CN113501896B - Ordered alkaline anion material, preparation method thereof and anion exchange membrane fuel cell - Google Patents
Ordered alkaline anion material, preparation method thereof and anion exchange membrane fuel cell Download PDFInfo
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- CN113501896B CN113501896B CN202110771262.8A CN202110771262A CN113501896B CN 113501896 B CN113501896 B CN 113501896B CN 202110771262 A CN202110771262 A CN 202110771262A CN 113501896 B CN113501896 B CN 113501896B
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000000446 fuel Substances 0.000 title claims abstract description 22
- 150000001450 anions Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002608 ionic liquid Substances 0.000 claims abstract description 40
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 26
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 25
- YFHWESHZRVUNHI-UHFFFAOYSA-N 1-ethenyl-4,5-dimethylimidazole Chemical compound CC=1N=CN(C=C)C=1C YFHWESHZRVUNHI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 239000011344 liquid material Substances 0.000 claims abstract description 20
- 238000005342 ion exchange Methods 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 10
- 239000002585 base Substances 0.000 claims abstract description 6
- 238000001338 self-assembly Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 150000001350 alkyl halides Chemical class 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 6
- 238000005349 anion exchange Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 13
- 239000012074 organic phase Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical group OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000003495 polar organic solvent Substances 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- 239000012265 solid product Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- WRYNUJYAXVDTCB-UHFFFAOYSA-M acetyloxymercury Chemical compound CC(=O)O[Hg] WRYNUJYAXVDTCB-UHFFFAOYSA-M 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- -1 halide ions Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000000235 small-angle X-ray scattering Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 2
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 239000012043 crude product Substances 0.000 description 2
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- 230000001678 irradiating effect Effects 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
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- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- JKOTZBXSNOGCIF-UHFFFAOYSA-N 1-bromopentadecane Chemical compound CCCCCCCCCCCCCCCBr JKOTZBXSNOGCIF-UHFFFAOYSA-N 0.000 description 1
- BFDNZQUBFCYTIC-UHFFFAOYSA-N 1-bromotridecane Chemical compound CCCCCCCCCCCCCBr BFDNZQUBFCYTIC-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000032258 transport Effects 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
-
- 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
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
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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
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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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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- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of fuel cells, and particularly relates to an ordered alkaline anion material, a preparation method thereof and an anion exchange membrane fuel cell. The preparation method of the ordered alkaline anion material provided by the invention comprises the following steps: dissolving 4, 5-dimethyl-1-vinylimidazole and halogenated alkane for nucleophilic substitution reaction to obtain vinylimidazole amphiphilic ionic liquid; self-assembling the vinyl imidazole amphiphilic ionic liquid in water to form an ordered liquid crystal system, and carrying out in-situ photopolymerization on the ordered liquid crystal system under ultraviolet light to obtain an ordered polyionic liquid material; the ordered polyion liquid material is mixed with a strong alkali solution for ion exchange to obtain the ordered alkaline anion material, so that the balance of the conductivity, the membrane strength and the stability of the ordered alkaline anion exchange membrane is realized, and meanwhile, the ordered polyion liquid material has high OH ‑ Transport efficiency and base stability.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to an ordered alkaline anion material, a preparation method thereof and an anion exchange membrane fuel cell.
Background
The Alkaline Anion Exchange Membrane Fuel Cell (AAEMFC) can use a non-noble metal catalyst, so that the cost of the fuel cell can be greatly reduced, and the alkaline anion exchange membrane fuel cell becomes a new hot spot in the field of fuel cells, but the performance of the alkaline anion exchange membrane fuel cell is still a certain difference from that of the current proton exchange membrane fuel cell. As the basic anion exchange membrane (AAEM) is used as a key material of AAEMFCE, the performance of the AAEM is directly determined by the output performance of the battery, so that the development of the high-performance AAEM material is important to the improvement of the AAEMFC performance.
However, there is a significant conflict between conductivity and stability of AAEM materials. Due to OH - Has a mobility lower than H + Thus, to obtain higher conductivity, AAEM materials usually require higher ion exchange capacity, which however leads to too high a water absorption (water absorption swelling) of the AAEM material, a decrease in mechanical strength, and thus a decrease in the effective ion concentration in the membrane, which is detrimental to OH - The structure of the AAEM material is modified by adopting compounding and crosslinking to inhibit swelling, but the improvement of ion conductivity is often influenced.
Research shows that the surface active ionic liquid self-assembles to form liquid crystal structure with molecular phase separation, and the hydrophilic area may be OH - The conduction of (2) provides an effective ion transport channel and the hydrophobic domain can effectively inhibit swelling of the membrane. However, most of anion exchange membranes based on ionic liquid self-assembled liquid crystal structures prepared at present use imidazole cationic ionic liquid, but the membranes prepared by the imidazole cationic ionic liquid have poor stability.
Disclosure of Invention
In view of the above, the invention provides an ordered alkaline anion material, a preparation method thereof and an anion exchange membrane fuel cell.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an ordered alkaline anion material, which comprises the following steps:
dissolving 4, 5-dimethyl-1-vinylimidazole and halogenated alkane for nucleophilic substitution reaction to obtain vinylimidazole amphiphilic ionic liquid;
self-assembling the vinyl imidazole amphiphilic ionic liquid in water to form an ordered liquid crystal system, and carrying out in-situ photopolymerization on the ordered liquid crystal system under ultraviolet light to obtain an ordered polyionic liquid material;
and mixing the ordered polyion liquid material with a strong alkali solution for ion exchange to obtain the ordered alkaline anion material.
Preferably, the haloalkane is C 12~16 Halogenated alkanes.
Preferably, the ratio of the amounts of the 4, 5-dimethyl-1-vinylimidazole and haloalkane is 1 (1.1-2).
Preferably, the temperature of the nucleophilic substitution reaction is 60-80 ℃, the time of the nucleophilic substitution reaction is 36-48 h, and the nucleophilic substitution reaction is carried out in a protective atmosphere.
Preferably, in the ionic liquid aqueous solution obtained by mixing the vinyl imidazole amphiphilic ionic liquid and water, the mass percentage of the vinyl imidazole amphiphilic ionic liquid is 50-85%.
Preferably, the self-assembly temperature is 25-40 ℃, and the self-assembly time is 30-50 days.
Preferably, the time of the in-situ photopolymerization is 0.5 to 2 hours.
Preferably, the molar concentration of the strong alkali solution is 1-5 mol/L; the time of the ion exchange is 36-48 h, and the ion exchange is carried out in a vacuum environment.
The invention provides the ordered alkaline anion material prepared by the preparation method.
The invention provides an anion exchange membrane fuel cell, and the membrane for the anion exchange membrane fuel cell is the ordered alkaline anion exchange material according to the technical scheme.
The invention provides a preparation method of an ordered alkaline anion material, which comprises the following steps: dissolving 4, 5-dimethyl-1-vinylimidazole and halogenated alkane for nucleophilic substitution reaction to obtain vinylimidazole amphiphilic ionic liquid; self-assembling the vinyl imidazole amphiphilic ionic liquid in water to form an ordered liquid crystal system, and then carrying out in-situ photopolymerization on the ordered liquid crystal system under ultraviolet light to obtain an ordered polyionic liquid material; the said device is provided withAnd mixing the ordered polyion liquid material with a strong alkali solution for ion exchange to obtain the ordered alkaline anion material. In the invention, 4, 5-dimethyl-1-vinyl imidazole and halogenated alkane carry out nucleophilic substitution reaction to obtain polymerizable imidazole amphiphilic ionic liquid with C4 and C5 substitution, and the polymerizable imidazole amphiphilic ionic liquid has good alkali resistance and stability; when the imidazole amphiphilic ionic liquid is in water, hydrophilic groups and hydrophobic groups are self-assembled to obtain an ordered structure, double bond functional groups in an ordered liquid crystal system are subjected to in-situ polymerization under ultraviolet irradiation to obtain an ordered polyionic liquid material retaining the microscopic ordered structure of the liquid crystal, and then halide ions in the ordered polyionic liquid material are exchanged into hydroxyl ions through ion exchange to finally obtain the ordered alkaline anionic material; the ordered alkaline anion material is obtained after self-assembly polymerization of the imidazole amphiphilic ionic liquid, a highly ordered liquid crystal microstructure is built in the film by self-assembly of hydrophilic groups and hydrophobic groups in the amphiphilic ionic liquid, a hydrophilic-hydrophobic phase separation structure in the film is enhanced, a highly ordered ion transmission channel is formed, the alkali-resistant stability is realized, the balance of the conductivity, the mechanical strength and the stability of the ordered alkaline anion material is realized, and the high OH is realized - Transport efficiency and base stability.
Detailed Description
The invention provides a preparation method of an ordered alkaline anion exchange membrane, which comprises the following steps:
dissolving 4, 5-dimethyl-1-vinylimidazole and halogenated alkane for nucleophilic substitution reaction to obtain vinylimidazole amphiphilic ionic liquid;
self-assembling the vinyl imidazole amphiphilic ionic liquid in water to form an ordered liquid crystal system, and carrying out in-situ photopolymerization on the ordered liquid crystal system under ultraviolet light to obtain an ordered polyionic liquid material;
and mixing the ordered polyion liquid material with a strong alkali solution for ion exchange to obtain the ordered alkaline anion material.
In the present invention, the raw materials used are commercially available products well known to those skilled in the art unless otherwise specified.
According to the invention, 4, 5-dimethyl-1-vinylimidazole and halogenated alkane are dissolved for nucleophilic substitution reaction (hereinafter referred to as first nucleophilic substitution reaction) to obtain vinylimidazole amphiphilic ionic liquid.
In the present invention, the polar organic solvent for dissolving 4, 5-dimethyl-1-vinylimidazole and haloalkane is preferably methanol and/or acetonitrile, more preferably methanol, and in the present invention, when the polar organic solvent is preferably a mixed solvent of methanol and acetonitrile, the specific ratio of the two solvents is not particularly limited.
The polar organic solvent used in the preparation method is preferably methanol and/or acetonitrile, and raw materials with high toxicity are not used, so that the preparation method is safe and environment-friendly.
The invention has no special requirement on the dosage of the polar organic solvent, and can realize complete dissolution of the 4, 5-dimethyl-1-vinyl imidazole and the halogenated alkane.
In the present invention, the preparation method of 4, 5-dimethyl-1-vinylimidazole preferably comprises the steps of:
mixing 4, 5-dimethyl imidazole, vinyl acetate and a catalyst to carry out an affinity substitution reaction (hereinafter referred to as a second nucleophilic substitution reaction) to obtain the 4, 5-dimethyl-1-vinyl imidazole.
In the present invention, the catalyst is preferably trifluoroacetic acid and/or mercury acetate, more preferably trifluoroacetic acid and mercury acetate, and the mass ratio of the trifluoroacetic acid to the mercury acetate is preferably (1-2): 1, more preferably 1.55:1.
In the present invention, the mass ratio of 4, 5-dimethylimidazole to vinyl acetate is preferably 1 (3.5 to 4), more preferably 1:3.9.
In the present invention, the mass ratio of the 4, 5-dimethylimidazole to the catalyst is preferably (1 to 1.5): 1, more preferably 1.45:1.
In the invention, a polymerization inhibitor is preferably added when the 4, 5-dimethylimidazole, the vinyl acetate and the catalyst are mixed, and the polymerization inhibitor has the function of inhibiting the vinyl acetate from undergoing intramolecular polymerization reaction; in the present invention, the polymerization inhibitor is preferably hydroquinone, and the mass of the polymerization inhibitor is 0.1 to 0.15% of the mass of the vinyl acetate, more preferably 0.12 to 0.14%.
The invention has no special requirements on the specific implementation mode of the 4, 5-dimethyl imidazole, vinyl acetate, catalyst and polymerization inhibitor when the 4, 5-dimethyl imidazole, vinyl acetate and catalyst are mixed or the 4, 5-dimethyl imidazole, vinyl acetate, catalyst and polymerization inhibitor are mixed uniformly.
In the present invention, the temperature of the second nucleophilic substitution reaction is preferably 60 to 80 ℃, more preferably 35 to 70 ℃, and the time of the second nucleophilic substitution reaction is preferably 2 to 6 hours, more preferably 3 to 5 hours.
In the present invention, the equation of the second nucleophilic substitution reaction is shown in formula I:
the reaction system obtained by the second nucleophilic substitution reaction is preferably subjected to post-treatment to obtain the 4, 5-dimethyl-1-vinylimidazole. In the present invention, the post-treatment preferably includes: removing unreacted vinyl acetate, dissolving, neutralizing, extracting to obtain an organic phase of the target product 4, 5-dimethyl-1-vinylimidazole, drying the organic phase and removing the extractant.
The unreacted vinyl acetate is preferably removed by distillation under reduced pressure; the invention has no special requirements on the specific implementation mode of the reduced pressure distillation; after the unreacted vinyl acetate is removed, the solid product after the ethyl acetate is removed is preferably subjected to dissolution and neutralization, in the invention, the solid product is preferably dissolved in the saturated sodium bicarbonate to perform neutralization reaction until the pH value of the neutralized solution is 7-8, and the catalyst is preferably removed by dissolution and neutralization during the first nucleophilic substitution reaction; the invention preferably extracts the solution after the neutralization reaction to obtain a water phase and an organic phase, wherein the organic phase contains the target product 4, 5-dimethyl-1-vinylimidazole; the extractant for extraction is preferably diethyl ether or dichloromethane, and in the invention, the extraction times are preferably 3-5 times; the invention has no special requirement on the dosage of the extraction solvent in each extraction, the invention preferably detects the content of the target product in the water phase by Thin Layer Chromatography (TLC), and when the water phase has no target product 4, 5-dimethyl-1-vinylimidazole; the organic phases of each extraction are preferably combined in the present invention. The invention preferably extracts the target product 4, 5-dimethyl-1-vinylimidazole into the organic phase by extraction, and preferably dries the organic phase containing the target product, in which the drying agent is preferably anhydrous magnesium sulfate; the extraction agent is preferably removed by reduced pressure distillation, and the method has no special requirement on the specific implementation mode of the reduced pressure distillation, and the extraction agent is removed completely.
In the present invention, the haloalkane is preferably C 12~16 A haloalkane, preferably a bromoalkane, more preferably a 1-bromoalkane; the haloalkane is more preferably C 12~16 Bromoalkane, in particular embodiments of the present invention, the haloalkane is preferably one or more of 1-bromododecane, 1-bromotridecane, 1-bromotetradecane, 1-bromopentadecane and 1-bromohexadecane, more preferably 1-bromododecane and/or 1-bromotetradecane; in the present invention, when the haloalkane is preferably two or more of the above-mentioned substances, the present invention has no particular requirement on the compounding relationship of the specific substances.
In the present invention, the ratio of the amounts of the 4, 5-dimethyl-1-vinylimidazole and haloalkane is preferably 1 (1.1 to 2), more preferably 1 (1.5 to 1.8).
In the present invention, the temperature of the first nucleophilic substitution reaction is preferably 60 to 80 ℃, more preferably 65 to 75 ℃; the time of the first nucleophilic substitution reaction is preferably 36 to 48 hours, more preferably 40 to 42 hours; the first nucleophilic substitution reaction is performed in a protective gas atmosphere, which is preferably an inert gas or nitrogen.
In a specific embodiment of the present invention, the equation of the first nucleophilic substitution reaction is shown in formula II:
in the present invention, n in the formula II is preferably a positive integer of 12 to 16.
The invention preferably carries out post-treatment on a reaction system obtained by the first nucleophilic substitution reaction to obtain the vinylimidazole amphiphilic ionic liquid; in the present invention, the post-treatment preferably includes: sequentially removing the polar organic solvent, recrystallizing and drying.
The polar organic solvent is preferably removed by distillation under reduced pressure; the invention has no special requirements on the specific implementation mode of the reduced pressure distillation; after removal of the polar organic solvent, the solid product from which the polar organic solvent is removed is preferably subjected to recrystallization in the present invention, which is preferably: the solid product is dissolved in a recrystallization solvent for recrystallization, wherein the recrystallization solvent is preferably diethyl ether and/or ethyl acetate, more preferably diethyl ether, and the specific implementation process of the recrystallization is not particularly limited, and the operation well known to those skilled in the art is adopted, and in the specific embodiment of the invention, the specific process of the recrystallization is as follows: and dissolving the solid product in the recrystallization solvent, and cooling to separate out. The present invention preferably provides for purification of the solid product by recrystallisation; the present invention preferably dries the recrystallized product, in which the drying temperature is preferably 40 to 60 ℃, and the present invention does not require any special time for the drying, and the recrystallized product is dried to a constant weight.
After the vinylimidazole amphiphilic ionic liquid is obtained, the vinylimidazole amphiphilic ionic liquid is self-assembled in water to form an ordered liquid crystal system.
In the present invention, the water is preferably deionized water.
In the invention, in the ionic liquid aqueous solution obtained by mixing the vinyl imidazole amphiphilic ionic liquid and water, the mass percentage of the vinyl imidazole amphiphilic ionic liquid is preferably 50-85%, more preferably 60-80%.
In the invention, the aqueous solution of the ionic liquid obtained by mixing the vinyl imidazole amphiphilic ionic liquid and water also preferably comprises a photoinitiator, and the photoinitiator is preferably used for initiating the in-situ photopolymerization reaction.
In the present invention, the photoinitiator is preferably one or more of 2-hydroxy-2-methylpropionacetone, 2-hydroxy-2-methyl-1-phenylketone and 1-hydroxy-cyclohexyl-phenylketone, more preferably 2-hydroxy-2-methylpropionacetone and/or 2-hydroxy-2-methyl-1-phenylketone, and in the present invention, when the photoinitiator is preferably two or more of the above, the compounding ratio of the above specific substances is not particularly required.
In the present invention, the mass percentage of the photoinitiator in the ionic liquid aqueous solution is preferably 0.1 to 0.5%, more preferably 0.2 to 0.4%.
In the present invention, the self-assembly temperature is preferably 25 to 40 ℃, more preferably 30 to 35 ℃; the self-assembly time is preferably 30 to 50 days, more preferably 35 to 45 days.
In the present invention, the self-assembly is preferably performed in a constant temperature and humidity cabinet.
In the invention, the vinyl imidazole amphiphilic ionic liquid is self-assembled in water, wherein hydrophilic groups and hydrophobic groups are self-assembled to form an ordered structure.
After forming an ordered liquid crystal system, the ordered liquid crystal system is subjected to in-situ photopolymerization under ultraviolet light to obtain the ordered polyion liquid material.
The wavelength of the ultraviolet light is not particularly limited in the present invention, and in a specific embodiment of the present invention, the wavelength of the ultraviolet light is preferably 365nm.
In the present invention, the time of the in-situ photopolymerization is preferably 0.5 to 2 hours, more preferably 1 to 1.5 hours. The temperature of the in situ photopolymerization reaction is preferably an internal room temperature.
In a specific embodiment of the present invention, the equation of the in situ photopolymerization is shown in formula III:
in the present invention, the polymerization degree m of the in-situ photopolymerization is preferably determined by the time of the photopolymerization.
The ordered polyionic liquid material is obtained through in-situ photopolymerization and polymerization reaction of double bond structures in an ordered liquid crystal system.
After the ordered polyion liquid material is obtained, the ordered polyion liquid material is mixed with a strong alkali solution for ion exchange, so that the ordered alkaline anion material is obtained.
In the present invention, the alkali solution is preferably an alkali metal hydroxide solution, more preferably a KOH solution or NaOH solution; the molar concentration of the strong alkali solution is preferably 1 to 5mol/L, more preferably 1.5 to 4mol/L; in the present invention, the strong base solution is preferably a nitrogen saturated strong base solution, and oxidation of the ordered polyionic liquid material by dissolved oxygen in the strong base solution is prevented.
The invention has no special requirement on the dosage of the strong alkali solution, and can ensure that the ordered polyion liquid material can be completely immersed in the strong alkali solution after being mixed with the strong alkali solution.
In the present invention, the time of the ion exchange is preferably 36 to 48 hours, more preferably 40 to 45 hours; the temperature of the ion exchange is preferably room temperature; the ion exchange is carried out in a vacuum environment, and the invention has no special requirement on the vacuum degree of the vacuum environment.
The ordered alkaline anion material is obtained by carrying out post-treatment on the product after ion exchange, wherein the post-treatment is preferably water washing and drying, the water washing is preferably flushing, and the strong alkali solution remained on the surface of the membrane is removed by the water washing; the invention has no special requirement on the specific implementation process of the drying, and the film drying value is constant.
The invention exchanges the halogen ions in the ordered polyion liquid membrane into hydroxyl ions through ion exchange.
In a specific embodiment of the present invention, the ion exchange equation is shown in formula VI:
the invention provides the ordered alkaline anion material prepared by the preparation method.
In the invention, the molecular structure of the ordered alkaline anionic material is a product shown in a formula VI.
The ordered alkaline anion exchange membrane provided by the invention is obtained by polymerization after self-assembly ordering of C4 and C5 substituted imidazole amphiphilic ionic liquid, and the OH is improved through highly ordered ion transmission channels constructed by the self-assembly of the ionic liquid - Ion transport efficiency; and the C4 and C5 substituted structure significantly improves the alkali stability of the alkali anion material.
The invention provides an anion exchange membrane fuel cell, and the membrane for the anion exchange membrane fuel cell is the ordered alkaline anion exchange material according to the technical scheme.
In the specific embodiment of the present invention, the ordered basic anion exchange material is prepared by adopting the preparation method of the ordered basic anion exchange membrane material, and the method is different in the steps: the ordered liquid crystal system is subjected to in-situ photopolymerization reaction under ultraviolet light to obtain ordered polyionic liquid material, which is replaced by: and (3) forming a film on the ordered liquid crystal system, and then carrying out in-situ photopolymerization under ultraviolet light to obtain the ordered polyion liquid film.
The invention has no special requirements on the specific implementation process of the film forming, and in the specific embodiment of the invention, the ordered liquid crystal system is poured into a surface dish or a culture dish, and the film is formed at the bottom of the surface dish or the culture dish or the ordered liquid crystal system is pressed between two quartz plates or glass slides to form the film.
In the invention, the electrode of the anion exchange membrane fuel cell is preferably a gas diffusion electrode, the cathode of the gas diffusion electrode is preferably Pt/C as a catalyst, and the cathode of the gas diffusion electrode is preferably oxygen; the anode of the gas diffusion electrode preferably takes PtRu/C as a catalyst, and the anode of the gas diffusion electrode is preferably hydrogen; the relative humidity of the inlet air of the gas diffusion electrode is preferably 100% RH, the flow rate of the hydrogen of the gas diffusion electrode is preferably 100mL/min, the flow rate of the oxygen of the gas diffusion electrode is preferably 200mL/min, and the back pressure on both sides of the cathode and anode of the gas diffusion electrode is preferably 0.2MPa.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
17.68g of 4, 5-dimethylimidazolium salt, 75mL of vinyl acetate, 4.8mL of trifluoroacetic acid, 4.75g of mercury acetate and 100mg of hydroquinone were mixed and subjected to an affinity substitution reaction at 80℃for 6 hours; removing excessive ethyl acetate from the reaction solution by reduced pressure distillation, dissolving a solid product in saturated sodium bicarbonate solution until the pH value of the neutralized solution is 7-8, adding methylene dichloride into the neutralized solution for extraction until target products cannot be detected in a water phase by TLC, combining extracted organic phases, drying the organic phases by adopting anhydrous magnesium sulfate, and removing the organic phases by reduced pressure distillation to obtain 4, 5-dimethyl-1-vinylimidazole;
dissolving 0.015mol of 4, 5-dimethyl-1-vinylimidazole and 0.023mol of 1-bromohexadecane in methanol, refluxing for 36 hours at 60 ℃ under nitrogen atmosphere, removing methanol solvent by rotary evaporation of the reacted mixture, and recrystallizing the crude product in diethyl ether for 3 times to obtain vinylimidazole amphiphilic ionic liquid;
mixing 3g of vinylimidazole amphiphilic ionic liquid, 1.95g of deionized water and 0.01g of 2-hydroxy-2-methyl propiophenone, standing at 40 ℃ for 30 days to perform self-assembly to form an ordered liquid crystal system, pouring the ordered liquid crystal system into a culture dish, coating the bottom of the culture dish to form a film, and irradiating the film formed by the ordered liquid crystal system with an ultraviolet light source of 365nm at room temperature for 30min to obtain an ordered polyionic liquid film;
and (3) soaking the ordered polyion liquid membrane in 1mol/LKOH solution for 36 hours under vacuum condition, washing the surface residual KOH solution with deionized water, and drying to constant weight to obtain the ordered alkaline anion exchange membrane. The ordered basic anion exchange membrane prepared in example 1 exhibits a ratio of 1 in the small angle X-ray scattering (SAXS) curve: the two scattering peaks of v 3 correspond to the (100) and (110) crystal planes of the hexagonal liquid crystal phase.
Example 2
17.68g of 4, 5-dimethylimidazolium salt, 75mL of vinyl acetate, 4.8mL of trifluoroacetic acid, 4.75g of mercury acetate and 100mg of hydroquinone were mixed and subjected to an affinity substitution reaction at 80℃for 6 hours; removing excessive ethyl acetate from the reaction solution by reduced pressure distillation, dissolving a solid product in saturated sodium bicarbonate solution until the pH value of the neutralized solution is 7-8, adding methylene dichloride into the neutralized solution for extraction until target products cannot be detected in a water phase by TLC, combining extracted organic phases, drying the organic phases by adopting anhydrous magnesium sulfate, and removing the organic phases by reduced pressure distillation to obtain 4, 5-dimethyl-1-vinylimidazole;
dissolving 0.015mol of 4, 5-dimethyl-1-vinylimidazole and 0.023mol of 1-bromohexadecane in methanol, refluxing for 36 hours at 60 ℃ under nitrogen atmosphere, removing methanol solvent by rotary evaporation of the reacted mixture, and recrystallizing the crude product in diethyl ether for 3 times to obtain vinylimidazole amphiphilic ionic liquid;
mixing 3g of vinylimidazole amphiphilic ionic liquid, 0.6g of deionized water and 0.01g of 2-hydroxy-2-methyl propiophenone, standing at 40 ℃ for 30 days to perform self-assembly to form an ordered liquid crystal system, pouring the ordered liquid crystal system into a culture dish, coating the bottom of the culture dish to form a film, and irradiating the film formed by the ordered liquid crystal system with an ultraviolet light source of 365nm at room temperature for 30min to obtain an ordered polyionic liquid film;
and (3) soaking the ordered polyion liquid membrane in 1mol/LKOH solution for 36 hours under a vacuum condition, washing the surface residual KOH solution with deionized water, and drying to constant weight to obtain the ordered alkaline anion exchange membrane. The ordered basic anion exchange membrane prepared in example 2 exhibits a ratio of 1 in the small angle X-ray scattering (SAXS) curve: 2, corresponding to the (100) and (200) crystal planes of the lamellar liquid crystal phase.
Test case
The ordered alkali anion exchange membrane prepared in the embodiment 1 is soaked in KOH of 1mol/L at 60 ℃ for 300 hours, and the swelling rate of a test product is 4%, which indicates that the ordered alkali anion exchange membrane prepared in the embodiment of the invention shows good dimensional stability in an alkali solution;
immersing the ordered alkaline anion exchange membrane prepared in the example 1 in KOH of 1mol/L at 60 ℃ for 300 hours, and testing the conductivity of the product before and after immersing, wherein the conductivity reduction rate is 7.4%; the ordered alkaline anion exchange membrane prepared by the embodiment of the invention shows good conductivity stability of alkaline solution.
Example 3
The product prepared in the example 1 is used as a diaphragm of an alkaline anion exchange membrane fuel cell, and is assembled into a single cell together with a commercial gas diffusion electrode, the performance of the cell is tested, the cell performance test is that under the condition of full humidification (100% humidification) at 60 ℃, hydrogen and oxygen are heated and humidified in a humidification tank and then are introduced into the cell, the flow rates of the hydrogen and the oxygen are respectively fixed at 100mL/min and 200mL/min, when the back pressure on two sides is 0.2MPa, the open circuit voltage of the cell is up to 0.94V, which indicates that the product membrane prepared in the example 1 has better gas blocking effect, and the highest power density of the cell is up to 50mW cm -2 The cell performance was good, indicating that the cell prepared in example 1 was suitable for use in an alkaline anion exchange membrane fuel cell.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the ordered alkaline anion material is characterized by comprising the following steps of:
dissolving 4, 5-dimethyl-1-vinylimidazole and halogenated alkane for nucleophilic substitution reaction to obtain vinylimidazole amphiphilic ionic liquid;
self-assembling the vinyl imidazole amphiphilic ionic liquid in water to form an ordered liquid crystal system, and carrying out in-situ photopolymerization on the ordered liquid crystal system under ultraviolet light to obtain an ordered polyionic liquid material;
and carrying out ion exchange on the ordered polyion liquid material and a strong alkali solution to obtain the ordered alkaline anion material.
2. The process of claim 1 wherein the haloalkane is C 12~16 Halogenated alkanes.
3. The process according to claim 1 or 2, wherein the ratio of the amounts of the 4, 5-dimethyl-1-vinylimidazole and haloalkane is 1 (1.1-2).
4. The method according to claim 1, wherein the nucleophilic substitution reaction is carried out in a protective atmosphere at a temperature of 60 to 80 ℃ for a time of 36 to 48 hours.
5. The preparation method of claim 1, wherein the mass percentage of the vinylimidazole amphiphilic ionic liquid in water is 50-85%.
6. The method according to claim 1 or 5, wherein the self-assembly temperature is 25 to 40 ℃ and the self-assembly time is 30 to 50 days.
7. The method of claim 1, wherein the in situ photopolymerization is carried out for a period of 0.5 to 2 hours.
8. The method according to claim 1, wherein the molar concentration of the strong base solution is 1 to 5mol/L; the time of the ion exchange is 36-48 h, and the ion exchange is carried out in a vacuum environment.
9. An ordered basic anion exchange material produced by the production method according to any one of claims 1 to 8.
10. An anion exchange membrane fuel cell characterized in that the membrane for an anion exchange membrane fuel cell is the ordered alkaline anion exchange material of claim 9.
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