CN117107297A - Composite diaphragm for enhancing gas barrier property and used for alkaline water electrolysis hydrogen production and preparation method thereof - Google Patents
Composite diaphragm for enhancing gas barrier property and used for alkaline water electrolysis hydrogen production and preparation method thereof Download PDFInfo
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- CN117107297A CN117107297A CN202311384388.5A CN202311384388A CN117107297A CN 117107297 A CN117107297 A CN 117107297A CN 202311384388 A CN202311384388 A CN 202311384388A CN 117107297 A CN117107297 A CN 117107297A
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- gas barrier
- composite membrane
- organic phase
- barrier property
- hydrogen production
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- 239000002131 composite material Substances 0.000 title claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- 239000007789 gas Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 230000004888 barrier function Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000002708 enhancing effect Effects 0.000 title claims description 4
- 238000005266 casting Methods 0.000 claims abstract description 66
- 239000012528 membrane Substances 0.000 claims abstract description 64
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 238000000576 coating method Methods 0.000 claims abstract description 52
- 239000012074 organic phase Substances 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000008346 aqueous phase Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000010954 inorganic particle Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 230000001112 coagulating effect Effects 0.000 claims abstract description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 27
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 22
- 229920002492 poly(sulfone) Polymers 0.000 claims description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 17
- 239000004695 Polyether sulfone Substances 0.000 claims description 14
- 229920006393 polyether sulfone Polymers 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 230000035699 permeability Effects 0.000 claims description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006277 sulfonation reaction Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 4
- -1 isocyanuric acid glycidyl ester Chemical class 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 70
- 230000000052 comparative effect Effects 0.000 description 22
- 238000007790 scraping Methods 0.000 description 21
- 239000011521 glass Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000004132 cross linking Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- 229920002873 Polyethylenimine Polymers 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000010345 tape casting Methods 0.000 description 6
- 239000010425 asbestos Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910052895 riebeckite Inorganic materials 0.000 description 5
- 239000000306 component Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- 108010081750 Reticulin Proteins 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 208000019693 Lung disease Diseases 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 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
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing 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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- 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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
-
- 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
Abstract
The invention relates to the technical field of composite diaphragms, in particular to a composite diaphragm for alkaline water electrolysis hydrogen production with enhanced gas barrier property and a preparation method thereof. The preparation method comprises the following steps: dispersing the binder, the pore-forming agent and the nano/micron inorganic particles into an organic solvent to obtain a casting solution; uniformly coating the casting solution on two sides of the supporting layer, and performing coagulating bath treatment to obtain a supporting net composite film containing the coating; dispersing a hydrophilic high molecular compound, a surfactant and a pore-forming agent into water to obtain an aqueous phase solution; dispersing an organic phase monomer into an organic phase solvent to obtain an organic phase solution; immersing the support net composite membrane containing the coating into an aqueous phase solution, immersing into an organic phase solution, and taking out and drying to obtain the composite membrane. The invention enhances the gas barrier property of the composite diaphragm through interfacial polymerization reaction, improves the safety of the alkaline water electrolysis hydrogen production device, and has the advantages of simple and easy preparation process and environmental protection.
Description
Technical Field
The invention relates to the technical field of composite diaphragms, in particular to a composite diaphragm for alkaline water electrolysis hydrogen production with enhanced gas barrier property and a preparation method thereof.
Background
Hydrogen has a high energy density (120-140 MJ) . kg -1 ) Flexibility and environmental friendliness, is an ideal energy carrier. Electrolytic water hydrogen production is widely studied by many researchers as the most potential green hydrogen energy supply mode. The current common modes of water electrolysis for hydrogen production are alkaline water electrolysis and proton exchange membrane water electrolysis (PEM), wherein the Proton Exchange Membrane (PEM) electrolysis has a relatively high current density (1-2A . cm -2 ) And shorter start-up times (5-10 min), but the bipolar plates require noble metals (platinum or iridium) and titanium powder as catalysts, and the cost of key components such as proton exchange membranes and platinum electrode catalysts is high, resulting in high manufacturing cost of PEM electrolytic cells; the alkaline water electrolysis has good compatibility with non-noble metal catalysts, high maturity and lower cost, and is a main industrial hydrogen production mode by water electrolysis.
The alkaline diaphragm electrolysis is mainly completed through an electrolytic tank with a cathode chamber and an anode chamber, and the diaphragm is used as a core component for ion conduction and isolation of oxyhydrogen gas permeation, so that the operation safety of the electrolytic device is ensured. The current diaphragms used for producing hydrogen by alkaline water electrolysis comprise inorganic diaphragms, organic diaphragms and inorganic-organic composite diaphragms. The inorganic diaphragm is mainly asbestos, but because of the swelling property and chemical instability of the asbestos diaphragm, the pure asbestos diaphragm can be seriously swelled in a specific running environment, particularly under high current load, so that the mechanical strength of the diaphragm is reduced, the service life of the diaphragm is shortened, the current efficiency is obviously reduced, and the asbestos dust also causes the damage of lung diseases. The organic diaphragm is mainly polyphenylene sulfide woven cloth, has large aperture, is difficult to effectively isolate gas, and cannot adapt to the pressurized operation environment to limit the performance and structural optimization of the electrolytic tank. Therefore, the inorganic-organic composite membrane becomes a research hot spot for producing hydrogen by electrolyzing water with an alkaline membrane.
For example, patent CN114432906a discloses a high-temperature-resistant alkaline water electrolysis cell composite diaphragm and a preparation method thereof, wherein polysulfone and ZrO are selected 2 Preparing slurry by using PPS (polyphenylene sulfide) reticular fibers as a support, soaking the PPS reticular fibers in the slurry, determining the thickness, then carrying out knife coating, pre-evaporating, carrying out phase inversion by using deionized water, and washing the slurry with the deionized water for multiple times to obtain the polyphenylene sulfide reticular support polysulfone-ZrO 2 And (3) a composite membrane.
CN114432905A discloses a non-asbestos alkaline electrolytic water composite diaphragm and a preparation method thereof, which uses high alkali resistance polysulfone resin and a high polymer reinforcing agent as polymers and ZrO 2 The polymer is subjected to hydrophilic modification, so that the surface resistance is effectively reduced, and the current efficiency is improved.
The composite diaphragm provided by the patent improves the current efficiency to a certain extent and has good corrosion resistance, but the composite diaphragm has poor gas barrier property and is only suitable for normal pressure hydrogen production equipment, and the safety problem of hydrogen and oxygen permeation exists after pressurization.
Disclosure of Invention
The purpose of the invention is that: the composite diaphragm for the alkaline water electrolysis hydrogen production, which enhances the gas barrier property, has good gas barrier property and hydrophilicity, has stable chemical property and improves the safety of the alkaline water electrolysis hydrogen production device; the invention also provides a preparation method of the preparation method, and the whole preparation process is simple and feasible and is environment-friendly.
The invention relates to a preparation method of a composite membrane for enhancing gas barrier property and used for alkaline water electrolysis hydrogen production, which comprises the following steps:
(1) Preparing a casting film liquid: dispersing the binder, the pore-forming agent and the nano/micron inorganic particles into an organic solvent to obtain a casting solution;
(2) Coating a casting film liquid: uniformly coating the casting solution on two sides of the supporting layer, and performing coagulating bath treatment to obtain a supporting net composite film containing the coating;
(3) Preparing a composite diaphragm: dispersing a hydrophilic high molecular compound, a surfactant and a pore-forming agent into water to obtain an aqueous phase solution; dispersing an organic phase monomer into an organic phase solvent to obtain an organic phase solution; immersing the support net composite membrane containing the coating into an aqueous phase solution for 5-10min, immersing into an organic phase solution for 5-10min, taking out and drying to obtain the composite membrane for alkaline electrolytic water hydrogen production with enhanced gas barrier property.
In the step (1), the binder is one or more of polysulfone, polyethersulfone, sulfonated polysulfone and sulfonated polyethersulfone; preferably, the sulfonation degree of the sulfonated polysulfone and the sulfonated polyether sulfone is 5-10%.
In the step (1), the pore-forming agent is one or two of polyvinylpyrrolidone and polyethylene glycol.
In the step (1), the particle size of the nano/micron inorganic particles is 30nm-100 μm; one or more oxides selected from IV-B group and III-B group elements; preferably one or more of zirconia, titania, ceria, zinc oxide, magnesium chloride, ferric chloride; further preferably one or both of zirconia and magnesium chloride. The addition of nano/micron inorganic particles is beneficial to improving the hydrophilicity and increasing micropores on the surface of the diaphragm.
In the step (1), the organic solvent is one or more of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; n-methylpyrrolidone is preferred.
In the step (1), the casting solution comprises the following raw materials in percentage by mass: 5-10% of binder, 5-10% of pore-forming agent, 20-30% of nano/micron inorganic particles and 50-60% of organic solvent.
In the step (1), during the preparation of the casting solution, the binder, the pore-forming agent and the nano/micron inorganic particles are dispersed into an organic solvent by adopting a normal pressure heating and stirring mode, and the heating temperature is 60-80 ℃.
In the step (2), the supporting layer is polyphenylene sulfide (PPS) fiber mesh cloth, and the mesh aperture of the mesh cloth is between 50 and 60 meshes.
In the step (2), the thickness of the single side coating of the casting solution is 100-300 mu m.
In one embodiment, when the casting solution is coated, a layer of casting solution is firstly coated on a glass plate, PPS fiber mesh cloth is attached to the surface of the casting solution, then the other side of the PPS fiber mesh cloth is coated on the PPS fiber mesh cloth, and the support net composite film containing the coating is obtained through coagulating bath treatment.
In the step (2), the coagulating bath is a water bath, and the treatment process is as follows: and standing the support layer coated with the casting solution in air for 20-40s, immersing in deionized water at 25-30 ℃, completely replacing the organic solvent to form a surface coating, and cleaning and drying to obtain the support net composite film containing the coating.
In the step (3), the aqueous phase solution comprises the following raw materials in percentage by mass: 3-5% of hydrophilic high molecular compound, 0.5-1% of surfactant, 0.5-2% of pore-forming agent and 92-96% of water.
Wherein the hydrophilic polymer compound is a polyacetylimine. The composite membrane is used for producing hydrogen by alkaline water electrolysis, and the electrolysis running environment is generally 30wt.% alkali liquor, so that the adopted hydrophilic high molecular compound needs to meet the requirements of hydrophilicity and alkali resistance, and polyethyleneimine is adopted as the hydrophilic high molecular compound. In addition, the polyethyleneimine has more amino and imino groups on the surface, and can provide favorable groups for the membrane to be used for hydrogen production by alkaline water electrolysis.
The surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and cetyltrimethylammonium bromide; sodium dodecyl sulfate is preferred. The addition of the surfactant allows for better contact of the aqueous solution with the membrane surface.
The pore-forming agent is one or two of polyvinylpyrrolidone and polyethylene glycol; polyvinylpyrrolidone is preferred. The purpose of adding the pore-forming agent is to make the crosslinking layer generate micropores to promote the electrolyte to pass through, so that the increase of electrolytic resistance is avoided.
In the step (3), the organic phase solution comprises the following raw materials in percentage by mass: 12-18% of organic phase monomer and 82-88% of organic phase solvent.
Wherein the organic phase monomer is glutaraldehyde or isocyanuric acid glycidyl ester.
The organic phase solvent is one or more of ethanol, n-propanol and isopropanol.
In the step (3), the infiltration temperature of the support net composite film containing the coating in the aqueous phase solution and the organic phase solution is 25-30 ℃.
In the step (3), the drying temperature is 60-80 ℃ and the drying time is 5-10min.
In the invention, the polyimide in the aqueous phase solution is a hydrophilic high molecular compound, which can be filled in the inner pore canal of the membrane to endow the membrane with excellent hydrophilicity; and meanwhile, the surface of the membrane reacts with an organic phase monomer (glutaraldehyde or isocyanuric acid glycidyl ester), a cross-linked membrane layer is formed on the surface of the membrane, and large-aperture micropores of the membrane surface are protected, so that the aperture of the membrane surface is reduced while the transmission of electrolyte is ensured, and the gas permeation is resisted in the electrolysis process, so that the gas permeation rate is reduced, and the effect of blocking the gas permeation is achieved. However, the adhesion of partial micro bubbles can cause the increase of the membrane surface resistance and reduce the electrolysis performance, so the invention records the pore-forming agent in the crosslinked membrane layer A, so that micropores are formed in the crosslinked layer to promote the passage of electrolyte, and the increase of the electrolysis resistance is avoided.
The invention also provides a composite membrane for alkaline water electrolysis hydrogen production, which is prepared by the preparation method and has enhanced gas barrier property, and the gas permeability is lower than 8.0 multiplied by 10 -7 m 3 /（m 2. Pa . s）。
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the cross-linking layer is formed on the surface of the composite membrane by reacting the polyacetylimine with glutaraldehyde or isocyanuric acid glycidyl ester, so that the large-aperture micropores of the membrane surface are protected, the membrane surface aperture is reduced while the electrolyte is ensured to be transmitted, the gas permeation is resisted in the electrolysis process, the gas permeability of the composite membrane is greatly reduced, the oxygen content in the hydrogen generated by the cathode and the anode is effectively reduced, and the safety of the alkaline electrolytic water hydrogen production device is improved;
(2) According to the invention, the crosslinking layer is formed on the surface of the composite diaphragm, so that the bubble point pressure of the composite diaphragm is improved, the bubble point aperture and the average aperture are reduced, the gas permeability is reduced, and simultaneously, the crosslinking layer can generate micropores by adding the pore-forming agent in the crosslinking layer, so that the electrolyte is promoted to pass through, the adhesion condition of micro bubbles at the diaphragm during electrolysis is reduced, and the increase of electrolytic resistance is avoided;
(3) The preparation process disclosed by the invention has the advantages of high flexibility, simplicity and easiness, and is suitable for large-scale production.
Drawings
FIG. 1 is a scanning electron microscope image of a surface coating of a support net composite film containing a coating according to example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a composite membrane according to example 1 of the present invention.
Detailed Description
The present invention will be further illustrated by the following examples, wherein the raw materials used in the examples are commercially available conventional raw materials unless otherwise specified; the process used in the examples, unless otherwise specified, is conventional in the art.
Example 1
The composite diaphragm for producing hydrogen by alkaline water electrolysis is prepared according to the following method:
(1) Preparing a casting film liquid: adding 8g of polysulfone and 2g of sulfonated polysulfone (with the sulfonation degree of 10%) into 50g of N-methylpyrrolidone at normal pressure and 60 ℃, stirring until the polysulfone and the 2g of sulfonated polysulfone are completely dissolved, adding 5g of polyvinylpyrrolidone, continuously stirring until the polyvinylpyrrolidone is completely dissolved, adding 20g of zirconia (with the particle size of 30-50 nm) and 3g of magnesium chloride (with the particle size of 80-100 mu m), and stirring and dispersing for 3h to obtain casting film liquid;
(2) Coating a casting film liquid: fixing a clean glass plate on a flat plate of a film scraping machine, adjusting the coating thickness of the casting solution (namely, the distance between a scraper and the glass plate) to be 100 mu m, setting the film scraping speed to be 50mm/min, taking the casting solution, placing the casting solution on the glass plate to start to carry out film scraping, attaching a polyphenylene sulfide woven net (mesh aperture of 50 meshes) on the casting solution layer, and then adjusting the coating thickness of the casting solution (namely, the distance between the scraper and the polyphenylene sulfide woven net) to be 100 mu m for carrying out secondary film scraping, so that the casting solution is uniformly coated on two sides of a supporting layer; after the doctor-blading is finished, standing for 30s in air, immersing in deionized water at 25 ℃, and completely replacing the solvent to form a surface coating, and cleaning and drying to obtain a support net composite film containing the coating;
(3) Preparing a composite diaphragm: adding 4g of polyethyleneimine, 1g of sodium dodecyl sulfate and 1g of polyvinylpyrrolidone into 94g of deionized water, and uniformly mixing to obtain a water phase solution; 15g of glutaraldehyde is added into 85g of ethanol and uniformly mixed to be used as an organic phase solution; immersing the support net composite membrane containing the coating into an aqueous phase solution, immersing for 5min at 25 ℃ for reaction, immersing into an organic phase solution, immersing for 5min at 25 ℃, taking out, and drying for 10min at 60 ℃ to obtain the composite membrane for alkaline electrolyzed water hydrogen production with enhanced gas barrier property.
The scanning electron microscope image of the surface coating of the support net composite membrane containing the coating is shown in figure 1, and the scanning electron microscope image of the composite membrane is shown in figure 2. From fig. 1, it can be observed that the pore size of the membrane surface structure without adding the crosslinking layer is larger and more densely distributed, and the gas generated by the cathode and anode flows along with the electrolyte in the electrolysis process. As can be seen from fig. 2, the micropores are obviously reduced after the surface of the membrane is filled with the crosslinked layer, so that most of gas can be blocked while the electrolyte is ensured to pass through.
Example 2
The composite diaphragm for producing hydrogen by alkaline water electrolysis is prepared according to the following method:
(1) Preparing a casting film liquid: adding 3g of polysulfone and 2g of sulfonated polysulfone (with the sulfonation degree of 10%) into 60g of N, N-dimethylformamide at normal pressure and 80 ℃, stirring until the polysulfone and the 2g of sulfonated polysulfone are completely dissolved, adding 3g of polyvinylpyrrolidone, continuously stirring until the polyvinylpyrrolidone is completely dissolved, adding 20g of titanium oxide (with the particle size of 30-50 nm) and 5g of zinc oxide (with the particle size of 80-100 mu m), and stirring and dispersing for 3 hours to obtain a casting film liquid;
(2) Coating a casting film liquid: fixing a clean glass plate on a flat plate of a film scraping machine, adjusting the coating thickness of the casting solution (namely, the distance between a scraper and the glass plate) to 300 mu m, setting the film scraping speed to 50mm/min, taking the casting solution, placing the casting solution on the glass plate to start the film scraping, attaching a polyphenylene sulfide woven net (with a mesh aperture of 60 meshes) on the casting solution layer, and adjusting the coating thickness of the casting solution (namely, the distance between the scraper and the polyphenylene sulfide woven net) to 300 mu m for secondary film scraping to uniformly coat the casting solution on two sides of a supporting layer; after the doctor-blading is finished, standing for 40s in air, immersing in deionized water at 25 ℃, and completely replacing the solvent to form a surface coating, and cleaning and drying to obtain a support net composite film containing the coating;
(3) Preparing a composite diaphragm: adding 3g of polyethyleneimine, 1g of sodium dodecyl sulfate and 2g of polyvinylpyrrolidone into 94g of deionized water, and uniformly mixing to obtain a water phase solution; adding 12g of glutaraldehyde into 88g of n-propanol, and uniformly mixing to obtain an organic phase solution; immersing the support net composite membrane containing the coating into an aqueous phase solution, immersing for 10min at 25 ℃ for reaction, immersing into an organic phase solution, immersing for 10min at 25 ℃, taking out, and drying for 5min at 80 ℃ to obtain the composite membrane for alkaline electrolyzed water hydrogen production with enhanced gas barrier property.
Example 3
The composite diaphragm for producing hydrogen by alkaline water electrolysis is prepared according to the following method:
(1) Preparing a casting film liquid: adding 5g of polyethersulfone and 3g of sulfonated polyethersulfone (with the sulfonation degree of 5%) into 55g of N, N-dimethylacetamide at the normal pressure and the temperature of 70 ℃, stirring until the polyethersulfone and the 3g of sulfonated polyethersulfone are completely dissolved, adding 8g of polyethylene glycol, continuously stirring until the polyethylene glycol is completely dissolved, adding 20g of cerium oxide (with the particle size of 30-50 nm) and 10g of ferric chloride (with the particle size of 80-100 mu m), and stirring and dispersing for 3 hours to obtain casting film liquid;
(2) Coating a casting film liquid: fixing a clean glass plate on a flat plate of a film scraping machine, adjusting the coating thickness of the casting solution (namely, the distance between a scraper and the glass plate) to be 100 mu m, setting the film scraping speed to be 50mm/min, taking the casting solution, placing the casting solution on the glass plate to start to carry out film scraping, attaching a polyphenylene sulfide woven net (mesh aperture of 50 meshes) on the casting solution layer, and then adjusting the coating thickness of the casting solution (namely, the distance between the scraper and the polyphenylene sulfide woven net) to be 100 mu m for carrying out secondary film scraping, so that the casting solution is uniformly coated on two sides of a supporting layer; after the doctor-blading is finished, standing for 30s in air, immersing in deionized water at 25 ℃, and completely replacing the solvent to form a surface coating, and cleaning and drying to obtain a support net composite film containing the coating;
(3) Preparing a composite diaphragm: adding 3g of polyethyleneimine, 0.5g of sodium dodecyl benzene sulfonate and 0.5g of polyvinylpyrrolidone into 96g of deionized water, and uniformly mixing to obtain an aqueous phase solution; 18g of glycidyl isocyanurate is added into 82g of isopropanol and uniformly mixed to be used as an organic phase solution; immersing the support net composite membrane containing the coating into an aqueous phase solution, immersing for 10min at 30 ℃ for reaction, immersing into an organic phase solution, immersing for 10min at 30 ℃, taking out, and drying for 10min at 60 ℃ to obtain the composite membrane for alkaline electrolyzed water hydrogen production with enhanced gas barrier property.
Example 4
The composite diaphragm for producing hydrogen by alkaline water electrolysis is prepared according to the following method:
(1) Preparing a casting film liquid: adding 8g of polyethersulfone and 2g of sulfonated polyethersulfone (with the sulfonation degree of 5%) into 70g of N-methylpyrrolidone at normal pressure and 60 ℃, stirring until the polyethersulfone and the 2g of sulfonated polyethersulfone are completely dissolved, adding 5g of polyvinylpyrrolidone, continuously stirring until the polyvinylpyrrolidone is completely dissolved, adding 18g of zirconia (with the particle size of 30-50 nm) and 2g of magnesium chloride (with the particle size of 80-100 mu m), and stirring and dispersing for 3 hours to obtain casting film liquid;
(2) Coating a casting film liquid: fixing a clean glass plate on a flat plate of a film scraping machine, adjusting the coating thickness of the casting solution (namely, the distance between a scraper and the glass plate) to be 100 mu m, setting the film scraping speed to be 50mm/min, taking the casting solution, placing the casting solution on the glass plate to start to carry out film scraping, attaching a polyphenylene sulfide woven net (mesh aperture of 50 meshes) on the casting solution layer, and then adjusting the coating thickness of the casting solution (namely, the distance between the scraper and the polyphenylene sulfide woven net) to be 100 mu m for carrying out secondary film scraping, so that the casting solution is uniformly coated on two sides of a supporting layer; after the doctor-blading is finished, standing for 30s in air, immersing in deionized water at 30 ℃ and completely replacing the solvent to form a surface coating, and cleaning and drying to obtain a support net composite film containing the coating;
(3) Preparing a composite diaphragm: adding 5g of polyethyleneimine, 1g of sodium dodecyl sulfate and 2g of polyethylene glycol into 92g of deionized water, and uniformly mixing to obtain an aqueous phase solution; 15g of glycidyl isocyanurate is added into 85g of ethanol and uniformly mixed to be used as an organic phase solution; immersing the support net composite membrane containing the coating into an aqueous phase solution, immersing for 8min at 30 ℃ for reaction, immersing into an organic phase solution, immersing for 8min at 30 ℃, taking out, and drying for 8min at 70 ℃ to obtain the composite membrane for alkaline electrolyzed water hydrogen production with enhanced gas barrier property.
Example 5
The composite diaphragm for producing hydrogen by alkaline water electrolysis is prepared according to the following method:
(1) Preparing a casting film liquid: adding 5g of polysulfone and 5g of sulfonated polysulfone (with the sulfonation degree of 10%) into 65g of N-methylpyrrolidone under normal pressure and 60 ℃, stirring until the polysulfone and the 5g of sulfonated polysulfone are completely dissolved, adding 10g of polyethylene glycol, continuously stirring until the polyethylene glycol is completely dissolved, adding 20g of zirconia (with the particle size of 30-50 nm) and 8g of zinc oxide (with the particle size of 80-100 mu m), and stirring and dispersing for 3 hours to obtain a casting film liquid;
(2) Coating a casting film liquid: fixing a clean glass plate on a flat plate of a film scraping machine, adjusting the coating thickness of the casting solution (namely, the distance between a scraper and the glass plate) to be 100 mu m, setting the film scraping speed to be 50mm/min, taking the casting solution, placing the casting solution on the glass plate to start to carry out film scraping, attaching a polyphenylene sulfide woven net (with a mesh aperture of 60 meshes) on the casting solution layer, and then adjusting the coating thickness of the casting solution (namely, the distance between the scraper and the polyphenylene sulfide woven net) to be 300 mu m for carrying out secondary film scraping, so that the casting solution is uniformly coated on two sides of a supporting layer; after the doctor-blading is finished, standing for 20s in air, immersing in deionized water at 30 ℃, and completely replacing the solvent to form a surface coating, and cleaning and drying to obtain a support net composite film containing the coating;
(3) Preparing a composite diaphragm: adding 4g of polyethyleneimine, 1g of cetyl trimethyl ammonium bromide and 1g of polyvinylpyrrolidone into 94g of deionized water, and uniformly mixing to obtain a water phase solution; 15g of glutaraldehyde is added into 85g of ethanol and uniformly mixed to be used as an organic phase solution; immersing the support net composite membrane containing the coating into an aqueous phase solution, immersing for 5min at 25 ℃ for reaction, immersing into an organic phase solution, immersing for 5min at 25 ℃, taking out, and drying for 10min at 60 ℃ to obtain the composite membrane for alkaline electrolyzed water hydrogen production with enhanced gas barrier property.
Comparative example 1
The comparative example provides a composite membrane for producing hydrogen by alkaline water electrolysis, wherein the support net composite membrane containing the coating prepared in the step (2) in the example 1 is directly used as the composite membrane for producing hydrogen by alkaline water electrolysis without interfacial polymerization reaction.
Comparative example 2
The comparative example was a Japanese Toli polyphenylene sulfide separator with a thickness of 0.5.+ -. 0.1mm.
Comparative example 3
This example differs from example 1 only in that the aqueous phase in step (3) is free of the surfactant sodium dodecyl sulfate.
Comparative example 4
This example differs from example 1 only in that the aqueous phase in step (3) is free of the porogen polyvinylpyrrolidone.
Comparative example 5
The present embodiment differs from embodiment 1 only in that the water phase composition in step (3) is: 1g of polyethyleneimine, 1g of sodium dodecyl sulfate, 1g of polyvinylpyrrolidone and 97g of deionized water.
The separators of each of the examples and comparative examples were subjected to the following tests for surface resistance, pore diameter, gas permeability and operating electrolysis voltage:
(1) Surface resistance test:
the surface resistance of the composite membrane is tested by adopting Prlington PARSTAT 3000-DX, the composite membrane is fixed by adopting a stainless steel clamp, KOH solution with the concentration of 30wt.% is added to two sides of the composite membrane, the composite membrane is packaged and sealed, and then an anode and a cathode are clamped by an electrode clamp for testing, and the test results are shown in table 1.
TABLE 1
As can be seen from table 1, the commercial polyphenylene sulfide separator of comparative example 2 has a higher surface resistance; the surface resistances of the surface cross-linked film samples of examples 1 to 5 were increased compared to the film sample of comparative example 1 which was not surface cross-linked; the cross-linked layer generated by the comparative example 4 without adding the pore-forming agent is compact, and the surface resistance of the film sample is large; in comparative examples 3 and 5, the crosslinked layer formed by the addition of no surfactant or the reduction of the organic phase component had a larger number of micropores, and the surface resistance was reduced as compared with example 1. In addition, for the film thickness, the difference exists in the film scraping process, the polyphenylene sulfide woven net is not necessarily in the middle position of the film casting liquid, so that the thickness of the pattern is deviated, the more dense the polyphenylene sulfide woven net with larger mesh number is, the less the film casting liquid permeates, and the larger the film thickness is.
(2) Pore size testing:
the composite membrane was tested for bubble point pressure, bubble point pore size, average pore size, gas permeability (oxygen) using Bei Shide BSD-PB and the test results are shown in table 2.
TABLE 2
As can be seen from table 2, the film sample without surface cross-linking layer treatment in comparative example 1 and the commercial polyphenylene sulfide membrane of comparative example 2 exhibited lower bubble point pressure and higher gas permeability values, which were detrimental to hydrogen production by water electrolysis; the film samples subjected to surface cross-linking treatment in examples 1 to 5 all have lower gas permeability and show better gas barrier capability; the cross-linked layer generated by the comparative example 4 without adding the pore-forming agent is compact, the bubble point pressure is high, and the oxygen permeability is low; in comparative examples 3 and 5, the crosslinked layer formed by adding no surfactant or reducing the organic phase component has more micropores, which is favorable for the electrolyte to pass through, so the bubble point pressure is slightly smaller and the oxygen permeability is slightly higher.
(3) Running current voltage test:
the composite diaphragm is installed in an electrolytic tank with the effective area of 50mm multiplied by 50mm, and the operation electrolysis voltage test of alkaline electrolyzed water is carried out, wherein the test conditions are as follows: 30wt.% KOH solution, 80 ℃,1.8V, 3 times with average value, and test results shown in Table 3.
TABLE 3 Table 3
As can be seen from table 3, the commercial polyphenylene sulfide separator of comparative example 2 has poor electrolytic performance; the film sample of comparative example 1, which was not treated with the surface cross-linking layer, exhibited the most excellent electrolysis performance, but the higher gas permeability value limited its application; the film samples subjected to surface crosslinking treatment in examples 1 to 5 exhibited good gas barrier ability and electrolytic performance; in the comparative example 4, the crosslinked layer generated without adding the pore-forming agent is compact, and the running current and the running voltage are lower due to the blockage of permeation of electrolyte and bubble removal; in the comparative example 3, the cross-linking layer generated by not adding the surfactant has more micropores, is beneficial to the passing of electrolyte and has higher running current and voltage; in comparative example 5, the organic phase component was reduced, the surface cross-linking layer active material was reduced, and the operation current and voltage were low, which was difficult to withstand the strongly alkaline operation environment.
The test results of tables 1-3 show that the composite diaphragm prepared by the invention has the advantages of increased bubble point pressure, reduced bubble point pore diameter and average pore diameter, and particularly greatly reduced gas permeability, and the gas-blocking crosslinked layer adopted in the invention has good effect. From the electrolyzed water operation data, although comparative example 1, which does not employ a crosslinking layer, obtained higher electrolysis efficiency, the addition of the crosslinking layer, from the viewpoint of device safety, obtained a significant improvement in hydrogen and oxygen gas barrier capability with less current density loss, was more advantageous than the disadvantage.
Claims (10)
1. A preparation method of a composite membrane for enhancing gas barrier property and producing hydrogen by alkaline water electrolysis is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing a casting film liquid: dispersing the binder, the pore-forming agent and the nano/micron inorganic particles into an organic solvent to obtain a casting solution;
(2) Coating a casting film liquid: uniformly coating the casting solution on two sides of the supporting layer, and performing coagulating bath treatment to obtain a supporting net composite film containing the coating;
(3) Preparing a composite diaphragm: dispersing a hydrophilic high molecular compound, a surfactant and a pore-forming agent into water to obtain an aqueous phase solution; dispersing an organic phase monomer into an organic phase solvent to obtain an organic phase solution; immersing the support net composite membrane containing the coating into an aqueous phase solution for 5-10min, immersing into an organic phase solution for 5-10min, taking out and drying to obtain the composite membrane for alkaline electrolytic water hydrogen production with enhanced gas barrier property.
2. The method for producing a composite membrane for alkaline water electrolysis hydrogen production with enhanced gas barrier property according to claim 1, characterized by comprising the steps of: in the step (1), the binder is one or more of polysulfone, polyethersulfone, sulfonated polysulfone and sulfonated polyethersulfone; wherein, the sulfonation degree of the sulfonated polysulfone and the sulfonated polyether sulfone is 5-10%.
3. The method for producing a composite membrane for alkaline water electrolysis hydrogen production with enhanced gas barrier property according to claim 1, characterized by comprising the steps of: in the step (1), the pore-forming agent is one or two of polyvinylpyrrolidone and polyethylene glycol;
the nanometer/micrometer inorganic matter particle is one or more of zirconia, titania, cerium oxide, zinc oxide, magnesium chloride and ferric chloride.
4. The method for producing a composite membrane for alkaline water electrolysis hydrogen production with enhanced gas barrier property according to claim 1, characterized by comprising the steps of: in the step (1), the organic solvent is one or more of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
5. The method for producing a composite membrane for alkaline water electrolysis hydrogen production with enhanced gas barrier property according to claim 1, characterized by comprising the steps of: in the step (1), the casting solution comprises the following raw materials in percentage by mass: 5-10% of binder, 5-10% of pore-forming agent, 20-30% of nano/micron inorganic particles and 50-60% of organic solvent.
6. The method for producing a composite membrane for alkaline water electrolysis hydrogen production with enhanced gas barrier property according to claim 1, characterized by comprising the steps of: in the step (2), the supporting layer is a polyphenylene sulfide fiber mesh, and the mesh aperture of the mesh is 50-60 meshes.
7. The method for producing a composite membrane for alkaline water electrolysis hydrogen production with enhanced gas barrier property according to claim 1, characterized by comprising the steps of: in the step (2), the thickness of the single-side coating film of the casting film liquid is 100-300 mu m.
8. The method for producing a composite membrane for alkaline water electrolysis hydrogen production with enhanced gas barrier property according to claim 1, characterized by comprising the steps of: in the step (3), the aqueous phase solution comprises the following raw materials in percentage by mass: 3-5% of hydrophilic high molecular compound, 0.5-1% of surfactant, 0.5-2% of pore-forming agent and 92-96% of water;
wherein the hydrophilic polymer compound is polyacetylimine;
the surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and cetyltrimethylammonium bromide;
the pore-forming agent is one or two of polyvinylpyrrolidone and polyethylene glycol.
9. The method for producing a composite membrane for alkaline water electrolysis hydrogen production with enhanced gas barrier property according to claim 1, characterized by comprising the steps of: in the step (3), the organic phase solution comprises the following raw materials in percentage by mass: 12-18% of organic phase monomer and 82-88% of organic phase solvent;
wherein the organic phase monomer is glutaraldehyde or isocyanuric acid glycidyl ester;
the organic phase solvent is one or more of ethanol, n-propanol and isopropanol.
10. A composite membrane for producing hydrogen by alkaline electrolysis of water with enhanced gas barrier properties, prepared by the preparation method of any one of claims 1 to 9, characterized in that: gas permeability of less than 8.0X10 -7 m 3 /（m 2. Pa . s）。
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