CN111013669A - Cation exchange membrane and preparation method and application thereof - Google Patents
Cation exchange membrane and preparation method and application thereof Download PDFInfo
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- CN111013669A CN111013669A CN201911227396.2A CN201911227396A CN111013669A CN 111013669 A CN111013669 A CN 111013669A CN 201911227396 A CN201911227396 A CN 201911227396A CN 111013669 A CN111013669 A CN 111013669A
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- exchange membrane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
Abstract
The cation exchange membrane and the preparation method and the application thereof belong to the field of high molecular function membrane materials, and the key point is that the double-bond ferrocene compound is adopted for polymerization, and then the cross-linking sulfonation reaction is carried out to obtain the cation exchange membrane.
Description
Technical Field
The invention belongs to the field of polymer functional membrane materials, and particularly relates to an ion exchange membrane for a flow battery, and a preparation method and application thereof.
Background
In the field of all-vanadium flow batteries, the perfluorosulfonic acid ion exchange membrane is the most widely used ion exchange membrane, and although the perfluorosulfonic acid ion exchange membrane has good corrosion resistance, the raw material cost is high, so that the application of the perfluorosulfonic acid membrane in the field is limited. At present, the non-fluorine type ion exchange membranes are gradually the hot points of research of researchers due to low cost of raw materials, and different types of non-fluorine type ion exchange membranes are researched and prepared. Chinese patent CN 103515634B provides a method for synthesizing and preparing a sulfonated polyaryletherketone ion exchange membrane; chinese patent CN 104804207B provides a polyether ether sulfone anion exchange membrane containing imidazolium pendant group; patent 201711473747.9 provides a method for preparing a non-fluorine type ion exchange membrane using a phenolic compound; the literature (Electrochimica Acta 2014,150, 114-; the literature (Journal of Membrane Science 2009,342, 215-. Although the ion exchange membrane obtained as described above can be preferably applied to the field of vanadium batteries, mechanical properties and ion exchange capacity as well as vanadium battery performance are limited to some extent, and therefore, development of a cation exchange membrane having high ion exchange capacity and maintaining good mechanical strength is a major direction of future development in this field.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a cation exchange membrane which develops high ion exchange capacity and keeps better mechanical strength, and a preparation method and application thereof. The ion exchange membrane is prepared from a ferrocene compound containing carbon-carbon double bonds, a chain transfer agent, an initiator, oxalyl chloride, a sulfonating agent and the like. The technical scheme of the invention is that the preparation method of the cation exchange membrane comprises the following steps:
(1) dissolving a ferrocene compound containing double bonds, a chain transfer agent and an initiator in an organic solvent, fully stirring and reacting for 5-40h at 70-100 ℃ in an inert gas atmosphere, stopping heating, cooling to 0-30 ℃, separating and washing a product, and fully drying to prepare powder;
(2) dissolving the powder and anhydrous aluminum trichloride in the step (1) in anhydrous dichloromethane, dropwise adding oxalyl chloride into the anhydrous dichloromethane at room temperature, after the reaction is finished, adding deionized water into the system, fully hydrolyzing, separating liquid to obtain an organic phase, fully drying the organic phase, and performing rotary evaporation to remove the solvent to obtain a solid powder product;
(3) adding a sulfonating agent into the powder obtained in the step (2), fully sulfonating at 40-60 ℃, cooling to 0-20 ℃, dropwise adding the reaction liquid into excessive deionized water, precipitating, filtering, washing and drying to obtain solid powder;
(4) dissolving the powder obtained in the step (3) in an organic solvent, and preparing the cation exchange membrane by a tape casting method;
the molar ratio of the ferrocene compound containing the double bond to the chain transfer agent is (200-400): 1; the molar ratio of the initiator to the chain transfer agent is (0.2-1) to 1; the molar ratio of the anhydrous aluminum trichloride to the ferrocene unit in the polymer obtained in the step (1) is (0.9-1.5): 1; the oxalyl chloride gives a molar ratio of ferrocene units in the polymer of (1.0-1.2): 1;
the chain transfer agent is an aliphatic mercaptan, preferably dodecyl mercaptan;
the ferrocene compound containing double bonds is one of 4-vinylphenyl ferrocene carboxylic ester, vinyl ferrocene, ferrocene vinyl ketone and the like.
The molar ratio of the ferrocene compound containing the double bond to the chain transfer agent is (300-400): 1;
the organic solvent used in the step (1) is petroleum ether, diethyl ether, toluene and dichloromethane;
the sulfonating agent is one of concentrated sulfuric acid, fuming sulfuric acid and chlorosulfonic acid;
the initiator is one or more of azo initiators and peroxide initiators;
in the step (4), the organic solvent is any polar high boiling point solvent, such as dimethyl sulfoxide (DMSO), dimethylformamide, m-cresol, ethylene glycol monomethyl ether, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and preferably dimethyl sulfoxide;
and the step (3) also comprises the steps of treating with 3% hydrogen peroxide and 0.5mol/L dilute sulfuric acid, and finally washing with distilled water to be neutral to obtain the cation exchange membrane.
Another object of the present invention is to claim a cation exchange membrane prepared by the above process.
The third purpose of the invention is to protect the application of the cation exchange membrane prepared by the method in a flow battery, in particular to the application in an all-vanadium flow battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a preparation method of a non-fluorine cation exchange membrane with mild preparation conditions and relatively simple process;
(2) the ion exchange membrane prepared by adopting the ferrocene compound containing carbon-carbon double bonds, the chain transfer agent, the initiator, the oxalyl chloride, the sulfonating agent and the like has good mechanical property, high ion exchange capacity and good cell efficiency.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods used in the present invention are conventional methods, and the experimental devices, materials, reagents, etc. used therein may be purchased from chemical companies or synthesized according to the literature.
The thickness of the ionic membrane is tested by a Fisher thickness tester, and 50 values of each sample are measured at different positions to calculate the average value;
the ionic membrane has the test of tensile strength and elongation at break according to the standard GB/T1040.3-2006 part 3 for the determination of the tensile property of plastics: test conditions for films and sheets, the film was cut into strips having a width of 10mm and an initial interval of clamps of 50mm, and the test was performed at a stretching rate of 200 mm/min;
the performance test conditions of the all-vanadium redox flow energy storage battery of the ionic membrane are as follows: at a current density of 80mA/cm2Performing charge-discharge experiment under the condition of charging to 1.55V and discharging to 1.00V, using graphite carbon felt produced by Beijing crystal Longte carbon technology Co., Ltd as reaction electrode, and the effective working area of the electrode is 48cm2The positive and negative electrolytes are VO2+/VO2 +And V2+/V3+The working temperature of the battery is 37 ℃.
The testing method of the ion exchange capacity of the ion exchange membrane is implemented according to the national standard GB/T20042.3-2009 proton exchange membrane testing method of the proton exchange membrane fuel cell, and the reciprocal value of the obtained ion exchange equivalent is the ion exchange capacity value.
Example 1
4-Vinylphenylferrocene carboxylate monomer was synthesized according to the Journal of Polymer Science, PartA: Polymer Chemistry 2016,54, 900-909.
Dissolving 69.2g (0.2mol) of 4-vinylphenyl ferrocene carboxylate, 0.202g (0.001mol) of dodecanethiol and 0.033g (0.0002mol) of azobisisobutyronitrile in 250mL of toluene, fully stirring and reacting for 5 hours at 70 ℃ in an inert gas atmosphere, stopping heating, cooling to 0-30 ℃, separating out a product, washing, and fully drying to prepare powder;
taking 34.6g of the powder (containing ferrocene side chain groups, about 0.1mol), adding 12g (0.09mol) of anhydrous aluminum trichloride powder and 250mL of anhydrous dichloromethane, gradually adding 12.7g (0.1mol) of oxalyl chloride at room temperature (-20 ℃), after the reaction is finished, adding deionized water into the system, fully hydrolyzing, separating to obtain an organic phase, fully drying the organic phase, and performing rotary evaporation to remove the solvent to obtain a solid powder product;
adding excessive concentrated sulfuric acid into the obtained powder, fully sulfonating at 40-60 ℃, cooling to 0-20 ℃, dropwise adding the reaction liquid into excessive deionized water, precipitating, filtering, washing and drying to obtain a solid; then dissolving the obtained powder in dimethyl sulfoxide, and preparing the cation exchange membrane by a tape casting method.
In this example, the molar ratio of 4-vinylphenyl ferrocene carboxylate monomer to dodecanethiol chain transfer agent was 200: 1; the molar ratio of the azobisisobutyronitrile initiator to the dodecanethiol chain transfer agent is 0.2: 1; the molar ratio of anhydrous aluminum trichloride to the obtained ferrocene unit in the polymer is 0.9: 1; the molar ratio of oxalyl chloride to ferrocene units in the obtained polymer is 1: 1.
Example 2
The mass of 4-vinyl phenyl ferrocene carboxylic ester is changed to 103.8g (0.3mol), the mass of the initiator is changed to 0.049g (0.0003mol), the mixture is fully stirred and reacted for 10 hours at the temperature of 70 ℃, and the other steps are kept the same as those of the example 1, so as to prepare the cation exchange membrane.
In this example, the molar ratio of 4-vinylphenyl ferrocene carboxylate monomer to dodecanethiol chain transfer agent was 300:1, the molar ratio of initiator to chain transfer agent was 0.3:1, and the others were kept constant.
Example 3
Changing the mass of 4-vinyl phenyl ferrocene carboxylic ester to 121.1g (0.35mol), changing the mass of initiator to 0.082g (0.0005mol), fully stirring and reacting for 20h under the condition of 70 ℃, and keeping the same as the example 1 to prepare the cation exchange membrane.
In this example, the molar ratio of 4-vinylphenyl ferrocene carboxylate monomer to dodecanethiol chain transfer agent was 350:1, the molar ratio of initiator to chain transfer agent was 0.5:1, and the others remained unchanged.
Example 4
The mass of 4-vinyl phenyl ferrocene carboxylic ester is changed to 138.4g (0.4mol), the mass of the initiator is changed to 0.131g (0.0008mol), the mixture is fully stirred and reacted for 30 hours at the temperature of 70 ℃, and the other steps are kept the same as those of the example 1, so as to prepare the cation exchange membrane.
In this example, the molar ratio of 4-vinylphenyl ferrocene carboxylate monomer to dodecanethiol chain transfer agent was 400:1, the molar ratio of initiator to chain transfer agent was 0.8:1, and the others were kept constant.
Example 5
The mass of 4-vinyl phenyl ferrocene carboxylic ester is changed to 173g (0.5mol), the mass of the initiator is changed to 0.164g (0.001mol), the mixture is fully stirred and reacted for 40 hours at the temperature of 100 ℃, and the rest is kept the same as that of the example 1, so as to prepare the cation exchange membrane.
In this example, the molar ratio of 4-vinylphenyl ferrocene carboxylate monomer to dodecanethiol chain transfer agent was 500:1, the molar ratio of initiator to chain transfer agent was 1:1, and the others were kept constant.
Example 6
Dissolving 63.6g (0.3mol) of vinyl ferrocene, 0.202g (0.001mol) of dodecanethiol and 0.066g (0.0004mol) of azobisisobutyronitrile in 250mL of petroleum ether with a boiling range of 60-90, fully stirring and reacting for 25h at 85 ℃ in an inert gas atmosphere, stopping heating, cooling to 0-30 ℃, separating and washing a product, and fully drying to prepare powder;
taking 21.2g of the powder (containing ferrocene side chain groups, about 0.1mol), adding 16g (0.12mol) of anhydrous aluminum trichloride powder and 250mL of anhydrous dichloromethane, gradually adding 13.97g (0.11mol) of oxalyl chloride at room temperature (-20 ℃), after the reaction is finished, adding deionized water into the system, fully hydrolyzing, separating to obtain an organic phase, fully drying the organic phase, and performing rotary evaporation to remove the solvent to obtain a solid powder product;
adding excessive chlorosulfonic acid into the obtained powder, fully sulfonating at 40-60 ℃, cooling to 0-20 ℃, dropwise adding the reaction liquid into excessive deionized water, precipitating, filtering, washing, and drying to obtain a solid; then dissolving the obtained powder in dimethyl sulfoxide, and preparing the cation exchange membrane by a tape casting method.
In this example, the molar ratio of vinylferrocene monomer to dodecanethiol chain transfer agent was 300: 1; the molar ratio of the azobisisobutyronitrile initiator to the dodecanethiol chain transfer agent is 0.4: 1; the molar ratio of anhydrous aluminum trichloride to the obtained ferrocene unit in the polymer is 1.2: 1; the molar ratio of oxalyl chloride to ferrocene units in the resulting polymer was 1.1: 1.
Example 7
Dissolving 84g (0.35mol) of ferrocenyl vinyl ketone, 0.202g (0.001mol) of dodecanethiol and 0.066g (0.0004mol) of azobisisobutyronitrile in 250mL of petroleum ether with a boiling range of 60-90, fully refluxing and stirring for reaction at 90 ℃ for 37h in an inert gas atmosphere, stopping heating, cooling to 0-30 ℃, separating a product, washing, fully drying to prepare powder;
taking 24g of the powder (containing ferrocene side chain groups, about 0.1mol), adding 20g (0.15mol) of anhydrous aluminum trichloride powder and 250mL of anhydrous dichloromethane, gradually adding 13.34g (0.105mol) of oxalyl chloride at room temperature (-20 ℃), after the reaction is finished, adding deionized water into the system, fully hydrolyzing, separating to obtain an organic phase, fully drying the organic phase, and performing rotary evaporation to remove the solvent to obtain a solid powder product;
adding excessive fuming sulfuric acid into the obtained powder, fully sulfonating at 40-60 ℃, cooling to 0-20 ℃, dropwise adding the reaction liquid into excessive deionized water, precipitating, filtering, washing and drying to obtain a solid; then dissolving the obtained powder in dimethyl sulfoxide, and preparing the cation exchange membrane by a tape casting method.
In this example, the molar ratio of vinylferrocene monomer to dodecanethiol chain transfer agent was 350: 1; the molar ratio of the azobisisobutyronitrile initiator to the dodecanethiol chain transfer agent is 0.4: 1; the molar ratio of anhydrous aluminum trichloride to the obtained ferrocene unit in the polymer is 1.5: 1; the molar ratio of oxalyl chloride to ferrocene units in the resulting polymer was 1.05: 1. The room temperature in each embodiment is about 20 degrees, and the temperature range may be 18-28 degrees.
Comparative example 1
Reducing the using amount of oxalyl chloride to 6.35g (0.05mol), wherein the ratio of the using amount of oxalyl chloride to the ferrocene unit is 0.5:1, and the rest is consistent with the embodiment 3 to prepare the cation exchange membrane;
comparative example 2
Increasing the using amount of oxalyl chloride to 25.4g (0.2mol), wherein the ratio of the using amount of oxalyl chloride to the ferrocene unit is 2:1, and the rest is consistent with the embodiment 3 to prepare the cation exchange membrane;
cation exchange membranes prepared according to examples 1 to 7 of the present invention and comparative examples 1 to 2 and a Nation series membrane developed by DuPont, USA
The performance test was performed, and the test results are shown in table 1.
TABLE 1 films prepared in examples 1-7 and comparative examples 1-2 and
film performance data
As can be seen from Table 1, the cation exchange membrane prepared by the invention has better tensile strength and breaking elongationThe long rate, namely the good mechanical property, and the ion exchange capacity of the ion exchange membrane is higher than that of the perfluorosulfonic acid ion exchange membrane with the same thickness of DuPont company, which shows that the ion exchange membrane synthesized by the invention has good ion exchange capacity and ion conductivity. Through applying the ion exchange membrane to the charge-discharge test experiment of the all-vanadium liquid flow energy storage battery, the fact that the thickness is equal to that of DuPont company is found
Compared with the experimental data of the examples, the comparative example shows that if the dosage of the cross-linking agent oxalyl chloride is less than the range limited by the invention, the cross-linking degree is low, and although the obtained membrane has higher ion exchange capacity (more sufficient sulfonation), the mechanical property is greatly reduced; if the amount of the crosslinking agent oxalyl chloride is more than the range defined in the present invention, the degree of crosslinking is high, and the ion exchange capacity is low (the crosslinking agent decreases the sulfonation sites) although the resulting membrane has high mechanical properties.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (10)
1. The preparation method of the cation exchange membrane is characterized by comprising the following steps:
(1) dissolving a ferrocene compound containing double bonds, a chain transfer agent and an initiator in an organic solvent, fully stirring and reacting for 5-40h at 70-100 ℃ in an inert gas atmosphere, stopping heating, cooling to 0-30 ℃, separating and washing a product, and fully drying to prepare powder;
(2) dissolving the powder obtained in the step (1) and anhydrous aluminum trichloride in anhydrous dichloromethane, dropwise adding oxalyl chloride, after the reaction is finished, adding deionized water into the system, fully hydrolyzing, separating liquid to obtain an organic phase, fully drying the organic phase, and performing rotary evaporation to remove the solvent to obtain a solid powder product;
(3) adding a sulfonating agent into the powder obtained in the step (2), fully sulfonating at 40-60 ℃, cooling to 0-20 ℃, dropwise adding the reaction liquid into excessive deionized water, precipitating, filtering, washing and drying to obtain solid powder;
(4) dissolving the powder obtained in the step (3) in an organic solvent, and preparing the cation exchange membrane by a tape casting method.
2. The method as claimed in claim 1, wherein the molar ratio of the ferrocene compound containing the double bond to the chain transfer agent is (200- > 500): 1, the molar ratio of the initiator to the chain transfer agent is (0.2-1):1, and the molar ratio of the anhydrous aluminum trichloride to the ferrocene unit in the polymer obtained in the step (1) is (0.9-1.5): 1, the molar ratio of the oxalyl chloride to the molar ratio of the ferrocene units in the obtained polymer is (1.0-1.1): 1.
3. The method as claimed in claim 1, wherein the molar ratio of the ferrocene compound containing the double bond to the chain transfer agent is (300- & 400): 1.
4. the method according to claim 1, wherein the ferrocene compound containing a double bond is one of 4-vinylphenylferrocene carboxylate, vinylferrocene, ferrocene vinylketone, and the like.
5. The method according to claim 1, characterized in that the chain transfer agent is an aliphatic thiol.
6. The method according to claim 1, wherein the organic solvent used in step (1) is one or more of petroleum ether, diethyl ether, toluene and dichloromethane; the sulfonating agent is one of concentrated sulfuric acid, fuming sulfuric acid and chlorosulfonic acid; the initiator is one or more of azo initiators and peroxide initiators.
7. The method according to claim 1, wherein the organic solvent used in step (4) is one or more selected from dimethyl sulfoxide, dimethylformamide, m-cresol, ethylene glycol monomethyl ether, N-methylpyrrolidone, and 1, 3-dimethyl-2-imidazolidinone.
8. The method according to claim 1, wherein oxalyl chloride is added dropwise thereto at room temperature in step (1).
9. A cation exchange membrane prepared by the method of any one of claims 1 to 7.
10. Use of the cation exchange membrane of claim 9 in a flow battery.
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