CN117199465B - High ion selectivity ionic membrane for vanadium redox flow battery and preparation method thereof - Google Patents
High ion selectivity ionic membrane for vanadium redox flow battery and preparation method thereof Download PDFInfo
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- CN117199465B CN117199465B CN202311466625.2A CN202311466625A CN117199465B CN 117199465 B CN117199465 B CN 117199465B CN 202311466625 A CN202311466625 A CN 202311466625A CN 117199465 B CN117199465 B CN 117199465B
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- 239000012528 membrane Substances 0.000 title claims abstract description 51
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 29
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 66
- 238000007731 hot pressing Methods 0.000 claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 18
- 125000000129 anionic group Chemical group 0.000 claims abstract description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000005266 casting Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 14
- 230000001376 precipitating effect Effects 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 29
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical group CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 6
- ZIRURAJAJIQZFG-UHFFFAOYSA-N 1-aminopropane-1-sulfonic acid Chemical compound CCC(N)S(O)(=O)=O ZIRURAJAJIQZFG-UHFFFAOYSA-N 0.000 claims description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 4
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 4
- PENHQSIKLZJFGQ-UHFFFAOYSA-N C=CC1N(CCCS(O)(=O)=O)C=CC=C1.O Chemical compound C=CC1N(CCCS(O)(=O)=O)C=CC=C1.O PENHQSIKLZJFGQ-UHFFFAOYSA-N 0.000 claims description 4
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical group CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- HLBBIDAENVNMKZ-UHFFFAOYSA-N N1C(=NC=C1)S(=O)(=O)OCCCC=C Chemical compound N1C(=NC=C1)S(=O)(=O)OCCCC=C HLBBIDAENVNMKZ-UHFFFAOYSA-N 0.000 claims description 4
- -1 azo diisobutyl amidine Chemical class 0.000 claims description 4
- QDHFHIQKOVNCNC-UHFFFAOYSA-M butane-1-sulfonate Chemical compound CCCCS([O-])(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-M 0.000 claims description 4
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 4
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims 2
- 239000000243 solution Substances 0.000 description 103
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 22
- 229910001456 vanadium ion Inorganic materials 0.000 description 18
- 238000012360 testing method Methods 0.000 description 11
- 230000010220 ion permeability Effects 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 7
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000000149 penetrating effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a preparation method of a high ion selectivity ionic membrane for a vanadium redox flow battery, which specifically comprises the steps of preparing an amphoteric polymer: taking 10-40 parts of anionic monomers, 10-40 parts of nitrogen-containing monomers, 20-80 parts of zwitterionic monomers and 400-900 parts of deionized water, adding 0.2-0.5 part of initiator after heating, reacting for 10-12 hours, adding ethanol, precipitating, filtering and drying to obtain an amphoteric polymer; respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a solvent to obtain a solution A and a solution B with the mass percent of 5-20%; uniformly mixing the solution A and the solution B according to the mass ratio of 200:1-10:1 to obtain a film-forming solution; vacuum defoamation is carried out on the film-making solution, casting is carried out on a glass plate, and a composite ion exchange film is obtained after heat treatment; and (3) carrying out hot pressing on the composite ion exchange membrane to obtain the high ion selectivity ion membrane for the vanadium redox flow battery. The amphoteric polymer synthesized by the invention can further adjust the ion selectivity of the composite ionic membrane by adjusting the proportion of the amphoteric ionic monomer, the anionic monomer and the nitrogenous monomer, thereby improving the efficiency of the battery.
Description
Technical Field
The invention relates to the technical field of ion exchange membranes, in particular to a high-ion-selectivity ion membrane for a vanadium redox flow battery and a preparation method thereof.
Background
Renewable energy sources have intermittent properties, resulting in a conflict between seasonal and unstable power generation and the need for a continuously stable power supply for end-use applications. Therefore, energy storage devices, including batteries, are critical to a stable power supply. The ideal energy storage technology requires low cost, environmental protection, long-term operation stability, high performance and high energy density. Redox flow batteries exhibit excellent performance in terms of stability, safety, efficiency, reliability, and flexibility. Among them, all-Vanadium Flow Battery (VFB) shows significant advantages in medium-to-large energy conversion and storage systems. The electrolyte storage tank comprises two electrolyte storage tanks, two electrodes and a separator or a membrane, and the same electrolyte is used for the positive electrode and the negative electrode, so that cross contamination of the electrolyte in the charging and discharging processes is avoided.
The membrane is one of the key components of VFB and must meet the reactive ion (H + 、H 3 O + 、 SO 4 2− 、SO 4 H − ) With little or no diffusion of vanadium ions. Living bodyThe diffusion of the cations through the membrane completes the current loop, however, the permeation of vanadium ions causes pressure imbalance and self-discharge across the cell, thereby reducing the coulomb efficiency of the VFB. The ideal membrane has higher ion selectivity, high proton transmission density and better vanadium resistance. However, the existing membrane still has higher ion selectivity, poor vanadium resistance and the phenomenon that vanadium ions shuttle each other, so that self-discharge is generated to attenuate the capacity of the battery.
Disclosure of Invention
In order to solve the problems, the invention aims to provide the high ion selectivity ionic membrane for the vanadium redox flow battery and the preparation method thereof, and the membrane has low vanadium ion permeability and higher ion conductivity, and can be applied to all-vanadium redox flow batteries (VFB) to effectively improve the performance.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the application discloses a preparation method of a high ion selectivity ionic membrane for a vanadium redox flow battery, which specifically comprises the following steps:
s1, preparing an amphoteric polymer: taking 10-40 parts of anionic monomers, 10-40 parts of nitrogen-containing monomers, 20-80 parts of zwitterionic monomers and 400-900 parts of deionized water, uniformly stirring and dissolving, removing air, adjusting the pH value to 6-8, heating, adding 0.2-0.5 part of initiator, reacting for 10-12 hours, adding ethanol, precipitating, filtering and drying to obtain an amphoteric polymer; the number average molecular weight of the amphoteric polymer is 500000-1000000, and the 5wt% solution viscosity is 2000-5000 Pa.s;
s2, respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a solvent to obtain a solution A and a solution B with mass percent of 5-20%;
s3, uniformly mixing the solution A and the solution B according to the mass ratio of 200:1-10:1 to obtain a film-making solution;
s4, vacuum defoamation is carried out on the film-making solution, casting is carried out on a glass plate, and a composite ion exchange film is obtained after heat treatment; and (3) carrying out hot pressing on the composite ion exchange membrane to obtain the high ion selectivity ion membrane for the vanadium redox flow battery.
Preferably, the anionic monomer is one or more of acrylic acid, vinyl sulfonic acid, p-styrene sulfonic acid and 2-acrylamido-2-methyl-1-propane sulfonic acid; the nitrogen-containing monomer is one or more of acrylamide, 1-vinyl imidazole and N-vinyl pyrrolidone; the zwitterionic monomer is one or more of 2- [ [2- (acryloyloxy) ethyl ] dimethyl ammonium group ] ethane-1-sulfonate, 4- [ (3-methacrylamidopropyl) dimethyl ammonium group ] butane-1-sulfonate, 2-acrylamido-2-methyl-1-propane sulfonate, 1- (3-sulfopropyl) -2-vinyl pyridine hydroxide inner salt, 1-vinyl-3-propyl imidazole sulfonate and 3- (N, N-diallyl-N-methyl) aminopropane sulfonate.
Preferably, the initiator is one or more of ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite and azo diisobutyl amidine dihydrochloride.
Preferably, the heating temperature in the step S1 is 30-50 ℃.
Preferably, the solvent in step S2 is any one or a mixture of two or more of the following: pure water, ethanol, ethylene glycol, propylene glycol, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide.
Preferably, in the step S3, the solution A and the solution B are mixed, heated and stirred uniformly according to the mass ratio of 200:1-10:1; wherein the heating temperature is 60-100 ℃, and the heating time is 0.5-3 h; the stirring speed is 300-700 r/min, and the stirring time is 0.5-3 h.
Preferably, the time for vacuum deaeration is 0.5-3 hours; the temperature of the heat treatment is 140-180 ℃, and the time of the heat treatment is 2-6 hours; the hot pressing temperature is 100-140 ℃, the hot pressing time is 0.5-2 min, and the hot pressing pressure is 0.5-2 MPa.
Preferably, in step S4, the heat treatment is preceded by a preheating treatment, where the temperature of the preheating treatment is 60-80 ℃ and the time of the preheating treatment is 0.5-2 hours.
The invention also discloses a high-ion-selectivity ion membrane for the vanadium redox flow battery, which is prepared by adopting the preparation method of the high-ion-selectivity ion membrane for the vanadium redox flow battery.
The invention has the beneficial effects that:
1. the anionic monomer of the amphoteric polymer in the composite ion exchange membrane contains carboxylic acid and sulfonic acid ion exchange groups, so that the proton transmission density of the membrane can be effectively increased.
2. The nitrogen-containing monomer of the amphoteric polymer in the composite ion exchange membrane can be combined with the sulfonic acid group in the perfluorinated sulfonic acid resin to form positive charges, so that the permeation of vanadium ions can be inhibited.
3. The quaternization group and the sulfonic acid group of the amphoteric polymer in the composite ion exchange membrane are on the same branched chain, and can effectively inhibit vanadium ion permeation due to the Dannon effect, and meanwhile, the proton transmission density can be further improved due to the presence of the sulfonic acid group.
4. The amphoteric polymer designed and synthesized by the invention can further adjust the ion selectivity of the composite ionic membrane by adjusting the proportion of the amphoteric ion monomer, the anionic monomer and the nitrogenous monomer, thereby improving the efficiency of the battery.
The features and advantages of the present invention will be described in detail by way of example with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a perfluorinated sulfonic acid resin/amphoteric polymer composite ion exchange membrane for a vanadium redox flow battery;
FIG. 2 is a schematic diagram of the process of preparing an amphoteric polymer according to an embodiment of the present invention.
FIG. 3 is an infrared spectrum of an amphoteric polymer according to an embodiment of the present invention.
FIG. 4 is an EDS spectrum of a composite film of example one and comparative example one of the present invention.
Detailed Description
The present invention will be further described in detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
Referring to fig. 1, the preparation method of the high ion selectivity ionic membrane for the vanadium redox flow battery provided by the invention specifically comprises the following steps:
s1, preparing an amphoteric polymer: taking 10-40 parts of anionic monomers, 10-40 parts of nitrogen-containing monomers, 20-80 parts of zwitterionic monomers and 400-900 parts of deionized water, uniformly stirring and dissolving, introducing nitrogen to remove air, adjusting the pH value to 6-8, heating, adding 0.2-0.5 part of initiator, reacting for 10-12 hours, adding ethanol, precipitating, filtering and drying to obtain an amphoteric polymer; the number average molecular weight of the amphoteric polymer is 500000-1000000, and the 5wt% solution viscosity is 2000-5000 Pa.s;
s2, respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a solvent to obtain a solution A and a solution B with mass percent of 5-20%;
s3, uniformly mixing the solution A and the solution B according to the mass ratio of 200:1-10:1 to obtain a film-making solution;
s4, vacuum defoamation is carried out on the film-making solution, casting is carried out on a glass plate, and a composite ion exchange film is obtained after heat treatment; and (3) carrying out hot pressing on the composite ion exchange membrane to obtain the high ion selectivity ion membrane for the vanadium redox flow battery.
In one possible embodiment, the anionic monomer is one or more of acrylic acid, vinylsulfonic acid, p-styrenesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid; the nitrogen-containing monomer is one or more of acrylamide, 1-vinyl imidazole and N-vinyl pyrrolidone; the zwitterionic monomer is one or more of 2- [ [2- (acryloyloxy) ethyl ] dimethyl ammonium group ] ethane-1-sulfonate, 4- [ (3-methacrylamidopropyl) dimethyl ammonium group ] butane-1-sulfonate, 2-acrylamido-2-methyl-1-propane sulfonate, 1- (3-sulfopropyl) -2-vinyl pyridine hydroxide inner salt, 1-vinyl-3-propyl imidazole sulfonate and 3- (N, N-diallyl-N-methyl) aminopropane sulfonate.
In one possible embodiment, the initiator is one or more of ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite, azo diisobutyl amidine dihydrochloride, or a combination thereof.
In one possible embodiment, the heating temperature in step S1 is 30 to 50 ℃.
In a possible embodiment, the solvent in step S2 is any one or a mixture of two or more of the following: pure water, ethanol, ethylene glycol, propylene glycol, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide.
In a feasible embodiment, in the step S3, mixing, heating and stirring the solution A and the solution B according to the mass ratio of 200:1-10:1 until the mixture is uniform; wherein the heating temperature is 60-100 ℃, and the heating time is 0.5-3 h; the stirring speed is 300-700 r/min, and the stirring time is 0.5-3 h.
In a possible embodiment, the time for vacuum deaeration is 0.5-3 hours; the temperature of the heat treatment is 140-180 ℃, and the time of the heat treatment is 2-6 hours; the hot pressing temperature is 100-140 ℃, the hot pressing time is 0.5-2 min, and the hot pressing pressure is 0.5-2 MPa.
In a possible embodiment, in step S4, the heat treatment is preceded by a preheating treatment, where the temperature of the preheating treatment is 60-80 ℃ and the time of the preheating treatment is 0.5-2 hours.
Embodiment one:
step 1: weighing 30 parts of acrylic acid, 20 parts of acrylamide, 50 parts of 2- [ [2- (acryloyloxy) ethyl ] dimethyl ammonium group ] ethane-1-sulfonate and 400 parts of deionized water according to parts by weight, stirring and dissolving uniformly, introducing nitrogen, adding NaOH to adjust pH to be 8, heating to 35 ℃, slowly adding 0.2 part of ammonium persulfate/sodium bisulfate, reacting for 10 hours, adding ethanol, precipitating, filtering and drying at 45 ℃ to obtain an amphoteric polymer; the number average molecular weight of the obtained amphoteric polymer is 700000, and the 5wt% solution viscosity is 3100mpa.s;
step 2: respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a mixed solvent of N, N-dimethylacetamide and pure water to obtain a solution A and a solution B with the mass percent of 5%;
step 3: mixing the solution A and the solution B according to the mass ratio of 100:1, heating at 60 ℃ for 1h, and magnetically stirring at 300r/min for 0.5h to obtain a film-making solution;
step 4: vacuum defoaming the film-forming solution for 0.5h;
step 5: casting the film-forming solution on a glass plate, preheating at 60 ℃ for 0.5h, and then heat-treating at 140 ℃ for 2h to obtain the composite ion exchange film.
Step 6: and (3) carrying out hot pressing on the composite ion exchange membrane prepared by the steps on a hot press, wherein the hot pressing temperature is 100 ℃, the hot pressing time is 0.5min, and the hot pressing pressure is 0.5MPa, so as to obtain the final finished membrane.
Embodiment two:
step 1: weighing 10 parts by weight of vinylsulfonic acid, 20 parts by weight of 1-vinylimidazole, 50 parts by weight of 4- [ (3-methacrylamidopropyl) dimethyl ammonium group ] butane-1-sulfonate and 400 parts by weight of deionized water, stirring and dissolving uniformly, introducing nitrogen, adding NaOH to adjust pH to be=6, heating to 30 ℃, slowly adding 0.2 part by weight of potassium persulfate/sodium bisulfate, reacting for 10 hours, adding ethanol, precipitating, filtering, and drying at 45 ℃ to obtain an amphoteric polymer; the number average molecular weight of the obtained amphoteric polymer is 800000, and the 5Wt% solution viscosity is 3800 Pa.s;
step 2: respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a mixed solvent of N-methyl pyrrolidone and pure water to obtain a solution A and a solution B with the mass percent of 10%;
step 3: mixing the solution A and the solution B according to the mass ratio of 200:1, heating at 100 ℃ for 0.5h, and magnetically stirring at 400r/min for 1h to obtain a film-making solution;
step 4: vacuum defoaming the film-forming solution for 3 hours;
step 5: casting the film-forming solution on a glass plate, preheating at 65 ℃ for 1h, and then heat-treating at 150 ℃ for 3h to obtain the composite ion exchange membrane.
Step 6: and (3) carrying out hot pressing on the composite ion exchange membrane prepared by the steps on a hot press, wherein the hot pressing temperature is 110 ℃, the hot pressing time is 1min, and the hot pressing pressure is 1MPa, so as to obtain the final finished membrane.
Embodiment III:
step 1: weighing 40 parts of p-styrenesulfonic acid, 40 parts of N-vinyl pyrrolidone, 30 parts of 2-acrylamido-2-methyl-1-propane sulfonate and 900 parts of deionized water according to parts by weight, stirring and dissolving uniformly, introducing nitrogen, adding NaOH to adjust pH to be 7, heating to 50 ℃, slowly adding 0.5 part of azo diisobutyl amidine dihydrochloride, reacting for 12 hours, adding ethanol, precipitating, filtering and drying at 45 ℃ to obtain an amphoteric polymer; the number average molecular weight of the obtained amphoteric polymer is 55000, and the 5wt% solution viscosity is 2700 Pa.s;
step 2: respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a mixed solvent of dimethyl sulfoxide and pure water to obtain a solution A and a solution B with the mass percentage of 15%;
step 3: mixing the solution A and the solution B according to the mass ratio of 10:1, heating at 70 ℃ for 2.5 hours, and magnetically stirring at 500r/min for 1.5 hours to obtain a film-making solution;
step 4: vacuum defoaming the film-forming solution for 2.5 hours;
step 5: casting the film-forming solution on a glass plate, preheating at 70 ℃ for 1.5h, and then heat-treating at 160 ℃ for 4h to obtain the composite ion exchange film.
Step 6: and (3) carrying out hot pressing on the composite ion exchange membrane prepared by the steps on a hot press, wherein the hot pressing temperature is 120 ℃, the hot pressing time is 1.5min, and the hot pressing pressure is 1.5MPa, so as to obtain the final finished membrane.
Embodiment four:
step 1: weighing 20 parts of 2-acrylamido-2-methyl-1-propane sulfonic acid, 20 parts of acrylamide, 20 parts of 1- (3-sulfopropyl) -2-vinylpyridine hydroxide inner salt and 600 parts of deionized water according to parts by weight, stirring and dissolving uniformly, then introducing nitrogen, adding NaOH to adjust pH to be 8, heating to 40 ℃, slowly adding 0.3 part of ammonium persulfate/sodium bisulfate, reacting for 11 hours, adding ethanol, precipitating, filtering, and drying at 45 ℃ to obtain an amphoteric polymer; the number average molecular weight of the obtained amphoteric polymer is 750000, and the 5wt% solution viscosity is 3400 Pa.s;
step 2: respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a mixed solvent of N, N-dimethylformamide and pure water to obtain a solution A and a solution B with the mass percent of 20%;
step 3: mixing the solution A and the solution B according to the mass ratio of 50:1, heating at 80 ℃ for 2 hours, and magnetically stirring at 600r/min for 2 hours to obtain a film-making solution;
step 4: vacuum defoaming a film-forming solution for 2 hours;
step 5: casting the film-forming solution on a glass plate, preheating at 80 ℃ for 2 hours, and then heat-treating at 180 ℃ for 6 hours to obtain the composite ion exchange membrane.
Step 6: and (3) carrying out hot pressing on the composite ion exchange membrane prepared by the steps on a hot press, wherein the hot pressing temperature is 140 ℃, the hot pressing time is 2min, and the hot pressing pressure is 2MPa, so that the final finished membrane is obtained.
Fifth embodiment:
step 1: weighing 30 parts of acrylic acid, 20 parts of acrylamide, 50 parts of 1-vinyl-3-propylimidazole sulfonate and 400 parts of deionized water according to parts by weight, stirring and dissolving uniformly, then introducing nitrogen, adding NaOH to adjust pH to 8, heating to 45 ℃, slowly adding 0.2 part of ammonium persulfate/sodium bisulfate, reacting for 10 hours, adding ethanol, precipitating, filtering and drying at 45 ℃ to obtain an amphoteric polymer; the number average molecular weight of the obtained amphoteric polymer is 650000, and the 5wt% solution viscosity is 3000 Pa.s;
step 2: respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a mixed solvent of ethylene glycol and propylene glycol to obtain a solution A and a solution B with the mass percent of 5%;
step 3: mixing the solution A and the solution B according to the mass ratio of 150:1, heating at 90 ℃ for 1.5 hours, and magnetically stirring at 700r/min for 0.5 hour to obtain a film-making solution;
step 4: vacuum defoaming the film-forming solution for 1.5h;
step 5: casting the film-forming solution on a glass plate, preheating at 60 ℃ for 0.5h, and then heat-treating at 140 ℃ for 2h to obtain the composite ion exchange film.
Step 6: and (3) carrying out hot pressing on the composite ion exchange membrane prepared by the steps on a hot press, wherein the hot pressing temperature is 100 ℃, the hot pressing time is 0.5min, and the hot pressing pressure is 0.5MPa, so as to obtain the final finished membrane.
Example six:
step 1: weighing 30 parts of acrylic acid, 10 parts of acrylamide, 80 parts of 3- (N, N-diallyl-N-methyl) aminopropane sulfonate and 400 parts of deionized water according to parts by weight, stirring and dissolving uniformly, then introducing nitrogen, adding NaOH to adjust pH to be 8, heating to 35 ℃, slowly adding 0.2 part of ammonium persulfate/sodium bisulfite, reacting for 10 hours, adding ethanol, precipitating, filtering and drying at 45 ℃ to obtain an amphoteric polymer; the number average molecular weight of the obtained amphoteric polymer is 700000, and the 5Wt% solution viscosity is 3200mPa.s;
step 2: respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a mixed solvent of ethanol and pure water to obtain a solution A and a solution B with the mass percent of 5%;
step 3: mixing the solution A and the solution B according to the mass ratio of 100:1, heating at 60 ℃ for 1h, and magnetically stirring at 300r/min for 3h to obtain a film-making solution;
step 4: vacuum defoaming a film-forming solution for 1h;
step 5: casting the film-forming solution on a glass plate, preheating at 60 ℃ for 0.5h, and then heat-treating at 140 ℃ for 2h to obtain the composite ion exchange film.
Step 6: and (3) carrying out hot pressing on the composite ion exchange membrane prepared by the steps on a hot press, wherein the hot pressing temperature is 100 ℃, the hot pressing time is 0.5min, and the hot pressing pressure is 0.5MPa, so as to obtain the final finished membrane.
Comparative example one: the preparation method is one-to-one with the embodiment, the difference is that the ion exchange membrane is only prepared from perfluorinated sulfonic acid resin, and amphoteric polymer compound is not added;
comparative example two:
step 1: weighing 30 parts of acrylic acid and 400 parts of deionized water according to parts by weight, stirring and dissolving uniformly, then introducing nitrogen, adding NaOH to adjust pH=8, heating to 35 ℃, slowly adding 0.2 part of ammonium persulfate/sodium bisulphite, reacting for 10 hours, adding ethanol, precipitating, filtering, and drying at 45 ℃ to obtain a polymer; the number average molecular weight of the obtained polymer was 800000, and the 5Wt% solution viscosity was 3800 Pa.s;
step 2: respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a mixed solvent of N, N-dimethylacetamide and pure water to obtain a solution A and a solution B with the mass percent of 5%;
step 3: mixing the solution A and the solution B according to the mass ratio of 100:1, heating at 60 ℃ for 1h, and magnetically stirring at 300r/min for 0.5h to obtain a film-making solution;
step 4: vacuum defoaming the film-forming solution for 0.5h;
step 5: casting the film-forming solution on a glass plate, preheating at 60 ℃ for 0.5h, and then heat-treating at 140 ℃ for 2h to obtain the composite ion exchange film.
Step 6: and (3) carrying out hot pressing on the composite ion exchange membrane prepared by the steps on a hot press, wherein the hot pressing temperature is 100 ℃, the hot pressing time is 0.5min, and the hot pressing pressure is 0.5MPa, so as to obtain the final finished membrane.
Comparative example three:
step 1: weighing 20 parts of acrylamide and 400 parts of deionized water according to parts by weight, stirring and dissolving uniformly, then introducing nitrogen, adding NaOH to adjust pH=8, heating to 35 ℃, slowly adding 0.2 part of ammonium persulfate/sodium bisulfate, reacting for 10 hours, adding ethanol, precipitating, filtering, and drying at 45 ℃ to obtain a polymer; the polymer obtained had a number average molecular weight of 900000 and a 5wt% solution viscosity of 4100mpa.s;
step 2: respectively dissolving perfluorinated sulfonic acid resin and polymer in a mixed solvent of N, N-dimethylacetamide and pure water to obtain a solution A and a solution B with the mass percentage of 5%;
step 3: mixing the solution A and the solution B according to the mass ratio of 100:1, heating at 60 ℃ for 1h, and magnetically stirring at 300r/min for 0.5h to obtain a film-making solution;
step 4: vacuum defoaming the film-forming solution for 0.5h;
step 5: casting the film-forming solution on a glass plate, preheating at 60 ℃ for 0.5h, and then heat-treating at 140 ℃ for 2h to obtain the composite ion exchange film.
Step 6: and (3) carrying out hot pressing on the composite ion exchange membrane prepared by the steps on a hot press, wherein the hot pressing temperature is 100 ℃, the hot pressing time is 0.5min, and the hot pressing pressure is 0.5MPa, so as to obtain the final finished membrane.
Comparative example four:
step 1: weighing 50 parts of 2- [ [2- (acryloyloxy) ethyl ] dimethyl ammonium group ] ethane-1-sulfonate, 400 parts of deionized water, stirring and dissolving uniformly, introducing nitrogen, adding NaOH to adjust pH to be 8, heating to 35 ℃, slowly adding 0.2 part of ammonium persulfate/sodium bisulfate, reacting for 10 hours, adding ethanol, precipitating, filtering, and drying at 45 ℃ to obtain a polymer; the number average molecular weight of the obtained polymer is 830000, and the 5wt% solution viscosity is 4000 Pa.s;
step 2: respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a mixed solvent of N, N-dimethylacetamide and pure water to obtain a solution A and a solution B with the mass percent of 5%;
step 3: mixing the solution A and the solution B according to the mass ratio of 100:1, heating at 60 ℃ for 1h, and magnetically stirring at 300r/min for 0.5h to obtain a film-making solution;
step 4: vacuum defoaming the film-forming solution for 0.5h;
step 5: casting the film-forming solution on a glass plate, preheating at 60 ℃ for 0.5h, and then heat-treating at 140 ℃ for 2h to obtain the composite ion exchange film.
Step 6: and (3) carrying out hot pressing on the composite ion exchange membrane prepared by the steps on a hot press, wherein the hot pressing temperature is 100 ℃, the hot pressing time is 0.5min, and the hot pressing pressure is 0.5MPa, so as to obtain the final finished membrane.
Comparative example five:
step 1: according to the weight portions, 10 portions of acrylic acid, 40 portions of acrylamide, 60 portions of 2- [ [2- (acryloyloxy) ethyl ] dimethyl ammonium group ] ethane-1-sulfonate and 400 portions of deionized water are weighed, evenly stirred and dissolved, nitrogen is introduced, naOH is added to adjust pH to be 8, the temperature is heated to 35 ℃, 0.2 portion of ammonium persulfate/sodium bisulfate is slowly added, ethanol is added after the reaction is carried out for 10 hours, and the amphoteric polymer is obtained through precipitation, filtration and drying at 45 ℃. The number average molecular weight of the obtained amphoteric polymer is 750000, and the 5wt% solution viscosity is 3300 Pa.s;
step 2: respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a mixed solvent of N, N-dimethylacetamide and pure water to obtain a solution A and a solution B with the mass percent of 5%;
step 3: mixing the solution A and the solution B according to the mass ratio of 100:1, heating at 60 ℃ for 1h, and magnetically stirring at 300r/min for 0.5h to obtain a film-making solution;
step 4: vacuum defoaming the film-forming solution for 0.5h;
step 5: casting the film-forming solution on a glass plate, preheating at 60 ℃ for 0.5h, and then heat-treating at 140 ℃ for 2h to obtain the composite ion exchange film.
Step 6: and (3) carrying out hot pressing on the composite ion exchange membrane prepared by the steps on a hot press, wherein the hot pressing temperature is 100 ℃, the hot pressing time is 0.5min, and the hot pressing pressure is 0.5MPa, so as to obtain the final finished membrane.
Experimental procedure and data:
the proton conductivity test method of the ion exchange membrane comprises the following steps: the inner chamber of the conductivity cell was immersed in 3.0mol/L aqueous sulfuric acid. The two half tanks of the conductivity cell are combined, the conductivity cell is tightly pressed by an iron clamp, a dropper is used for adding Kong Dijia 3.0.0 mol/L sulfuric acid aqueous solution into the conductivity cell, and foaming is eliminated. Clamping test wires of a counter electrode and a reference electrode of an electrochemical workstation on an electrode at one end of a conductivity cell at the same time, and clamping a working electrode test wire on the electrode at the other end of the conductivity cell; measuring the impedance of the battery cell, and reading the resistance value of the high-frequency region intersected with the real axis after the measurement is finished, namely the blank impedance R of the conductivity cell 1 The method comprises the steps of carrying out a first treatment on the surface of the The films of examples and comparative examples were cut to a certain size (15 mm. Times.15 mm) and immersed in a 3.0mol/L aqueous sulfuric acid solution, and allowed to stand at room temperature for 24 hours. Clamping the pretreated film sample between two semicircular slot round holes of a conductivity testing device, and testing the impedance R of a conductivity cell of the film sample by using an electrochemical workstation 2 . The measurements were repeated 3 times, all impedance data were recorded and the average calculated and recorded as. Film conductivityWherein d is the average thickness of the film, A is the effective area of the film, < >>Resistance of the conductivity cell to which the film sample was not attachedResistance value, ->Impedance values of the conductivity cell to which the film sample was attached.
The vanadium ion permeability test method of the ion exchange membrane comprises the following steps: self-made vanadium ion permeability testing device, wherein the diffusion cells on the left and right sides are respectively added with mixed aqueous solutions (1.5M VOSO on the left) of different substances with the same volume 4 + 3.0M H 2 SO 4 Right side 1.5M MgSO 4 + 3.0M H 2 SO 4 ) Placing the film to be measured in the middle to separate the films; detecting the absorbance of the solution at the right side in different time periods by an ultraviolet-visible spectrophotometer, analyzing and calculating to obtain the concentration of vanadium ions penetrating through the film to be detected, and according to the formulaFitting to obtain the vanadium ion permeability. (P is vanadium ion permeability in cm 2 •min -1 ；C L Representing VO in the left-side cavity 2+ Concentration in mol.L -1 ；C R (t) Representation oftVO in cavity at right side of moment 2+ Is a concentration of (2); v (V) R Represents the volume of solution in the right cavity in ml; a represents the effective area of the film sample in cm 2 L represents the thickness of the film sample in μm. )
The ratio of proton conductivity to vanadium ion permeability is used to characterize the ion selectivity of the membrane. In general, the greater the ion selectivity value, the better the ion selectivity of the ion exchange membrane. The results of the ion selectivity test are shown in table 1.
The ion exchange membranes prepared in the examples and the comparative examples are respectively assembled with a cell stack to perform charge and discharge tests under the same test conditions, and the charge and discharge current density is 100mA/cm 2 The battery coulombic efficiency, voltage efficiency, energy efficiency, and capacity retention for 100 cycles were recorded, and the test results are shown in table 1.
TABLE 1 ion selectivity and charge-discharge test results for ion exchange membranes
In example one, a mechanism diagram of the preparation process of the amphoteric polymer is shown in FIG. 2, an infrared spectrum diagram of the amphoteric polymer is shown in FIG. 3, and 3413cm of the amphoteric polymer can be found -1 The absorption peak at the position is an N-H telescopic vibration absorption peak of 2923cm -1 And 2849cm -1 C-H stretching vibration absorption peak of methyl and methylene is 1660cm -1 Characteristic absorption peak at c=o, 1176cm -1 And 1079cm -1 The S=O stretching vibration absorption peak is shown, and the infrared spectrum absorption peak is consistent with the expectation, which shows that the amphoteric polymer is successfully synthesized. Referring to fig. 4, a1, a2 are O element profiles of comparative example one and example one, respectively, and b1, b2 are N element profiles of comparative example one and example one, respectively; the EDS spectra of the composite membrane of the first example and the comparative example show that the content of the O, N element in the first example is obviously more than that in the first comparative example, and O, N elements are uniformly distributed, which indicates that the amphoteric polymer is uniformly dispersed in the composite ion exchange membrane, and the composite ion exchange membrane is successfully prepared.
As can be seen from Table 1, the composite ion exchange membranes prepared in examples one to six have higher ion selectivity than that of comparative example one, and the composite ion exchange membrane is prepared by amphoteric polymer/perfluorinated sulfonic acid resin, and the anionic groups can effectively improve the proton transmission density of the membrane, and the nitrogen-containing groups can effectively inhibit the vanadium ion permeability of the membrane, so that the ion selectivity of the membrane is improved. The higher coulombic efficiency, voltage efficiency, and capacity retention in the test data of examples one to six than comparative example one further indicate that the composite membrane has excellent ion selectivity. The higher proton conductivity and voltage efficiency of the second comparative example compared with the first comparative example show that the anionic monomer of the polymer in the composite ion exchange membrane contains carboxylic acid and sulfonic acid ion exchange groups, so that the proton transmission density of the membrane can be effectively increased, and the lower coulomb efficiency and higher vanadium ion permeability of the second comparative example compared with the first comparative example of course show that the vanadium resistance of the membrane can be influenced to a certain extent only by the anionic monomer in the polymer. Comparative example three has higher coulombic efficiency, capacity retention and ion selectivity than comparative example one, demonstrating that the nitrogen-containing groups of the polymer nitrogen-containing monomers in the composite ion exchange membrane combine with sulfonic acid groups in the perfluorosulfonic acid resin to form positive charges, which can inhibit vanadium ion permeation. The fourth comparative example has higher coulombic efficiency, voltage efficiency, capacity retention, ion conductivity, and vanadium ion permeability than the first comparative example, which indicates that the quaternization groups of the amphoteric polymer in the composite ion-exchange membrane can effectively inhibit the vanadium ion permeation due to the Dannon effect, and the existence of the sulfonic acid groups can further improve the proton transmission density. The main difference between the first embodiment and the second to fourth embodiments is that the amphoteric polymer in the composite ion exchange membrane is formed by copolymerizing a zwitterionic monomer, an anionic monomer and a nitrogen-containing monomer, and the respective excellent performances of the three monomers are combined and balanced, so that the energy efficiency, the capacity retention rate and the ion selectivity are more excellent than those of the second to fourth embodiments. The difference between the first embodiment and the fifth embodiment is mainly that the proportion of the zwitterionic monomer, the anionic monomer and the nitrogenous monomer is different when the amphoteric polymer is synthesized, and the coulomb efficiency, the voltage efficiency, the ion conductivity, the vanadium ion permeability and the ion selectivity of the corresponding composite membrane are all different, so that the amphoteric polymer can further adjust the ion selectivity of the composite ionic membrane by adjusting the proportion of the zwitterionic monomer, the anionic monomer and the nitrogenous monomer, and the efficiency of the battery is improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (8)
1. The preparation method of the high-ion-selectivity ionic membrane for the vanadium redox flow battery is characterized by comprising the following steps of:
s1, preparing an amphoteric polymer: taking 10-40 parts by weight of anionic monomers, 10-40 parts by weight of nitrogen-containing monomers, 20-80 parts by weight of zwitterionic monomers and 400-900 parts by weight of deionized water, uniformly stirring and dissolving, removing air, adjusting the pH value to 6-8, adding 0.2-0.5 part by weight of initiator after heating, reacting for 10-12 hours, adding ethanol, precipitating, filtering and drying to obtain an amphoteric polymer; the number average molecular weight of the amphoteric polymer is 500000-1000000, and the 5wt% solution viscosity is 2000-5000 Pa.s;
s2, respectively dissolving perfluorinated sulfonic acid resin and an amphoteric polymer in a solvent to obtain a solution A and a solution B with mass percent of 5-20%;
s3, uniformly mixing the solution A and the solution B according to the mass ratio of 200:1-10:1 to obtain a film-making solution;
s4, vacuum defoamation is carried out on the film-making solution, casting is carried out on a glass plate, and a composite ion exchange film is obtained after heat treatment; carrying out hot pressing on the composite ion exchange membrane to obtain the high ion selectivity ion membrane for the vanadium redox flow battery;
the time for vacuum defoamation is 0.5-3 h; the temperature of the heat treatment is 140-180 ℃, and the time of the heat treatment is 2-6 hours; the hot pressing temperature is 100-140 ℃, the hot pressing time is 0.5-2 min, and the hot pressing pressure is 0.5-2 MPa.
2. The method for preparing the high ion selectivity ionic membrane for the vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: the anionic monomer is one or more of acrylic acid, vinyl sulfonic acid, p-styrene sulfonic acid and 2-acrylamido-2-methyl-1-propane sulfonic acid; the nitrogen-containing monomer is one or more of acrylamide, 1-vinyl imidazole and N-vinyl pyrrolidone; the zwitterionic monomer is one or more of 2- [ [2- (acryloyloxy) ethyl ] dimethyl ammonium group ] ethane-1-sulfonate, 4- [ (3-methacrylamidopropyl) dimethyl ammonium group ] butane-1-sulfonate, 2-acrylamido-2-methyl-1-propane sulfonate, 1- (3-sulfopropyl) -2-vinyl pyridine hydroxide inner salt, 1-vinyl-3-propyl imidazole sulfonate and 3- (N, N-diallyl-N-methyl) aminopropane sulfonate.
3. The method for preparing the high ion selectivity ionic membrane for the vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: the initiator is one or more of ammonium persulfate/sodium hydrogen sulfite, potassium persulfate/sodium hydrogen sulfite and azo diisobutyl amidine dihydrochloride.
4. The method for preparing the high ion selectivity ionic membrane for the vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: the heating temperature in the step S1 is 30-50 ℃.
5. The method for preparing the high ion selectivity ionic membrane for the vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: in the step S2, the solvent is any one or more than two of the following mixture: pure water, ethanol, ethylene glycol, propylene glycol, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide.
6. The method for preparing the high ion selectivity ionic membrane for the vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: in the step S3, the solution A and the solution B are mixed, heated and stirred according to the mass ratio of 200:1-10:1 until being uniform; wherein the heating temperature is 60-100 ℃, and the heating time is 0.5-3 h; the stirring speed is 300-700 r/min, and the stirring time is 0.5-3 h.
7. The method for preparing the high ion selectivity ionic membrane for the vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: in the step S4, the heat treatment is preceded by a preheating treatment, wherein the temperature of the preheating treatment is 60-80 ℃, and the time of the preheating treatment is 0.5-2 h.
8. A high ion selectivity ionic membrane for a vanadium redox flow battery is characterized in that: the vanadium redox flow battery is prepared by the preparation method of the high-ion-selectivity ionic membrane for the vanadium redox flow battery according to any one of claims 1-7.
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