CN117926293A - Alkaline membrane electrode type electrolytic tank for producing hydrogen by alkaline water electrolysis and preparation method thereof - Google Patents
Alkaline membrane electrode type electrolytic tank for producing hydrogen by alkaline water electrolysis and preparation method thereof Download PDFInfo
- Publication number
- CN117926293A CN117926293A CN202310280017.6A CN202310280017A CN117926293A CN 117926293 A CN117926293 A CN 117926293A CN 202310280017 A CN202310280017 A CN 202310280017A CN 117926293 A CN117926293 A CN 117926293A
- Authority
- CN
- China
- Prior art keywords
- membrane electrode
- diffusion layer
- cathode
- anode
- catalyst
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 126
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 184
- 238000009792 diffusion process Methods 0.000 claims abstract description 99
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 114
- 229910052759 nickel Inorganic materials 0.000 claims description 55
- 239000002002 slurry Substances 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000010959 steel Substances 0.000 claims description 14
- 239000004695 Polyether sulfone Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 229920002492 poly(sulfone) Polymers 0.000 claims description 12
- 229920006393 polyether sulfone Polymers 0.000 claims description 12
- 238000012546 transfer Methods 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000010023 transfer printing Methods 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 7
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000005240 physical vapour deposition Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 2
- 238000000429 assembly Methods 0.000 claims 1
- 230000000712 assembly Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 229910000564 Raney nickel Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 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
- 239000013077 target material Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229930188620 butyrolactone Natural products 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910003310 Ni-Al Inorganic materials 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 241001479434 Agfa Species 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910002440 Co–Ni Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001849 group 12 element Inorganic materials 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007738 vacuum evaporation 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- 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
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
-
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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)
Abstract
The invention provides an alkaline membrane electrode type electrolytic tank for producing hydrogen by alkaline water electrolysis and a preparation method thereof. The alkaline membrane electrode type electrolytic cell comprises an electrolytic unit and end plates arranged on two sides of the electrolytic unit, the electrolytic unit comprises an electrolytic cell, and the electrolytic cell comprises a bipolar plate, an anode diffusion layer, a membrane electrode, a cathode diffusion layer and a bipolar plate which are stacked in sequence; the membrane electrode comprises a diaphragm, and an anode catalyst layer and a cathode catalyst layer which are respectively supported on the two side surfaces of the diaphragm; the membrane is a porous membrane or an alkaline anion exchange membrane; the thickness of the bipolar plate is 1-3mm, the thicknesses of the anode diffusion layer and the cathode diffusion layer are respectively 0.02-4mm, and the mesh numbers of the anode diffusion layer and the cathode diffusion layer are respectively 50-500 meshes.
Description
Technical Field
The invention relates to the technical field of hydrogen production by alkaline water electrolysis, in particular to an alkaline membrane electrode type electrolytic tank for hydrogen production by alkaline water electrolysis and a preparation method thereof.
Background
With the increasing attention of environmental protection and decarbonization worldwide and the progress of renewable energy power generation technology, the hydrogen production by using renewable energy sources such as wind power, photoelectricity, hydropower and the like is an important way for realizing green hydrogen energy economy. The hydrogen energy can be widely applied to methanol production, oil hydrogenation, ammonia synthesis, metal smelting, heat supply, vehicle transportation and the like. The total amount of renewable energy sources is obviously increased, the renewable energy sources become one of main energy sources, the power generation cost is continuously reduced along with the maturity of technology and the expansion of scale, and the renewable energy sources are expected to have market competitiveness for hydrogen production. In addition, the renewable energy source hydrogen production can consume the wind, light and water discarding power, and low-cost hydrogen is obtained.
The technology for producing hydrogen by water electrolysis comprises alkaline water electrolysis, proton exchange membrane water electrolysis, anion exchange membrane water electrolysis and solid oxide water electrolysis. Among them, the hydrogen production technology by alkaline electrolysis of water is the most mature, and has been widely used in the fields of thermal power plants and precision electronic product production. The electrolytic cell structure of the conventional alkaline electrolytic cell is schematically shown in fig. 4, which comprises a bipolar plate, an anode nickel screen electrode, a separator, a cathode nickel screen electrode, and a bipolar plate stacked in this order, wherein the nickel screen electrode is shown in fig. 5. The alkaline water electrolysis hydrogen production technology has the advantages of low equipment cost, long service life and robustness, is suitable for preparing green hydrogen on a large scale, but the existing electrolytic tank for alkaline water electrolysis hydrogen production still has the defects of low current density and high electrolysis energy consumption. Lowering the cell voltage of alkaline electrolyzed water is critical to improving the energy efficiency and current density of the electrolysis.
Patent application CN104364425A discloses a bipolar alkaline water electrolysis unit and an electrolysis cell, wherein the bipolar alkaline water electrolysis unit is assembled in an electrolysis cell for electrolyzing an electrolyte composed of alkaline water to obtain oxygen and hydrogen, and the bipolar alkaline water electrolysis unit comprises an anode for oxygen evolution, a cathode for hydrogen evolution, a conductive partition wall for separating the anode and the cathode, and an annular outer frame surrounding the conductive partition wall, wherein a passage part for gas and the electrolyte is arranged at the upper part of the conductive partition wall and/or the outer frame, and a passage part for the electrolyte is arranged at the lower part of the conductive partition wall and/or the outer frame. In this embodiment, by providing the outer frame surrounding the partition wall of the bipolar alkaline water electrolysis unit, even if electrolysis is performed at a high current density of 3kA/m 2 or more, the ion permeable separator or the electrodes (anode and cathode) are not damaged, and the installation is easy, and the equipment cost can be suppressed. The main improvement of the proposal aims at providing a bipolar alkaline water electrolysis unit and an electrolytic tank which have low equipment cost and can perform stable electrolysis.
Disclosure of Invention
The invention provides an alkaline membrane electrode type electrolytic cell for producing hydrogen by alkaline water electrolysis and a preparation method thereof, wherein the alkaline membrane electrode type electrolytic cell has lower cell voltage in the hydrogen production by alkaline water electrolysis, and is beneficial to reducing the energy consumption of the alkaline water electrolysis.
The invention provides the following technical scheme for achieving the purpose:
The invention provides an alkaline membrane electrode type electrolytic tank for producing hydrogen by alkaline water electrolysis, which comprises an electrolytic unit and end plates arranged on two sides of the electrolytic unit, wherein the electrolytic unit comprises an electrolytic cell, and the electrolytic cell comprises a bipolar plate, an anode diffusion layer, a membrane electrode, a cathode diffusion layer and a bipolar plate which are sequentially stacked;
the membrane electrode comprises a diaphragm, and an anode catalyst layer and a cathode catalyst layer which are respectively supported on the two side surfaces of the diaphragm; the membrane is a porous membrane or an alkaline anion exchange membrane;
The thickness of the bipolar plate is 1-3mm, the thicknesses of the anode diffusion layer and the cathode diffusion layer are respectively 0.02-4mm, and the mesh numbers of the anode diffusion layer and the cathode diffusion layer are respectively 50-500 meshes.
Preferably, the thicknesses of the anode catalyst layer and the cathode catalyst layer are respectively 2-50 μm, preferably more than or equal to 2 μm and less than 10 μm; further preferably, the ratio of the thicknesses of the anode catalyst layer and the cathode catalyst layer is 1 to 3.
In some embodiments, the porous membrane is made of one or more selected from polyethersulfone, polysulfone, polyphenylene sulfide, polytetrafluoroethylene, polyvinylidene fluoride, and polyvinyl chloride.
In some embodiments, the basic anion exchange membrane is selected from a quaternary ammonium salt type anion exchange membrane, a polyethersulfone type anion exchange membrane, and a polyphenylene ether type anion exchange membrane.
In some embodiments, the separator has a porosity of 30-80% and a thickness of 0.05-0.7mm.
Preferably, the bipolar plate is a nickel-plated steel plate or a titanium plate; preferably, the bipolar plate has a nickel plating layer 1-200 μm thick.
Preferably, the anode diffusion layer and the cathode diffusion layer are respectively selected from nickel mesh, nickel felt, porous nickel plate, porous nickel foil, nickel plated steel mesh, nickel plated porous steel plate, nickel plated titanium mesh or nickel plated porous titanium plate.
Preferably, the catalysts in the anode catalyst layer and the cathode catalyst layer are respectively selected from one or more of a metal including nickel element, a metal oxide including nickel element; preferably, the catalyst loadings in the anode catalyst layer and the cathode catalyst layer are 0.5-20mg/cm 2, respectively.
Preferably, the electrolysis unit comprises more than two electrolysis cells.
Preferably, in the electrolysis cell, among the bipolar plate, the anode diffusion layer, the membrane electrode, the cathode diffusion layer and the bipolar plate stacked in order, sealing gaskets are respectively arranged between two adjacent components.
Preferably, the thicknesses of the bipolar plates are respectively 2-3mm, the thicknesses of the anode diffusion layer and the cathode diffusion layer are respectively 0.1-0.2mm, and the mesh numbers of the anode diffusion layer and the cathode diffusion layer are respectively 150-250 meshes.
The invention also provides a preparation method of the alkaline membrane electrode type electrolytic cell, wherein the end plates are respectively arranged on two sides of the electrolytic cell, and the alkaline membrane electrode type electrolytic cell is obtained by assembling.
In some embodiments, the step of preparing the membrane electrode in the electrolysis cell comprises: and respectively loading and forming an anode catalyst layer and a cathode catalyst layer on the surfaces of two sides of the diaphragm by a physical vapor deposition method, a transfer printing method or a direct coating method to obtain the membrane electrode.
In some embodiments, the transfer method comprises the following operations: coating the catalyst slurry with the catalyst dispersed on a transfer film, and then drying; and then placing the membrane on two sides of the membrane, and obtaining the membrane electrode through transfer printing.
In some embodiments, the direct coating process comprises the following operations: coating catalyst slurry with dispersed catalyst on the two side surfaces of the diaphragm, drying and hot-pressing to obtain the membrane electrode; preferably, the drying is performed at 80-150 ℃, and the hot pressing is performed at 130-210 ℃ and 0.5-10 MPa.
In some embodiments, the binder used in the catalyst slurry is selected from one or more of polysulfone, polyethersulfone, polyphenylene sulfide, and perfluorosulfonic acid resin;
preferably, in the catalyst slurry, the solvent used is selected from one or more of esters, ketones, amides, alcohols and aqueous solvents;
Further preferably, the catalyst in the catalyst slurry: and (2) a binder: the mass ratio of the solvent is 1:0.01-5:0.4-50.
The technical scheme provided by the invention has the following beneficial effects:
The invention discloses an electrolytic tank for producing hydrogen by alkaline electrolysis water, which is formed by combining bipolar plates with specific thickness and cathode and anode diffusion layers with specific thickness and mesh, is applied to producing hydrogen by alkaline electrolysis water and has lower cell voltage, and can obviously reduce the energy consumption of the alkaline electrolysis water.
Drawings
FIG. 1 is a schematic view of an alkaline membrane electrode type electrolyzer for producing hydrogen by alkaline electrolysis of water, according to one embodiment of the present invention;
FIG. 2 is a photograph showing the appearance of a membrane electrode according to an embodiment of the present invention;
FIG. 3 is a schematic view showing a partial structure of a membrane electrode according to an embodiment of the present invention;
FIG. 4 is a schematic view showing the structure of an electrolysis cell of a conventional alkaline electrolyzer;
FIG. 5 is a schematic view of a nickel screen electrode used in a conventional alkaline electrolytic cell.
Detailed Description
In order that the invention may be readily understood, a further description of the invention will be provided with reference to the following examples. It should be understood that the following examples are only for better understanding of the present invention and are not meant to limit the present invention to the following examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The term "and/or" as may be used herein includes any and all combinations of one or more of the associated listed items.
Where specific experimental steps or conditions are not noted in the examples, they may be performed according to the operations or conditions of the corresponding conventional experimental steps in the art. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides an alkaline membrane electrode type electrolytic tank for producing hydrogen by alkaline water electrolysis, which has basically the same structure as the existing electrolytic tank and mainly aims at improving an electrolytic cell. A schematic partial structure of the electrolytic cell of the present invention is shown in fig. 1. Specifically, the alkaline membrane electrode type electrolytic tank comprises an electrolytic unit and end plates arranged on two sides of the electrolytic unit, wherein the electrolytic unit comprises an electrolytic cell, and the electrolytic cell comprises a bipolar plate, an anode diffusion layer, a membrane electrode, a cathode diffusion layer and a bipolar plate which are sequentially stacked. The membrane electrode comprises a membrane, and an anode catalyst layer and a cathode catalyst layer which are respectively supported on two side surfaces of the membrane, and can be seen in fig. 2 and 3; the membrane is a porous membrane or an alkaline anion exchange membrane; the membrane electrode is of an integrated structure of an anode catalyst layer, a diaphragm and a cathode catalyst layer. Wherein the thickness of the bipolar plate is 1-3mm, the thicknesses of the anode diffusion layer and the cathode diffusion layer are 0.02-4mm, and the mesh numbers of the anode diffusion layer and the cathode diffusion layer are 50-500 meshes.
The invention develops an alkaline membrane electrode type electrolytic tank for producing hydrogen by alkaline water electrolysis based on a specific membrane electrode, wherein the specific membrane electrode takes a porous diaphragm or an alkaline anion exchange membrane as a diaphragm, and anode catalyst layers and cathode catalyst layers are respectively loaded on the surfaces of two sides of the diaphragm; based on the specific membrane electrode, the bipolar plate, the anode diffusion layer and the cathode diffusion layer are assembled into an electrolysis cell, the thickness of the bipolar plate is respectively controlled to be 1-3mm, the thicknesses of the anode diffusion layer and the cathode diffusion layer are respectively controlled to be 0.02-4mm, the mesh numbers of the anode diffusion layer and the cathode diffusion layer are respectively controlled to be 50-500 meshes, and the obtained electrolysis cell shows lower cell voltage when being applied to hydrogen production by alkaline electrolysis of water.
In some preferred embodiments, the thicknesses of the anode catalyst layer and the cathode catalyst layer are respectively 2-50 μm, and the catalyst layer with the thickness range is adopted, so that the application performance of the electrolytic cell in alkaline water electrolysis hydrogen production is improved; more preferably, the thicknesses of the anode catalyst layer and the cathode catalyst layer are respectively more than or equal to 2 mu m and less than 10 mu m, and the inventor finds that in the electrolytic cell of the invention, the catalyst layer with the preferable thickness range can provide a sufficient number of catalytic active sites, and simultaneously reduce the distance between the anode and the cathode, thereby being beneficial to further reducing the voltage of an electrolytic cell; even more preferably, the ratio of the thicknesses of the anode catalyst layer and the cathode catalyst layer is 1 to 3, which is advantageous for further improving the performance of the electrolytic cell in alkaline electrolyzed water.
In the alkaline membrane electrode type electrolytic tank provided by the invention, the membrane in the used membrane electrode is a porous membrane or an alkaline anion exchange membrane, and preferably, the material of the porous membrane is one or more selected from polyethersulfone, polysulfone, polyphenylene sulfide, polytetrafluoroethylene, polyvinylidene fluoride and polyvinyl chloride; preferably, the basic anion exchange membrane is made of a material selected from quaternary ammonium salt type anion exchange membranes, polyether sulfone type anion exchange membranes or polyphenyl ether type anion exchange membranes.
In some preferred embodiments, in the alkaline membrane electrode type electrolytic cell provided by the invention, the porosity of a membrane in a used membrane electrode is 30-80%, the thickness is 0.05-0.7mm, in the electrolytic cell provided by the invention, too thick membrane thickness is not needed, and the obtained electrolytic cell has better performance in alkaline water electrolysis hydrogen production, and is beneficial to reducing the cell voltage.
In some preferred embodiments, the bipolar plate is a nickel plated steel or titanium plate; preferably, the bipolar plate has a nickel plating layer 1-200 μm thick; the adoption of the preferable nickel-plated bipolar plate is beneficial to improving the application stability of the electrolytic tank in hydrogen production by alkaline water electrolysis.
In some preferred embodiments, the anode diffusion layer and the cathode diffusion layer are each selected from the group consisting of nickel mesh, nickel felt, porous nickel plate, porous nickel foil, nickel plated steel mesh, nickel plated porous steel plate, nickel plated titanium mesh, and nickel plated porous titanium plate. The adoption of the anode diffusion layer and the cathode diffusion layer is favorable for improving the application stability of the electrolytic tank in hydrogen production by water electrolysis. The shape of the holes of the anode diffusion layer and the cathode diffusion layer is not particularly limited, and may be any shape such as a circle, a diamond, a square, a rectangle, or an irregular shape.
In the present invention, the catalyst used in the anode catalyst layer and the cathode catalyst layer of the membrane electrode may be of a catalyst type conventionally used in the art, for example, the anode catalyst layer may be an oxygen evolution catalyst having an oxygen evolution activity conventionally used, and the cathode catalyst layer may be a hydrogen evolution catalyst having a hydrogen evolution activity conventionally used, without particular limitation. Preferably, the catalysts in the anode catalyst layer and the cathode catalyst layer are respectively selected from metal containing nickel element and/or metal oxide containing nickel element, and the nickel-based catalyst has higher hydrogen evolution or oxygen evolution performance in alkaline environment and good stability; the catalyst may further contain, as required, other metal elements such as one or more selected from group IIB, group ivb, group VB, group vib, group viib, group viii, group iva and rare earth elements, for example, group IIB elements such as Zn, and/or group ivb elements such as Ti and/or Zr, and/or group VB elements such as V, and/or group VB elements such as one or more selected from Cr, mo and W, and/or group viib elements such as Mn, and/or group viii elements such as Fe and/or Co, and/or group iva elements such as Sn, and/or group rare earth elements such as Ce and/or La. In some embodiments, the other metallic element is one or more of Mo, W, mn, fe, co, zn, ce and La. In some embodiments, in the nickel-based catalyst used in the anode catalyst layer and the cathode catalyst layer, the mass ratio of the other metal element to the nickel element is respectively and independently 0 to 20:1. in some embodiments, by way of example, nickel-based catalysts such as, but not limited to, nickel spinel, nickel iron hydrotalcite, nickel cobalt catalysts, nickel molybdenum catalysts, iron cobalt nickel catalysts, raney nickel catalysts, and the like.
Preferably, the catalyst loading in the anode catalyst layer and the cathode catalyst layer is in the range of 0.5-20mg/cm 2, respectively, with the preferred catalyst loading being advantageous for providing a sufficient number of catalytically active sites, and having a relatively small catalyst layer thickness, being advantageous for reducing the anode and cathode spacing, reducing the electrolysis cell voltage.
In some embodiments, the electrolysis cell of the electrolysis cell comprises more than two of said electrolysis cells, for example two or more, a plurality of electrolysis cells being arranged in a repeated stack, the bipolar plates between adjacent two electrolysis cells being sharable.
In a specific embodiment, a sealing gasket is respectively arranged between two adjacent components in each electrolysis cell, namely the bipolar plate, the anode diffusion layer, the membrane electrode, the cathode diffusion layer and the bipolar plate.
In some more preferred embodiments, in the alkaline membrane electrode type electrolytic cell of the invention, the thicknesses of the bipolar plates are respectively 2-3mm, the thicknesses of the anode diffusion layer and the cathode diffusion layer are respectively 0.1-0.2mm, and the mesh numbers of the anode diffusion layer and the cathode diffusion layer are respectively 150-250 meshes; the inventor discovers that the adoption of the preferable scheme is beneficial to further remarkably reducing the cell voltage of the electrolytic tank in alkaline water electrolysis hydrogen production.
The invention also provides a preparation method of the alkaline membrane electrode type electrolytic cell, which specifically comprises the following steps: end plates are respectively arranged at two sides of the electrolysis unit, the end plates are used for fixing, and the alkaline membrane electrode type electrolysis tank is obtained through assembly; the assembly of the cell of the present invention may be performed by those skilled in the art using conventional assembly operations, which will not be described in detail.
In some embodiments, the step of preparing the membrane electrode in the electrolysis cell comprises: and respectively loading and forming an anode catalyst layer and a cathode catalyst layer on the surfaces of two sides of the diaphragm by a physical vapor deposition method, a transfer printing method or a direct coating method to obtain the membrane electrode.
Regarding the physical vapor deposition method, the specific operation thereof may refer to the corresponding conventional process operation in the art, for example, vacuum evaporation, sputtering coating, arc plasma coating, ion coating and molecular beam epitaxy or magnetron sputtering method may be specifically adopted to load the corresponding catalysts on the two side surfaces of the diaphragm, respectively. Preferably, the magnetron sputtering method is adopted, for example, the method can comprise the following steps: preparing a target material from the catalyst, filling argon under a vacuum condition, carrying out glow discharge on the argon under a high pressure to form argon ions, enabling the argon ions to bombard the target material under the action of an electric field force to sputter the target material, and depositing the target material on a porous diaphragm according to a load proportion. The catalyst in the catalyst layer formed by the magnetron sputtering method has high dispersion degree, is favorable for further reducing the overpotential of the electrolytic water, forms a firm catalyst layer which is not easy to fall off, and finally is favorable for improving the application stability of the electrolytic tank in hydrogen production by alkaline water electrolysis.
In some embodiments, the transfer method comprises the following operations: coating the catalyst slurry with the catalyst dispersed on a transfer film, and then drying; and then placing the membrane on two sides of the membrane, and obtaining the membrane electrode through transfer printing. The transfer film is, for example, but not limited to, one of PET, PTFE, or PI. Wherein, the drying is vacuum drying, and the drying temperature is 80-150 deg.C. The transfer conditions include, for example: the transfer temperature is 110-230 ℃ and the pressure is 0.5-10 MPa.
In some embodiments, the direct coating process includes the following operations: coating catalyst slurry with dispersed catalyst on the two side surfaces of the diaphragm, and drying and hot-pressing to obtain the membrane electrode; preferably, the drying is performed at 80-150 ℃, and the hot pressing is performed at 130-210 ℃ and 0.5-10 MPa.
In the above transfer method and direct coating method, the binder used in the catalyst slurry is preferably one or more selected from polysulfone, polyethersulfone, polyphenylene sulfide and perfluorosulfonic acid resin. In the catalyst slurry, the solvent used is preferably one or more selected from esters, ketones, amides, alcohols and aqueous solvents; in some preferred embodiments, the solvent is one or more of butyl ester, butyrolactone, valerolactone, acetone, butanone, cyclohexanone, dimethylformamide, dimethylacetamide, propanol, isopropanol, ethanol, and water. In some preferred embodiments, the catalyst in the catalyst slurry: and (2) a binder: the mass ratio of the solvent is 1:0.01-5:0.4-50, preferably 1:0.02-3:1-5. The preparation of the catalyst slurry may specifically comprise the following operations: the catalyst, the binder and the solvent are prepared into slurry by stirring or ultrasonic dispersion.
Among the transfer method and the direct coating method, the coating method is not particularly limited, and may be performed by a coating method which is conventional in the art, for example, by applying a uniform slurry to a transfer film or directly to a separator by a spray coating method, a blade coating method, a roll-to-roll method, or a slit coating method.
The schematic structure of the electrolysis cell in the following embodiment is shown in fig. 1 (in which the sealing gasket is not shown), the structure of the membrane electrode is shown in fig. 3, and the structures of the electrolysis cell and the membrane electrode are not specifically described in the following, and the description thereof will not be repeated one by one.
The following examples or comparative examples are given with reference to the starting materials used in part:
NiFe 2O4: beijing De Kodak gold technologies Co., ltd;
NiZnFe 2O4: beijing De Kodak gold technologies Co., ltd;
NiCo 2O4: beijing De Kodak gold technologies Co., ltd;
raney nickel catalyst: jiangsu Raney Metal technologies Co., ltd;
iron cobalt nickel alloy: beijing De Kodak gold technologies Co., ltd;
Polysulfone composite high molecular porous membrane: agfa zirfon 220,220;
Polyether sulfone composite high molecular porous diaphragm: beijing Michaelis biofilm technology Co.
Cell performance test: the electrolytic cell of each of the following examples or comparative examples was mounted on an electrolyzed water testing platform under test conditions including: the reaction medium is 30wt% KOH aqueous solution; the cell voltage of the cell was measured at a reaction temperature of 80℃and a reaction pressure of normal pressure at a current density of 0.4A/cm 2 and 0.8A/cm 2.
Example 1:
in the electrolytic unit of the electrolytic cell of the embodiment, the electrolytic cells are assembled in the order of bipolar plate-gasket-anode diffusion layer-gasket-membrane electrode-gasket-cathode diffusion layer-gasket-bipolar plate, and the electrolytic cell comprises a plurality of electrolytic cells; and placing end plates on two sides of the electrolysis unit and fixing the end plates to assemble the electrolysis tank.
Wherein the thickness of the bipolar plate is 2mm, and the bipolar plate adopts a steel plate with a nickel plating layer with the thickness of 80 mu m; the anode diffusion layer and the cathode diffusion layer are nickel screen diffusion layers, the thickness is 0.3mm respectively, and the mesh numbers are 100 meshes respectively.
The catalyst in the anode catalyst layer of the membrane electrode was NiFe 2O4, the thickness of the anode catalyst layer was 50 μm, and the catalyst loading of the anode catalyst layer was 2.5mg/cm 2. The catalyst in the cathode catalyst layer of the membrane electrode is Raney nickel catalyst, the thickness of the cathode catalyst layer is 25 mu m, and the catalyst loading of the cathode catalyst layer is 2.5mg/cm 2. The membrane of the membrane electrode adopts a polysulfone composite high-molecular porous membrane, the thickness of the membrane is 0.22mm, and the porosity is 60%.
In this embodiment, the preparation steps of the membrane electrode include:
1) Anode catalyst, binder and solvent are mixed according to the mass ratio of 1:0.12:4, uniformly stirring to obtain anode catalyst slurry; cathode catalyst, binder and solvent are mixed according to the mass ratio of 1:0.03:1, uniformly stirring to obtain cathode catalyst slurry; wherein the binder adopts polysulfone, and the solvent adopts ketone solution (mixed solution of 50wt% cyclohexanone, 40wt% butanone and 10wt% butyrolactone);
Coating anode catalyst slurry and cathode catalyst slurry on the two side surfaces of a diaphragm respectively, drying at 120 ℃ for 2 hours, putting into a hot press, and hot-pressing at 150 ℃ and 5MPa for 5 minutes to form anode catalyst layers and cathode catalyst layers on the two side surfaces of the diaphragm respectively, thus obtaining the membrane electrode.
The cells of this example were tested for cell voltage at current densities of 0.4A/cm 2 and 0.8A/cm 2, with the results shown in Table 1.
Example 2:
in the electrolytic unit of the electrolytic cell of the embodiment, the electrolytic cells are assembled in the order of bipolar plate-gasket-anode diffusion layer-gasket-membrane electrode-gasket-cathode diffusion layer-gasket-bipolar plate, and the electrolytic cell comprises a plurality of electrolytic cells; and placing end plates on two sides of the electrolysis unit and fixing the end plates to assemble the electrolysis tank.
Wherein the thickness of the bipolar plate is 3mm, and the bipolar plate adopts a titanium plate with a nickel plating layer with the thickness of 50 mu m; the anode diffusion layer and the cathode diffusion layer are nickel screen diffusion layers, the thickness is 0.15mm respectively, and the mesh numbers are 200 meshes respectively.
The catalyst in the anode catalyst layer of the membrane electrode was NiZnFe 2O4, the thickness of the anode catalyst layer was 30 μm, and the catalyst loading of the anode catalyst layer was 1.5mg/cm 2. The catalyst in the cathode catalyst layer of the membrane electrode is Fe-Co-Ni alloy, the thickness of the cathode catalyst layer is 10 mu m, and the catalyst loading of the cathode catalyst layer is 1mg/cm 2. The membrane of the membrane electrode adopts a polyether sulfone composite high molecular porous membrane, the thickness of the membrane is 0.25mm, and the porosity is 70%.
In this embodiment, the preparation steps of the membrane electrode include:
1) Anode catalyst, binder and solvent are mixed according to the mass ratio of 1:0.2:2, uniformly stirring to obtain anode catalyst slurry; cathode catalyst, binder and solvent are mixed according to the mass ratio of 1:0.2:1.5, uniformly stirring to obtain cathode catalyst slurry; wherein the adhesive adopts perfluorinated sulfonic acid resin, and the solvent adopts isopropanol alcohol water solution with the concentration of 25 weight percent;
coating anode catalyst slurry and cathode catalyst slurry on the two side surfaces of a diaphragm respectively, drying at 80 ℃ for 12 hours, putting into a hot press, and hot-pressing at 130 ℃ and 3MPa for 10 minutes to form anode catalyst layers and cathode catalyst layers on the two side surfaces of the diaphragm respectively, thus obtaining the membrane electrode.
The cells of this example were tested for cell voltage at current densities of 0.4A/cm 2 and 0.8A/cm 2, with the results shown in Table 1.
Example 3:
in the electrolytic unit of the electrolytic cell of the embodiment, the electrolytic cells are assembled in the order of bipolar plate-gasket-anode diffusion layer-gasket-membrane electrode-gasket-cathode diffusion layer-gasket-bipolar plate, and the electrolytic cell comprises a plurality of electrolytic cells; and placing end plates on two sides of the electrolysis unit and fixing the end plates to assemble the electrolysis tank.
Wherein the thickness of the bipolar plate is 2mm, and the bipolar plate adopts a steel plate with a nickel plating layer with the thickness of 120 mu m; the anode diffusion layer and the cathode diffusion layer are nickel screen diffusion layers, the thicknesses of the anode diffusion layer and the cathode diffusion layer are respectively 0.09mm, and the mesh numbers of the anode diffusion layer and the cathode diffusion layer are respectively 300 meshes.
The catalyst in the anode catalyst layer of the membrane electrode is NiFe 2O4, the thickness of the anode catalyst layer is 20 mu m, and the catalyst loading of the anode catalyst layer is 1mg/cm 2. The catalyst in the cathode catalyst layer of the membrane electrode is Raney nickel catalyst, the thickness of the cathode catalyst layer is 10 mu m, and the catalyst loading of the cathode catalyst layer is 1mg/cm 2. The membrane of the membrane electrode adopts a polysulfone composite high-molecular porous membrane, the thickness of the membrane is 0.22mm, and the porosity is 60%.
In this embodiment, the preparation steps of the membrane electrode include:
1) Anode catalyst, binder and solvent are mixed according to the mass ratio of 1:0.075:1.5, uniformly stirring to obtain anode catalyst slurry; cathode catalyst, binder and solvent are mixed according to the mass ratio of 1:0.09:1.8, uniformly stirring to obtain cathode catalyst slurry; wherein the adhesive adopts polyethersulfone, and the solvent adopts ketone solution (mixed solution of 50wt% cyclohexanone, 20wt% butanone and 30wt% butyrolactone);
Anode catalyst sizing agent and cathode catalyst sizing agent are respectively coated on a transfer printing film (PTFE), then are dried at 100 ℃, then the transfer printing film loaded with the catalyst is placed on two sides of a diaphragm, and hot-press transfer printing is carried out on a hot press device to obtain a membrane electrode, wherein the transfer printing temperature is 180 ℃ and the pressure is 10MPa.
The cells of this example were tested for cell voltage at current densities of 0.4A/cm 2 and 0.8A/cm 2, with the results shown in Table 1.
Example 4:
in the electrolytic unit of the electrolytic cell of the embodiment, the electrolytic cells are assembled in the order of bipolar plate-gasket-anode diffusion layer-gasket-membrane electrode-gasket-cathode diffusion layer-gasket-bipolar plate, and the electrolytic cell comprises a plurality of electrolytic cells; and placing end plates on two sides of the electrolysis unit and fixing the end plates to assemble the electrolysis tank.
Wherein the thickness of the bipolar plate is 1mm, and the bipolar plate adopts a steel plate with a nickel plating layer with the thickness of 20 mu m; the anode diffusion layer and the cathode diffusion layer are nickel screen diffusion layers, the thicknesses of the anode diffusion layer and the cathode diffusion layer are respectively 0.05mm, and the mesh numbers of the anode diffusion layer and the cathode diffusion layer are respectively 400 meshes.
The catalyst in the anode catalyst layer of the membrane electrode was NiCo 2O4, the thickness of the anode catalyst layer was 25 μm, and the catalyst loading of the anode catalyst layer was 1.3mg/cm 2. The catalyst in the cathode catalyst layer of the membrane electrode is Raney nickel catalyst, the thickness of the cathode catalyst layer is 15 mu m, and the catalyst loading of the cathode catalyst layer is 1.5mg/cm 2. The membrane of the membrane electrode adopts a polysulfone composite high-molecular porous membrane, the thickness of the membrane is 0.22mm, and the porosity is 60%.
In this embodiment, the preparation steps of the membrane electrode include:
1) Anode catalyst, binder and solvent are mixed according to the mass ratio of 1:0.27:1.8, uniformly stirring to obtain anode catalyst slurry; cathode catalyst, binder and solvent are mixed according to the mass ratio of 1:0.3:2, uniformly stirring to obtain cathode catalyst slurry; wherein the adhesive adopts perfluorinated sulfonic acid resin, and the solvent adopts n-propanol aqueous solution with the concentration of 40 wt%;
Coating anode catalyst slurry and cathode catalyst slurry on the two side surfaces of a diaphragm respectively, drying at 150 ℃ for 0.5h, putting into a hot press, and hot-pressing at 160 ℃ and 2MPa for 3min to form anode catalyst layers and cathode catalyst layers on the two side surfaces of the diaphragm respectively, thus obtaining the membrane electrode.
The cells of this example were tested for cell voltage at current densities of 0.4A/cm 2 and 0.8A/cm 2, with the results shown in Table 1.
Example 5
This example was conducted with reference to example 1, except that the thickness of the anode diffusion layer and the cathode diffusion layer was 3mm, and the mesh numbers were 80 mesh, respectively.
The cells of this example were tested for cell voltage at current densities of 0.4A/cm 2 and 0.8A/cm 2, with the results shown in Table 1.
Example 6
Reference example 2 was made, except that: the thickness of the anode catalyst layer and the cathode catalyst layer is less than 10 μm, the thickness of the anode catalyst layer is 5 μm, and the thickness of the cathode catalyst layer is 2 μm.
The cells of this example were tested for cell voltage at current densities of 0.4A/cm 2 and 0.8A/cm 2, the results of which are shown in Table 1
Example 7
Reference example 2 was made, except that: the thickness of the anode catalyst layer and the cathode catalyst layer is less than 10 μm, the thickness of the anode catalyst layer is 9 μm, and the thickness of the cathode catalyst layer is 5 μm.
The cells of this example were tested for cell voltage at current densities of 0.4A/cm 2 and 0.8A/cm 2, with the results shown in Table 1.
Comparative example 1:
The difference between the present comparative example and the electrolytic cell of example 1 is the structure of the electrolytic cell comprising a bipolar plate, an anode electrode, a separator, a cathode electrode and a bipolar plate stacked in this order. Wherein the thickness of the bipolar plate is 2mm, and the bipolar plate is made of a steel plate with a nickel plating layer with the thickness of 80 mu m. The anode electrode and the cathode electrode are electrodes commonly used in commercial alkaline electrolytic baths, the thickness of each electrode is 0.5mm, the anode electrode is nickel screen, the cathode electrode is nickel screen sprayed with Ni-Al alloy, and the cathode electrode is soaked in 10wt% NaOH aqueous solution for 24 hours before being used and is washed by deionized water until the solution is neutral. The separator was a polyphenylene sulfide nonwoven fabric (thickness 1 mm) commonly used in commercial alkaline cells, and bipolar plates, nonwoven fabric, anode electrode and cathode electrode were assembled into an electrolytic cell, which was tested for cell voltages at current densities of 0.4A/cm 2 and 0.8A/cm 2.
Comparative example 2:
The difference between the present comparative example and the electrolytic cell of example 1 is the structure of the electrolytic cell comprising a bipolar plate, an anode electrode, a separator, a cathode electrode and a bipolar plate stacked in this order. The thickness of the bipolar plate was 2mm, and the bipolar plate was made of a steel plate having a nickel plating layer 80 μm thick. The anode electrode and the cathode electrode are electrodes commonly used in commercial alkaline electrolytic baths, the thickness of each electrode is 0.5mm, the anode electrode is nickel screen, the cathode electrode is nickel screen sprayed with Ni-Al alloy, and the cathode electrode is soaked in 10wt% NaOH aqueous solution for 24 hours before being used and is washed by deionized water until the solution is neutral. The membrane was a polysulfone composite polymeric porous membrane (thickness 0.22 mm), and bipolar plate, composite polymeric porous membrane, anode electrode and cathode electrode were assembled into an electrolytic cell, which was tested for cell voltages at current densities of 0.4A/cm 2 and 0.8A/cm 2.
Comparative example 3
This comparative example was performed with reference to example 1, except that: the thickness of the bipolar plate is 10mm, the thicknesses of the anode diffusion layer and the cathode diffusion layer are 5mm respectively, and the mesh numbers are 40 meshes respectively.
The cells of this example were tested for cell voltage at current densities of 0.4A/cm 2 and 0.8A/cm 2, with the results shown in Table 1.
Comparative example 4
This comparative example was performed with reference to example 1, except that: the thickness of the bipolar plate is 0.8mm, the thicknesses of the anode diffusion layer and the cathode diffusion layer are respectively 0.015mm, and the mesh numbers are respectively 600 meshes.
The cells of this example were tested for cell voltage at current densities of 0.4A/cm 2 and 0.8A/cm 2, with the results shown in Table 1.
Comparative example 5
This comparative example was performed with reference to example 1, except that: the thickness of the bipolar plate is 0.8mm, the thicknesses of the anode diffusion layer and the cathode diffusion layer are respectively 0.015mm, and the mesh numbers are respectively 40 meshes.
The cells of this example were tested for cell voltage at current densities of 0.4A/cm 2 and 0.8A/cm 2, with the results shown in Table 1.
TABLE 1
TABLE 2
From the experimental results in tables 1 and 2, it can be seen that the electrolytic cell of the embodiment of the invention can obtain lower cell electrolysis compared with the existing electrolytic cell for producing hydrogen by alkaline electrolyzed water in comparative examples 1 and 2, which is beneficial to reducing the energy consumption of alkaline electrolyzed water. As can be seen from comparison of experimental results of the electrolytic cell of the embodiment of the invention and comparative examples 3-5, the electrolytic cell of the invention simultaneously satisfies that the thickness of the bipolar plate is 1-3mm, the thicknesses of the anode diffusion layer and the cathode diffusion layer are respectively 0.02-4mm, and the mesh numbers of the anode diffusion layer and the cathode diffusion layer are respectively 50-500 meshes. Further, it can be seen by comparing example 2 with examples 6 and 7 that it is preferable to control the thicknesses of the anode catalyst layer and the cathode catalyst layer to be not less than 2 μm and less than 10 μm, which is advantageous for further reducing the cell voltage.
It will be readily appreciated that the above embodiments are merely examples given for clarity of illustration and are not meant to limit the invention thereto. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The alkaline membrane electrode type electrolytic tank for producing hydrogen by alkaline water electrolysis is characterized by comprising an electrolytic unit and end plates arranged on two sides of the electrolytic unit, wherein the electrolytic unit comprises an electrolytic cell, and the electrolytic cell comprises a bipolar plate, an anode diffusion layer, a membrane electrode, a cathode diffusion layer and a bipolar plate which are sequentially stacked;
the membrane electrode comprises a diaphragm, and an anode catalyst layer and a cathode catalyst layer which are respectively supported on the two side surfaces of the diaphragm; the membrane is a porous membrane or an alkaline anion exchange membrane;
The thickness of the bipolar plate is 1-3mm, the thicknesses of the anode diffusion layer and the cathode diffusion layer are respectively 0.02-4mm, and the mesh numbers of the anode diffusion layer and the cathode diffusion layer are respectively 50-500 meshes.
2. Alkaline membrane electrode type electrolyzer according to claim 1, characterized in that the thickness of the anode catalyst layer and the cathode catalyst layer is 2-50 μm, preferably not less than 2 μm and less than 10 μm, respectively;
further preferably, the ratio of the thicknesses of the anode catalyst layer and the cathode catalyst layer is 1 to 3.
3. The alkaline membrane electrode type electrolytic cell according to claim 1, wherein the porous membrane is made of one or more selected from polyethersulfone, polysulfone, polyphenylene sulfide, polytetrafluoroethylene, polyvinylidene fluoride and polyvinyl chloride;
And/or the material of the alkaline anion exchange membrane is selected from a quaternary ammonium salt type anion exchange membrane, a polyether sulfone type anion exchange membrane or a polyphenyl ether type anion exchange membrane;
and/or the porosity of the diaphragm is 30-80%, and the thickness is 0.05-0.7mm.
4. An alkaline membrane electrode assembly cell according to any one of claims 1 to 3, wherein the bipolar plate is a nickel plated steel or titanium plate; preferably, the bipolar plate has a nickel plating layer 1-200 μm thick;
And/or the anode diffusion layer and the cathode diffusion layer are respectively selected from nickel mesh, nickel felt, porous nickel plate, porous nickel foil, nickel plated steel mesh, nickel plated porous steel plate, nickel plated titanium mesh or nickel plated porous titanium plate.
5. A basic membrane electrode assembly according to any one of claims 1 to 3, wherein the catalysts in the anode catalyst layer and the cathode catalyst layer are each selected from one or more of a metal comprising elemental nickel, a metal oxide comprising elemental nickel;
preferably, the catalyst loadings in the anode catalyst layer and the cathode catalyst layer are 0.5-20mg/cm 2, respectively.
6. A basic membrane electrode assembly according to any one of claims 1 to 3, wherein the electrolysis cell comprises two or more of the electrolysis cells;
And/or sealing gaskets are respectively arranged between two adjacent assemblies in the electrolysis cell among the bipolar plate, the anode diffusion layer, the membrane electrode, the cathode diffusion layer and the bipolar plate which are sequentially stacked.
7. A basic membrane electrode assembly according to any one of claims 1 to 3, wherein the bipolar plates have a thickness of 2 to 3mm, the anode diffusion layer and the cathode diffusion layer have a thickness of 0.1 to 0.2mm, respectively, and the anode diffusion layer and the cathode diffusion layer have a mesh size of 150 to 250 mesh, respectively.
8. The method for producing an alkaline membrane electrode assembly cell according to any one of claims 1 to 7, wherein the alkaline membrane electrode assembly cell is obtained by providing the end plates on both sides of the electrolysis cell, respectively.
9. The method according to claim 8, wherein the step of preparing the membrane electrode in the electrolysis unit comprises: and respectively loading and forming an anode catalyst layer and a cathode catalyst layer on the surfaces of two sides of the diaphragm by a physical vapor deposition method, a transfer printing method or a direct coating method to obtain the membrane electrode.
10. The method of manufacturing according to claim 9, wherein the transfer method comprises the operations of: coating the catalyst slurry with the catalyst dispersed on a transfer film, and then drying; then placing the membrane on two sides of the membrane, and obtaining the membrane electrode through transfer printing;
And/or, the direct coating method comprises the following operations: coating catalyst slurry with dispersed catalyst on the two side surfaces of the diaphragm, drying and hot-pressing to obtain the membrane electrode; preferably, the drying is performed at 80-150 ℃, and the hot pressing is performed at 130-210 ℃ and 0.5-10 MPa;
Preferably, in the catalyst slurry, the binder used is selected from one or more of polysulfone, polyethersulfone, polyphenylene sulfide and perfluorosulfonic acid resin;
preferably, in the catalyst slurry, the solvent used is selected from one or more of esters, ketones, amides, alcohols and aqueous solvents;
Further preferably, the catalyst in the catalyst slurry: and (2) a binder: the mass ratio of the solvent is 1:0.01-5:0.4-50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310280017.6A CN117926293A (en) | 2023-03-21 | 2023-03-21 | Alkaline membrane electrode type electrolytic tank for producing hydrogen by alkaline water electrolysis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310280017.6A CN117926293A (en) | 2023-03-21 | 2023-03-21 | Alkaline membrane electrode type electrolytic tank for producing hydrogen by alkaline water electrolysis and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117926293A true CN117926293A (en) | 2024-04-26 |
Family
ID=90767288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310280017.6A Pending CN117926293A (en) | 2023-03-21 | 2023-03-21 | Alkaline membrane electrode type electrolytic tank for producing hydrogen by alkaline water electrolysis and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117926293A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190127863A1 (en) * | 2014-10-21 | 2019-05-02 | Dioxide Materials, Inc. | Water Electrolyzers Employing Anion Exchange Membranes |
| CN110023542A (en) * | 2017-01-26 | 2019-07-16 | 旭化成株式会社 | Bipolar electrolyzer, buck electrolysis bipolar electrolyzer and hydrogen manufacturing method |
| CN110791773A (en) * | 2018-08-02 | 2020-02-14 | 国家能源投资集团有限责任公司 | Method and device for producing hydrogen by electrolyzing water |
| CN111433391A (en) * | 2017-12-05 | 2020-07-17 | 株式会社德山 | Membrane-electrode-gasket composite for alkaline water electrolysis |
| CN113549942A (en) * | 2021-07-15 | 2021-10-26 | 杭州兴态环保科技有限公司 | Method and device for improving hydrogen production efficiency by electrolyzing water |
| CN115074775A (en) * | 2022-07-22 | 2022-09-20 | 北京化工大学 | Integrated composite membrane, preparation method thereof and application thereof in alkaline hydrolysis hydrogen production |
| WO2022244644A1 (en) * | 2021-05-19 | 2022-11-24 | パナソニックＩｐマネジメント株式会社 | Anode gas diffusion layer for water electrolysis cells, water electrolysis cell, and water electrolysis device |
-
2023
- 2023-03-21 CN CN202310280017.6A patent/CN117926293A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190127863A1 (en) * | 2014-10-21 | 2019-05-02 | Dioxide Materials, Inc. | Water Electrolyzers Employing Anion Exchange Membranes |
| CN110023542A (en) * | 2017-01-26 | 2019-07-16 | 旭化成株式会社 | Bipolar electrolyzer, buck electrolysis bipolar electrolyzer and hydrogen manufacturing method |
| CN111433391A (en) * | 2017-12-05 | 2020-07-17 | 株式会社德山 | Membrane-electrode-gasket composite for alkaline water electrolysis |
| CN110791773A (en) * | 2018-08-02 | 2020-02-14 | 国家能源投资集团有限责任公司 | Method and device for producing hydrogen by electrolyzing water |
| WO2022244644A1 (en) * | 2021-05-19 | 2022-11-24 | パナソニックＩｐマネジメント株式会社 | Anode gas diffusion layer for water electrolysis cells, water electrolysis cell, and water electrolysis device |
| CN113549942A (en) * | 2021-07-15 | 2021-10-26 | 杭州兴态环保科技有限公司 | Method and device for improving hydrogen production efficiency by electrolyzing water |
| CN115074775A (en) * | 2022-07-22 | 2022-09-20 | 北京化工大学 | Integrated composite membrane, preparation method thereof and application thereof in alkaline hydrolysis hydrogen production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10889903B2 (en) | Oxygen-generating anode | |
| US6022634A (en) | Membrane electrochemical cell provided with gas diffusion electrodes in contact with porour, flat, metal current conductors having highly distributed contact area | |
| JP6282321B2 (en) | catalyst | |
| CN101008087B (en) | Preparation method of film electrode for solid polymer electrolyte water electrolysis | |
| CN105742652B (en) | It is a kind of for membrane electrode with double-metal layer anode of electrolysis water and preparation method thereof | |
| CN107949662B (en) | Diaphragm-electrode assembly for alkaline water electrolysis cells | |
| US9988727B2 (en) | Composite electrodes for the electrolysis of water | |
| US20190112720A1 (en) | Pulsed current catalyzed gas diffusion electrodes for high rate, efficient co2 conversion reactors | |
| KR20090073098A (en) | Structures for gas diffusion electrodes | |
| CN112481656A (en) | Bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen, preparation method and application thereof | |
| CN115595617A (en) | Nickel-nickel-containing nitride composite electrode and preparation method and application thereof | |
| CN110400953A (en) | A kind of solid electrolyte water electrolysis membrane electrode and preparation method thereof | |
| CN115044939A (en) | Preparation method and application of self-supporting nickel-based bimetal hydroxide oxygen evolution electrode | |
| Hornés et al. | 3D printing of fuel cells and electrolyzers | |
| CN113308707A (en) | Gas diffusion electrode for electrochemical reduction of carbon dioxide | |
| CN114737211B (en) | Proton exchange composite reinforced membrane, preparation method, water electrolysis membrane electrode and application | |
| EP1724863A1 (en) | Metal foam materials in alkaline fuel cells and alkaline electrolysers | |
| EP1724861A1 (en) | Novel materials for alkaline electrolysers and alkaline fuel cells | |
| CN117926293A (en) | Alkaline membrane electrode type electrolytic tank for producing hydrogen by alkaline water electrolysis and preparation method thereof | |
| Jiang et al. | Deep reconstruction of Ni–Al-based pre-catalysts for a highly efficient and durable anion-exchange membrane (AEM) electrolyzer | |
| CN116262977A (en) | Porous membrane electrode for hydrogen production by alkaline water electrolysis and preparation method thereof | |
| KR102580737B1 (en) | METHOD OF MANUFACTURING NiCoFe LAYERED DOUBLE HYDROXIDE, ELECTRODE, MEMBRANE ELECTRODE ASSEMBLY AND WATER ELECTROYSISING SYSTEM COMPRISING THE SAME | |
| CN114381757B (en) | Carbon-coated nickel-molybdenum-vanadium hydrogen evolution electrode and preparation method and application thereof | |
| CN220926975U (en) | Composite polar plate for electrolytic cell and electrolytic cell | |
| CN116190679A (en) | Membrane electrode assembly and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |