CN116731366A - Hyperbranched anion exchange membrane and preparation method and application thereof - Google Patents
Hyperbranched anion exchange membrane and preparation method and application thereof Download PDFInfo
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 51
- 239000000446 fuel Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 aryl compound Chemical class 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 38
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical group OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 239000012456 homogeneous solution Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 6
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical group IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 6
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229940102396 methyl bromide Drugs 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000008961 swelling Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 abstract 2
- 230000021615 conjugation Effects 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 11
- 239000012528 membrane Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
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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
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Abstract
The invention discloses a hyperbranched anion exchange membrane, a preparation method and application thereof, wherein an aryl compound with the functionality degree more than or equal to 3 is introduced into a polyareneaulide piperidine polymer, and the hyperbranched anion exchange membrane with large plane conjugation is prepared by a one-pot method, and the prepared anion exchange membrane has a free volume larger than that of a linear polymer, thereby showing thatThe conductive performance is ultrahigh, and the alkali resistance stability is excellent; meanwhile, the anion exchange membrane prepared by the invention has lower water absorption swelling and good mechanical property, is suitable for alkaline fuel cells, and has the power density of up to 1.45W/cm 2 Has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a hyperbranched anion exchange membrane and a preparation method and application thereof.
Background
The problems of energy shortage and environmental pollution are the main problems faced by the development of the society today. In order to cope with the energy crisis, development of renewable clean energy is urgent. The advantages of the hydrogen fuel cell, which is not limited by the carnot cycle, has an energy conversion efficiency 2-3 times higher than that of the internal combustion engine, and the reaction product is water, which does not cause environmental pollution, make the hydrogen fuel cell one of the most potential and interesting ways. Unlike proton exchange membrane fuel cells, alkaline fuel cells can use non-noble metal catalysts to greatly reduce production costs, with great commercial potential. The anion exchange membrane serves as a key component of the alkaline fuel cell and serves as fuel isolation and OH conduction - Is required to have high ionic conductivity, excellent mechanical properties, and alkaline stability.
At present, a great deal of research shows that increasing the free volume in the membrane is one of effective methods for constructing ion transmission rapid channels, and can greatly reduce the dependence on IEC, thereby improving the mechanical stability of the membrane. Due to the branched structure of the hyperbranched polymer, chain entanglement can be effectively reduced, the stacking density of a main chain is reduced, and the free volume in the membrane is increased, so that the mass transfer resistance of ions in the membrane is reduced. However, the hyperbranched anion exchange membranes reported so far mainly use alkyl chains as main chains, and are difficult to form self-supporting membranes due to weak chain entanglement.
Disclosure of Invention
The invention aims to solve the technical problems that: provides a hyperbranched anion exchange membrane, a preparation method and application thereof, and aims to solve the technical problems of low conductivity, poor mechanical stability and poor chemical stability of the anion exchange membrane.
In order to achieve the above purpose, the invention adopts the following technical scheme: the hyperbranched anion exchange membrane is formed by polymerizing an Ar1 monomer, an Ar2 monomer and an N-methyl-4-piperidone monomer, and has the following structural general formula:
wherein M is - Is I - 、Br - 、Cl - 、OH - Or HCO 3 2- X is more than 0 and less than or equal to 60, and x is an integer;
ar1 monomer is aryl compound with functionality more than or equal to 3, and the chemical structure is as follows:
ar2 monomer is one of the following compounds:
the invention also discloses a preparation method of the hyperbranched anion exchange membrane, which comprises the following steps:
s1: firstly, dissolving Ar1 monomer and Ar2 monomer in a solvent I, stirring for 5-20min, then adding N-methyl-4-piperidone monomer, and continuously stirring for 5-20min; the molar ratio of Ar1 monomer to Ar2 monomer is m: (100-m), wherein m is an integer from 5 to 60; the molar ratio of the sum of Ar1 monomer and Ar2 monomer to N-methyl-4-piperidone monomer is 1:1-1.4, wherein the concentration of the sum of all monomers in the solution is 20-60wt%;
s2: adding a catalyst into the mixed solution obtained in the step S1, reacting for 5-8 hours at the temperature of minus 10-10 ℃, then adding the mixed solution into an inverse precipitant, regulating the pH value of the solution to be more than or equal to 7, reacting for 24-48 hours at the temperature of 60-80 ℃, and filtering to obtain a polymer; washing the polymer with pure water for 3-5 times, and drying in a vacuum environment at 75-85 ℃ for 20-26h;
s3: dissolving a polymer in a second solvent at 60-80 ℃ to obtain a polymer solution with the concentration of 5-30wt%, cooling the polymer solution to room temperature, adding an ionization reactant to react for 12-48h, adding the polymer solution into an anti-precipitant, filtering the precipitate, washing the precipitate with ethyl acetate for 3-5 times, and drying the precipitate in a vacuum environment at 60-80 ℃ for 12-24h;
s4: dissolving the dried precipitate in a second solvent to obtain a homogeneous solution with the concentration of 5-30wt%, pouring the homogeneous solution on a forming plate, drying at 60-80 ℃ for 8-24 hours to obtain a dried film, and then soaking the dried film in 1M KOH at 60 ℃ for 12-48 hours to obtain the hyperbranched anion exchange membrane.
Further, the first solvent is dichloromethane.
Further, the catalyst is trifluoroacetic acid and trifluoromethanesulfonic acid, and the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid is 1-6:1-20.
Further, the volume ratio of the catalyst to the solvent I is 2-26:5-30.
Further, the anti-precipitant is K 2 CO 3 KOH or NaOH.
Further, the second solvent is at least one of tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
Further, the ionization reactant is methyl iodide, ethyl iodide or methyl bromide, and the mass ratio of the ionization reactant to the polymer is 1-5:1.
further, the mass ratio of the ionizing reactant to the polymer is 2:1.
the invention also discloses application of the hyperbranched anion exchange membrane in preparing a fuel cell.
The invention has the following beneficial effects:
1. the hyperbranched anion exchange membrane prepared by the invention has low water absorption swelling, high mechanical strength and free volume larger than that of a linear polymer, thereby bringing ultrahigh conductivity and alkali resistance stability;
2. the hyperbranched anion exchange membrane prepared by the invention has excellent performance, and the peak power density is as high as 1.45W/cm 2 。
Drawings
FIG. 1 is a water swelling diagram of the anion exchange membranes prepared in examples 1-4 and comparative example of the present invention;
FIG. 2 is a graph showing the change in conductivity with temperature of the anion exchange membranes prepared in examples 1 to 4 and comparative example of the present invention;
FIG. 3 is a plot of conductivity versus time for hyperbranched anion exchange membranes prepared in example 2;
FIG. 4 is a graph of the power curve and I-V curve of a hyperbranched anion exchange membrane fuel cell prepared in example 2.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
a hyperbranched anion exchange membrane having the structural formula:
the chemical structure of Ar1 monomer is:
the chemical structure of Ar2 monomer is:
a method for preparing a hyperbranched anion exchange membrane, comprising the following steps:
s1: firstly, ar1 monomer and Ar2 monomer are mixed with 5:95 molar ratio is dissolved in dichloromethane, and after stirring for 5min, N-methyl-4-piperidone monomer is added and stirring is continued for 5min; the molar ratio of the sum of Ar1 monomer and Ar2 monomer to N-methyl-4-piperidone monomer is 1:1.4, the concentration of the sum of all monomers in the solution being 20% by weight;
s2: adding trifluoroacetic acid and trifluoromethanesulfonic acid into the mixed solution obtained in the step S1, wherein the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to the dichloromethane is 1:5:20, a step of; then reacting for 5 hours at the temperature of minus 10 ℃, then adding the mixed solution into 1MKOH solution, adjusting the pH value of the solution to 8, then reacting for 24 hours at the temperature of 60 ℃, and filtering to obtain a polymer; washing the polymer with pure water for 3 times, and then drying the polymer in a vacuum environment at 80 ℃ for 24 hours;
s3: dissolving a polymer in tetrahydrofuran at 60 ℃ to obtain a polymer solution with the concentration of 10wt%, and adding methyl iodide to react for 12 hours after the polymer solution is cooled to room temperature, wherein the mass ratio of the methyl iodide to the polymer is 2:1, a step of; then adding the polymer solution into ethyl acetate, filtering the precipitate, washing the precipitate with ethyl acetate for 3 times, and then drying the precipitate for 12 hours in a vacuum environment at 60 ℃;
s4: dissolving the dried precipitate in tetrahydrofuran to obtain homogeneous solution with concentration of 5wt%, pouring the homogeneous solution onto glass plate, stoving at 60 deg.c for 24 hr to obtain dried film, soaking the dried film in 1M KOH at 60 deg.c for 48 hr to obtain the hyperbranched anion exchange film.
Example 2:
a hyperbranched anion exchange membrane having the structural formula:
the chemical structure of Ar1 monomer is:
the chemical structure of Ar2 monomer is:
a method for preparing a hyperbranched anion exchange membrane, comprising the following steps:
s1: ar1 monomer and Ar2 monomer are firstly mixed according to a ratio of 60:40 in molar ratio in dichloromethane, stirring for 10min, adding N-methyl-4-piperidone monomer, and stirring for 10min; the molar ratio of the sum of Ar1 monomer and Ar2 monomer to N-methyl-4-piperidone monomer is 1:1.3, the concentration of the sum of all monomers in the solution being 30% by weight;
s2: adding trifluoroacetic acid and trifluoromethanesulfonic acid into the mixed solution obtained in the step S1, wherein the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to the dichloromethane is 3:20:30; then reacted at 0℃for 8 hours, after which the mixture was added to 2MK 2 CO 3 In the solution, regulating the pH value of the solution to 7.5, then reacting for 24 hours at 80 ℃, and filtering to obtain a polymer; washing the polymer with pure water for 4 times, and then drying the polymer in a vacuum environment at 80 ℃ for 24 hours;
s3: dissolving a polymer in acetonitrile at 60 ℃ to obtain a polymer solution with the concentration of 20wt%, and adding ethyl iodide to react for 48 hours after the polymer solution is cooled to room temperature, wherein the mass ratio of the ethyl iodide to the polymer is 1:1, a step of; then adding the polymer solution into ethyl acetate, filtering the precipitate, washing the precipitate with ethyl acetate for 4 times, and drying the precipitate for 12 hours in a vacuum environment at 80 ℃;
s4: dissolving the dried precipitate in acetonitrile to obtain a homogeneous solution with the concentration of 15wt%, pouring the homogeneous solution on a glass plate, drying at 80 ℃ for 8 hours to obtain a dried film, and then soaking the dried film in 1M KOH at 60 ℃ for 12 hours to obtain the hyperbranched anion-exchange membrane.
Example 3:
a hyperbranched anion exchange membrane having the structural formula:
the chemical structure of Ar1 monomer is:
the chemical structure of Ar2 monomer is:
a method for preparing a hyperbranched anion exchange membrane, comprising the following steps:
s1: ar1 monomer and Ar2 monomer are firstly mixed according to the ratio of 10: dissolving the mixture in methylene dichloride according to the molar ratio of 90, stirring for 10min, adding the N-methyl-4-piperidone monomer, and continuously stirring for 10min; the molar ratio of the sum of Ar1 monomer and Ar2 monomer to N-methyl-4-piperidone monomer is 1:1, the concentration of the sum of all monomers in the solution is 50wt%;
s2: adding trifluoroacetic acid and trifluoromethanesulfonic acid into the mixed solution obtained in the step S1, wherein the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to the dichloromethane is 2:15:20, a step of; then reacting for 5 hours at the temperature of 2 ℃, then adding the mixed solution into 5M NaOH solution, adjusting the pH value of the solution to 9, then reacting for 24 hours at the temperature of 70 ℃, and filtering to obtain a polymer; washing the polymer with pure water for 4 times, and then drying the polymer in a vacuum environment at 80 ℃ for 24 hours;
s3: dissolving a polymer in acetonitrile at 60 ℃ to obtain a polymer solution with the concentration of 30wt%, and adding bromomethane to react for 24 hours after the polymer solution is cooled to room temperature, wherein the mass ratio of bromomethane to the polymer is 4:1, a step of; then adding the polymer solution into ethyl acetate, filtering the precipitate, washing the precipitate with ethyl acetate for 3 times, and then drying the precipitate for 24 hours in a vacuum environment at 80 ℃;
s4: dissolving the dried precipitate in acetonitrile to obtain a homogeneous solution with the concentration of 20wt%, pouring the homogeneous solution on a glass plate, drying at 80 ℃ for 24 hours to obtain a dried film, and then soaking the dried film in 1M KOH at 60 ℃ for 48 hours to obtain the hyperbranched anion-exchange membrane.
Example 4:
a hyperbranched anion exchange membrane having the structural formula:
the chemical structure of Ar1 monomer is:
the chemical structure of Ar2 monomer is:
a method for preparing a hyperbranched anion exchange membrane, comprising the following steps:
s1: ar1 monomer and Ar2 monomer are firstly mixed according to the ratio of 10: dissolving the mixture in methylene dichloride according to the molar ratio of 90, stirring for 20min, adding the N-methyl-4-piperidone monomer, and continuously stirring for 20min; the molar ratio of the sum of Ar1 monomer and Ar2 monomer to N-methyl-4-piperidone monomer is 1:1.4, the concentration of the sum of all monomers in the solution being 60% by weight;
s2: adding trifluoroacetic acid and trifluoromethanesulfonic acid into the mixed solution obtained in the step S1, wherein the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to the dichloromethane is 6:1:20, a step of; then reacting for 5 hours at 10 ℃, then adding the mixed solution into 2MKOH solution, adjusting the pH value of the solution to 10, then reacting for 48 hours at 70 ℃, and filtering to obtain a polymer; washing the polymer with pure water for 5 times, and then drying the polymer in a vacuum environment at 80 ℃ for 20 hours;
s3: dissolving a polymer in N, N-dimethylformamide at 80 ℃ to obtain a polymer solution with the concentration of 30wt%, and adding methyl iodide to react for 12 hours after the polymer solution is cooled to room temperature, wherein the mass ratio of methyl iodide to the polymer is 5:1, a step of; then adding the polymer solution into ethyl acetate, filtering the precipitate, washing the precipitate with ethyl acetate for 3 times, and then drying the precipitate for 20 hours in a vacuum environment at 80 ℃;
s4: dissolving the dried precipitate in N, N-dimethylformamide to obtain a homogeneous solution with the concentration of 30wt%, pouring the homogeneous solution on a glass plate, drying at 80 ℃ for 12 hours to obtain a dried film, and then soaking the dried film in 1M KOH at 60 ℃ for 48 hours to obtain the hyperbranched anion-exchange membrane.
Experimental example:
1. anion exchange Membrane Performance test
Three A, B, C sets of experiments were performed, two A, B sets of 4 samples each. The anion exchange membranes prepared in examples 1 to 4 and comparative example were cut into 40 samples of 3cm×3cm total, all of which were immersed in a 1m koh solution at 60 ℃ for 24 hours, and then the samples were washed with deionized water to be neutral.
(1) Membrane water absorption swelling test
The length change and weight change of the group A samples after soaking in deionized water at 20, 40, 60 and 80℃for 12 hours, respectively, were measured, and the results are shown in FIG. 1.
(2) Film conductivity test
Group B samples were tested using a Solartron 1287&1260 ac impedance meter at 20 ℃, 40 ℃, 60 ℃ and 80 ℃ and the results are shown in figure 2.
(3) Alkali resistance test of film
The anion exchange membrane prepared in example 2 was cut into a 1cm×3cm group C sample, which was immersed in a 1M KOH solution at 80 ℃ and the conductivity of the anion exchange membrane was measured at 25 ℃ every 300 hours, and the results are shown in fig. 3.
2. Fuel cell performance testing
1g of a commercially available 60wt% Pt/C and PtRu/C catalyst was weighed into a sample tube, followed by 40. Mu.L of an anion exchange resin solution (5 wt% DMSO solution) and 0.5mL of isopropyl alcohol, and the sample tube was sonicated in a water bath for 0.5-1h to form a catalyst ink. Cutting the anion exchange membrane prepared in example 2 into sample membrane with a length of 5×5cm, spraying catalyst ink on two sides of the sample membrane to form a cathode catalytic layer and an anode catalytic layer, wherein the catalyst layer loading is 0.4mg/cm 2 The prepared structure is a fuel cell membrane electrode (CCM); finally, the CCM is assembled in a fuel cell testing system (850e Multi Range,Scribner Associates Co) for cell performance testing. The test conditions were: the temperature of the cell is 80 ℃, pure hydrogen is used as fuel, pure oxygen and air (without CO 2 ) As an oxidizing agent, the test results are shown in fig. 4.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The hyperbranched anion exchange membrane is characterized by being formed by polymerizing an Ar1 monomer, an Ar2 monomer and an N-methyl-4-piperidone monomer, and has the following structural general formula:
wherein M is - Is I - 、Br - 、Cl - 、OH - Or HCO 3 2- X is more than 0 and less than or equal to 60, and x is an integer;
the Ar1 monomer is an aryl compound with the functionality degree more than or equal to 3, and the chemical structure is as follows:
the Ar2 monomer is one of the following compounds:
2. the method for preparing the hyperbranched anion exchange membrane according to claim 1, characterized by comprising the following steps:
s1: firstly, dissolving Ar1 monomer and Ar2 monomer in a solvent I, stirring for 5-20min, then adding N-methyl-4-piperidone monomer, and continuously stirring for 5-20min; the molar ratio of the Ar1 monomer to the Ar2 monomer is m: (100-m), wherein m is an integer from 5 to 60; the molar ratio of the sum of the Ar1 monomer and the Ar2 monomer to the N-methyl-4-piperidone monomer is 1:1-1.4, wherein the concentration of the sum of all monomers in the solution is 20-60wt%;
s2: adding a catalyst into the mixed solution obtained in the step S1, reacting for 5-8 hours at the temperature of minus 10-10 ℃, then adding the mixed solution into an inverse precipitant, regulating the pH value of the solution to be more than or equal to 7, reacting for 24-48 hours at the temperature of 60-80 ℃, and filtering to obtain a polymer; washing the polymer with pure water for 3-5 times, and drying in a vacuum environment at 75-85 ℃ for 20-26h;
s3: dissolving a polymer in a second solvent at 60-80 ℃ to obtain a polymer solution with the concentration of 5-30wt%, cooling the polymer solution to room temperature, adding an ionization reactant to react for 12-48h, adding the polymer solution into an anti-precipitant, filtering the precipitate, washing the precipitate with ethyl acetate for 3-5 times, and drying the precipitate in a vacuum environment at 60-80 ℃ for 12-24h;
s4: dissolving the dried precipitate in a second solvent to obtain a homogeneous solution with the concentration of 5-30wt%, pouring the homogeneous solution on a forming plate, drying at 60-80 ℃ for 8-24 hours to obtain a dried film, and then soaking the dried film in 1M KOH at 60 ℃ for 12-48 hours to obtain the hyperbranched anion exchange membrane.
3. The method for preparing the hyperbranched anion exchange membrane according to claim 2, characterized in that: the first solvent is dichloromethane.
4. The method for preparing the hyperbranched anion exchange membrane according to claim 2, characterized in that: the catalyst is trifluoroacetic acid and trifluoromethanesulfonic acid, and the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid is 1-6:1-20.
5. The method for preparing the hyperbranched anion exchange membrane according to claim 2, characterized in that: the volume ratio of the catalyst to the solvent I is 2-26:5-30.
6. The method for preparing the hyperbranched anion exchange membrane according to claim 2, characterized in that: the reverse precipitant is K 2 CO 3 KOH or NaOH.
7. The method for preparing the hyperbranched anion exchange membrane according to claim 2, characterized in that: the second solvent is at least one of tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
8. The method for preparing the hyperbranched anion exchange membrane according to claim 2, characterized in that: the ionization reactant is methyl iodide, ethyl iodide or methyl bromide, and the mass ratio of the ionization reactant to the polymer is 1-5:1.
9. the method for preparing the hyperbranched anion exchange membrane according to claim 8, characterized in that: the mass ratio of the ionization reactant to the polymer is 2:1.
10. use of the hyperbranched anion-exchange membrane of claim 1 in the preparation of a fuel cell.
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