CN111454475A - Proton exchange membrane material for hydrogen fuel cell and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a proton exchange membrane material for a hydrogen fuel cell and a preparation method and application thereof, wherein the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is one of the following formulas:
Description
Technical Field
The invention relates to the technical field of hydrogen fuel cells, in particular to a proton exchange membrane material for a hydrogen fuel cell and a preparation method and application thereof.
Background
The hydrogen fuel cell has the advantages of green, no pollution, high starting speed, long service life, high efficiency and the like, and is considered as an ideal power generation device with the best prospect in the field of fuel cells. The main application range comprises the fields of dispersive power stations, transportation energy sources, power supplies and the like, and the power supply device is also an ideal power supply device for portable mobile equipment such as mobile phones, notebook computers, electric automobiles and the like. Proton exchange membranes are one of the key components of the cell. Its "health" directly affects the quality and power of the fuel cell. To improve efficiency, the distance between the catalyst and the gas diffusion layer in the fuel cell is shortened, and it is integrated in the electrode layer to accelerate the reaction. When the fuel cell is operated, fuel and oxidant are continuously supplied to the anode and the cathode of the cell, after the fuel is catalyzed and oxidized at the anode, protons obtained by catalysis pass through a proton membrane from the anode to the cathode of the cell, and the contemporaneous electrons move to the cathode through an external circuit. The oxidant undergoes an electron reduction reaction in the cathode catalyst layer and combines with protons to form water. In theory, the cell can continue to produce current stably as long as the fuel and oxidant are continuously supplied.
Currently, the most commercialized proton exchange membranes in the world are perfluorosulfonic acid type proton exchange membranes, in which a polystyrene main chain structure constitutes a hydrophobic portion and a hydrophilic portion is composed of a sulfonic acid group of a side chain. The most successful of these are a series of Nafion membranes developed by dupont, usa. In addition, the Dow film, Aciplex film, Flemion film, and Aquivion film, which are developed in the countries such as the american day, have been already exposed to the head and corner in the near future, and commercialization on a certain scale has been achieved.
The obvious hydrophilic-hydrophobic phase separation structure has the advantages that the hydrophilic side chain is far away from the main chain to form a continuous proton transmission channel, and the super acid structure exists, so that the super acid structure has high proton conductivity under complete hydration. In addition, due to the special structure, the main chain is not easy to be attacked and decomposed by free radicals, the F atom has strong electronegativity, and the bond energy of C-F is up to 489kJ/mol, so that the perfluorosulfonic acid film has excellent stability and strong mechanical property. However, although Nafion membranes are the most commercially highest proton exchange membrane currently available in the fuel cell field, there are still significant short plates: (1) the manufacturing cost is high, the cost is high, and the manufacturing process is complex; (2) the fuel permeability is high, and particularly when methanol is used as the fuel, the permeation phenomenon is serious, so that the open-circuit voltage of the battery is reduced sharply, and serious potential safety hazards exist; (3) the dependence on water is high, and the proton conductivity is greatly reduced only under the conditions of low temperature (< 80 ℃) and high humidity (RH ═ 100%), and under the conditions of more than 100 ℃ or low humidity. Where water management becomes the primary factor limiting battery operation. Therefore, researchers have conducted a great deal of research and exploration, and it is a new research direction to prepare proton exchange membranes which can safely and stably operate at high temperature.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a proton exchange membrane material for a hydrogen fuel cell, and a preparation method and application thereof, and aims to solve the problems that the existing proton exchange membrane material has high dependence on water and can only be suitable for low-temperature and high-humidity conditions.
The technical scheme of the invention is as follows:
a proton exchange membrane material for a hydrogen fuel cell, wherein the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is as follows:
A proton exchange membrane material for a hydrogen fuel cell, wherein the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is as follows:
A proton exchange membrane material for a hydrogen fuel cell, wherein the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is as follows:
A proton exchange membrane material for a hydrogen fuel cell, wherein the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is as follows:
A proton exchange membrane material for a hydrogen fuel cell, wherein the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is one of the following structures:
wherein n is more than or equal to 8000 and less than or equal to 25000.
A proton exchange membrane material for a hydrogen fuel cell, wherein the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is one of the following structures:
wherein n is more than or equal to 8000 and less than or equal to 25000.
A proton exchange membrane material for a hydrogen fuel cell, wherein the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is one of the following structures:
wherein n is more than or equal to 8000 and less than or equal to 25000.
A method for producing a proton exchange membrane material for a hydrogen fuel cell as described above, comprising the steps of:
reacting 3-bromopropylene with imidazole to prepare propylene-substituted N-propenyl imidazole;
carrying out ring-opening reaction on N-propenyl imidazole and 1, 3-propane sultone to prepare N-allyl propane sulfonic acid imidazole inner salt;
carrying out polymerization reaction on N-allyl propanesulfonic acid imidazole inner salt to obtain a compound 1 a;
wherein n is more than or equal to 8000 and less than or equal to 25000.
A method for producing a proton exchange membrane material for a hydrogen fuel cell as described above, comprising the steps of:
reacting iodoethylene with biimidazole to obtain ethylene-substituted N, N-vinyl biimidazole;
carrying out ring-opening reaction on N, N-vinyl-biimidazole and 1, 3-propane sultone to prepare N, N-vinyl-propane sultone inner salt;
carrying out conjugated polymerization on the N, N-vinyl propanesulfonic acid biimidazole inner salt to obtain a compound 2 a;
wherein n is more than or equal to 8000 and less than or equal to 25000
Use of a proton exchange membrane material according to any of the present invention in a hydrogen fuel cell.
Has the advantages that: the polymeric sulfonic acid imidazole inner salt provided by the invention has an inner salt structure, molecules of the polymeric sulfonic acid imidazole inner salt have imidazole cations and sulfonic acid anions, protons can be transferred after acidification, hydroxide ions can be transferred after alkalization, and a proton exchange membrane prepared from the sulfonic acid imidazole inner salt has good conductivity and mechanical property due to high polymerization degree.
Detailed Description
The invention provides a proton exchange membrane material for a hydrogen fuel cell and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a proton exchange membrane material for a hydrogen fuel cell, wherein the proton exchange membrane material is polysulfonate imidazole type inner salt, and the structural formula of the polysulfonate imidazole type inner salt is one of the following structures:
wherein n is more than or equal to 8000 and less than or equal to 25000. That is, the minimum value of n is 8000, and the higher the degree of polymerization is, the better the moldability and mechanical properties of the resulting film are. Further, n is more than or equal to 15000 and less than or equal to 25000.
The inventors of the present invention have conducted extensive studies to design a polymeric imidazole sulfonate inner salt having four molecular structures of compound 1a, compound 1b, compound 2a and compound 2b, wherein compound 1a and compound 2a are fluorine-free polymer structures, and compound 1b and compound 2b are polymers formed by replacing hydrogen atoms in a polymer chain with fluorine on the basis of compound 1a and compound 1 b. The polymeric sulfonic acid imidazole inner salt has an inner salt structure, molecules of the polymeric sulfonic acid imidazole inner salt have imidazole cations and sulfonic acid anions, protons can be transferred after acidification, and hydroxide ions can be transferred after alkalization (it should be noted that the polymeric sulfonic acid imidazole inner salt does not need to be acidified and alkalized, but can transfer protons and anions, but the transfer effect after acidification and alkalization is better), and the proton exchange membrane prepared from the sulfonic acid imidazole inner salt has good conductivity and mechanical property due to high polymerization degree.
In the compound 1b and the compound 2b of the present embodiment, since the C — F bond has good water repellency and strong bond energy, and can enhance the mechanical strength of the polymer, the H in the polymer chain is replaced by F atom, so that a better polymer proton exchange membrane can be obtained.
The embodiment of the invention provides a proton exchange membrane material for a hydrogen fuel cell, wherein the proton exchange membrane material is polysulfonate imidazole type inner salt, and the structural formula of the polysulfonate imidazole type inner salt is one of the following structures:
In the embodiment, the carbon-hydrogen bond between the sulfonate and the imidazole salt is replaced by a carbon-fluorine bond, so that the water repellency and the mechanical strength of the polymer can be enhanced, and the CH connected with the sulfonate is replaced2CF with radical changed into strong electron-withdrawing group2The acidity of the polymer film is greatly improved, and the conductivity is better.
The embodiment of the invention provides a proton exchange membrane material for a hydrogen fuel cell, wherein the proton exchange membrane material is polysulfonate imidazole type inner salt, and the structural formula of the polysulfonate imidazole type inner salt is one of the following structures:
In the embodiment, hydrogen on the polymer chain, hydrogen between the sulfonate and the imidazole salt are simultaneously replaced by fluorine atoms, so that the water repellency, the mechanical strength and the conductivity of the polymer can be further enhanced.
The embodiment of the invention provides a proton exchange membrane material for a hydrogen fuel cell, wherein the proton exchange membrane material is polysulfonate imidazole type inner salt, and the structural formula of the polysulfonate imidazole type inner salt is one of the following structures:
In the embodiment, the carbon chain length between the sulfonate and the imidazolium salt is variable, and the polymers with the carbon chain lengths have better mechanical strength and electrical conductivity. The nucleophilic substitution reagent used in the synthesis process is 1, 3-propane sultone, and if the nucleophilic substitution reagent is 1, 4-butane sultone, 1, 5-pentane sultone and 1, 6-hexane sultone, the length of a carbon chain between a sulfonate and an imidazole salt can be prolonged, and the carbon chain is from a four-carbon chain, a five-carbon chain to a six-carbon chain.
The embodiment of the invention provides a preparation method of the proton exchange membrane material for the hydrogen fuel cell, which comprises the following steps:
reacting 3-bromopropylene with imidazole to prepare propylene-substituted N-propenyl imidazole;
carrying out ring-opening reaction on N-propenyl imidazole and 1, 3-propane sultone to prepare N-allyl propane sulfonic acid imidazole inner salt;
carrying out polymerization reaction on N-allyl propanesulfonic acid imidazole inner salt to obtain a compound 1 a;
In the embodiment, 3-bromopropylene is reacted with imidazole to prepare propylene substituted N-propenyl imidazole, then the propylene substituted N-propenyl imidazole is subjected to a ring opening reaction with 1, 3-propane sultone to prepare an imidazole sulfonate monomer, and then the imidazole sulfonate monomer is polymerized to prepare a compound 1 a. The compound 1a of this example was prepared by a simple process without the use of expensive perfluoroolefins. Compound 1b is prepared analogously to compound 1a, except that the hydrogen atoms in the monomeric 3-bromopropene are replaced by fluorine atoms.
The embodiment of the invention provides a preparation method of the proton exchange membrane material for the hydrogen fuel cell, which comprises the following steps:
reacting iodoethylene with biimidazole to obtain ethylene-substituted N, N-vinyl biimidazole;
carrying out ring-opening reaction on N, N-vinyl-biimidazole and 1, 3-propane sultone to prepare N, N-vinyl-propane sultone inner salt;
carrying out conjugated polymerization on the N, N-vinyl propanesulfonic acid biimidazole inner salt to obtain a compound 2 a;
In the embodiment, vinyl iodide and biimidazole react to prepare ethylene-substituted N, N-vinyl biimidazole, then the vinyl-substituted N, N-vinyl biimidazole reacts with 1, 3-propane sultone to prepare a gemini imidazole sulfonate monomer, and then conjugated polymerization is carried out to prepare a compound 2a with a tricyclic structure. The compound 2a of this example was prepared by a simple process without the use of expensive perfluoroolefins. Compound 2b is prepared similarly to compound 2a except that the hydrogen atoms in the monomeric iodoethylene are replaced with fluorine atoms.
An embodiment of the present invention provides an application of the proton exchange membrane material as described in any one of the above in a hydrogen fuel cell.
In one embodiment, the proton exchange membrane is prepared by the steps of: the proton exchange membrane material of this example is dissolved in a solvent (e.g., DMSO) to obtain a proton exchange membrane material solution. The filtered proton exchange membrane material solution was then poured onto an ultra-flat petri dish and dried for 24-48 hours to give a white transparent polymer membrane (average thickness 60-80 μm). The polymer membranes were peeled off, rinsed with distilled water, and soaked in hydrochloric acid solution to convert them into acid type PEM membranes. Or soaked with NaOH solution to convert them to alkaline hydroxide ion exchange membranes. And finally, washing the excessive hydrochloric acid or sodium hydroxide on the surface of the membrane by deionized water and drying for later use.
Compared with the prior art, the proton exchange membrane material provided by the embodiment has the following advantages:
firstly, the synthesis process is simple and the cost is low;
secondly, the catalyst has an inner salt structure, and can transfer protons or hydroxide ions or transfer two ions (anions and cations) simultaneously without acidification or alkalization;
the prepared proton exchange membrane has good ion conductivity due to the internal salt structure, so that the proton exchange membrane has good conductivity;
fourthly, the mechanical strength is high, and particularly, the compound 2a skillfully adopts a conjugated polymerization mode, so that three rings in a molecule are connected in parallel (two imidazole rings and one piperazine ring), the molecule has a stronger rigid structure, and the polymer membrane has good mechanical strength;
and requirements on temperature and humidity are not high, and normal operation can be performed within a wide temperature and humidity range as long as the polymerization degree of molecules is high enough and the dependence on the temperature and the humidity is small.
The present invention is described in detail below with reference to specific examples.
Example 1: preparation of compound 1a (n ═ 20000)
(1) A100 ml three-necked flask was charged with 30ml of DMF (N, N-dimethylformamide) and 5ml of 40% aqueous NaOH solution, and 34mmol of imidazole (2.3g) was added to the above mixed solution. 37mmol (4.48g) of bromopropene was dissolved in 20ml of DMF, the three-necked flask was heated to a temperature of the mixed solution of 55 ℃ and the DMF solution containing bromopropene was slowly added dropwise to the imidazole solution, after completion of the addition, the temperature was lowered to room temperature and the reaction mixture was stirred overnight. The reaction mixture was then introduced into 300ml of purified water and extracted with chloroformCollecting three times (3 × 200ml), drying chloroform solution with anhydrous sodium sulfate, filtering, distilling off chloroform solvent under reduced pressure, and purifying the crude product with column Chromatography (CH)2Cl2/CH3OH 25:1) gave the product N-allylimidazole (compound 3).1H NMR(400MHz，CDCl3):＝7.93(s,1H),7.18(d,1H),6.65(d，1H),6.07(m，1H)，5.45(d，1H),5.23(d，1H),5.10(d，2H)；MS(EI)m/z 108(M+)。
(2) 21mmol (2.27g) of N-allylimidazole (compound 3) was dissolved in 40ml of acetone, 21mmol (2.6g) of 1, 3-propanesultone was dissolved in 10ml of acetone, and the solution was slowly added dropwise thereto, and the reaction was stirred at room temperature under a nitrogen atmosphere for 72 hours. The precipitated imidazole propanesulfonate inner salt 4 was filtered and washed with acetone to give 3.7g (Compound 4) of pure N-allyl imidazole propanesulfonate inner salt in 76.6% yield. 1H NMR (400MHz, CD)3OD):＝8.92(s,1H),7.92(d,1H),7.75(d，1H),6.07(m，1H)，5.54(d，1H),5.23(d，1H),5.10(d，2H),5.01(t，2H),2.10(m，2H),1.30(t，2H)；MS(EI)m/z 230(M+).
(3) A250 ml three-neck flask was taken, 25mmol (5.75g) of N-allylimidazole propanesulfonic acid inner salt (compound 4) was dissolved in 100ml of anhydrous ethanol and added to the flask, an initiator azobisisobutyronitrile AIBN2.5mmol (0.41g) was added, replaced with nitrogen three times, the mixture in the flask was slowly heated to slight boiling, reacted for 8 hours, then cooled, and quenched with liquid nitrogen. The solvent ethanol was evaporated under reduced pressure and the remaining solid was washed repeatedly three times with dichloromethane to give about 4.86g of the final product 1a after drying.1H NMR(400MHz，CD3OD):＝8.92(s,1H),7.92(d,1H),7.75(d,1H),5.01(t，2H),3.77-3.52(m，2H),2.10(m，2H),1.55-1.50(m，3H),1.30(t，2H)。
Example two: preparation of Compound 2a (n 12000)
(1) The preparation process of the biimidazole is mature, and is not repeated herein, and reference may be made to related documents. The preparation procedure of compound 5 was as follows: taking a 100ml three-neck flask, adding30ml of DMF (N, N-dimethylformamide) and 5ml of 40% aqueous NaOH solution, 25mmol of biimidazole (3.35g) are added to the above mixed solution, 75mmol (11.55g) of iodoethylene is dissolved in 20ml of DMF, the solution of DMF in which the iodoethylene is dissolved is slowly added dropwise to the biimidazole solution, after the dropwise addition, the reaction mixture is stirred overnight, after which the reaction mixture is poured into 300ml of purified water, extracted three times with chloroform (3 × 200ml), the chloroform solution is then dried over anhydrous sodium sulfate, filtered, the chloroform solvent is distilled off under reduced pressure, and the crude product is purified by column Chromatography (CH)2Cl2/CH3OH ═ 20:1) to give the product N, N-vinyl biimidazole (compound 5).1H NMR(400MHz，CDCl3):＝7.46(d,2H),7.02(d,2H),5.45(d，2H),5.30(d，2H)，5.20(s，2H)；MS(EI)m/z 186(M+)。
(2) 21mmol (3.91g) of N, N-vinyl-biimidazole (compound 5) was dissolved in 50ml of acetone, 63mmol (7.68g) of 1, 3-propanesultone was dissolved in 20ml of acetone, and the solution was slowly added dropwise thereto, and the reaction was stirred at room temperature for 72 hours under a nitrogen atmosphere. The precipitated imidazolium propanesulfonate was filtered and washed with acetone to give 6.8g (Compound 6) of pure N, N-vinyl propanesulfonate biimidazole inner salt in 75.4% yield.1H NMR(400MHz，CD3OD):＝7.92(d,2H),7.75(d,2H),5.45(d，2H),5.30(d，2H)，5.20(s，2H),5.01(t，4H),2.10(m，4H),1.30(t，4H)；MS(EI)m/z 430(M+)。
(3) A500 ml three-neck flask was taken, 25mmol (10.75g) of N, N-vinyl biimidazole propanesulfonic acid inner salt (compound 6) was dissolved in 200ml of anhydrous ethanol and added to the flask, 5mmol (0.82g) of azobisisobutyronitrile AIBN as an initiator was added, replaced with nitrogen gas three times, the mixture in the flask was slowly heated to slight boiling, reacted for 8 hours, then cooled, and quenched with liquid nitrogen. The solvent ethanol was evaporated under reduced pressure and the remaining solid was washed repeatedly three times with dichloromethane to give about 9.76g of the final product 2a after drying.1HNMR(400MHz，CD3OD):＝7.92(d,2H),7.75(d,2H),5.01(t，4H),3.50(m，2H),2.59(m，4H),2.55(t，4H),1.75(m，4H)。
EXAMPLE III preparation of Polymer proton exchange Membrane
Compound 1a prepared in example 1 and Compound 2a prepared in example 2 were dissolved in DMSO to give solutions having a concentration of 10 wt%, respectively. The filtered solution was then poured onto an ultra-flat petri dish and dried in an oven at 60 ℃ for 48 hours to give a white transparent polymer film (thickness 70 μm). The polymer membranes were peeled off, rinsed with distilled water, and immersed in a 2M hydrochloric acid solution for 24 hours to convert them into acid type PEM membranes. Or soaked with 2M NaOH solution for 24 hours to convert them to alkaline hydroxide ion exchange membranes. And finally, washing the excessive hydrochloric acid or sodium hydroxide on the surface of the membrane by deionized water and drying for later use.
The performance test results of the polymer proton exchange membrane 2a are as follows:
(1) the existence of a high-stability biimidazole piperazine tricyclic structure improves the thermal stability, oxidation resistance stability and mechanical properties of the polymer 2a to a certain extent, the polymer does not crack in a Fenton reagent for 120 hours, the tensile strength of the polymer is between 10.14MPa and 89MPa, and the thermal decomposition temperature is more than 300 ℃.
(2) The proton conductivity of the membrane prepared by the 2a compound can reach 0.069S under the anhydrous state at 180 DEG C.cm-1. Is superior to the prior Nafion membrane.
In summary, compared with the prior art, the proton exchange membrane material for the hydrogen fuel cell and the preparation method and application thereof provided by the invention have the following advantages: firstly, the synthesis process is simple and the cost is low; secondly, the catalyst has an inner salt structure, and can transfer protons or hydroxide ions or transfer two ions (anions and cations) simultaneously without acidification or alkalization; the prepared proton exchange membrane has good ion conductivity due to the internal salt structure, so that the proton exchange membrane has good conductivity; fourthly, the mechanical strength is high, and particularly, the compound 2a skillfully adopts a conjugated polymerization mode, so that three rings in a molecule are connected in parallel (two imidazole rings and one piperazine ring), the molecule has a stronger rigid structure, and the polymer membrane has good mechanical strength; and requirements on temperature and humidity are not high, and normal operation can be performed within a wide temperature and humidity range as long as the polymerization degree of molecules is high enough and the dependence on the temperature and the humidity is small.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A proton exchange membrane material for a hydrogen fuel cell is characterized in that the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is as follows:
2. A proton exchange membrane material for a hydrogen fuel cell is characterized in that the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is as follows:
3. A proton exchange membrane material for a hydrogen fuel cell is characterized in that the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is as follows:
4. A proton exchange membrane material for a hydrogen fuel cell is characterized in that the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is as follows:
5. A proton exchange membrane material for a hydrogen fuel cell is characterized in that the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is one of the following formulas:
wherein n is more than or equal to 8000 and less than or equal to 25000.
6. A proton exchange membrane material for a hydrogen fuel cell is characterized in that the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is one of the following formulas:
wherein n is more than or equal to 8000 and less than or equal to 25000.
7. A proton exchange membrane material for a hydrogen fuel cell is characterized in that the proton exchange membrane material is polysulfonic acid imidazole type inner salt, and the structural formula of the polysulfonic acid imidazole type inner salt is one of the following formulas:
wherein n is more than or equal to 8000 and less than or equal to 25000.
8. A method for producing a proton exchange membrane material for a hydrogen fuel cell according to claim 1, characterized by comprising the steps of:
reacting 3-bromopropylene with imidazole to prepare propylene-substituted N-propenyl imidazole;
carrying out ring-opening reaction on N-propenyl imidazole and 1, 3-propane sultone to prepare N-allyl propane sulfonic acid imidazole inner salt;
carrying out polymerization reaction on N-allyl propanesulfonic acid imidazole inner salt to obtain a compound 1 a;
wherein n is more than or equal to 8000 and less than or equal to 25000.
9. A method for producing a proton exchange membrane material for a hydrogen fuel cell according to claim 2, characterized by comprising the steps of:
reacting iodoethylene with biimidazole to obtain ethylene-substituted N, N-vinyl biimidazole;
carrying out ring-opening reaction on N, N-vinyl-biimidazole and 1, 3-propane sultone to prepare N, N-vinyl-propane sultone inner salt;
carrying out conjugated polymerization on the N, N-vinyl propanesulfonic acid biimidazole inner salt to obtain a compound 2 a;
wherein n is more than or equal to 8000 and less than or equal to 25000.
10. Use of the proton exchange membrane material of any one of claims 1-7 in a hydrogen fuel cell.
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|---|---|---|---|---|
| US20040005490A1 (en) * | 2002-07-05 | 2004-01-08 | Qinbai Fan | High stability membrane for proton exchange membrane fuel cells |
| WO2010022963A2 (en) * | 2008-08-29 | 2010-03-04 | Ewe-Forschungszentrum Für Energietechnologie E.V. | Proton exchange membrane for use in proton exchange membrane fuel cells |
| CN104624067A (en) * | 2014-12-25 | 2015-05-20 | 长春工业大学 | Imidazole functionalized polyether sulfone anion-exchange membrane and preparation method thereof |
| US20170114196A1 (en) * | 2014-06-12 | 2017-04-27 | Thomas Häring | Combined material system for ion exchange membranes and their use in electrochemical processes |
| WO2019058270A1 (en) * | 2017-09-19 | 2019-03-28 | Embion Technologies Sa | Ionic polymers and use thereof in biomass processing |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040005490A1 (en) * | 2002-07-05 | 2004-01-08 | Qinbai Fan | High stability membrane for proton exchange membrane fuel cells |
| WO2010022963A2 (en) * | 2008-08-29 | 2010-03-04 | Ewe-Forschungszentrum Für Energietechnologie E.V. | Proton exchange membrane for use in proton exchange membrane fuel cells |
| US20170114196A1 (en) * | 2014-06-12 | 2017-04-27 | Thomas Häring | Combined material system for ion exchange membranes and their use in electrochemical processes |
| CN104624067A (en) * | 2014-12-25 | 2015-05-20 | 长春工业大学 | Imidazole functionalized polyether sulfone anion-exchange membrane and preparation method thereof |
| WO2019058270A1 (en) * | 2017-09-19 | 2019-03-28 | Embion Technologies Sa | Ionic polymers and use thereof in biomass processing |
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