CN109860675B - New energy automobile fuel cell ion exchange membrane and preparation method thereof - Google Patents
New energy automobile fuel cell ion exchange membrane and preparation method thereof Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 44
- DGNFBTNLXUJXDK-UHFFFAOYSA-N 5-ethenyl-2-fluoro-1H-imidazole Chemical compound C(=C)C=1N=C(NC=1)F DGNFBTNLXUJXDK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012528 membrane Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000005342 ion exchange Methods 0.000 claims abstract description 15
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 claims abstract description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 230000005855 radiation Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000002390 rotary evaporation Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- GSGPUGZLDGHFDO-UHFFFAOYSA-N 2-(chloromethoxy)propane Chemical compound CC(C)OCCl GSGPUGZLDGHFDO-UHFFFAOYSA-N 0.000 claims description 9
- LNFZAUNJFRYZLE-UHFFFAOYSA-N 2-fluoro-1h-imidazole Chemical compound FC1=NC=CN1 LNFZAUNJFRYZLE-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- AGJNVRIYBAVIMG-UHFFFAOYSA-N C=C[N+]1=CNC=C1.[F-] Chemical compound C=C[N+]1=CNC=C1.[F-] AGJNVRIYBAVIMG-UHFFFAOYSA-N 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- -1 vinyl fluoride imidazole salt Chemical compound 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- GPRYQDDHZJJZRK-UHFFFAOYSA-N C=CC1=NC=CN1.F Chemical compound C=CC1=NC=CN1.F GPRYQDDHZJJZRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-O 1-ethenylimidazole;hydron Chemical compound C=CN1C=C[NH+]=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-O 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000003011 anion exchange membrane Substances 0.000 description 9
- SKCUYCAPQSWGBP-UHFFFAOYSA-N bis(2-methylprop-2-enyl) carbonate Chemical compound CC(=C)COC(=O)OCC(C)=C SKCUYCAPQSWGBP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a preparation method of an ion exchange membrane for a new energy automobile fuel cell, which comprises the following steps: preparing vinyl fluoroimidazole, (II) preparing vinyl fluoroimidazole salt, (III) preparing vinyl fluoroimidazole salt, 2,3,4,5, 6-pentafluorostyrene, acrylonitrile and a bis (2-methallyl) carbonate copolymer membrane material, and (IV) carrying out ion exchange. The invention also discloses the ion exchange membrane for the fuel cell of the energy automobile, which is prepared according to the preparation method. The ion exchange membrane for the fuel cell of the energy automobile disclosed by the invention has the advantages of better alkali resistance, mechanical property, higher ionic conductivity, thermal stability and chemical stability.
Description
Technical Field
The invention relates to the technical field of new energy automobiles, in particular to an ion exchange membrane of a fuel cell of a new energy automobile and a preparation method thereof.
Background
In recent years, with the increasing environmental and energy problems, the demand for improving the global environment and improving the physical quality of the body is more and more urgent, and the attention on the utilization of clean and renewable energy is higher and higher. The typical representative new energy automobile reasonably utilizing clean renewable energy is widely used due to the advantages of zero emission, low noise, high energy utilization rate and the like, and gradually enters thousands of households, so that the new energy automobile becomes a main vehicle for people to travel. According to different driving, the new energy automobile mainly comprises a fuel cell automobile, a hybrid electric automobile and a hydrogen energy power automobile. Among them, fuel cell vehicles have attracted extensive attention from research in the industry because of their advantages of environmental protection, long duration, etc.
The key part in the fuel cell automobile is the fuel cell, the comfort and the safety of the automobile are directly determined by the performance of the fuel cell, and the fuel cell has great influence on the development of new energy automobiles. Fuel cells are classified into different types according to the electrolyte used, and among them, anion exchange membrane fuel cells are a popular subject of research in recent years. The anion exchange membrane is one of the important parts of the anion exchange membrane, plays a dual role in blocking fuel and transferring anions in the fuel cell, and the service life and the cell efficiency of the fuel cell are directly influenced by the performance of the anion exchange membrane.
The traditional anion exchange membrane for the fuel cell is a quaternary ammonium salt polymer membrane, the position and the degree of halomethylation of the membrane are difficult to accurately control in the halomethylation process, so that a plurality of side reactions are caused, the overall performance of the polymer is influenced, and the polymer anion exchange membrane obtained by the traditional preparation process has poor thermal stability and chemical stability, is easy to degrade particularly at a higher temperature or under an alkaline condition, so that the performance and the service life of the fuel cell are influenced. The imidazole salt anion-exchange membrane has better chemical stability due to the pi-conjugation effect of imidazole rings, thereby causing extensive attention of researchers. However, it was found that imidazole salt based anion exchange membranes also degrade under strongly alkaline conditions.
Therefore, a more effective method is sought, and the ion exchange membrane for the new energy automobile fuel cell, which has good alkali resistance, excellent mechanical properties, good heat resistance and good chemical stability, is developed, meets the market demand, has wide market value and application prospect, and has a positive effect on promoting the development of the new energy automobile industry.
Disclosure of Invention
The invention mainly aims to provide an ion exchange membrane for a new energy automobile fuel cell, which has better alkali resistance, mechanical property, higher ionic conductivity, thermal stability and chemical stability, and a preparation method of the ion exchange membrane for the new energy automobile fuel cell.
In order to achieve the above purpose, the invention provides a preparation method of an ion exchange membrane for a new energy automobile fuel cell, which comprises the following steps:
step S1 preparation of vinyl fluoroimidazole: dissolving fluoroimidazole and 1, 2-epoxy-4-vinylcyclohexane in an organic solvent, adding an alkaline catalyst and a polymerization inhibitor, stirring and reacting for 6-8 hours at 70-80 ℃, filtering, carrying out rotary evaporation, adding dichloromethane and a sodium hydroxide solution with the mass fraction of 5-10%, separating, taking an oil phase, washing with water for 3-5 times, removing water by using anhydrous magnesium sulfate, filtering, and removing dichloromethane by rotary evaporation to obtain vinylfluoroimidazole;
step S2 preparation of vinylimidazolium fluoride salt: stirring the vinyl fluoroimidazole and chloromethyl isopropyl ether prepared in the step S1 at room temperature for 12-15 hours under the nitrogen atmosphere, washing the product with diethyl ether for 3-5 times, and then carrying out vacuum drying at room temperature for 18-24 hours to obtain vinyl fluoroimidazole salt;
step S3 preparation of membrane material: mixing the vinyl fluoride imidazole salt prepared in the step S2, 2,3,4,5, 6-pentafluorostyrene, acrylonitrile and bis (2-methallyl) carbonate, performing ultrasonic treatment for 10-15 minutes, dripping the mixture into a template, placing the template into a radiation field in the atmosphere of nitrogen or inert gas, and performing radiation by adopting a cobalt 60-gamma radiation method for 35-45 minutes to perform polymerization reaction to obtain a membrane material;
step S4 ion exchange: soaking the membrane material prepared in the step S3 in 0.5-1mol/L KOH solution at the temperature of 55-65 ℃ for 24-48 hours for ion exchange; the membrane is washed by deionized water until the eluent is neutral.
Preferably, the mass ratio of the fluoroimidazole, the 1, 2-epoxy-4-vinylcyclohexane, the organic solvent, the basic catalyst and the polymerization inhibitor in the step S1 is 2.8:1 (20-25): 1-2: 0.3-0.5.
Preferably, the organic solvent is selected from one or more of dichloromethane, tetrahydrofuran and isopropanol.
Preferably, the basic catalyst is at least one selected from sodium carbonate and potassium carbonate.
Further, the polymerization inhibitor is preferably hydroquinone.
Preferably, the mass ratio of the vinyl fluoroimidazole to the chloromethyl isopropyl ether in step S2 is 4.35: 1.
Preferably, the mass ratio of the vinyl imidazole fluoride salt, the 2,3,4,5, 6-pentafluorostyrene, the acrylonitrile and the bis (2-methallyl) carbonate in the step S3 is 4:1:1 (0.1-0.3).
Preferably, the inert gas is selected from one of helium, neon and argon.
An ion exchange membrane for a new energy automobile fuel cell is prepared by adopting the preparation method of the ion exchange membrane for the new energy automobile fuel cell.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the ion exchange membrane for the new energy automobile fuel cell disclosed by the invention is simple and easy to prepare, low in equipment dependence, mild in reaction condition, easy to obtain raw materials, low in preparation cost, safe and environment-friendly to use, and does not use medicines which pollute the environment greatly.
(2) The ion exchange membrane for the new energy automobile fuel cell disclosed by the invention overcomes the technical problems of poor dimensional stability, weather resistance and chemical resistance stability, poor conductivity, especially weak alkali resistance of the traditional ion exchange membrane for the fuel cell, and has better alkali resistance, mechanical property, higher ionic conductivity, thermal stability and chemical stability.
(3) According to the ion exchange membrane for the new energy automobile fuel cell, active hydrogen at the 2-position of an imidazole ring is replaced by trifluoromethyl, the imidazole ring is connected with cyclohexane and a hydroxyl substituent for supplying electrons through reaction with 1, 2-epoxy-4-vinylcyclohexane, and the electronic effect and the steric effect have synergistic effect, so that the alkali resistance of the ion exchange membrane is improved; due to the addition of the fluorine-containing structure, on the other hand, the comprehensive performance, particularly the weather resistance and the dimensional stability of the film are improved; the bis (2-methallyl) carbonate is introduced to act as a cross-linking agent, so that a three-dimensional network structure is formed, and the comprehensive performance of the membrane is improved; the components have synergistic effect, so that the composite material has excellent comprehensive performance, does not contain toxic and harmful substances, has small environmental pollution, and is safe and environment-friendly to use.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
The raw materials used in the examples of the present invention were purchased from Mobei (Shanghai) Biotech limited.
Example 1
A preparation method of an ion exchange membrane for a new energy automobile fuel cell comprises the following steps:
step S1 preparation of vinyl fluoroimidazole: dissolving 28g of fluoroimidazole and 10g of 1, 2-epoxy-4-vinylcyclohexane in 200g of dichloromethane, adding 10g of sodium carbonate and 3g of hydroquinone, stirring and reacting at 70 ℃ for 6 hours, filtering, performing rotary evaporation, adding dichloromethane and a sodium hydroxide solution with the mass fraction of 5% for separating liquid, taking an oil phase, washing the oil phase for 3 times, removing water by using anhydrous magnesium sulfate, filtering, and removing the dichloromethane by rotary evaporation to obtain the vinylfluoroimidazole;
step S2 preparation of vinylimidazolium fluoride salt: 26.1g of vinyl fluoroimidazole prepared in the step S1 and 6g of chloromethyl isopropyl ether are stirred at room temperature for 12 hours under the nitrogen atmosphere, then products are washed by ethyl ether for 3 times, and then vacuum drying is carried out at room temperature for 18 hours, so as to obtain vinyl fluoroimidazole salt;
step S3 preparation of membrane material: mixing 24g of vinyl fluoride imidazole salt prepared in the step S2, 6g of 2,3,4,5, 6-pentafluorostyrene, 6g of acrylonitrile and 0.6g of bis (2-methylallyl) carbonate, performing ultrasonic treatment for 10 minutes, dripping the mixture into a template, placing the template into a radiation field in a nitrogen atmosphere, and performing radiation by using a cobalt 60-gamma radiation method for 35 minutes to perform polymerization reaction to obtain a membrane material;
step S4 ion exchange: soaking the membrane material prepared in the step S3 in 0.5mol/LKOH solution at 55 ℃ for 24 hours for ion exchange; the membrane is washed by deionized water until the eluent is neutral.
An ion exchange membrane for a new energy automobile fuel cell is prepared by adopting the preparation method of the ion exchange membrane for the new energy automobile fuel cell.
Example 2
A preparation method of an ion exchange membrane for a new energy automobile fuel cell comprises the following steps:
step S1 preparation of vinyl fluoroimidazole: dissolving 28g of fluoroimidazole and 10g of 1, 2-epoxy-4-vinylcyclohexane in 215g of tetrahydrofuran, adding 12g of potassium carbonate and 3.5g of hydroquinone, stirring at 73 ℃ for reaction for 6.5 hours, filtering, performing rotary evaporation, adding dichloromethane and a sodium hydroxide solution with the mass fraction of 6% for separating liquid, taking an oil phase, washing with water for 4 times, removing water by using anhydrous magnesium sulfate, filtering, and performing rotary evaporation to remove dichloromethane to obtain the vinylfluoroimidazole;
step S2 preparation of vinylimidazolium fluoride salt: stirring 26.1g of vinyl fluoroimidazole prepared in step S1 and 6g of chloromethyl isopropyl ether at room temperature for 13 hours under the nitrogen atmosphere, washing the product with diethyl ether for 4 times, and then performing vacuum drying at room temperature for 19.5 hours to obtain vinyl fluoroimidazole salt;
step S3 preparation of membrane material: mixing 24g of vinyl fluoride imidazole salt prepared in the step S2, 6g of 2,3,4,5, 6-pentafluorostyrene, 6g of acrylonitrile and 1g of bis (2-methylallyl) carbonate, performing ultrasonic treatment for 12.5 minutes, dripping the mixture into a template, placing the template into a radiation field in a helium atmosphere, and performing radiation by using a cobalt 60-gamma radiation method for 37 minutes to perform polymerization reaction to obtain a membrane material;
step S4 ion exchange: soaking the membrane material prepared in the step S3 in 0.6mol/LKOH solution at 57 ℃ for 30 hours for ion exchange; the membrane is washed by deionized water until the eluent is neutral.
An ion exchange membrane for a new energy automobile fuel cell is prepared by adopting the preparation method of the ion exchange membrane for the new energy automobile fuel cell.
Example 3
A preparation method of an ion exchange membrane for a new energy automobile fuel cell comprises the following steps:
step S1 preparation of vinyl fluoroimidazole: dissolving 28g of fluoroimidazole and 10g of 1, 2-epoxy-4-vinylcyclohexane in 235g of isopropanol, adding 16g of sodium carbonate and 4g of hydroquinone, stirring and reacting at 75 ℃ for 7 hours, filtering, performing rotary evaporation, adding dichloromethane and a sodium hydroxide solution with the mass fraction of 8% for separating, taking an oil phase, washing with water for 4 times, removing water by using anhydrous magnesium sulfate, filtering, and removing the dichloromethane by rotary evaporation to obtain the vinylfluoroimidazole;
step S2 preparation of vinylimidazolium fluoride salt: 26.1g of vinyl fluoroimidazole prepared in step S1 and 6g of chloromethyl isopropyl ether are stirred at room temperature for 14 hours under nitrogen atmosphere, and then products are washed by ethyl ether for 4 times and then vacuum-dried at room temperature for 22 hours to obtain vinyl fluoroimidazole salt;
step S3 preparation of membrane material: mixing 24g of vinyl imidazole fluoride salt prepared in the step S2, 6g of 2,3,4,5, 6-pentafluorostyrene, 6g of acrylonitrile and 1.2g of bis (2-methylallyl) carbonate, performing ultrasonic treatment for 13 minutes, dripping the mixture into a template, placing the template into a radiation field in a neon atmosphere, and performing radiation by using a cobalt 60-gamma radiation method for 40 minutes to perform polymerization reaction to obtain a membrane material;
step S4 ion exchange: soaking the membrane material prepared in the step S3 in 0.8mol/LKOH solution at 60 ℃ for 32g hours for ion exchange; the membrane is washed by deionized water until the eluent is neutral.
An ion exchange membrane for a new energy automobile fuel cell is prepared by adopting the preparation method of the ion exchange membrane for the new energy automobile fuel cell.
Example 4
A preparation method of an ion exchange membrane for a new energy automobile fuel cell comprises the following steps:
step S1 preparation of vinyl fluoroimidazole: dissolving 28g of fluoroimidazole and 10g of 1, 2-epoxy-4-vinylcyclohexane in 240g of organic solvent, adding 18g of basic catalyst and 4.5g of hydroquinone, stirring and reacting at 78 ℃ for 7.8 hours, filtering, carrying out rotary evaporation, adding dichloromethane and a sodium hydroxide solution with the mass fraction of 9% for separating liquid, taking an oil phase, washing with water for 5 times, removing water by using anhydrous magnesium sulfate, filtering, and carrying out rotary evaporation to remove dichloromethane to obtain the vinylfluoroimidazole; the organic solvent is a mixture formed by mixing dichloromethane, tetrahydrofuran and isopropanol according to a mass ratio of 2:1: 2; the alkaline catalyst is a mixture formed by mixing sodium carbonate and potassium carbonate according to the mass ratio of 3: 5;
step S2 preparation of vinylimidazolium fluoride salt: stirring 21.6g of vinyl fluoroimidazole prepared in step S1 and 6g of chloromethyl isopropyl ether at room temperature for 14.5 hours under the nitrogen atmosphere, washing the product with diethyl ether for 5 times, and then drying in vacuum at room temperature for 23 hours to obtain vinyl fluoroimidazole salt;
step S3 preparation of membrane material: mixing 24g of vinyl fluoride imidazole salt prepared in the step S2, 6g of 2,3,4,5, 6-pentafluorostyrene, 6g of acrylonitrile and 1.5g of bis (2-methylallyl) carbonate, performing ultrasonic treatment for 14 minutes, dripping the mixture into a template, placing the template into a radiation field in an argon atmosphere, and performing radiation by using a cobalt 60-gamma radiation method for 43 minutes to perform polymerization reaction to obtain a membrane material;
step S4 ion exchange: soaking the membrane material prepared in the step S3 in 0.9mol/LKOH solution at 63 ℃ for 42 hours for ion exchange; the membrane is washed by deionized water until the eluent is neutral.
An ion exchange membrane for a new energy automobile fuel cell is prepared by adopting the preparation method of the ion exchange membrane for the new energy automobile fuel cell.
Example 5
A preparation method of an ion exchange membrane for a new energy automobile fuel cell comprises the following steps:
step S1 preparation of vinyl fluoroimidazole: dissolving 28g of fluoroimidazole and 10g of 1, 2-epoxy-4-vinylcyclohexane in 250g of tetrahydrofuran, adding 20g of sodium carbonate and 5g of hydroquinone, stirring and reacting at 80 ℃ for 8 hours, filtering, performing rotary evaporation, adding dichloromethane and a sodium hydroxide solution with the mass fraction of 10% for separating, taking an oil phase, washing with water for 5 times, removing water by using anhydrous magnesium sulfate, filtering, and removing the dichloromethane by rotary evaporation to obtain the vinylfluoroimidazole;
step S2 preparation of vinylimidazolium fluoride salt: stirring 26.1g of vinyl fluoroimidazole prepared in step S1 and 6g of chloromethyl isopropyl ether at room temperature for 15 hours under the nitrogen atmosphere, washing the product with diethyl ether for 5 times, and then performing vacuum drying at room temperature for 24 hours to obtain vinyl fluoroimidazole salt;
step S3 preparation of membrane material: mixing 24g of vinyl fluoride imidazole salt prepared in the step S2, 6g of 2,3,4,5, 6-pentafluorostyrene, 6g of acrylonitrile and 1.8g of bis (2-methylallyl) carbonate, performing ultrasonic treatment for 15 minutes, dripping the mixture into a template, placing the template into a radiation field in a nitrogen atmosphere, and performing radiation by using a cobalt 60-gamma radiation method for 45 minutes to perform polymerization reaction to obtain a membrane material;
step S4 ion exchange: soaking the membrane material prepared in the step S3 in 1mol/LKOH solution at 65 ℃ for 48 hours for ion exchange; the membrane is washed by deionized water until the eluent is neutral.
An ion exchange membrane for a new energy automobile fuel cell is prepared by adopting the preparation method of the ion exchange membrane for the new energy automobile fuel cell.
Comparative example
An anion exchange membrane for a fuel cell is prepared by adopting the preparation method of the embodiment 1 of the Chinese invention patent CN 105694078B.
Meanwhile, in order to evaluate the specific technical effects of the ion exchange membrane for a fuel cell according to the present invention, the specific properties of examples 1 to 5 and the comparative example were tested in terms of ion conductivity, tensile properties, alkali resistance, and the like, respectively. The conductivity was measured by a two-electrode AC impedance method at an electrochemical workstation (Zahner IM6 EX), and the alkali resistance of the membrane was measured by immersing the membrane in 1mol/LKOH at 80 ℃ for 60 days and calculating the rate of change of the conductivity. The tensile properties of the films were measured at 25 ℃ using a universal prototype (Instron Model 3365) at a tensile rate of 5 mm/min. Each sample was tested 3 times and an average was obtained. Specific test data are shown in table 1:
TABLE 1
| Group number | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example |
| Alkali resistance (%) | 0.7 | 0.6 | 0.5 | 0.3 | 0.3 | 1 |
| Conductivity (Scm)-1) | 0.0480 | 0.0530 | 0.0560 | 0.0590 | 0.0620 | 0.0360 |
| Tensile Strength (MPa) | 44 | 45 | 45 | 47 | 48 | 40 |
| Elongation at Break (%) | 200 | 203 | 208 | 215 | 227 | 180 |
As can be seen from Table 1, compared with the ion exchange membrane in the prior art, the ion exchange membrane for the new energy automobile fuel cell prepared by the invention has improved performance indexes in the aspects of ionic conductivity, tensile property, alkali resistance and the like, and meets the use requirements of the ion exchange membrane for the fuel cell.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A preparation method of an ion exchange membrane for a new energy automobile fuel cell is characterized by comprising the following steps:
step S1 preparation of vinyl fluoroimidazole: dissolving fluoroimidazole and 1, 2-epoxy-4-vinylcyclohexane in an organic solvent, adding an alkaline catalyst and a polymerization inhibitor, stirring and reacting for 6-8 hours at 70-80 ℃, filtering, carrying out rotary evaporation, adding dichloromethane and a sodium hydroxide solution with the mass fraction of 5-10%, separating, taking an oil phase, washing with water for 3-5 times, removing water by using anhydrous magnesium sulfate, filtering, and removing dichloromethane by rotary evaporation to obtain vinylfluoroimidazole;
step S2 preparation of vinylimidazolium fluoride salt: stirring the vinyl fluoroimidazole and chloromethyl isopropyl ether prepared in the step S1 at room temperature for 12-15 hours under the nitrogen atmosphere, washing the product with diethyl ether for 3-5 times, and then carrying out vacuum drying at room temperature for 18-24 hours to obtain vinyl fluoroimidazole salt;
step S3 preparation of membrane material: mixing the vinyl fluoride imidazole salt prepared in the step S2, 2,3,4,5, 6-pentafluorostyrene, acrylonitrile and bis (2-methallyl) carbonate, performing ultrasonic treatment for 10-15 minutes, dripping the mixture into a template, placing the template into a radiation field in the atmosphere of nitrogen or inert gas, and performing radiation by adopting a cobalt 60-gamma radiation method for 35-45 minutes to perform polymerization reaction to obtain a membrane material;
step S4 ion exchange: soaking the membrane material prepared in the step S3 in 0.5-1mol/L KOH solution at the temperature of 55-65 ℃ for 24-48 hours for ion exchange; the membrane is washed by deionized water until the eluent is neutral.
2. The method for preparing an ion exchange membrane for a new energy automobile fuel cell as claimed in claim 1, wherein the mass ratio of the fluoroimidazole, the 1, 2-epoxy-4-vinylcyclohexane, the organic solvent, the alkaline catalyst and the polymerization inhibitor in step S1 is 2.8:1 (20-25): 1-2: 0.3-0.5.
3. The preparation method of the ion exchange membrane for the new energy automobile fuel cell according to claim 1, wherein the organic solvent is one or more selected from dichloromethane, tetrahydrofuran and isopropanol.
4. The preparation method of the ion exchange membrane for the new energy automobile fuel cell according to claim 1, wherein the alkaline catalyst is at least one selected from sodium carbonate and potassium carbonate.
5. The preparation method of the ion exchange membrane for the new energy automobile fuel cell as claimed in claim 1, wherein the polymerization inhibitor is hydroquinone.
6. The method according to claim 1, wherein in step S2, the mass ratio of the vinylimidazolium to the chloromethyl isopropyl ether is 4.35: 1.
7. The method according to claim 1, wherein the mass ratio of the vinylimidazole fluoride salt, 2,3,4,5, 6-pentafluorostyrene, acrylonitrile and bis (2-methallyl) carbonate in step S3 is 4:1:1 (0.1-0.3).
8. The method for preparing the ion exchange membrane for the new energy automobile fuel cell according to claim 1, wherein the inert gas is selected from one of helium, neon and argon.
9. The ion exchange membrane for the new energy automobile fuel cell is prepared by the preparation method of the ion exchange membrane for the new energy automobile fuel cell according to any one of claims 1 to 8.
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