CN108570157B - Preparation method of polymer anionic membrane based on methylpyrrolidine cations - Google Patents
Preparation method of polymer anionic membrane based on methylpyrrolidine cations Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 92
- 229920000642 polymer Polymers 0.000 title claims abstract description 53
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- -1 methylpyrrolidine cations Chemical class 0.000 title claims description 16
- 125000000129 anionic group Chemical group 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000005266 casting Methods 0.000 claims abstract description 21
- 238000002791 soaking Methods 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 18
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 76
- 229920003060 Poly(vinyl benzyl chloride) Polymers 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 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 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229920006260 polyaryletherketone Polymers 0.000 claims description 2
- 239000012779 reinforcing material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000446 fuel Substances 0.000 description 6
- 230000008961 swelling Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000007265 chloromethylation reaction Methods 0.000 description 3
- 238000004176 ammonification Methods 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 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
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- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—After-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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Abstract
The invention belongs to the technical field of new materials and membranes, and provides a preparation method of a polymer anion exchange membrane based on methylpyrrolidine. The preparation method comprises the following steps: (1) respectively dissolving PVBC, MPy and PEK-cardo in a polar organic solvent, heating and stirring until the PVBC, the MPy and the PEK-cardo are completely dissolved; (2) mixing the MPy solution, the PEK-cardo enhanced polymer solution and the PVBC solution, heating and stirring to obtain a uniform and transparent solution; (3) obtaining a composite membrane material by adopting a solution casting method; (4) and completely soaking the composite membrane in 1mol/L KOH solution for alkali exchange, and then washing with a large amount of deionized water to obtain the anion exchange membrane. According to the invention, the balance between the conductivity and the mechanical property is realized by regulating and controlling the content of PEK-cardo in the membrane.
Description
Technical Field
The invention belongs to the technical field of new materials and membranes, and relates to a preparation method of a polymer anion membrane based on methylpyrrolidine cations.
Background
Anion Exchange Membrane Fuel Cells (AEMFCs) have the advantages of high fuel oxidation rate, low liquid alcohol fuel permeability, use of non-noble metal catalysts and the like, and are increasingly paid more attention by people. As one of the core components of an AEMFC, the performance of an Anion Exchange Membrane (AEM) will directly affect the operating efficiency and service life of the fuel cell.
In the conventional preparation process of AEM, chloromethylation step often requires the use of highly toxic carcinogenic reagents, and chloromethylation and ammonification reagents may cause damage to the membrane or cause non-uniform ammonification. In addition, the traditional polymer AEM has low thermal and chemical stability, and quaternary ammonium groups in the polymer are easily degraded under high temperature or alkaline conditions, so that the ion exchange capacity and the conductivity are reduced, and the service life of a fuel cell is influenced. In addition to the requirements of thermal and chemical stability, the mechanical properties of the polymeric anionic membrane (including tensile strength and flexibility) are also key indicators of application.
Disclosure of Invention
Aiming at the technical problems, the invention introduces methyl pyrrolidine group into PVBC skeleton based on nucleophilic substitution reaction between poly (vinyl benzyl chloride) (PVBC) and methyl pyrrolidine (MPy) compounds, simultaneously uses polyaryletherketone (PEK-cardo) as a polymer reinforcing component, and adopts a polymer compounding method to prepare the membrane material which has high conductivity, high alkali-resistant stability and good mechanical property, and has low cost and high conductivity, and the prepared polymer electrolyte membrane is a transparent, uniform and compact membrane material.
The technical scheme of the invention is as follows:
a method for preparing a polymeric anionic membrane based on methylpyrrolidine cations comprises the following steps:
(1) respectively adding PVBC, MPy and PEK-cardo into a polar organic solvent at the temperature of 30-60 ℃, and stirring for dissolving to obtain transparent PVBC, MPy and PEK-cardo solutions with the mass fraction of 1-3%; the chemical structure of the reinforcing material PEK-cardo is as follows:
(2) mixing the PVBC solution and the MPy solution in a molar ratio of 1:1, magnetically stirring for 30min, further adding a PEK-cardo solution serving as a reinforced polymer into the mixed solution, and continuously stirring to obtain a transparent and uniform casting film solution, wherein the mass ratio of PEK-cardo to the sum of PEK-cardo and PVBC is 0.15-0.50: 1;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 60-100 ℃ in the membrane forming process, and the membrane forming time is 12-48 hours; (4) and completely soaking the composite membrane material in a 1mol/L KOH solution at room temperature for alkali exchange, and removing KOH on the surface of the membrane by using deionized water after soaking for 24-72 hours to obtain the hydrogen-oxygen type polymer anion exchange membrane based on the methylpyrrolidine cations.
Further, the polar organic solvent in the step is one of N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
The invention has the beneficial effects that:
(a) the preparation method is simple, a chloromethylation process in the preparation process of the traditional anion exchange membrane is not needed, and the use of carcinogenic reagents in the chloromethyl process is avoided.
(b) The PEK-cardo reinforced polymer with good compatibility is introduced into the PVBC grafted MPy composite membrane, so that the mechanical and dimensional stability of the composite membrane is enhanced, and the composite membrane shows good stability;
(c) the adopted enhanced PEK-cardo polymer has the advantages of easily obtained raw materials, low price, simple and feasible process and suitability for large-scale industrial production;
(d) the conductivity, the water content and the ion exchange capacity of the prepared anion exchange membrane can be simply regulated and controlled by the mass ratio of PEK-cardo to PVBC.
Drawings
FIG. 1 is a graph of conductivity versus temperature for PEK-cardo composite membranes of different mass fractions obtained in examples 1-4. The abscissa of the graph shows Temperature (. degree. C.) and the ordinate shows Conductivity (mS/cm).
Fig. 2 is a graph showing elongation at break of PEK-cardo composite films of different mass fractions obtained in examples 1 to 4. In the figure, the abscissa is PEK-cardo composite membrane with different mass fractions, and the ordinate is Tensile Strength Tensil Strength (MPa).
FIG. 3 shows the results of the alkali stability test at 60 ℃ in 1M KOH solution of the PEK-cardo composite membranes with different mass fractions obtained in examples 1 to 4.The abscissa of the graph is time (time) Time (h) and the ordinate is Conductivity (mS cm)-1)。
Detailed description of the preferred embodiments
The present invention will be described in further detail below by way of examples with reference to the accompanying drawings.
Example 1 method for preparing PVBC-MPy/15% PEK-cardo composite film
(1) Weighing 0.15g of PVBC, and dissolving the PVBC in a 15g N, N-dimethylacetamide solution under the condition of stirring at the temperature of 30 ℃ to obtain a transparent polymer solution with the polymer mass fraction of 1%;
(2) adding MPy solution into the PVBC solution according to the proportion that the molar ratio is PVBC: MPy is 1:1, adding the reinforced polymer PEK-cardo into the mixed solution according to the proportion that the mass ratio of PEK-cardo (PVBC + PEK-cardo) is 0.15:1, and continuously stirring to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(4) completely soaking the composite membrane in 1mol/L KOH solution at room temperature for alkali exchange, and removing KOH on the surface of the membrane by using deionized water after soaking for 48 hours at room temperature to obtain the hydrogen-oxygen type polymer anion exchange membrane based on the methylpyrrolidine cations.
The obtained polymer anion exchange membrane has good conductivity and alkali resistance stability, the conductivity is 49.9mS/cm at 80 ℃, the conductivity of the membrane material is only lost by 15.18 percent after the membrane material is placed in a KOH solution of 1mol/L at 60 ℃ for 18 days, the membrane material also has good flexibility and size stability, the volume swelling rate and the water content of the membrane material are 72 percent and 31 percent respectively, and the comprehensive performance is good.
Example 2 method for preparing PVBC-MPy/25% PEK-cardo composite film
(1) Weighing 0.15g of PVBC, and dissolving the PVBC in a 15g N, N-dimethylformamide solution at 40 ℃ under a stirring condition to obtain a transparent polymer solution with the polymer mass fraction of 1%;
(2) adding MPy solution into the PVBC solution according to the proportion that the molar ratio is PVBC: MPy is 1:1, adding the reinforced polymer PEK-cardo into the mixed solution according to the proportion that the mass ratio of PEK-cardo (PVBC + PEK-cardo) is 0.25:1, and continuously stirring to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(4) completely soaking the composite membrane in 1mol/L KOH solution at room temperature for alkali exchange, and removing KOH on the surface of the membrane by using deionized water after soaking for 48 hours at room temperature to obtain the hydrogen-oxygen type polymer anion exchange membrane based on the methylpyrrolidine cations.
The obtained polymer anion exchange membrane has good conductivity and alkali resistance stability, the conductivity is 37.9mS/cm at 80 ℃, the conductivity of the membrane material is only lost by 7.96 percent after the membrane material is placed in a KOH solution of 1mol/L at 60 ℃ for 18 days, the membrane material also has good flexibility and size stability, the volume swelling rate and the water content of the membrane material are respectively 56 percent and 31 percent, and the comprehensive performance is good.
Example 3 method for preparing PVBC-MPy (1: 1)/35% PEK-cardo composite film
(1) Weighing 0.15g of PVBC, and dissolving in 15g of dimethyl sulfoxide solution at 50 ℃ under the stirring condition to obtain a transparent polymer solution with the polymer mass fraction of 1%;
(2) adding MPy solution into the PVBC solution according to the proportion that the molar ratio is PVBC: MPy is 1:1, adding the reinforced polymer PEK-cardo into the mixed solution according to the proportion that the mass ratio of PEK-cardo (PVBC + PEK-cardo) is 0.35:1, and continuously stirring to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(4) completely soaking the composite membrane in 1mol/L KOH solution at room temperature for alkali exchange, and removing KOH on the surface of the membrane by using deionized water after soaking for 48 hours at room temperature to obtain the hydrogen-oxygen type polymer anion exchange membrane based on the methylpyrrolidine cations.
The obtained polymer anion exchange membrane has good conductivity and alkali resistance stability, the conductivity is 28.4mS/cm at 80 ℃, the conductivity of the membrane material is only lost by 8.70 percent after the membrane material is placed in a KOH solution of 1mol/L at 60 ℃ for 18 days, the membrane material also has good flexibility and size stability, the volume swelling rate and the water content of the membrane material are respectively 41 percent and 31 percent, and the comprehensive performance is good.
Example 4 method for preparing PVBC-MPy (1: 1)/45% PEK-cardo composite film
(1) Weighing 0.15g of PVBC, and dissolving in a 15g N-methyl pyrrolidone solution at 60 ℃ under stirring to obtain a transparent polymer solution with the polymer mass fraction of 1%;
(2) adding MPy solution into the PVBC solution according to the proportion that the molar ratio is PVBC: MPy is 1:1, adding the reinforced polymer PEK-cardo into the mixed solution according to the proportion that the mass ratio of PEK-cardo (PVBC + PEK-cardo) is 0.50:1, and continuously stirring to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(4) completely soaking the composite membrane in 1mol/L KOH solution at room temperature for alkali exchange, and removing KOH on the surface of the membrane by using deionized water after soaking for 48 hours at room temperature to obtain the hydrogen-oxygen type polymer anion exchange membrane based on the methylpyrrolidine cations.
The obtained polymer anion exchange membrane has good conductivity and alkali resistance stability, the conductivity is 15.3mS/cm at 80 ℃, the conductivity of the membrane material is only lost by 6.72 percent after the membrane material is placed in a KOH solution of 1mol/L at 60 ℃ for 18 days, the membrane material also has good flexibility and size stability, the volume swelling rate and the water content of the membrane material are respectively 40 percent and 16 percent, and the comprehensive performance is good.
The test results of the above embodiments are integrated, and the prepared methylpyrrolidine cation polymer anion exchange membrane has high conductivity of 15.3-49.9 mS/cm and good alkali resistance stability, the membrane material only loses 6.72% -15.18% after 18 days in 1mol/L KOH solution at 60 ℃, and has good dimensional stability and volume swelling rate of 40% -72%. The anion exchange membrane material with higher conductivity and good dimensional stability prepared by the embodiment can be used for an anion exchange membrane fuel cell.
Claims (6)
1. A method for preparing a polymer anionic membrane of a methylpyrrolidine cation is characterized by comprising the following steps:
(1) respectively adding poly (vinylbenzyl chloride) PVBC, methylpyrrolidine MPy and polyaryletherketone PEK-cardo into a polar organic solvent at the temperature of 30-60 ℃, stirring and dissolving to obtain transparent PVBC, MPy and PEK-cardo solutions with the mass fraction of 1-3%, wherein the chemical structure of the reinforcing material PEK-cardo is as follows:
(2) mixing the PVBC solution and the MPy solution in a molar ratio of 1:1, magnetically stirring for 30min, further adding a PEK-cardo solution serving as a reinforced polymer into the mixed solution, and continuously stirring to obtain a transparent and uniform casting film solution, wherein the mass ratio of PEK-cardo to the sum of PEK-cardo and PVBC is 0.15-0.50: 1;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 60-100 ℃ in the membrane forming process, and the membrane forming time is 12-48 hours;
(4) and completely soaking the composite membrane material in a 1mol/L KOH solution at room temperature for alkali exchange, and removing KOH on the surface of the membrane by using deionized water after soaking for 24-72 hours to obtain the hydrogen-oxygen type polymer anion exchange membrane based on the methylpyrrolidine cations.
2. The method of claim 1, wherein the polar organic solvent is one of N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone.
3. The method for producing a polymeric anionic membrane according to claim 1 or 2,
(1) weighing 0.15g of PVBC, and dissolving the PVBC in a 15g N, N-dimethylacetamide solution under the condition of stirring at the temperature of 30 ℃ to obtain a transparent polymer solution with the polymer mass fraction of 1%;
(2) adding MPy solution into the PVBC solution according to the proportion that the molar ratio is PVBC: MPy is 1:1, adding the reinforced polymer PEK-cardo into the mixed solution according to the proportion that the mass ratio of PEK-cardo (PVBC + PEK-cardo) is 0.15:1, and continuously stirring to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(4) completely soaking the composite membrane in 1mol/L KOH solution at room temperature for alkali exchange, and removing KOH on the surface of the membrane by using deionized water after soaking for 48 hours at room temperature to obtain the hydrogen-oxygen type polymer anion exchange membrane based on the methylpyrrolidine cations.
4. The method for producing a polymeric anionic membrane according to claim 1 or 2,
(1) weighing 0.15g of PVBC, and dissolving the PVBC in a 15g N, N-dimethylformamide solution at 40 ℃ under a stirring condition to obtain a transparent polymer solution with the polymer mass fraction of 1%;
(2) adding MPy solution into the PVBC solution according to the proportion that the molar ratio is PVBC: MPy is 1:1, adding the reinforced polymer PEK-cardo into the mixed solution according to the proportion that the mass ratio of PEK-cardo (PVBC + PEK-cardo) is 0.25:1, and continuously stirring to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(4) completely soaking the composite membrane in 1mol/L KOH solution at room temperature for alkali exchange, and removing KOH on the surface of the membrane by using deionized water after soaking for 48 hours at room temperature to obtain the hydrogen-oxygen type polymer anion exchange membrane based on the methylpyrrolidine cations.
5. The method for producing a polymeric anionic membrane according to claim 1 or 2,
(1) weighing 0.15g of PVBC, and dissolving in 15g of dimethyl sulfoxide solution at 50 ℃ under the stirring condition to obtain a transparent polymer solution with the polymer mass fraction of 1%;
(2) adding MPy solution into the PVBC solution according to the proportion that the molar ratio is PVBC: MPy is 1:1, adding the reinforced polymer PEK-cardo into the mixed solution according to the proportion that the mass ratio of PEK-cardo (PVBC + PEK-cardo) is 0.35:1, and continuously stirring to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(4) completely soaking the composite membrane in 1mol/L KOH solution at room temperature for alkali exchange, and removing KOH on the surface of the membrane by using deionized water after soaking for 48 hours at room temperature to obtain the hydrogen-oxygen type polymer anion exchange membrane based on the methylpyrrolidine cations.
6. The method for producing a polymeric anionic membrane according to claim 1 or 2,
(1) weighing 0.15g of PVBC, and dissolving in a 15g N-methyl pyrrolidone solution at 60 ℃ under stirring to obtain a transparent polymer solution with the polymer mass fraction of 1%;
(2) adding MPy solution into the PVBC solution according to the proportion that the molar ratio is PVBC: MPy is 1:1, adding the reinforced polymer PEK-cardo into the mixed solution according to the proportion that the mass ratio of PEK-cardo (PVBC + PEK-cardo) is 0.50:1, and continuously stirring to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(4) completely soaking the composite membrane in 1mol/L KOH solution at room temperature for alkali exchange, and removing KOH on the surface of the membrane by using deionized water after soaking for 48 hours at room temperature to obtain the hydrogen-oxygen type polymer anion exchange membrane based on the methylpyrrolidine cations.
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| CN106887629A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院大连化学物理研究所 | Semi-IPN or interpenetrating networks alkaline anion-exchange membrane is prepared and exchange membrane and application |
| CN107189291A (en) * | 2017-05-03 | 2017-09-22 | 东北大学 | A kind of preparation method of the heat-resistant polymer dielectric film based on polyvinyl chloride |
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| "Anion exchange membranes for alkaline fuel cells: A review";Géraldine Merle, et al.;《Journal of Membrane Science》;20110430;第377卷(第1-2期);全文 * |
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