CN117659482B - Cation-anion irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane and preparation method and application thereof - Google Patents
Cation-anion irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane and preparation method and application thereof Download PDFInfo
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- CN117659482B CN117659482B CN202311662315.8A CN202311662315A CN117659482B CN 117659482 B CN117659482 B CN 117659482B CN 202311662315 A CN202311662315 A CN 202311662315A CN 117659482 B CN117659482 B CN 117659482B
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- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000003460 sulfonic acids Chemical class 0.000 title description 31
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011812 mixed powder Substances 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 23
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical class OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001450 anions Chemical class 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 18
- 150000001768 cations Chemical class 0.000 claims abstract description 17
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 10
- KQBQGJUYKRHHKW-UHFFFAOYSA-N [F].OS(F)(=O)=O Chemical compound [F].OS(F)(=O)=O KQBQGJUYKRHHKW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000011049 filling Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical group FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 2
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 claims 1
- 230000005251 gamma ray Effects 0.000 abstract description 7
- 238000005266 casting Methods 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 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 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 229910000851 Alloy steel Inorganic materials 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229910001456 vanadium ion Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 3
- 239000003011 anion exchange membrane Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010096 film blowing Methods 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 1
- -1 4-vinylbenzyl Chemical group 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明公开了一种阴阳离子辐照接枝改性全氟磺酸离子交换膜及其制备方法和应用。制备方法包括以下步骤：将包含全氟磺酸氟型树脂粉料、阴离子改性剂、阳离子改性剂和接枝助剂的原料混合，烘干得到混合粉料，置于反应釜中，加热升温，排除气体并充入惰性气体后密封，伽马射线辐照，冷却至室温，得到接枝混合粉料；将接枝混合粉料挤出造粒，冷却，干燥，得到母粒；将母料再次加热，进行二次伽马射线辐照，冷却至室温，得到辐照接枝母料；将辐照接枝母料熔融挤出流延成膜，冷却后得到阴阳离子辐照接枝改性全氟磺酸树脂膜；将阴阳离子辐照接枝改性全氟磺酸树脂膜依次经钠化和氢化，得到阴阳离子辐照接枝改性全氟磺酸离子交换膜。The invention discloses an anion and cation irradiation grafted modified perfluorosulfonic acid ion exchange membrane and its preparation method and application. The preparation method comprises the following steps: mixing raw materials including perfluorosulfonic acid fluorine resin powder, anion modifier, cation modifier and grafting auxiliary agent, drying to obtain a mixed powder, placing in a reaction kettle, heating and raising the temperature, removing gas and filling with inert gas and sealing, gamma ray irradiation, cooling to room temperature, and obtaining a grafted mixed powder; extruding and granulating the grafted mixed powder, cooling, and drying to obtain a master batch; heating the master batch again, performing secondary gamma ray irradiation, and cooling to room temperature to obtain an irradiated grafted master batch; melt-extruding and casting the irradiated grafted master batch into a film, and obtaining anion and cation irradiation grafted modified perfluorosulfonic acid resin membrane after cooling; and sequentially subjecting the anion and cation irradiation grafted modified perfluorosulfonic acid resin membrane to sodiumization and hydrogenation to obtain anion and cation irradiation grafted modified perfluorosulfonic acid ion exchange membrane.
Description
Technical Field
The invention relates to an anion-cation irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane and a preparation method and application thereof, belonging to the field of vanadium battery ion exchange membranes.
Background
Compared with other energy storage batteries, the all-vanadium redox flow battery (VRB) has the characteristics of high energy efficiency, short response time, low self-discharge rate, long cycle life and the like, and is widely focused and applied. The vanadium redox flow battery is considered as an efficient energy storage/conversion system, has a design capacity which is much larger than that of a conventional battery, has obvious advantages, can be connected to a power system in a large scale, and can be widely applied to large-scale energy storage equipment such as load balancing, power grid peak shaving, uninterruptible Power Supply (UPS) and the like.
Currently, as one of the key components of redox flow batteries, membrane materials are used to separate both positive and negative half-cells, and also provide channels for charge balancing ions to ensure the cell circuit. In recent years, basic research and industrial application research on membrane materials for vanadium batteries have been paid attention to and have been greatly developed, and the membrane materials for vanadium batteries can be classified into Cation Exchange Membranes (CEM), anion Exchange Membranes (AEMS), amphoteric ion exchange membranes (ALEM) and porous membranes according to the mechanism exerted. The resin material of the Nafion membrane is sulfonated tetrafluoroethylene polymer, has high conductivity and is the most widely used cation exchange membrane material, but the vanadium permeability is high; while anion exchange membranes reduce vanadium ion permeation due to Donnan rejection, but are limited by low conductivity; thus, the preparation of amphoteric ion exchange membranes having both high conductivity and low vanadium ion permeability in a manner suitable for mass production is a research direction in the art.
Disclosure of Invention
In view of the problems existing in the background art, the invention aims to provide an anion-cation irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane and a preparation method thereof, which are characterized in that the perfluorinated sulfonic acid fluororesin is subjected to high-efficiency and uniform anion-cation irradiation grafting modification, on one hand, a branched structure with a higher proportion is given to the perfluorinated sulfonic acid fluororesin, the crystallinity of the resin is reduced, the amorphous proportion is improved, the resin has stable fluidity and viscoelasticity in a processing temperature range, the processing and the forming are easier, and the amphoteric perfluorinated sulfonic acid ion exchange membrane with uniform thickness and smooth and flat surface is successfully prepared by an extrusion casting method; on the other hand, the anion-cation irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane prepared by the method has uniformly distributed grafted anions and cations, so that the anions maintain good conductivity of the membrane, the Donnan rejection effect of the cations reduces the permeation of vanadium ions, the barrier property of the vanadium ions is improved, and the comprehensive service performance of the vanadium battery membrane is greatly improved.
In order to achieve the above purpose, the invention provides a preparation method of cation-anion irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane, which comprises the following steps: (1) Fully mixing raw materials comprising perfluorosulfonic acid fluorine resin powder, an anionic modifier, a cationic modifier and a grafting auxiliary agent in a high-speed stirrer according to a proportion, drying to obtain mixed powder, drying the mixed powder, placing the mixed powder into a reaction kettle, heating to 95-100 ℃, discharging gas, filling inert gas, sealing, performing gamma ray irradiation, and cooling to room temperature at an irradiation dose of 2.5-3Mrad to obtain grafting mixed powder; (2) Extruding and granulating the grafting mixed powder in the step (1) by using an exhaust double-screw extruder, cooling and drying to obtain master batch; (3) Heating the master batch in the step (2) to 95-100 ℃ again, performing secondary gamma ray irradiation with the irradiation dose of 2.5-3.5Mrad, and cooling to room temperature to obtain an irradiation grafting master batch; (4) Putting the irradiation grafting master batch in the step (3) into a single screw extruder, carrying out melt extrusion casting to form a film, and cooling to obtain an anion-cation irradiation grafting modified perfluorinated sulfonic acid resin film; (5) And (3) sequentially carrying out sodium modification and hydrogenation on the anion-cation irradiation grafting modified perfluorinated sulfonic acid resin membrane in the step (4) to obtain the anion-cation irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane.
Optionally, the anionic modifier is one or a combination of styrene sulfonic acid, sodium styrene sulfonate and 3-propyl methacrylate sulfonate.
Optionally, the cationic modifier is one or a combination of dimethylaminoethyl methacrylate, N- (4-vinylbenzyl) -N, N-dialkylamine, N-isopropylacrylamide, methacryloyloxyethyl trimethyl ammonium chloride and 1-allyl-3-vinylimidazole acetate.
Optionally, the grafting aid is para-fluorostyrene.
Optionally, the feedstock further comprises a solvent; the solvent is dichloroethane or toluene.
Optionally, the mass ratio of the perfluorosulfonic acid fluorine resin powder to the anionic modifier to the cationic modifier to the grafting auxiliary to the solvent is 100 (3-5): 5-8): 0.8-1.2: (10-20).
Optionally, the drying temperature in the step (1) is 90-100 ℃; the times of exhausting the gas and filling the inert gas are 3-5 times; the inert gas is nitrogen or argon.
Optionally, the vented twin screw extruder of step (2) and the single screw extruder of step (3) have screws, barrels and dies made of corrosion-resistant nickel-base alloy steel; the temperature of each section of the exhaust double-screw extruder is 275-295 ℃, and the temperature of a machine head is 280-285 ℃; the temperature of each section of the single screw extruder is 270-295 ℃, and the temperature of the machine head is 286-290 ℃.
Optionally, the sodium modification and hydrogenation of the step (5) are carried out, specifically, the anion-cation irradiation grafting modified perfluorinated sulfonic acid resin membrane in the step (4) is sequentially subjected to sodium modification by Na0H methanol solution with the concentration of 25wt% and hydrogenation by hydrochloric acid solution with the concentration of 16wt%, and deionized water is used for cleaning and drying, thus obtaining the anion-cation irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane.
The invention also provides the cation-anion irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane prepared by the method.
The invention also provides application of the cation-anion irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane, which is used for vanadium batteries.
The beneficial effects of the invention are as follows:
1. According to the application, the anionic modifier, the cationic modifier and the grafting auxiliary agent are uniformly distributed on the surface of the powder through the solvent, then the solvent is removed by drying, then the activated resin is irradiated by gamma rays under the protection of inert gas, the specific anionic and cationic modifier is grafted on the activated perfluorinated sulfonic acid fluororesin by the grafting auxiliary agent, the branching degree of the perfluorinated sulfonic acid fluororesin is improved, the perfluorinated sulfonic acid fluororesin keeps stable fluidity in the processing process, the shearing-thinning non-Newtonian fluid property is weakened, the proper viscoelasticity is provided, and the amphoteric perfluorinated sulfonic acid ion exchange membrane is convenient to prepare by extrusion casting processing.
2. The method can obtain the amphoteric perfluorinated sulfonic acid resin film with uniform film thickness and smooth surface, and the permeability of vanadium ions of the amphoteric perfluorinated sulfonic acid resin film is obviously reduced under the condition of keeping good conductivity.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Raw materials: perfluorosulfonic acid fluoro resin powder, dupont; other raw materials are commercially available.
Example 1
(1) Fully mixing raw materials of perfluorosulfonic acid fluorine-type resin powder, sodium styryl sulfonate, dimethylaminoethyl methacrylate, p-fluorostyrene and dichloroethane in a high-speed stirrer according to a proportion, drying at 90 ℃ to obtain mixed powder, drying the mixed powder, placing the mixed powder in a reaction kettle, heating to 95 ℃, removing gas, filling nitrogen or argon for 3 times, sealing, radiating with gamma rays, and cooling to room temperature to obtain grafted mixed powder; the mass ratio of perfluorosulfonic acid fluorine resin powder to styryl sodium sulfonate to dimethylaminoethyl methacrylate to p-fluorostyrene to dichloroethane is 100:3:5:0.8:10;
(2) Extruding and granulating the grafting mixed powder in the step (1) by using an exhaust double-screw extruder, cooling and drying to obtain master batch; the vented twin screw extruder has a screw, barrel and die head made of corrosion resistant nickel-based alloy steel; the temperature of each section of the exhaust double-screw extruder is 290-295 ℃ and the temperature of the machine head is 285 ℃;
(3) Heating the master batch in the step (2) to 95 ℃ again, performing secondary gamma ray irradiation with the irradiation dose of 2.5Mrad, and cooling to room temperature to obtain an irradiation grafting master batch;
(4) Putting the irradiation grafting master batch in the step (3) into a single screw extruder, carrying out melt extrusion casting to form a film, and cooling to obtain an anion-cation irradiation grafting modified perfluorinated sulfonic acid resin film; the single screw extruder has a screw, a barrel, and a die head made of a corrosion-resistant nickel-base alloy steel; the temperature of each section of the single screw extruder is 290-295 ℃ and the temperature of the machine head is 290 ℃;
(5) And (3) sequentially carrying out sodium treatment on the cation-anion irradiation grafting modified perfluorinated sulfonic acid resin membrane in the step (4) by using a Na0H methanol solution with the concentration of 25wt% and hydrogenation by using a hydrochloric acid solution with the concentration of 16wt%, washing by using deionized water, and drying to obtain the cation-anion irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane.
Example 2
(1) Fully mixing perfluorosulfonic acid fluorine-type resin powder, methacrylic acid 3-sulfonic acid propyl ester, N-isopropyl acrylic acid amide, p-fluorostyrene and toluene in a high-speed stirrer according to a proportion, drying at 100 ℃ to obtain mixed powder, drying the mixed powder, placing the mixed powder into a reaction kettle, heating to 100 ℃, exhausting gas, filling nitrogen or argon for 5 times, sealing, radiating with gamma rays, radiating with the dose of 3Mrad, and cooling to room temperature to obtain grafted mixed powder; the mass ratio of perfluorosulfonic acid fluorine resin powder to methacrylic acid 3-sulfopropyl ester to N-isopropyl acrylamide to p-fluorostyrene to toluene is 100:5:8:1.2:20;
(2) Extruding and granulating the grafting mixed powder in the step (1) by using an exhaust double-screw extruder, cooling and drying to obtain master batch; the vented twin screw extruder has a screw, barrel and die head made of corrosion resistant nickel-based alloy steel; the temperature of each section of the exhaust double-screw extruder is 275-285 ℃ and the temperature of a machine head is 280 ℃;
(3) Heating the master batch in the step (2) to 100 ℃ again, performing secondary gamma ray irradiation with the irradiation dose of 3.5Mrad, and cooling to room temperature to obtain an irradiation grafting master batch;
(4) Putting the irradiation grafting master batch in the step (3) into a single screw extruder, carrying out melt extrusion, carrying out blow molding to form a film through a film blowing machine head, and cooling to obtain an anion-cation irradiation grafting modified perfluorinated sulfonic acid resin film; the single screw extruder has a screw, a barrel, and a die head made of a corrosion-resistant nickel-base alloy steel; the temperature of each section of the single screw extruder is 270-288 ℃ and the temperature of the machine head is 286 ℃;
(5) And (3) sequentially carrying out sodium treatment on the cation-anion irradiation grafting modified perfluorinated sulfonic acid resin membrane in the step (4) by using a Na0H methanol solution with the concentration of 25wt% and hydrogenation by using a hydrochloric acid solution with the concentration of 16wt%, washing by using deionized water, and drying to obtain the cation-anion irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane.
Example 3
(1) Fully mixing perfluorosulfonic acid fluorine-type resin powder, methacrylic acid 3-sulfonic acid propyl ester, 1-allyl-3-vinyl imidazole acetate, p-fluorostyrene and dichloroethane in a high-speed stirrer according to a proportion, drying at 95 ℃ to obtain mixed powder, drying the mixed powder, placing the mixed powder in a reaction kettle, heating to 98 ℃, exhausting gas, filling nitrogen or argon for 4 times, sealing, radiating with gamma rays, radiating with the dose of 2.8Mrad, and cooling to room temperature to obtain grafted mixed powder; the mass ratio of perfluorosulfonic acid fluorine resin powder to methacrylic acid 3-sulfonic acid propyl ester to 1-allyl-3-vinyl imidazole acetate to p-fluorostyrene to dichloroethane is 100:4:6.5:1:15;
(2) Extruding and granulating the grafting mixed powder in the step (1) by using an exhaust double-screw extruder, cooling and drying to obtain master batch; the vented twin screw extruder has a screw, barrel and die head made of corrosion resistant nickel-based alloy steel; the temperature of each section of the exhaust double-screw extruder is 280-290 ℃, and the temperature of a machine head is 283 ℃;
(3) Heating the master batch in the step (2) to 98 ℃ again, performing secondary gamma ray irradiation with the irradiation dose of 2.8Mrad, and cooling to room temperature to obtain an irradiation grafting master batch;
(4) Putting the irradiation grafting master batch in the step (3) into a single screw extruder, carrying out melt extrusion, carrying out blow molding to form a film through a film blowing machine head, and cooling to obtain an anion-cation irradiation grafting modified perfluorinated sulfonic acid resin film; the single screw extruder has a screw, a barrel, and a die head made of a corrosion-resistant nickel-base alloy steel; the temperature of each section of the single-screw extruder is 285-290 ℃ and the temperature of a machine head is 288 ℃;
(5) And (3) sequentially carrying out sodium treatment on the cation-anion irradiation grafting modified perfluorinated sulfonic acid resin membrane in the step (4) by using a Na0H methanol solution with the concentration of 25wt% and hydrogenation by using a hydrochloric acid solution with the concentration of 16wt%, washing by using deionized water, and drying to obtain the cation-anion irradiation grafting modified perfluorinated sulfonic acid ion exchange membrane.
Comparative example 1
The procedure of example 3 was repeated except that p-fluorostyrene was not added.
Performance testing
The properties of the example and comparative resins and films, respectively, were tested and the specific test data are shown in Table 1 below.
TABLE 1
| Test item | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Appearance of | Smooth surface | Smooth surface | Smooth surface | Micro roughness of surface |
| Thickness/um | 20±0.6 | 20±0.6 | 20±0.6 | 23±1 |
| Conductivity/mS/cm at 25 ℃ | 102.0 | 102.5 | 101.8 | 100.5 |
| Vanadium ion permeability/cm -2/cm | 0.75×10-7 | 0.82×10-7 | 0.71×10-7 | 1.3×10-7 |
As can be seen from the data of examples and comparative examples, the invention adopts the perfluorosulfonic acid fluororesin assisted by the para-fluorostyrene to carry out anion-cation irradiation grafting modification, so that the grafting rate of the perfluorosulfonic acid fluororesin is greatly improved, the viscoelasticity of the resin is further improved under the condition that the flow rate and the thermal stability of a branched structure are maintained, the processability is improved, the film product prepared by extrusion casting is flat and smooth, the thickness is thinner and more uniform, the dimensional stability is good, the conductivity retention rate of the perfluorosulfonic acid ion exchange film after sodium treatment and acidification treatment is high, the vanadium ion isolation effect is obviously improved, and the comprehensive performance requirements of practical use are met.
The above examples are given for clarity of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (5)
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