CN119020821A - A method for preparing a corrosion-resistant diaphragm for producing hydrogen by electrolyzing alkaline water - Google Patents
A method for preparing a corrosion-resistant diaphragm for producing hydrogen by electrolyzing alkaline water Download PDFInfo
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- CN119020821A CN119020821A CN202411121496.8A CN202411121496A CN119020821A CN 119020821 A CN119020821 A CN 119020821A CN 202411121496 A CN202411121496 A CN 202411121496A CN 119020821 A CN119020821 A CN 119020821A
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- Prior art keywords
- polysulfone
- diaphragm
- corrosion
- alkaline water
- hydrogen production
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000001257 hydrogen Substances 0.000 title claims abstract description 58
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000005260 corrosion Methods 0.000 title claims abstract description 43
- 230000007797 corrosion Effects 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 82
- 239000007822 coupling agent Substances 0.000 claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 28
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 17
- 238000011282 treatment Methods 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 14
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims abstract description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 50
- 238000004519 manufacturing process Methods 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 46
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000007790 scraping Methods 0.000 claims description 10
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 229950000688 phenothiazine Drugs 0.000 claims description 7
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 125000000129 anionic group Chemical group 0.000 abstract description 4
- 125000002091 cationic group Chemical group 0.000 abstract description 4
- 238000005660 chlorination reaction Methods 0.000 abstract description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 125000005395 methacrylic acid group Chemical group 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- OUKZUIOFTUUCEN-UHFFFAOYSA-N 7$l^{6}-thiabicyclo[4.1.0]hepta-1,3,5-triene 7,7-dioxide Chemical compound C1=CC=C2S(=O)(=O)C2=C1 OUKZUIOFTUUCEN-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920013655 poly(bisphenol-A sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 sulfonic group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000012546 transfer 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本发明公开了一种耐腐蚀的电解碱性水制氢隔膜的制备方法，属于电解碱性水制氢技术领域，用于解决现有技术中的聚砜材料制备的隔膜存在亲水性差、导电性差、隔膜机械性能有待进一步提高的技术问题；本发明包括以下步骤：两性离子改性聚砜、NMP和微孔添加剂混合，得到铸膜液，铸膜液经后工艺处理，得到一种耐腐蚀的电解碱性水制氢隔膜，聚砜进行氯化处理、接枝阴离子单体甲基丙烯磺酸钠和阳离子单体4‑乙烯基吡啶，从而提高聚砜的导电性能，研磨至微米级的氧化铝、二氧化锆和二氧化钛采用复配偶联剂改性，得到的微孔添加剂具有机械强度高、亲水性强的优点。The invention discloses a method for preparing a corrosion-resistant diaphragm for producing hydrogen by electrolysis of alkaline water, belongs to the technical field of producing hydrogen by electrolysis of alkaline water, and is used to solve the technical problems that a diaphragm prepared from a polysulfone material in the prior art has poor hydrophilicity, poor electrical conductivity, and the mechanical properties of the diaphragm need to be further improved. The invention comprises the following steps: zwitterion-modified polysulfone, NMP and a microporous additive are mixed to obtain a casting solution, the casting solution is subjected to a post-process treatment to obtain a corrosion-resistant diaphragm for producing hydrogen by electrolysis of alkaline water, the polysulfone is subjected to chlorination treatment, an anionic monomer sodium methacrylic sulfonate and a cationic monomer 4-vinyl pyridine are grafted to improve the electrical conductivity of the polysulfone, aluminum oxide, zirconium dioxide and titanium dioxide ground to micrometer level are modified by a complex coupling agent, and the obtained microporous additive has the advantages of high mechanical strength and strong hydrophilicity.
Description
Technical Field
The invention relates to the technical field of hydrogen production by alkaline water electrolysis, in particular to a corrosion-resistant preparation method of a hydrogen production diaphragm by alkaline water electrolysis.
Background
The hydrogen energy is used as a clean energy source with 'zero carbon', has the characteristics of rich reserve, regeneration, cleanness, high efficiency and the like, only discharges water and no other harmful gas or solid particles in the use process, and the development and the utilization of the hydrogen energy are the necessary trend of the future energy development, and the green hydrogen generation way comprises biomass hydrogen production, solar water photolysis hydrogen production, renewable electric power water electrolysis hydrogen production and the like, and the water electrolysis hydrogen production technology has the advantages of stability, large-scale mass production and the like and is increasingly favored by the market.
The membrane occupies an important position in the electrolytic tank, and in the alkaline water electrolysis hydrogen production process, the anode and the cathode respectively generate oxygen and hydrogen, so that the membrane can prevent the hydrogen and the oxygen from being mixed with each other to ensure the purity of the hydrogen, and allow ions in the solution to pass through to ensure that the electrolytic process is continuously carried out.
Common diaphragms comprise asbestos diaphragms, polyphenylene sulfide diaphragms, polyether-ether-ketone diaphragms, polysulfone diaphragms and the like, wherein the polysulfone diaphragms are high molecular compounds taking phenylene sulfone as a structural unit, the polysulfone structural unit contains 4 benzene rings and is of a symmetrical structure, and the polysulfone resin has stronger thermal stability and mechanical strength due to the conjugated effect and rigid structure of the benzene rings; however, the polysulfone membrane has poor hydrophilicity, tiny bubbles of hydrogen and oxygen are easily accumulated on the surface of the membrane in the water electrolysis process, the flow of electrolyte is influenced, the current efficiency is reduced, the energy consumption is increased, if the hydrophilicity of the polysulfone membrane can be enhanced, the polysulfone membrane has more excellent application prospect in the field of water electrolysis membranes, and in addition, the technical problem of how to improve the ionic conductivity of the polysulfone membrane is still needed to be solved.
Patent application CN117822048A discloses a temperature-resistant alkaline water electrolysis hydrogen production diaphragm and a preparation method thereof, wherein the temperature-resistant alkaline water electrolysis hydrogen production diaphragm is prepared from a fiber mesh double-sided composite porous coating, the solid component of the porous coating comprises zirconia particles and resin, and the resin at least comprises one or two of polyphenylene sulfide, polyether sulfone or bisphenol A polysulfone; however, the zirconia particles and the organic resin are not compatible themselves, thereby reducing the hydrophilicity of the prepared separator, and furthermore, the zirconia particles are filled in the resin, so that the pore size of the prepared separator is reduced, further reducing the conductivity of the prepared separator.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a corrosion-resistant electrolytic alkaline water hydrogen production diaphragm, which is used for solving the technical problems that the mechanical property of the diaphragm prepared from polysulfone materials in the prior art needs to be further improved, and the hydrophilicity and the conductivity of the diaphragm are poor.
The aim of the invention can be achieved by the following technical scheme: a preparation method of corrosion-resistant electrolytic alkaline water hydrogen production diaphragm comprises the following steps:
S1, mixing and stirring zwitterionic modified polysulfone and NMP to obtain uniformly dispersed mixed solution; adding the microporous additive into the mixed solution, and stirring at room temperature for 24 hours at 500r/min to obtain a casting solution;
s2, pouring the casting solution on a glass plate, and rapidly scraping a film on the glass plate by using a film scraping rod until the thickness of a liquid film on the glass plate is 500-600 mu m; taking deionized water as a coagulating bath, putting a glass plate into the deionized water, and taking out liquid film gel to obtain a diaphragm; the diaphragm is treated by post-process to obtain the corrosion-resistant diaphragm for producing hydrogen by electrolyzing alkaline water.
NMP is used as a solvent to dissolve zwitterionic modified polysulfone, then a microporous additive is added to prepare corresponding casting solution, and the casting solution is subjected to a series of post-process treatments to prepare the corrosion-resistant electrolytic alkaline water hydrogen production diaphragm.
Further, in step S1, the preparation method of the zwitterionic modified polysulfone includes the following steps:
A1, adding polysulfone and chloroform into a three-neck flask, mixing and stirring until the polysulfone is completely dissolved in the chloroform to obtain a solution; introducing chlorine into the three-neck flask, wherein the flow speed of the chlorine is 15mL/min;
a2, carrying out ultraviolet irradiation on the three-neck flask by adopting an ultra-high pressure spherical mercury lamp at 50-60 ℃ to obtain a product; heating to 65 ℃ and volatilizing all the chloroform solvent to obtain a solid; washing the solid by deionized water, and drying the solid in vacuum until the weight is constant to obtain chlorinated polysulfone;
Because of the unique molecular structure of polysulfone, the main chain of polysulfone is easy to undergo nucleophilic substitution reaction, and polysulfone itself contains electron donating ether bond, so that the chlorination of polysulfone can be realized, chloroform is used as solvent to dissolve polysulfone solid, so as to obtain corresponding dissolving solution, chlorine is introduced into the dissolving solution, and under the action of ultraviolet irradiation, the nucleophilic substitution reaction of polysulfone and chlorine in the dissolving solution is performed, so that the chlorinated polysulfone is prepared.
The polysulfone reacts with chlorine to prepare the chlorinated polysulfone with the following reaction formula:
A3, mixing the chlorinated polysulfone, 4-vinylpyridine, sodium methallyl sulfonate and DMSO to obtain mixed solid-liquid; adding cuprous bromide into the mixed solid-liquid under the nitrogen atmosphere, and reacting for 12 hours at 100-120 ℃ with mechanical stirring at 100-200r/min to obtain a product;
a4, transferring the product into methanol, precipitating and filtering repeatedly, and cleaning with methanol to obtain a solid with cuprous bromide removed; the solid was dried under vacuum at 80 ℃ to constant weight to give a solid zwitterionic modified polysulfone.
The polymer chain of the chlorinated polysulfone is attached with a functional group with negative charge; taking DMSO as a solvent, cuprous bromide as a catalyst, and organic halide chlorinated polysulfone as an initiator to carry out atom transfer free polymerization reaction, and then grafting anionic monomer sodium methacrylate and cationic monomer 4-vinyl pyridine to prepare the solid amphoteric ion modified polysulfone.
The reaction formula of the chlorinated polysulphone, 4-vinylpyridine and sodium methallyl sulfonate is as follows:
Further, in the step A1, the dosage ratio of polysulfone to chloroform is 50g to 100mL; in the step A2, the frequency of ultraviolet irradiation is 10-20KHz, and the duration of ultraviolet irradiation is 30-60min.
Further, in the step A3, the dosage ratio of the polysulfone chloride, the 4-vinylpyridine, the sodium methacrylate sulfonate, the DMSO and the cuprous bromide is 30g:5-10g:15-20g:100mL; in step A4, the amount of methanol was 300mL.
Further, in step S1, the preparation method of the microporous additive includes the following steps:
B1, uniformly mixing trimethoxy silane and a platinum catalyst S-201, and then adding the rest trimethoxy silane, methyl methacrylate and a polymerization inhibitor phenothiazine to obtain a mixture; reacting the mixture at 100-110 ℃ for 2 hours, and then decompressing, distilling and filtering to obtain coupling agent liquid;
Platinum is used as a catalyst, trimethoxysilane with SiH groups and methyl methacrylate containing double bonds are subjected to addition reaction, and the coupling agent liquid is obtained.
The reaction principle of the addition reaction of trimethoxysilane and methyl methacrylate is as follows:
Wherein, the mass spectrum analysis and the element analysis data of the trimethoxysilane and methyl methacrylate synthesized product are as follows: m/z 208.08 (100.0%), 209.08 (13.0%), 210.07 (3.4%), 210.08 (1.7%)
B2, uniformly mixing gamma-mercaptopropyl trimethoxy silane and coupling agent liquid to obtain complex coupling agent liquid;
B3, mixing aluminum oxide, zirconium dioxide and titanium dioxide to obtain an inorganic mixture; adding the inorganic mixture into a 1mol/L NaOH solution, mixing and stirring for 5-10min at room temperature at 100r/min, and filtering to obtain an inorganic mixture after alkali treatment; adding the inorganic mixture subjected to alkali treatment into a ball mill for ball milling until the particle size of the inorganic mixture is 300-400 mu m to obtain an inorganic powder mixture; mixing the inorganic powder mixture with the compound coupling agent liquid, and stirring at high speed to obtain the microporous additive.
The method comprises the steps of taking a mixture of coupling agent liquid and gamma-mercaptopropyl trimethoxy silane as a compound coupling agent, modifying an inorganic powder mixture, taking aluminum oxide, zirconium dioxide and titanium dioxide as inorganic powder mixture components, and treating the inorganic powder mixture in advance by adopting alkali liquor, so that the content of hydroxyl on the surface of the inorganic powder mixture is improved, and the modification degree of the compound coupling agent on the inorganic powder mixture is improved.
Further, in the step B1, the dosage ratio of trimethoxysilane to platinum catalyst S-201 is 12g to 5g; the dosage ratio of the rest trimethoxy silane, methyl methacrylate and polymerization inhibitor phenothiazine is 110g to 100-126g to 2-3g.
Further, in the step B2, the dosage ratio of the gamma-mercaptopropyl trimethoxy silane to the coupling agent liquid is 20g to 10-20g.
Further, in the step B2, the dosage ratio of alumina, zirconia and titania is 100g to 100g; the dosage ratio of the inorganic powder mixture to the coupling agent liquid is 300g to 10-20g.
Further, the use amount ratio of the zwitterionic modified polysulfone, the NMP and the micropore additive is 30-50g:200mL:5-10g.
Further, the post-process steps include: pre-pressing the diaphragm to form, and then adding the diaphragm into deionized water to clean for three times to obtain a cleaned diaphragm; and (3) putting the diaphragm into a vacuum drying oven at 70 ℃ to be dried for 10-20min, so as to obtain the corrosion-resistant electrolytic alkaline water hydrogen production diaphragm.
The invention has the following beneficial effects:
1. The method comprises the steps of pre-chlorinating polysulfone to prepare chlorinated polysulfone containing chloride ions; and then, through atom transfer radical polymerization reaction, grafting an anionic monomer sodium methacrylate and a cationic monomer 4-vinyl pyridine, preparing the solid amphoteric ion modified polysulfone. The polysulfone is modified by various functional groups such as sulfonic group, pyridyl group, chloride ion and the like, so that the conductivity of the polysulfone is improved.
2. When the corrosion-resistant electrolytic alkaline water hydrogen production diaphragm is prepared by adopting a precipitation phase inversion method, a micropore additive is added, and the micropore additive is used as a supporting layer to prepare the organic-inorganic composite diaphragm, so that the mechanical property and corrosion resistance of the prepared diaphragm are improved. The micropore additive is specifically a modified inorganic powder mixture, and the inorganic powder mixture comprises a mixture. The invention adopts the compound coupling agent to modify the inorganic mixed powder in advance, thereby improving the compatibility of the inorganic mixed powder and polysulfone material; in addition, the functional group of the zwitterionic modified polysulfone can be electrostatically adsorbed with the mercapto group and the ester group functional group of the complexing agent, thereby improving the complexing property of the microporous additive and the polysulfone material. In order to avoid that a large amount of inorganic particles block the lithium ion channel, the impedance of the diaphragm is increased, and the dosage of the micropore additive is further regulated.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a corrosion-resistant microporous additive for an electrolytic alkaline water hydrogen production diaphragm, which comprises the following steps:
B1, mixing 12g of trimethoxysilane and 5g of platinum catalyst S-201, adding the mixture into a 500mL three-neck flask, and uniformly mixing; then 110g of trimethoxy silane, 100g of methyl methacrylate and 2g of polymerization inhibitor phenothiazine are added into a three-neck flask to obtain a mixture; and transferring the three-neck flask into an oil bath pot, setting the temperature of the oil bath pot to be 100 ℃, reacting for 2 hours, and then decompressing, distilling and filtering the solid to obtain the coupling agent liquid.
And B2, uniformly mixing 20g of gamma-mercaptopropyl trimethoxy silane and 10g of coupling agent liquid to obtain a compound coupling agent liquid.
B3, mixing 100g of aluminum oxide, 100g of zirconium dioxide and 100g of titanium dioxide to obtain an inorganic mixture; mixing and stirring the inorganic mixture with 1000mL of 1mol/L NaOH solution at room temperature at 100r/min for 5min, and filtering to obtain an inorganic mixture after alkali treatment; adding the inorganic mixture subjected to alkali treatment into a ball mill for ball milling until the particle size is ground to 300 mu m to obtain an inorganic powder mixture; adding the inorganic powder mixture and 10g of compound coupling agent liquid into a high-speed mixing stirrer, mixing and stirring for 30min at 500r/min, wherein the rotation speed of a rotor of the high-speed mixing stirrer is 4000r/min, and the stirring temperature is 100 ℃, so as to obtain the microporous additive.
Example 2
The embodiment provides a preparation method of a corrosion-resistant microporous additive for an electrolytic alkaline water hydrogen production diaphragm, which comprises the following steps:
B1, mixing 12g of trimethoxysilane and 5g of platinum catalyst S-201, adding the mixture into a 500mL three-neck flask, and uniformly mixing; then 110g of trimethoxy silane, 115g of methyl methacrylate and 3g of polymerization inhibitor phenothiazine are added into a three-neck flask to obtain a mixture; and transferring the three-neck flask into an oil bath pot, setting the temperature of the oil bath pot to be 105 ℃, reacting for 2 hours, and then decompressing, distilling and filtering the solid to obtain the coupling agent liquid.
And B2, uniformly mixing 20g of gamma-mercaptopropyl trimethoxy silane and 15g of coupling agent liquid to obtain a compound coupling agent liquid.
B3, mixing 100g of aluminum oxide, 100g of zirconium dioxide and 100g of titanium dioxide to obtain an inorganic mixture; mixing and stirring the inorganic mixture with 1000mL of 1mol/L NaOH solution at room temperature at 100r/min for 6min, and filtering to obtain an inorganic mixture after alkali treatment; adding the inorganic mixture subjected to alkali treatment into a ball mill for ball milling until the particle size is ground to 350 mu m to obtain an inorganic powder mixture; adding the inorganic powder mixture and 15g of compound coupling agent liquid into a high-speed mixing stirrer, mixing and stirring for 40min at 500r/min, wherein the rotation speed of a rotor of the high-speed mixing stirrer is 4500r/min, and the stirring temperature is 102 ℃, so as to obtain the microporous additive.
Example 3
The embodiment provides a preparation method of a corrosion-resistant microporous additive for an electrolytic alkaline water hydrogen production diaphragm, which comprises the following steps:
B1, mixing 12g of trimethoxysilane and 5g of platinum catalyst S-201, adding the mixture into a 500mL three-neck flask, and uniformly mixing; then 110g of trimethoxy silane, 126g of methyl methacrylate and 3g of polymerization inhibitor phenothiazine are added into a three-neck flask to obtain a mixture; and transferring the three-neck flask into an oil bath pot, setting the temperature of the oil bath pot to be 110 ℃, reacting for 2 hours, and then decompressing, distilling and filtering the solid to obtain the coupling agent liquid.
And B2, uniformly mixing 20g of gamma-mercaptopropyl trimethoxy silane and 20g of coupling agent liquid to obtain a compound coupling agent liquid.
B3, mixing 100g of aluminum oxide, 100g of zirconium dioxide and 100g of titanium dioxide to obtain an inorganic mixture; mixing and stirring the inorganic mixture and 1000mL of 1mol/L NaOH solution at room temperature for 10min at 100r/min, and filtering to obtain an inorganic mixture after alkali treatment; adding the inorganic mixture subjected to alkali treatment into a ball mill for ball milling until the particle size is 400 mu m, and obtaining an inorganic powder mixture; adding the inorganic powder mixture and 20g of compound coupling agent liquid into a high-speed mixing stirrer, mixing and stirring for 60min at 500r/min, wherein the rotation speed of a rotor of the high-speed mixing stirrer is 5000r/min, and the stirring temperature is 105 ℃, so as to obtain the microporous additive.
Example 4
The embodiment provides a preparation method of corrosion-resistant zwitterionic modified polysulfone for an electrolytic alkaline water hydrogen production diaphragm, which comprises the following steps:
A1, adding 50g of polysulfone and 100mL of chloroform into a 250mL three-neck flask, mixing and stirring until the polysulfone is completely dissolved in the chloroform to obtain a solution; the three-neck flask is connected with the condenser and the three-way valve, one side of the three-way valve is connected with chlorine, the flow rate of the chlorine is 15mL/min, and one side of the three-neck flask is connected with the vacuum pump.
A2, transferring the three-neck flask to a water bath kettle, and setting the temperature of the water bath kettle to be 50 ℃; an ultra-high pressure spherical mercury lamp is used as an ultraviolet light source to carry out ultraviolet irradiation on the three-neck flask; the frequency of ultraviolet irradiation is 10KHz, and the duration of ultraviolet irradiation is 30min, so as to obtain the product; heating the three-neck flask to 65 ℃ and reacting until all the chloroform solvent is evaporated to obtain a solid; the solid was washed with deionized water and then dried in a vacuum oven at 80 ℃ until constant weight was achieved to give chlorinated polysulfone.
A3, weighing 30g of polysulfone chloride, 5g of 4-vinylpyridine, 15g of sodium methallyl sulfonate and 100mL of DMSO, adding into a 250mL three-neck flask, and mixing and stirring for 10min at 100r/min to obtain mixed solid-liquid; introducing high-purity N 2 for 15min into the three-neck flask to remove oxygen, adding 0.2g of catalyst cuprous bromide into the three-neck flask, and sealing the port of the three-neck flask; the three-necked flask was transferred to a water bath kettle, and reacted at 100℃for 12 hours with mechanical stirring at 100r/min to obtain a product.
A4, stopping the reaction, cooling the three-neck flask to room temperature, transferring the product into 300mL of methanol, precipitating a precipitate, repeatedly carrying out suction filtration, and washing with methanol to obtain a solid with cuprous bromide removed; the solid was dried under vacuum at 80 ℃ to constant weight to give a zwitterionic modified polysulfone.
Example 5
The embodiment provides a preparation method of corrosion-resistant zwitterionic modified polysulfone for an electrolytic alkaline water hydrogen production diaphragm, which comprises the following steps:
A1, adding 50g of polysulfone and 100mL of chloroform into a 250mL three-neck flask, mixing and stirring until the polysulfone is completely dissolved in the chloroform to obtain a solution; the three-neck flask is connected with the condenser and the three-way valve, one side of the three-way valve is connected with chlorine, the flow rate of the chlorine is 15mL/min, and one side of the three-neck flask is connected with the vacuum pump.
A2, transferring the three-neck flask to a water bath kettle, wherein the temperature of the water bath kettle is set to be 55 ℃; an ultra-high pressure spherical mercury lamp is used as an ultraviolet light source to carry out ultraviolet irradiation on the three-neck flask; the frequency of ultraviolet irradiation is 15KHz, and the duration of ultraviolet irradiation is 40min, so as to obtain a product; heating the three-neck flask to 65 ℃ and reacting until all the chloroform solvent is evaporated to obtain a solid; the solid was washed with deionized water and then dried in a vacuum oven at 80 ℃ until constant weight was achieved to give chlorinated polysulfone.
A3, weighing 30g of polysulfone chloride, 8g of 4-vinylpyridine, 18g of sodium methallyl sulfonate and 100mL of DMSO, adding into a 250mL three-neck flask, and mixing and stirring for 16min at 140r/min to obtain mixed solid-liquid; introducing high-purity N 2 for 15min into the three-neck flask to remove oxygen, adding 0.2g of catalyst cuprous bromide into the three-neck flask, and sealing the port of the three-neck flask; the three-necked flask was transferred to a water bath kettle, and reacted at 110℃for 12 hours with 160r/min mechanical stirring to obtain a product.
A4, stopping the reaction, cooling the three-neck flask to room temperature, transferring the product into 300mL of methanol, precipitating a precipitate, repeatedly carrying out suction filtration, and washing with methanol to obtain a solid with cuprous bromide removed; the solid was dried under vacuum at 80 ℃ to constant weight to give a zwitterionic modified polysulfone.
Example 6
The embodiment provides a preparation method of corrosion-resistant zwitterionic modified polysulfone for an electrolytic alkaline water hydrogen production diaphragm, which comprises the following steps:
A1, adding 50g of polysulfone and 100mL of chloroform into a 250mL three-neck flask, mixing and stirring until the polysulfone is completely dissolved in the chloroform to obtain a solution; the three-neck flask is connected with the condenser and the three-way valve, one side of the three-way valve is connected with chlorine, the flow rate of the chlorine is 15mL/min, and one side of the three-neck flask is connected with the vacuum pump.
A2, transferring the three-neck flask to a water bath kettle, wherein the temperature of the water bath kettle is set to be 60 ℃; an ultra-high pressure spherical mercury lamp is used as an ultraviolet light source to carry out ultraviolet irradiation on the three-neck flask; the frequency of ultraviolet irradiation is 20KHz, and the duration of ultraviolet irradiation is 60min, so as to obtain a product; heating the three-neck flask to 65 ℃ and reacting until all the chloroform solvent is evaporated to obtain a solid; the solid was washed with deionized water and then dried in a vacuum oven at 80 ℃ until constant weight was achieved to give chlorinated polysulfone.
A3, weighing 30g of polysulfone chloride, 10g of 4-vinylpyridine, 20g of sodium methallyl sulfonate and 100mL of DMSO, adding into a 250mL three-neck flask, and mixing and stirring for 20min at 200r/min to obtain mixed solid-liquid; introducing high-purity N 2 for 15min into the three-neck flask to remove oxygen, adding 0.2g of catalyst cuprous bromide into the three-neck flask, and sealing the port of the three-neck flask; the three-neck flask is transferred to a water bath kettle, and is mechanically stirred at 100-200r/min to react for 12 hours at 120 ℃ to obtain a product.
A4, stopping the reaction, cooling the three-neck flask to room temperature, transferring the product into 300mL of methanol, precipitating a precipitate, repeatedly carrying out suction filtration, and washing with methanol to obtain a solid with cuprous bromide removed; the solid was dried under vacuum at 80 ℃ to constant weight to give a zwitterionic modified polysulfone.
Example 7
The embodiment provides a preparation method of a corrosion-resistant electrolytic alkaline water hydrogen production diaphragm, which comprises the following steps:
S1, adding 30g of the zwitterionic modified polysulfone prepared in the example 4 and 200mL of NMP into a 500mL beaker, and mechanically stirring until a uniformly dispersed mixed solution is obtained; 5g of the microporous additive prepared in example 1 was weighed and added to the above-mentioned mixed solution, the beaker was transferred to a constant temperature magnetic stirrer, the beaker was sealed, and stirred at 500r/min for 24 hours at room temperature to obtain a casting solution.
S2, pouring the casting film liquid on a glass plate, and then rapidly scraping a film on the glass plate by using a film scraping rod until the thickness of a liquid film on the glass plate is 500 mu m; taking deionized water as a coagulating bath, putting a glass plate into the deionized water, enabling liquid film gel to fall off, and taking out the liquid film from the deionized water to obtain a diaphragm; pre-pressing the diaphragm to form, and then adding the diaphragm into deionized water to clean for three times to obtain a cleaned diaphragm; and (3) putting the diaphragm into a vacuum drying oven at 70 ℃ for drying for 10min to obtain the corrosion-resistant electrolytic alkaline water hydrogen production diaphragm.
Example 8
The embodiment provides a preparation method of a corrosion-resistant electrolytic alkaline water hydrogen production diaphragm, which comprises the following steps:
S1, adding 40g of the zwitterionic modified polysulfone prepared in the example 5 and 200mL of NMP into a 500mL beaker, and mechanically stirring until a uniformly dispersed mixed solution is obtained; 6g of the microporous additive prepared in example 2 was weighed and added to the above mixed solution, the beaker was transferred to a constant temperature magnetic stirrer, the beaker was sealed, and stirred at 500r/min for 24 hours at room temperature to obtain a casting solution.
S2, pouring the casting film liquid on a glass plate, and then rapidly scraping a film on the glass plate by using a film scraping rod until the thickness of a liquid film on the glass plate is 5800 mu m; taking deionized water as a coagulating bath, putting a glass plate into the deionized water, enabling liquid film gel to fall off, and taking out the liquid film from the deionized water to obtain a diaphragm; pre-pressing the diaphragm to form, and then adding the diaphragm into deionized water to clean for three times to obtain a cleaned diaphragm; and (3) putting the diaphragm into a vacuum drying oven at 70 ℃ for drying for 10min to obtain the corrosion-resistant electrolytic alkaline water hydrogen production diaphragm.
Example 9
The embodiment provides a preparation method of a corrosion-resistant electrolytic alkaline water hydrogen production diaphragm, which comprises the following steps:
S1, adding 50g of the zwitterionic modified polysulfone prepared in the example 6 and 200mL of NMP into a 500mL beaker, and mechanically stirring until a uniformly dispersed mixed solution is obtained; 10g of the microporous additive prepared in example 3 was weighed and added to the above-mentioned mixed solution, the beaker was transferred to a constant temperature magnetic stirrer, the beaker was sealed, and stirred at 500r/min for 24 hours at room temperature to obtain a casting solution.
S2, pouring the casting film liquid on a glass plate, and then rapidly scraping a film on the glass plate by using a film scraping rod until the thickness of a liquid film on the glass plate is 600 mu m; taking deionized water as a coagulating bath, putting a glass plate into the deionized water, enabling liquid film gel to fall off, and taking out the liquid film from the deionized water to obtain a diaphragm; pre-pressing the diaphragm to form, and then adding the diaphragm into deionized water to clean for three times to obtain a cleaned diaphragm; and (3) putting the diaphragm into a vacuum drying oven at 70 ℃ for drying for 10min to obtain the corrosion-resistant electrolytic alkaline water hydrogen production diaphragm.
Comparative example 1
This comparative example differs from example 9 in that the zwitterionic modified polysulfone was prepared without chlorination treatment.
Comparative example 2
This comparative example differs from example 9 in that the zwitterionic modified polysulfone was replaced by a chlorinated polysulfone.
Comparative example 3
This comparative example differs from example 9 in that the gamma-mercaptopropyl trimethoxysilane was replaced with a coupling agent liquid in the preparation of the microporous additive.
Performance test:
1. The corrosion-resistant electrolytic alkaline water hydrogen production diaphragm prepared in examples 7 to 9 was cut into a sample with a length of 50mm and a width of 15mm, the cut sample was washed and soaked with deionized water for 3 times, and then placed in a vacuum drying oven at 50 ℃ for sufficient drying, and the tensile strength of the sample was measured.
2. The alkali absorption rate of the corrosion-resistant electrolytic alkaline water hydrogen production membrane prepared in examples 7 to 9 was measured according to SJ-J10171.7-91 determination of alkali absorption rate of membrane.
3. The porosity of the corrosion-resistant electrolytic alkaline water hydrogen production membrane prepared in examples 7 to 9 was measured.
4. The pure water contact angles of the corrosion-resistant electrolytic alkaline water hydrogen production diaphragms prepared in examples 7 to 9 were measured by a contact angle measuring instrument. The specific test results are shown in the following table:
Table-performance test data table
Data analysis:
The corrosion-resistant electrolytic alkaline water hydrogen production diaphragm prepared in the embodiments 7 to 9 of the invention has excellent mechanical properties by doping the microporous additive, and shows that the tensile strength value is increased. The corrosion-resistant electrolytic alkaline water hydrogen production diaphragms prepared in the embodiments 7 to 9 have excellent conductivity, and are large in alkali absorption rate value; however, in comparative example 1, polysulfone was not subjected to the chlorination treatment, and in comparative example 2, the chlorinated polysulfone was not grafted with the anionic monomer and the cationic monomer, thereby decreasing the conductive properties of the prepared separator, which is manifested in a decrease in the alkali absorption value of the separator.
In the corrosion-resistant electrolytic alkaline water hydrogen production diaphragm prepared in the embodiments 7 to 9, polysulfone is modified for a plurality of times, and the microporous additive is modified by adopting a compound coupling agent, so that the hydrophilic group of the prepared diaphragm is increased, the hydrophilicity of the prepared diaphragm is improved, and the degree of the water contact angle is reduced. However, comparative examples 1, 2 and 3 reduced the kinds and amounts of hydrophilic groups for preparing a separator to various degrees, which was shown as a decrease in hydrophilicity of the separator and an increase in the degree of water contact angle.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. The preparation method of the corrosion-resistant electrolytic alkaline water hydrogen production diaphragm is characterized by comprising the following steps of:
S1, mixing and stirring zwitterionic modified polysulfone and NMP to obtain uniformly dispersed mixed solution; adding the microporous additive into the mixed solution, and stirring at room temperature for 24 hours at 500r/min to obtain a casting solution;
s2, pouring the casting solution on a glass plate, and rapidly scraping a film on the glass plate by using a film scraping rod until the thickness of a liquid film on the glass plate is 500-600 mu m; taking deionized water as a coagulating bath, putting a glass plate into the deionized water, and taking out liquid film gel to obtain a diaphragm; the diaphragm is treated by post-process to obtain the corrosion-resistant diaphragm for producing hydrogen by electrolyzing alkaline water.
2. The method for preparing the corrosion-resistant electrolytic alkaline water hydrogen production membrane according to claim 1, wherein in the step S1, the method for preparing the zwitterionic modified polysulfone comprises the following steps:
A1, adding polysulfone and chloroform into a three-neck flask, mixing and stirring until the polysulfone is completely dissolved in the chloroform to obtain a solution; introducing chlorine into the three-neck flask, wherein the flow speed of the chlorine is 15mL/min;
a2, carrying out ultraviolet irradiation on the three-neck flask by adopting an ultra-high pressure spherical mercury lamp at 50-60 ℃ to obtain a product; heating to 65 ℃ and volatilizing all the chloroform solvent to obtain a solid; washing the solid by deionized water, and drying the solid in vacuum until the weight is constant to obtain chlorinated polysulfone;
A3, mixing the chlorinated polysulfone, 4-vinylpyridine, sodium methallyl sulfonate and DMSO to obtain mixed solid-liquid; adding cuprous bromide into the mixed solid-liquid under the nitrogen atmosphere, and reacting for 12 hours at 100-120 ℃ with mechanical stirring at 100-200r/min to obtain a product;
a4, transferring the product into methanol, precipitating and filtering repeatedly, and cleaning with methanol to obtain a solid with cuprous bromide removed; the solid was dried under vacuum at 80 ℃ to constant weight to give a solid zwitterionic modified polysulfone.
3. The method for preparing the corrosion-resistant alkaline water electrolysis hydrogen production membrane according to claim 2, wherein in the step A1, the dosage ratio of polysulfone to chloroform is 50g to 100mL; in the step A2, the frequency of ultraviolet irradiation is 10-20KHz, and the duration of ultraviolet irradiation is 30-60min.
4. The method for preparing the corrosion-resistant alkaline water electrolysis hydrogen production membrane according to claim 3, wherein in the step A3, the dosage ratio of the polysulfone chloride, the 4-vinylpyridine, the sodium methallyl sulfonate, the DMSO and the cuprous bromide is 30g:5-10g:15-20g:100mL; in step A4, the amount of methanol was 300mL.
5. The method for preparing the corrosion-resistant electrolytic alkaline water hydrogen production membrane according to claim 1, wherein in the step S1, the method for preparing the microporous additive comprises the following steps:
B1, uniformly mixing trimethoxy silane and a platinum catalyst S-201, and then adding the rest trimethoxy silane, methyl methacrylate and a polymerization inhibitor phenothiazine to obtain a mixture; reacting the mixture at 100-110 ℃ for 2 hours, and then decompressing, distilling and filtering to obtain coupling agent liquid;
B2, uniformly mixing gamma-mercaptopropyl trimethoxy silane and coupling agent liquid to obtain complex coupling agent liquid;
b3, mixing aluminum oxide, zirconium dioxide and titanium dioxide to obtain an inorganic mixture; mixing and stirring the inorganic mixture and 1mol/L NaOH solution for 5-10min, and filtering to obtain an inorganic mixture after alkali treatment; ball milling the inorganic mixture after alkali treatment to obtain an inorganic powder mixture with the particle size of 300-400 mu m; mixing the mixture of the upper and inorganic powder and the compound agent liquid, and stirring at high speed to obtain the microporous additive.
6. The method for preparing the corrosion resistant alkaline water electrolysis hydrogen production membrane according to claim 5, wherein in the step B1, the dosage ratio of trimethoxysilane to platinum catalyst S-201 is 12g to 5g; the dosage ratio of the rest trimethoxy silane, methyl methacrylate and polymerization inhibitor phenothiazine is 110g to 100-126g to 2-3g.
7. The method for preparing the corrosion resistant alkaline water electrolysis hydrogen production membrane according to claim 6, wherein in the step B2, the dosage ratio of gamma-mercaptopropyl trimethoxysilane to coupling agent liquid is 20g:10-20g.
8. The method for preparing the corrosion resistant electrolytic alkaline water hydrogen production membrane according to claim 7, wherein in the step B2, the dosage ratio of alumina, zirconia and titania is 100g to 100g; the dosage ratio of the inorganic powder mixture to the coupling agent liquid is 300g to 5-10g.
9. The method for preparing the corrosion-resistant alkaline water electrolysis hydrogen production diaphragm according to claim 1, wherein the dosage ratio of the zwitterionic modified polysulfone to the NMP to the microporous additive is 30-50g:200mL:5-10g.
10. The method for preparing a corrosion resistant electrolytic alkaline water hydrogen production membrane according to claim 1, wherein the post-process treatment step comprises: pre-pressing the diaphragm to form, and then adding the diaphragm into deionized water to clean for three times to obtain a cleaned diaphragm; and (3) putting the diaphragm into a vacuum drying oven at 70 ℃ to be dried for 10-20min, so as to obtain the corrosion-resistant electrolytic alkaline water hydrogen production diaphragm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4996271A (en) * | 1987-12-11 | 1991-02-26 | National Research Council Of Canada/Conseil De Recherches Canada | Method of manufacturing halogenated aromatic polysulfone compounds and the compounds so produced |
| US4999415A (en) * | 1987-12-11 | 1991-03-12 | National Research Council Of Canada/Conseil De Recherches Canada | Aromatic polysulfone compounds and their manufacture |
| US5789487A (en) * | 1996-07-10 | 1998-08-04 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
| JP5664818B1 (en) * | 2013-09-20 | 2015-02-04 | ダイキン工業株式会社 | Polymer porous membrane and method for producing polymer porous membrane |
| CN105085847A (en) * | 2014-05-23 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Aromatic polymer sulfonamide, and preparation method and application thereof |
| CN117866262A (en) * | 2024-01-23 | 2024-04-12 | 武汉理工大学 | Preparation method of diaphragm for hydrogen production by alkaline water electrolysis |
| WO2024140890A1 (en) * | 2022-12-28 | 2024-07-04 | 嘉庚创新实验室 | Organic-inorganic composite separator for production of hydrogen by alkaline water electrolysis, and preparation method therefor |
-
2024
- 2024-08-15 CN CN202411121496.8A patent/CN119020821A/en active Pending
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| US4996271A (en) * | 1987-12-11 | 1991-02-26 | National Research Council Of Canada/Conseil De Recherches Canada | Method of manufacturing halogenated aromatic polysulfone compounds and the compounds so produced |
| US4999415A (en) * | 1987-12-11 | 1991-03-12 | National Research Council Of Canada/Conseil De Recherches Canada | Aromatic polysulfone compounds and their manufacture |
| US5789487A (en) * | 1996-07-10 | 1998-08-04 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
| JP5664818B1 (en) * | 2013-09-20 | 2015-02-04 | ダイキン工業株式会社 | Polymer porous membrane and method for producing polymer porous membrane |
| WO2015041119A1 (en) * | 2013-09-20 | 2015-03-26 | ダイキン工業株式会社 | Polymer porous membrane and method for manufacturing polymer porous membrane |
| CN105085847A (en) * | 2014-05-23 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Aromatic polymer sulfonamide, and preparation method and application thereof |
| WO2024140890A1 (en) * | 2022-12-28 | 2024-07-04 | 嘉庚创新实验室 | Organic-inorganic composite separator for production of hydrogen by alkaline water electrolysis, and preparation method therefor |
| CN117866262A (en) * | 2024-01-23 | 2024-04-12 | 武汉理工大学 | Preparation method of diaphragm for hydrogen production by alkaline water electrolysis |
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