of compact finely dispersed or porous solids determine.
- the amount of nitrogen that physiorizes on the accessible surface of the sample is measured in a static volumetric analyzer by adding a well-defined amount of nitrogen gas into the sample cell. At the same time, the pressure increase due to the added gas is recorded after the equilibrium state is reached.
- the total area in the measuring cell the smaller the increase in pressure (in equilibrium), since the nitrogen content adsorbed on the surface can not contribute to the increase in pressure.
- Form the adsorbed molar amount of nitrogen on a sample the total area of the sample can be calculated by multiplying the molar amount with the known adsorbent gas adsorption area.
- Sample surface are evaporated. Thus, the sample was kept under vacuum conditions at 200 ° C for several hours.
- Particle sizes were obtained by laser diffraction on a Malvern Mastersizer MS2000 Hydro MU instrument.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP17177031.6A EP3418429A1 (de) | 2017-06-21 | 2017-06-21 | Gasdiffusionselektrode zur reduktion von kohlendioxid |
PCT/EP2018/066293 WO2018234322A1 (de) | 2017-06-21 | 2018-06-19 | Gasdiffusionselektrode zur reduktion von kohlendioxid |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3642391A1 true EP3642391A1 (de) | 2020-04-29 |
EP3642391B1 EP3642391B1 (de) | 2023-08-02 |
Family
ID=59093481
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17177031.6A Withdrawn EP3418429A1 (de) | 2017-06-21 | 2017-06-21 | Gasdiffusionselektrode zur reduktion von kohlendioxid |
EP18735210.9A Active EP3642391B1 (de) | 2017-06-21 | 2018-06-19 | Verfahren, verwendung und elektrolysezelle mit gasdiffusionselektrode zur reduktion von kohlendioxid |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17177031.6A Withdrawn EP3418429A1 (de) | 2017-06-21 | 2017-06-21 | Gasdiffusionselektrode zur reduktion von kohlendioxid |
Country Status (6)
Country | Link |
---|---|
US (1) | US20200208283A1 (de) |
EP (2) | EP3418429A1 (de) |
JP (1) | JP7222933B2 (de) |
KR (1) | KR20200020714A (de) |
CN (1) | CN110770370B (de) |
WO (1) | WO2018234322A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102018210457A1 (de) * | 2018-06-27 | 2020-01-02 | Siemens Aktiengesellschaft | Gasdiffusionselektrode zur Kohlendioxid-Verwertung, Verfahren zu deren Herstellung sowie Elektrolysezelle mit Gasdiffusionselektrode |
CN114373940A (zh) * | 2021-12-16 | 2022-04-19 | 清华大学 | 气体扩散电极及其制备方法和应用 |
KR20240010402A (ko) | 2022-07-15 | 2024-01-23 | 주식회사 엘지화학 | 전기화학적 이산화탄소 전환 시스템 |
KR20240031100A (ko) | 2022-08-29 | 2024-03-07 | 주식회사 엘지화학 | 전기 화학적 이산화 탄소 전환 시스템의 구동 방법 |
WO2024185870A1 (ja) * | 2023-03-09 | 2024-09-12 | 三井金属鉱業株式会社 | 電極触媒、電気化学反応装置及び電極触媒の製造方法 |
CN116876005B (zh) * | 2023-07-21 | 2024-07-16 | 深圳先进技术研究院 | 用于电催化co2还原制co的气相扩散电极、制备方法及应用 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3342969A1 (de) | 1983-11-28 | 1985-06-05 | Varta Batterie Ag, 3000 Hannover | Poroese gaselektrode |
DE3710168A1 (de) | 1987-03-27 | 1988-10-13 | Varta Batterie | Verfahren zur herstellung einer kunststoffgebundenen gasdiffusionselektrode mit metallischen elektrokatalysatoren |
DE4444114C2 (de) | 1994-12-12 | 1997-01-23 | Bayer Ag | Elektrochemische Halbzelle mit Druckkompensation |
US6402930B1 (en) | 1999-05-27 | 2002-06-11 | De Nora Elettrodi S.P.A. | Process for the electrolysis of technical-grade hydrochloric acid contaminated with organic substances using oxygen-consuming cathodes |
IT1317753B1 (it) | 2000-02-02 | 2003-07-15 | Nora S P A Ora De Nora Impiant | Cella di elettrolisi con elettrodo a diffusione di gas. |
DE10148599A1 (de) | 2001-10-02 | 2003-04-10 | Bayer Ag | Verfahren zur Herstellung von Gasdiffusionselektroden aus trockenen Pulvermischungen mittels Walzen |
JP2006219694A (ja) * | 2005-02-08 | 2006-08-24 | Permelec Electrode Ltd | ガス拡散電極 |
DE102005023615A1 (de) | 2005-05-21 | 2006-11-23 | Bayer Materialscience Ag | Verfahren zur Herstellung von Gasdiffusionselektroden |
US8900750B2 (en) * | 2006-09-22 | 2014-12-02 | Bar-Ilan University | Porous clusters of silver powder promoted by zirconium oxide for use as a catalyst in gas diffusion electrodes, and method for the production thereof |
JP5264737B2 (ja) | 2006-09-22 | 2013-08-14 | バーイラン ユニバーシティー | ガス拡散電極内の触媒として使用可能な、酸化ジルコニウムによって活性が高められた銀粉の多孔質クラスター、及びその製造方法 |
JP5031336B2 (ja) * | 2006-11-21 | 2012-09-19 | ペルメレック電極株式会社 | 食塩電解用酸素ガス拡散陰極 |
EP2055807B1 (de) * | 2007-10-31 | 2010-07-14 | Daiki Ataka Engineering Co., Ltd. | Elektrode für Sauerstoffentwicklung |
US10047446B2 (en) * | 2010-07-04 | 2018-08-14 | Dioxide Materials, Inc. | Method and system for electrochemical production of formic acid from carbon dioxide |
JP6021074B2 (ja) | 2011-02-28 | 2016-11-02 | 国立大学法人長岡技術科学大学 | 二酸化炭素の還元固定化システム、二酸化炭素の還元固定化方法、及び有用炭素資源の製造方法 |
US9714472B2 (en) | 2011-09-23 | 2017-07-25 | Covestro Deutschland Ag | Gas diffusion electrodes and process for production thereof |
US10329676B2 (en) | 2012-07-26 | 2019-06-25 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
EP3149228B1 (de) * | 2014-05-29 | 2021-03-03 | Avantium Knowledge Centre B.V. | Verfahren zur elektrochemischen reduktion von kohlendioxid mit einer gasdiffusionselektrode |
AU2015315620B2 (en) * | 2014-09-08 | 2019-02-07 | 3M Innovative Properties Company | Ionic polymer membrane for a carbon dioxide electrolyzer |
DE102015212504A1 (de) * | 2015-07-03 | 2017-01-05 | Siemens Aktiengesellschaft | Elektrolysesystem und Reduktionsverfahren zur elektrochemischen Kohlenstoffdioxid-Verwertung, Alkalicarbonat- und Alkalihydrogencarbonaterzeugung |
DE102017204096A1 (de) * | 2017-03-13 | 2018-09-13 | Siemens Aktiengesellschaft | Herstellung von Gasdiffusionselektroden mit Ionentransport-Harzen zur elektrochemischen Reduktion von CO2 zu chemischen Wertstoffen |
-
2017
- 2017-06-21 EP EP17177031.6A patent/EP3418429A1/de not_active Withdrawn
-
2018
- 2018-06-19 KR KR1020197037391A patent/KR20200020714A/ko not_active Application Discontinuation
- 2018-06-19 US US16/623,437 patent/US20200208283A1/en active Pending
- 2018-06-19 JP JP2019570373A patent/JP7222933B2/ja active Active
- 2018-06-19 EP EP18735210.9A patent/EP3642391B1/de active Active
- 2018-06-19 WO PCT/EP2018/066293 patent/WO2018234322A1/de unknown
- 2018-06-19 CN CN201880041586.2A patent/CN110770370B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN110770370B (zh) | 2022-11-25 |
CN110770370A (zh) | 2020-02-07 |
EP3642391B1 (de) | 2023-08-02 |
JP7222933B2 (ja) | 2023-02-15 |
JP2020524742A (ja) | 2020-08-20 |
EP3418429A1 (de) | 2018-12-26 |
KR20200020714A (ko) | 2020-02-26 |
US20200208283A1 (en) | 2020-07-02 |
WO2018234322A1 (de) | 2018-12-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3642391B1 (de) | Verfahren, verwendung und elektrolysezelle mit gasdiffusionselektrode zur reduktion von kohlendioxid | |
EP2398101B1 (de) | Gasdiffusionselektrode und Verfahren zu ihrer Herstellung | |
EP1728896B1 (de) | Verfahren zur Herstellung von Gasdiffusionselektroden | |
EP2385996A2 (de) | Strukturierte gasdiffusionselektrode für elektrolysezellen | |
EP1402587B1 (de) | Verfahren zum herstellen von gasdiffusionselektroden | |
WO2018210515A1 (de) | Herstellung von dendritischen elektrokatalysatoren zur reduktion von co2 und/oder co | |
DE102011005454A1 (de) | Verfahren zur Herstellung von Sauerstoffverzehrelektroden | |
EP2573211B1 (de) | Verfahren zur Herstellung von Gasdiffusionselektroden | |
WO2015135858A1 (de) | Verfahren zur herstellung von katalytisch aktiven pulvern aus metallischem silber oder aus mischungen aus von metallischem silber mit silberoxid zur herstellung von gasdiffusionselektroden | |
EP2609649B1 (de) | Sauerstoffverzehrelektrode und verfahren zu ihrer herstellung | |
WO2016037867A1 (de) | Kohlenstoffnanorohrchen enthaltende sauerstoffverzehrelektrode und verfahren zu ihrer herstellung | |
EP3191620B1 (de) | Sauerstoffverzehrelektrode und verfahren zu ihrer herstellung | |
EP2573213B1 (de) | Sauerstoffverzehrelektrode und verfahren zu ihrer herstellung | |
EP3788184A1 (de) | Gasdiffusionselektrode zur kohlendioxid-verwertung, verfahren zu deren herstellung sowie elektrolysezelle mit gasdiffusionselektrode | |
EP2573210B1 (de) | Sauerstoffverzehrelektrode und Verfahren zu ihrer Herstellung | |
DE102022004678A1 (de) | Verfahren zur Elektrolyse von Kohlendioxid mit Vorreduktion einer Silberoxid-enthaltenden Gasdiffusionselektrode | |
DE3125173A1 (de) | Elektrolysezelle mit einer kathode, die eine einlagerungsverbindung von graphit und einem uebergangsmetall aufweist, und ihre verwendung |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20200121 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: COVESTRO DEUTSCHLAND AG |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: COVESTRO INTELLECTUAL PROPERTY GMBH & CO. KG |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20201210 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 502018012875 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: C25B0001000000 Ipc: C25B0001230000 Ref country code: DE Ref legal event code: R079 Free format text: PREVIOUS MAIN CLASS: C25B0001000000 Ipc: C25B0001230000 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C25B 11/081 20210101ALI20230125BHEP Ipc: C25B 11/032 20210101ALI20230125BHEP Ipc: C25B 1/23 20210101AFI20230125BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20230313 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502018012875 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231202 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231204 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231102 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231202 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231103 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502018012875 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20240527 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240516 Year of fee payment: 7 |
|
26N | No opposition filed |
Effective date: 20240503 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240522 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230802 |