CN116253817A - Fluorine ion exchange membrane and preparation method thereof - Google Patents
Fluorine ion exchange membrane and preparation method thereof Download PDFInfo
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- CN116253817A CN116253817A CN202310257120.9A CN202310257120A CN116253817A CN 116253817 A CN116253817 A CN 116253817A CN 202310257120 A CN202310257120 A CN 202310257120A CN 116253817 A CN116253817 A CN 116253817A
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- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 76
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 33
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 19
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 21
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- 239000012046 mixed solvent Substances 0.000 claims description 15
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 abstract description 20
- 230000008961 swelling Effects 0.000 abstract description 18
- 229910052720 vanadium Inorganic materials 0.000 abstract description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 23
- 229910001456 vanadium ion Inorganic materials 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 150000003460 sulfonic acids Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 102000004310 Ion Channels Human genes 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 239000012453 solvate Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- -1 sulfate radical Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- 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
- H01M8/0239—Organic resins; Organic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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 Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a fluoride ion exchange membrane and a preparation method thereof, and belongs to the technical field of ion exchange membrane preparation. The preparation method of the fluoride ion exchange membrane comprises the following steps of preprocessing fluoride ion exchange resin, and then preparing and drying the fluoride ion exchange resin to obtain the fluoride ion exchange membrane. The preparation method of the fluoride ion exchange membrane has scientific and reasonable design and simple steps, and the prepared fluoride ion exchange membrane has good vanadium resistance, can solve the problem of short service life of the membrane caused by excessive swelling of the membrane in electrolyte, improves the electrochemical performance of the vanadium battery, prolongs the service life of the battery and improves the benefit.
Description
Technical Field
The invention relates to the technical field of ion exchange membrane preparation, in particular to a fluoride ion exchange membrane and a preparation method thereof.
Background
The vanadium battery is called an all-vanadium redox flow battery (Vanadium Redox Battery), and is a redox battery with active substances in a circulating flowing liquid state. The vanadium battery mainly comprises three parts of electrolyte solution, electrodes and a diaphragm, and the electrolyte solution, the electrodes and the diaphragm jointly determine the comprehensive performance of the vanadium battery. Vanadium cell separators are ion selective semipermeable membranes, typically made from ions or polymers. It is sandwiched between two electrodes of electrolyte, and can be used as separator between positive electrode and negative electrode of cell, at the same time it also can be used as ion transmission channel for transmitting proton or sulfate radical plasma so as to maintain charge balance in the interior of cell.
The common diaphragm of the vanadium battery is provided with a fluoride ion exchange membrane, and the preparation method of the fluoride ion exchange membrane is usually a dynamic open stretching method, an extrusion film method and a casting method, but has the defects of complex process, expensive equipment and high membrane preparation cost, and the prepared fluoride ion exchange membrane has the defects of low crystallinity, anisotropy and the like. The fluoride ion exchange membrane prepared by the solution casting method has the advantages of uniform thickness, high crystallinity, isotropy and the like. However, the solvent used in the process of film preparation has a remarkable pungent smell, a lot of steam is generated under the high temperature condition in the film casting process, and polymer molecules and one or more solvent molecules form crystalline substances together in a certain combination form in the crystallization process, namely solvates.
Therefore, the battery diaphragm made of the perfluorosulfonic acid ion exchange resin is commonly used at present, and the battery diaphragm has relatively good vanadium resistance due to more sulfonic acid groups, so the battery diaphragm is more commonly used. However, proton transmission of the membrane excessively depends on sulfonation degree, sulfonic acid is a strong electrolyte, molecular chains of the membrane are negatively charged after ionization, and the ionic groups tend to straighten the conformation due to strong electrostatic repulsion, so that the volume of the membrane in electrolyte is expanded, and meanwhile, the sulfonic acid groups are strong polar groups, so that the liquid absorption rate and swelling degree of the membrane are increased, vanadium ion permeation is increased, and the service life of the membrane is shortened. Therefore, there is a need to find a fluoride ion-exchange membrane which prevents excessive swelling with a large residual amount of solvates in the electrolyte and has good vanadium-blocking performance.
Disclosure of Invention
In view of the above, the present invention is to provide a fluoride ion exchange membrane and a preparation method thereof, so as to solve the problem that the residual amount of solvate is large and the swelling degree is excessively increased in the preparation process of the fluoride ion exchange membrane, so that the vanadium resistance is reduced.
The invention solves the technical problems by the following technical means:
a fluoride ion exchange membrane comprising the following raw materials:
3-5 parts of perfluorosulfonic acid ion exchange resin, 20-40 parts of absolute ethyl alcohol, 22-46 parts of pure water, 4-9 parts of ethylene glycol, 15-30 parts of 1, 3-dimethyl imidazole cationic liquid, 0.1-0.5 part of N-methylolacrylamide and 5-9 parts of anhydrous sodium sulfate.
Further, the resistivity of the pure water is >0.5mΩ cm.
Further, the equivalent weight EW of the perfluorinated ion exchange resin is 900-1100g/eq.
The preparation method of the fluoride ion exchange membrane comprises the following steps:
(1) Adding perfluorosulfonic acid ion exchange resin into 1, 3-dimethyl imidazole cationic liquid, mechanically stirring at the water bath temperature of 60-70 ℃ to fully mix and dissolve, adding glycol, stirring and dissolving, then carrying out ice bath to reduce the temperature to 45 ℃, adding N-methylolacrylamide, vacuumizing to remove bubbles, pouring into a mould, curing at 115-125 ℃ for 6 hours, and taking out a cured product;
(2) Uniformly mixing absolute ethyl alcohol and pure water to prepare a mixed solvent, and dissolving a solidified substance in the mixed solvent to prepare a casting solution;
(3) Pouring the prepared casting solution into a casting plate, starting a heating device for heating, taking out the casting plate after all solvents in the casting solution are evaporated, adding anhydrous sodium sulfate on the surface for drying, and obtaining the fluoride ion exchange membrane with the thickness of 0.020-0.030 cm.
Further, the dissolution temperature of the solidified material in the step (2) is 200-220 ℃ and the dissolution time is 4-6h.
Further, the mass concentration of the casting solution in the step (2) is 1-5%.
Further, the temperature of the evaporating solvent in the step (3) is 105-115 ℃, and the heating time is 5-6h.
Further, in the step (3), the drying temperature is set to 40-55 ℃ and the drying time is set to 0.5-1h.
At a higher temperature, the perfluorinated sulfonic acid ion exchange resin is dissolved in the 1, 3-dimethyl imidazole cationic liquid, the ion channels of the perfluorinated sulfonic acid ion exchange resin are fully opened, the effective volume of the pore channels is increased, but the vanadium ion permeability is also increased, so that the 1, 3-dimethyl imidazole cationic liquid is grafted on the resin to form a uniform and effective medium with a sulfonate ion network to accelerate proton transfer, the conductivity of the resin is enhanced, the vanadium resistance is improved due to the uniform distribution of the medium on the membrane, but the formed medium is too much to reduce the ion channels, so that other ions are not beneficial to permeation. The 1, 3-dimethyl imidazole cationic liquid is fixed on a fluorine-containing resin molecular chain through chemical covalent bond, and further ethylene glycol and N-methylolacrylamide are added, so that the solid three-dimensional network structure can be formed by continuous hydrogen bond crosslinking on the perfluorosulfonic acid ion exchange resin to obtain a solidified substance, a certain ion channel can be maintained, meanwhile, the ion channel is prevented from being excessively swelled, the polarity is reduced, the subsequent diaphragm is limited to carry out hydration in the electrolyte, excessive bound water is avoided, and the residual solvent is reduced. The three-dimensional network structure formed on the surface reduces the expansion of the polymer network beam, reduces the difference of the ion concentration inside and outside, and reduces the free water from entering the polymer network to hydrolyze the groups. The solidified material is dissolved in a mixed solvent, the crystallinity on the diaphragm is increased by a solution casting method, the fluorine ion exchange membrane is prepared by a drying step and removing redundant solvent on the membrane by anhydrous sodium sulfate, and the prepared fluorine ion exchange membrane is not easy to excessively swell in electrolyte, has stable vanadium resistance, good electrochemical performance and prolonged service life.
The beneficial effects are that:
1. the fluorine ion exchange membrane prepared by the invention improves the structure of an ion channel, has low vanadium ion transmittance, good vanadium resistance and higher electrochemical performance, prolongs the service life in the use process, and improves the benefit.
2. The fluorine ion exchange membrane prepared by the invention prevents swelling caused by long-time soaking of the membrane in electrolyte while ensuring good electrochemical properties, and can maintain the volume problem and the vanadium ion permeability problem of the fluorine ion exchange membrane in the electrolyte environment for a long time.
Detailed Description
The present invention will be described in detail with reference to examples below:
the invention provides a fluoride ion exchange membrane and a preparation method thereof, but raw materials are required to be weighed before the fluoride ion exchange membrane is prepared, and the raw materials are weighed according to the data of table 1, and the specific proportions are as follows:
table 1 (Unit: g)
The starting materials were weighed according to table 1 to prepare fluoride ion-exchange membranes, wherein the preparation methods of examples 1-3 and comparative examples 1-8 were as follows:
example 1: preparation of fluoride ion exchange Membrane
The specific preparation steps of this example are as follows:
(1) Taking perfluorinated sulfonic acid ion exchange resin with equivalent weight EW of 1000g/eq, adding 1, 3-dimethyl imidazole cationic liquid, stirring at a mechanical stirring rate of 180r/min at a water bath temperature of 70 ℃ to fully mix and dissolve, adding ethylene glycol to continuously stir and dissolve at a rate of 180r/min, then carrying out ice bath, reducing the temperature to 45 ℃, adding N-methylolacrylamide, vacuumizing to remove bubbles, pouring into a mould, curing at 120 ℃ for 6h, and taking out a cured product;
(2) Uniformly mixing absolute ethyl alcohol with pure water with resistivity more than 0.5M omega cm to prepare a mixed solvent, adding a solidified substance, dissolving in a reaction kettle, keeping the temperature at 210 ℃ in the dissolving process, dissolving for 5 hours, and dissolving the solidified substance in the mixed solvent to prepare a casting solution with the mass concentration of 4%;
(3) Pouring the prepared casting solution into a casting plate, starting a heating device to heat to 110 ℃ and keeping for 5.5 hours, taking out the casting plate after all the solvent in the casting solution is evaporated, adding anhydrous sodium sulfate on the surface, putting into a baking oven to adjust the temperature to 50 ℃ for baking, and obtaining the fluoride ion exchange membrane after 45 minutes.
Example 2: preparation of fluoride ion exchange Membrane
The specific preparation steps of this example are as follows:
(1) Taking perfluorinated sulfonic acid ion exchange resin with equivalent weight EW of 1000g/eq, adding 1, 3-dimethyl imidazole cationic liquid, stirring at a mechanical stirring rate of 150r/min at a water bath temperature of 60 ℃ to fully mix and dissolve, adding ethylene glycol to continuously stir and dissolve at a rate of 150r/min, then carrying out ice bath, reducing the temperature to 45 ℃, adding N-methylolacrylamide, vacuumizing to remove bubbles, pouring into a mould, curing at 125 ℃ for 6h, and taking out a cured product;
(2) Uniformly mixing absolute ethyl alcohol with pure water with resistivity more than 0.5M omega cm to prepare a mixed solvent, adding a solidified substance, dissolving in a reaction kettle, keeping the temperature at 220 ℃ in the dissolving process, dissolving for 4 hours, and dissolving the solidified substance in the mixed solvent to prepare a casting solution with mass concentration of 5%;
(3) Pouring the prepared casting solution into a casting plate, starting a heating device to heat to 105 ℃ and keeping for 6 hours, taking out the casting plate after all solvents in the casting solution are evaporated, adding anhydrous sodium sulfate on the surface, putting into a baking oven to adjust the temperature to 55 ℃ for baking, and obtaining the fluoride ion exchange membrane after 0.5 hour.
Example 3: preparation of fluoride ion exchange Membrane
The specific preparation steps of this example are as follows:
(1) Taking perfluorinated sulfonic acid ion exchange resin with equivalent weight EW of 1000g/eq, adding 1, 3-dimethyl imidazole cationic liquid, stirring at 80 ℃ at a mechanical stirring rate of 200r/min to fully mix and dissolve, adding ethylene glycol to continuously stir and dissolve at a rate of 200r/min, then carrying out ice bath to reduce the temperature to 45 ℃, adding N-methylolacrylamide, vacuumizing to remove bubbles, pouring into a mould, curing at 115 ℃ for 6h, and taking out a cured product;
(2) Uniformly mixing absolute ethyl alcohol with pure water with resistivity more than 0.5M omega cm to prepare a mixed solvent, adding a solidified substance, dissolving in a reaction kettle, keeping the temperature at 200 ℃ in the dissolving process, dissolving for 6 hours, and dissolving the solidified substance in the mixed solvent to prepare a casting solution with mass concentration of 1%;
(3) Pouring the prepared casting solution into a casting plate, starting a heating device to heat to 115 ℃ and keeping for 6 hours, taking out the casting plate after all solvents in the casting solution are evaporated, adding anhydrous sodium sulfate on the surface, putting into a baking oven to adjust the temperature to 40 ℃ for baking, and obtaining the fluoride ion exchange membrane after 1 hour.
Comparative example 1: preparation of fluoride ion exchange membranes
This comparative example is in contrast to the fluoride ion-exchange membrane prepared in example 1, except that 1, 3-dimethylimidazole cationic liquid was not used in step (1) of this comparative example, and the remaining steps and raw materials used were the same as those in example 1. The specific steps of the step (1) are as follows:
(1) Adding glycol into perfluorosulfonic acid ion exchange resin with equivalent weight EW of 1000g/eq at water bath temperature of 70 ℃, stirring and dissolving at a speed of 180r/min, then carrying out ice bath to reduce the temperature to 45 ℃, adding N-methylolacrylamide, vacuumizing to remove bubbles, pouring into a mould, curing at 120 ℃ for 6 hours, and taking out the cured product.
Comparative example 2: preparation of fluoride ion exchange membranes
This comparative example was compared with the fluoride ion-exchange membrane prepared in example 1, except that N-methylolacrylamide and ethylene glycol were not used in step (1) of this comparative example, and the remaining steps and raw materials used were the same as in example 1. The specific steps of the step (1) are as follows:
(1) Taking perfluorinated sulfonic acid ion exchange resin with equivalent weight EW of 1000g/eq, adding 1, 3-dimethyl imidazole cationic liquid, stirring at a mechanical stirring rate of 180r/min at a water bath temperature of 70 ℃ to fully mix and dissolve, vacuumizing to remove bubbles, pouring into a mould, curing at 120 ℃ for 6 hours, and taking out a cured product.
Comparative example 3: preparation of fluoride ion exchange membranes
This comparative example was compared with the fluorine ion-exchange membrane prepared in example 1, except that pure water having a resistivity of < 0.5 m.OMEGA.cm was used in the step (2) of this comparative example, and the remaining steps and raw materials were the same as in example 1. The specific steps of the step (2) are as follows:
(2) And (3) uniformly mixing absolute ethyl alcohol with pure water with resistivity less than 0.5M omega cm to prepare a mixed solvent, adding a solidified substance, dissolving in a reaction kettle, keeping the temperature at 210 ℃ in the dissolving process, dissolving for 5 hours, and dissolving the solidified substance in the mixed solvent to prepare the casting film liquid with the mass concentration of 4%.
Comparative example 4: preparation of fluoride ion exchange membranes
This comparative example was compared with the fluoride ion-exchange membrane prepared in example 1, except that anhydrous sodium sulfate was not used in step 4 of this comparative example, and the remaining steps and raw materials used were the same as in example 1. The specific steps of the step (3) are as follows:
(3) And heating the prepared casting solution to 110 ℃ and keeping the temperature for 5.5 hours, fully evaporating the solvent in the casting solution, adjusting the temperature to 50 ℃ and drying for 45 minutes to obtain the fluoride ion exchange membrane.
Comparative example 5: preparation of fluoride ion exchange membranes
This comparative example is in contrast to the fluoride ion-exchange membrane prepared in example 1, except that the perfluorosulfonic acid ion-exchange resin in this comparative example was not subjected to the treatment of step (1) in example 1, and was directly subjected to the treatment of step (2), and the steps and raw materials used were the same as in example 1, with the following specific steps:
(1) Uniformly mixing absolute ethyl alcohol with pure water with resistivity more than 0.5M omega cm to prepare a mixed solvent, keeping the temperature in a reaction kettle at 210 ℃ for 5 hours, and dissolving perfluorosulfonic acid ion exchange resin with equivalent weight EW of 1000g/eq in the mixed solvent to prepare a casting solution with mass concentration of 4%;
(2) Pouring the prepared casting solution into a casting plate, starting a heating device to heat to 110 ℃ and keeping for 5.5 hours, taking out the casting plate after all the solvent in the casting solution is evaporated, adding anhydrous sodium sulfate on the surface, putting into a baking oven to adjust the temperature to 50 ℃ for baking, and obtaining the fluoride ion exchange membrane after 45 minutes.
Comparative example 6: preparation of fluoride ion exchange membranes
This comparative example was compared with the fluorine ion-exchange membrane prepared in example 1, except that the treatment of step (2) in example 1 was not performed in this comparative example, the treatment of step (1) was performed directly after the treatment of step (3), and the steps and raw materials used were the same as those in example 1, and the specific steps were as follows:
(1) Taking perfluorinated sulfonic acid ion exchange resin with equivalent weight EW of 1000g/eq, adding 1, 3-dimethyl imidazole cationic liquid, stirring at a mechanical stirring rate of 180r/min at a water bath temperature of 70 ℃ to fully mix and dissolve, adding glycol to continuously stir and dissolve at a rate of 180r/min, then carrying out ice bath, reducing the temperature to 45 ℃, and adding N-methylolacrylamide to prepare casting film liquid;
(2) And heating the prepared casting solution to 110 ℃ and keeping the temperature for 5.5 hours, adjusting the temperature to 50 ℃ after all the solvent in the casting solution is evaporated, adding anhydrous sodium sulfate, and drying for 45 minutes to obtain the fluoride ion exchange membrane.
Comparative example 7: preparation of fluoride ion exchange membranes
This comparative example is in contrast to the fluoride ion-exchange membrane prepared in example 1, except that step (3) in this comparative example is not subjected to a drying treatment, and the remaining steps and raw materials used are the same as in example 1, with the specific step (3) as follows:
(3) Pouring the prepared casting solution into a casting plate, starting a heating device to heat to 110 ℃ and keeping for 5.5 hours, taking out the casting plate after the solvent in the casting solution is completely evaporated, and adding anhydrous sodium sulfate on the surface for 45 minutes to obtain the fluoride ion exchange membrane.
Experiment one, performance test on fluoride ion exchange Membrane
1. The preparation method comprises the following steps:
experimental group: experiment group 1 the preparation method of example 1 was selected to prepare a fluoride ion-exchange membrane;
control group: control groups 1-7 were prepared using the preparation method of the fluoride ion-exchange membranes of comparative examples 1-7;
nafion115 membrane: a commercially available us Du Bangquan fluorosulfonic acid ion membrane Nafion115 membrane was used.
2. The specific experimental method comprises the following steps:
soaking the fluoride ion exchange membranes prepared in the experimental group 1 and the control groups 1-7 in electrolyte for 3 hours at the temperature of 60 ℃, measuring the soaked sizes of the fluoride ion exchange membranes of each group, and calculating the size swelling ratio;
the above experiments were repeated three times to average, and the specific results are shown in table 2:
TABLE 2
And (2) testing II: the fluoride ion exchange membranes prepared in the experiment group 1, the control groups 1-7 and the blank control group are subjected to performance test by taking an all-vanadium redox flow battery as an example, and the experiment is repeated three times to obtain an average value, and the specific result is shown in the table 3.
TABLE 3 Table 3
From the data analysis of tables 2 and 3, it is possible to:
1. the original size of the fluoride ion-exchange membrane of experiment group 1 is 1455mm, the equilibrium size after swelling is 1546mm, the swelling rate is 6.3%, and the measured vanadium ion transmittance is 0.65X10 -6 cm 2 The film surface resistance per minute was 1.03. Omega. Cm 2 The water content is8.52%. The fluoride ion exchange membrane prepared in the control group 1 lacks N-methylolacrylamide and 1, 3-dimethyl imidazole cationic liquid, hydrogen bonds on the perfluorosulfonic acid ion exchange resin can not be crosslinked with the 1, 3-dimethyl imidazole cationic liquid and N-methylolacrylamide to form a stable three-dimensional network structure, when the fluoride ion exchange membrane is soaked in electrolyte for a long time, the membrane is hydrated to absorb water and swell, the pore canal is spread, part of vanadium ions can smoothly pass through, so that the battery is irreversibly damaged, meanwhile, an effective medium is not formed to accelerate proton transfer, the swelling rate is 9.27%, the original size is 1466mm, the balance size is 1602mm, and the measured vanadium ion transmittance is 0.99 multiplied by 10 -6 cm 2 The film surface resistance was 1.25. Omega. Cm per minute 2 The water content is 12.98%, so that the fluoride ion exchange membrane with good vanadium resistance, low swelling rate and small solvate residual quantity can be prepared by the treatment method;
2. the swelling ratio of the fluoride ion-exchange membrane prepared in the control group 2 was 9.27%, in which the original size was 1473mm, the equilibrium size was 1579mm, and the measured transmittance of vanadium ions was 0.94×10 -6 cm 2 The film surface resistance is 1.18Ω cm 2 The water content is 9.87%, because the control group 2 lacks N-methylolacrylamide and ethylene glycol, a three-dimensional network structure is not formed, the expansion of a polymer network beam is reduced, and the osmotic pressure is increased due to the increase of ion concentration difference; the treatment method can prepare the fluoride ion exchange membrane with good vanadium resistance and low swelling rate.
3. Since the solvent used in step 2 of control group 3 was only absolute ethanol, the swelling ratio of the resulting fluoride ion-exchange membrane was 6.61%, the original size was 1447mm, the equilibrium size was 1543mm, and the vanadium ion transmittance was 0.81×10 -6 cm 2 The film surface resistance was 1.73Ω cm per minute 2 The water content was 10.02%, the swelling ratio of the fluoride ion-exchange membrane prepared in control group 4 was 6.45%, the original size was 1450mm, the equilibrium size was 1544mm, and the transmittance of vanadium ions was 0.8X10 -6 cm 2 The film surface resistance was 1.24 Ω cm per minute 2 The water content was 9.32%, anhydrous sodium sulfate was not used in control group 4, and the solvent of the membrane was permeated in the polymer network during the preparation process and was not removedThe fluorine ion exchange membrane prepared by the treatment method has good vanadium resistance, low swelling rate and small residual solvate amount because of using various solvents.
4. The difference between the control group 5 and the experimental group 1 is that the ion pore canal is completely opened and the three-dimensional network structure is not bound when the treatment of the step (1) is not carried out, the swelling rate of the prepared fluoride ion exchange membrane is 12.54%, the original size is 1449mm, the equilibrium size is 1631mm, and the measured vanadium ion transmittance is 1.17 multiplied by 10 -6 cm 2 The film surface resistance per minute was 1.56. Omega. Cm 2 The water content was 13.25%, the control group 6 was not subjected to the step (2) during the membrane formation, the control group 7 was not subjected to the step (3) during the membrane formation, the swelling ratio of the obtained fluoride ion-exchange membrane was 6.86%, and the measured vanadium ion transmittance was 0.88×10 -6 cm 2 The film surface resistance was 1.51Ω & cm per minute 2 The water content is 8.19%, and only the cooperation of the steps (1) and (3) ensures the electrochemical performance of the membrane and has small swelling degree.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention. The technology, shape, and construction parts of the present invention, which are not described in detail, are known in the art.
Claims (8)
1. The fluoride ion exchange membrane is characterized by comprising the following raw materials:
3-5 parts of perfluorosulfonic acid ion exchange resin, 20-40 parts of absolute ethyl alcohol, 22-46 parts of pure water, 4-9 parts of ethylene glycol, 15-30 parts of 1, 3-dimethyl imidazole cationic liquid, 0.1-0.5 part of N-methylolacrylamide and 5-9 parts of anhydrous sodium sulfate.
2. A fluoride ion exchange membrane according to claim 1, wherein the resistivity of pure water is >0.5mΩ cm.
3. A fluoride ion exchange membrane according to claim 1, wherein the equivalent weight EW of the perfluorinated ion exchange resin is 900-1100g/eq.
4. A method for preparing a fluoride ion-exchange membrane, comprising the steps of:
(1) Adding perfluorosulfonic acid ion exchange resin into 1, 3-dimethyl imidazole cationic liquid, mechanically stirring at 60-70 ℃ in a water bath to fully mix, adding glycol, stirring to dissolve, reducing the temperature to 45 ℃, adding N-methylolacrylamide, removing bubbles, pouring into a mould, curing at 115-125 ℃ for 6 hours, and taking out a cured product;
(2) Uniformly mixing absolute ethyl alcohol and pure water to prepare a mixed solvent, and dissolving a solidified substance in the mixed solvent to prepare a casting solution;
(3) And heating the prepared casting solution, completely evaporating the solvent in the casting solution, adding anhydrous sodium sulfate, and drying to obtain the fluoride ion exchange membrane.
5. The method according to claim 1, wherein the dissolution temperature of the solidified material in the step (2) is 200 to 220 ℃ and the dissolution time is 4 to 6 hours.
6. The method for preparing a fluoride ion-exchange membrane according to claim 1, wherein the mass concentration of the casting solution in the step (2) is 1-5%.
7. The method for preparing a fluoride ion-exchange membrane according to claim 1, wherein the temperature of the evaporating solvent in the step (3) is 105-115 ℃ and the heating time is 5-6 hours.
8. The method according to claim 1, wherein in the step (3), the drying temperature is set to 40-55 ℃ and the drying time is set to 0.5-1h.
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