CN113429561A - Cross-linking polyether-ether-ketone anion exchange membrane for fuel cell and preparation method thereof - Google Patents
Cross-linking polyether-ether-ketone anion exchange membrane for fuel cell and preparation method thereof Download PDFInfo
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- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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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
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- 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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- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
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Abstract
The invention discloses a cross-linking polyether-ether-ketone anion exchange membrane for a fuel cell and a preparation method thereof, wherein the anion exchange membrane is prepared by polymerizing methyl hydroquinone and 4, 4-difluorobenzophenone, and the preparation method comprises the following steps: step one, preparing a polyether-ether-ketone main chain; step two, carrying out bromination reaction on the methyl on the polyether-ether-ketone main chain obtained in the step one, wherein the bromination reaction needs nitrogen protection and light-proof treatment to obtain a brominated polyether-ether-ketone main chain; step three, adding 1, 2-bis (4-pyridyl) ethane into the brominated polyether-ether-ketone solution obtained in the step two to obtain a mixed solution; step four: and C, filtering the mixed solution obtained in the step three, pouring the filtered mixed solution into a polytetrafluoroethylene mold, standing, and carrying out forced air drying to obtain the cross-linked polyether-ether-ketone anion exchange membrane for the fuel cell. The cross-linking type polyether-ether-ketone anion exchange membrane with high ionic conductivity and strong alkali-resistant stability is successfully prepared, and the preparation method is simple, the raw materials are easy to obtain, the cost is low, and the cross-linking type polyether-ether-ketone anion exchange membrane is expected to be applied to the field of fuel cells.
Description
Technical Field
The invention belongs to the fields of polymer chemistry and anion exchange membrane fuel cells, and particularly relates to a preparation method of a cross-linked polyether-ether-ketone anion exchange membrane for a fuel cell.
Background
As an important component of fuel cells, ion exchange membranes can not only transport ions but also isolate fuel, and the performance of the membrane determines the efficiency and life of the cell system. The pem fuel cell is the first polymer electrolyte membrane fuel cell developed and is currently the closest fuel cell to commercialization. However, the proton exchange membrane needs to use noble metal as a catalyst, so the cost is very expensive; anion exchange membrane fuel cells have recently received much attention from the fuel cell and energy communities because of their good power density and significant cost advantages when using catalysts that do not contain noble metals such as platinum group.
The anion exchange membranes developed at present still have the problem of low ionic conductivity. The most direct method for improving the ionic conductivity is to increase the number of conductive functional groups in the polymer membrane, but the membrane can be excessively swelled to weaken the interaction force among polymer chains, so that the mechanical property and the alkali resistance stability of the anion exchange membrane are greatly reduced, and finally the membrane is broken in alkali liquor when reaching the limit. Therefore, the regulation and control of the balance between the alkali-resistant stability and the ion conductivity is a key problem in the research and development of the anion exchange membrane material.
(Hydrogen Energy,2021,46, 8156-; but the alkali resistance stability is not good, and the ionic conductivity is lost by 39.7 percent after the membrane is soaked in 1M KOH solution for 30 days. (Journal of Membrane Science,2019,587,117-118) reported a two-network anion exchange Membrane with excellent flexibility and stability. The cross-linked structure can enhance the dimensional stability of the membrane without loss of ionic conductivity.
Disclosure of Invention
The invention aims to provide a preparation method of a cross-linking polyether-ether-ketone anion-exchange membrane for a fuel cell, wherein the anion-exchange membrane has high mechanical stability and alkali-resistant stability. Meanwhile, the preparation method is simple to operate, low in cost and wide in prospect.
The invention starts from molecular design, selects methyl hydroquinone, hexafluorobisphenol A and 4, 4-difluorobenzophenone to synthesize the polyether-ether-ketone main chain, and has good mechanical property, dimensional stability, thermal stability and chemical stability. And the aromatic ether bond allows more rotational freedom along the polymer backbone, and has strong mobility and good film-forming properties. However, the ether bond is susceptible to OH-Leading to backbone cleavage. The anion exchange membrane with the cross-linked structure can form a microphase separation structure, and a high-efficiency ion transmission channel is constructed, so that the ionic conductivity of the membrane is improved. 1, 2-bis (4-pyridyl) ethane is adopted as a cross-linking agent, a certain steric hindrance effect prevents functional groups from being attacked by hydroxide ions, and the prepared membrane has excellent alkali resistance stability. By changing the molar ratio of the methyl hydroquinone to the hexafluorobisphenol A, the content of cationic groups can be regulated and controlled, and the influence of the cationic groups on the membrane performance can be researched.
A cross-linking polyether-ether-ketone anion exchange membrane for a fuel cell is characterized in that the anion exchange membrane is prepared by polymerizing methyl hydroquinone, hexafluorobisphenol A and 4, 4-difluorobenzophenone, and the structural formula of the membrane is as follows:
wherein x represents the molar ratio of the methyl hydroquinone to the 4, 4-difluorobenzophenone, and is 0.3, 0.5, 0.7 and 1.0 respectively.
Furthermore, the cross-linking type polyether-ether-ketone anion exchange membrane for the fuel cell has the cross-linking agent of 1, 2-bis (4-pyridyl) ethane, and the larger the molar ratio of the methyl hydroquinone is, the more functional sites are, and the number of the cross-linking agents is increased.
A preparation method of a cross-linking polyether-ether-ketone anion exchange membrane for a fuel cell is characterized by comprising the following steps:
the method comprises the following steps: preparing a polyether-ether-ketone main chain;
step two: carrying out bromination reaction on the methyl on the polyether-ether-ketone main chain obtained in the step one, wherein the bromination reaction needs nitrogen protection and light-proof treatment to obtain a brominated polyether-ether-ketone main chain;
step three: adding 1, 2-bis (4-pyridyl) ethane into the brominated polyether-ether-ketone solution obtained in the second step to obtain a mixed solution;
step four: and filtering the mixed solution obtained in the third step, pouring the filtered mixed solution into a polytetrafluoroethylene mold, standing for 2 hours, and carrying out forced air drying to obtain the cross-linked polyether-ether-ketone anion exchange membrane for the fuel cell.
Further, the step one comprises the following specific steps: methyl hydroquinone, 4-difluorobenzophenone, hexafluorobisphenol A and salt forming agent K are added into a 100ml three-necked bottle2CO3Toluene as a water-carrying agent and DMAC as a solvent; the reaction system is vacuumized and filled with nitrogen for three cycles. Heating to 140 ℃, refluxing at constant temperature for 4h, and heating to 170 ℃ for reaction for 24 h; pouring the reaction solution into deionized water, allowing flocculent precipitate to appear, filtering the obtained precipitate, washing with methanol solution for three times, and vacuum drying at 80 ℃ for 24h to obtain the polyether-ether-ketone main chain.
Further, the second step specifically comprises the following steps: completely dissolving a polyether-ether-ketone main chain in a chlorobenzene solution, and then adding an NBS brominating agent and an AIBN initiator, wherein the molar ratio of the polyether-ether-ketone main chain to the NBS is 1: 1.1; reacting for 24h at 75 ℃ to obtain the brominated polyether-ether-ketone main chain.
Further, the third step specifically comprises: and (2) dissolving the brominated polyether ether ketone obtained in the step two in NMP, stirring for 2 hours, and adding 1, 2-bis (4-pyridyl) ethane to obtain a mixed solution.
Further, the air blast drying in the fourth step is drying in an air blast oven at the temperature of 60-80 ℃ for 12-24 h.
Further, alkalizing the exchange membrane dried in the fourth step, and performing Br treatment on the exchange membrane-Replacement by OH-And then the surface is cleaned by deionized water.
The invention has the beneficial effects that: 1. the invention successfully prepares the cross-linking polyether-ether-ketone anion exchange membrane with high ionic conductivity and strong alkali-resistant stability. When x is 0.5, the ion conductivity of the crosslinked anion-exchange membrane of the present invention at 80 ℃ is 70.86mS cm-1The membrane was immersed in a 1M aqueous KOH solution, and the ionic conductivity of the membrane was measured by periodic sampling. After 1440h of testing, the PEEK-QA-x film remained intact, free from cracking and still had excellent flexibility. Wherein, the PEEK-QA-0.5 film retains 91.74 percent of the ionic conductivity. 2. The method for preparing the cross-linked polyether-ether-ketone anion-exchange membrane is simple, the raw materials are easy to obtain, the cost is low, and the cross-linked polyether-ether-ketone anion-exchange membrane is expected to be applied to the field of fuel cells.
Drawings
FIG. 1 is an infrared spectrum of a cross-linked PEEK-QA-x film prepared in examples 1-4 of the present invention.
FIG. 2 is a scanning electron microscope image of the cross-linked PEEK-QA-x film prepared in examples 1-4 of the present invention.
FIG. 3 is a temperature change curve of the ionic conductivity of PEEK-QA-x films obtained in examples 1 to 4 of the present invention.
FIG. 4 is a graph showing the change of the ion conductivity of PEEK-QA-x films obtained in examples 1 to 4 of the present invention with time.
FIG. 5 shows the thermogravimetric curves of PEEK-QA-x films obtained in examples 1 to 4 of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the present invention are described below in conjunction with the examples, but it is to be understood that the specific examples described herein are for purposes of further illustrating the features and advantages of the present invention and are not to be construed as limiting the claims which follow.
The invention firstly provides a cross-linking polyether-ether-ketone anion exchange membrane for a fuel cell, which has the following structural formula:
wherein x represents the molar ratio of the methyl hydroquinone to the 4, 4-difluorobenzophenone, and is 0.3, 0.5, 0.7 and 1.0 respectively.
The invention also provides a preparation method of the cross-linking polyether-ether-ketone anion-exchange membrane for the fuel cell, which comprises the following steps:
the method comprises the following steps: preparing a polyether-ether-ketone main chain;
methyl hydroquinone, 4' -difluorobenzophenone, hexafluorobisphenol A and salt forming agent K are added into a 100ml three-necked bottle2CO3Toluene as a water-carrying agent and DMAc as a solvent; the reaction system is vacuumized and filled with nitrogen for three cycles. Heating to 140 ℃, refluxing at constant temperature for 4h, and heating to 170 ℃ for reaction for 24 h; pouring the reaction solution into deionized water, allowing flocculent precipitate to appear, filtering the obtained precipitate, washing with methanol solution for three times, and vacuum drying at 80 ℃ for 24h to obtain the polyether-ether-ketone main chain.
The reaction formula is as follows:
step two: preparing a brominated polyether-ether-ketone main chain;
completely dissolving the polyether-ether-ketone main chain in the first step into chlorobenzene solution, heating to 75 ℃, and adding an NBS brominating agent and an AIBN initiator under the protection of nitrogen; and the reaction needs to be protected from light. After 24h of reaction, the temperature of the system is reduced to room temperature, white powder precipitates in the ethanol solution, the mixture is filtered, washed by absolute ethyl alcohol for many times, and dried for 24h in vacuum at 80 ℃.
The reaction formula is as follows:
step three: preparing a cross-linking polyether-ether-ketone anion exchange membrane;
dissolving the brominated polyether-ether-ketone obtained in the step two in an NMP solution, stirring for 2 hours, and adding 1, 2-bis (4-pyridyl) ethane to obtain a mixed solution; pouring the mixed solution into a polytetrafluoroethylene mold, and carrying out forced air drying at 60 ℃ for 12 h; and (3) carrying out alkalization treatment on the dried membrane, and cleaning the surface by using deionized water to obtain the cross-linked polyether-ether-ketone anion exchange membrane.
Wherein x represents the molar ratio of the methyl hydroquinone to the 4, 4-difluorobenzophenone, and is 0.3, 0.5, 0.7 and 1.0 respectively.
The present invention is described in further detail below with reference to specific examples, in which the starting materials are all commercially available.
Example 1
(1) 2g of 4, 4-difluorobenzophenone (9.166mmol), 2.157g of hexafluorobisphenol A (6.416mmol), 0.3414g of methylhydroquinone (2.750mmol) and 2.534g of anhydrous potassium carbonate (18.322mmol) are placed in a 100mL three-necked flask, 40mL of DMAc and 10mL of toluene are added to the three-necked flask, and a magnetic stirrer is added. A gas inlet and outlet, a water separator and a condenser pipe are arranged on a three-mouth flask, the three-mouth flask is stirred at room temperature to uniformly mix the system, and the reaction system is protected by nitrogen. Reacting at 140 ℃ for 4 h; and then, continuously heating to 170 ℃, observing the reaction along with the increase of the viscosity of the system, finishing the reaction after 24 hours, slowly pouring the reaction liquid into deionized water at the temperature of 0 ℃ after the reaction liquid is cooled to the room temperature, and enabling the water to generate light purple agglomeration precipitates. Filtering to remove inorganic salt dissolved in water, washing precipitate with methanol solution for three times, and drying the obtained precipitate in a vacuum drying oven at 80 deg.C for 24 hr to obtain light purple polymer PEEK-CH3-0.3。
(2) 1g of the above PEEK-CH was taken3After-0.3 (2.609mmol) was completely dissolved in 40ml of chlorobenzene solution, 0.1393g of NBS (0.783mmol) and 0.016g of AIBN (0.102mmol) were added as initiators to a three-necked flask, the reaction was warmed to 75 ℃ and N was continuously introduced during the reaction2And keeping away from light, stopping reaction after 24h, slowly pouring the reaction solution into ethanol solution after the reaction solution is cooled to room temperature to obtain white powder precipitate, performing suction filtration, washing with ethanol solution for several times, and vacuum drying at 80 ℃ for 24h to obtain white polymer PEEK-CH2Br-0.3。
(3) 1g of the above brominated product PEEK-CH was taken2Br-0.3 was completely dissolved in 20ml of NMP solution, insoluble matter was removed by filtration through 400 mesh filter cloth, 0.179g of 1, 2-bis (4-pyridyl) ethane was added thereto and stirred at normal temperature, and filtration was again carried out to obtain a quaternized polymer solution PEEK-QA-0.3. Pouring the filtered polymer solution into a clean and dry polytetrafluoroethylene mold, taking care not to generate bubbles in the solution during the process, otherwise the prepared AEM generates defects; and (3) putting the mould into a blast oven at 80 ℃ for drying for 24h, taking out the mould, and soaking and stripping the mould in water to obtain complete AEMs. Immersing the obtained anion membrane in 1M NaOH solution for 48h, and Br on the membrane-Replacement by OH-. And then cleaning the prepared polymer film to be neutral by using de-aerated deionized water to obtain the PEEK-QA-0.3 anionic membrane.
Example 2
(1) 2g of 4, 4-difluorobenzophenone (9.166mmol), 1.5409g of hexafluorobisphenol A (4.583mmol), 0.5689g of methylhydroquinone (4.583mmol) and 2.534g of anhydrous potassium carbonate (18.322mmol) are placed in a 100mL three-neck flask, 40mL of DMAc and 10mL of toluene are added to the three-neck flask, and a magnetic stirrer is added. A gas inlet and outlet, a water separator and a condenser pipe are arranged on a three-mouth flask, the three-mouth flask is stirred at room temperature to uniformly mix the system, and the reaction system is protected by nitrogen. Reacting at 140 ℃ for 4 h; and then, continuously heating to 170 ℃, observing the reaction along with the increase of the viscosity of the system, finishing the reaction after 24 hours, slowly pouring the reaction liquid into deionized water at the temperature of 0 ℃ after the reaction liquid is cooled to the room temperature, and enabling the water to generate light purple agglomeration precipitates. Filtering to remove inorganic salt dissolved in water, washing precipitate with methanol solution for three times, and drying the obtained precipitate in a vacuum drying oven at 80 deg.C for 24 hr to obtain light purple polymer PEEK-CH3-0.5。
(2) 1.327g of the above PEEK was taken-CH3After-0.5 g (1.626mmol) of N was completely dissolved in 40ml of chlorobenzene solution, 0.28945g of NBS (1.626mmol) and 0.016g of AIBN (0.0976mmol) were added as initiators to the three-necked flask, the reaction was warmed to 75 ℃ and N was continuously introduced during the reaction2And keeping away from light, stopping reaction after 24h, slowly pouring the reaction solution into an ethanol solution after the reaction solution is cooled to room temperature to obtain white powder precipitate, performing suction filtration, and vacuum drying at 80 ℃ for 24h to finally obtain the white polymer PEEK-CH2Br-0.5。
(3) 1g of the above brominated product PEEK-CH was taken2Br-0.5 was completely dissolved in 20ml of NMP solution, insoluble matter was removed by filtration through 400 mesh filter cloth, 0.209g of 1, 2-bis (4-pyridyl) ethane was added thereto and stirred at normal temperature, and filtration was again carried out to obtain a quaternized polymer solution PEEK-QA-0.5. Pouring the filtered polymer solution into a clean and dry polytetrafluoroethylene mold, taking care not to generate bubbles in the solution during the process, otherwise the prepared AEM generates defects; and (3) putting the mould into a blast oven at 80 ℃ for drying for 24h, taking out the mould, and soaking and stripping the mould in water to obtain complete AEMs. Immersing the obtained anion membrane in 1M NaOH solution for 48h, and Br on the membrane-Replacement by OH-. And then cleaning the prepared polymer film to be neutral by using de-aerated deionized water to obtain the PEEK-QA-0.5 anionic membrane.
Example 3
(1) 2g of 4, 4-difluorobenzophenone (9.166mmol), 0.925g of hexafluorobisphenol A (2.750mmol), 0.796g of methylhydroquinone (6.416mmol), 2.534g of anhydrous potassium carbonate (18.322mmol) are placed in a 100mL three-necked flask, 40mL of DMAc and 10mL of toluene are added to the three-necked flask, and a magnetic stirrer is added. A gas inlet and outlet, a water separator and a condenser pipe are arranged on a three-mouth flask, the three-mouth flask is stirred at room temperature to uniformly mix the system, and the reaction system is protected by nitrogen. Reacting at 140 ℃ for 4 h; and then, continuously heating to 170 ℃, observing the reaction along with the increase of the viscosity of the system, finishing the reaction after 24 hours, slowly pouring the reaction liquid into deionized water at the temperature of 0 ℃ after the reaction liquid is cooled to the room temperature, and enabling the water to generate light purple agglomeration precipitates. Filtering to remove inorganic salt dissolved in water, and washing the precipitate with methanol solutionPrecipitating for three times, and drying the obtained precipitate in a vacuum drying oven at 80 deg.C for 24 hr to obtain light purple polymer PEEK-CH3-0.7。
(2) 1g of the above PEEK-CH was taken3After-0.7 (2.97mmol) was completely dissolved in 40ml of chlorobenzene solution, 0.370g of NBS (2.078mmol) and 0.025g of AIBN were added as initiators to a three-necked flask, the reaction was warmed to 75 ℃ and N was continuously added during the reaction2And keeping away from light, stopping reaction after 24h, slowly pouring the reaction solution into an ethanol solution after the reaction solution is cooled to room temperature to obtain white powder precipitate, performing suction filtration, and vacuum drying at 80 ℃ for 24h to finally obtain the white polymer PEEK-CH2Br-0.7。
(3) 1g of the above brominated product PEEK-CH was taken2Br-0.7 was completely dissolved in 20ml of NMP solution, insoluble matter was removed by filtration through 400 mesh filter cloth, 0.152g of 1, 2-bis (4-pyridyl) ethane was added thereto and stirred at normal temperature, and filtration was again carried out to obtain a quaternized polymer solution PEEK-QA-0.7. Pouring the filtered polymer solution into a clean and dry polytetrafluoroethylene mold, taking care not to generate bubbles in the solution during the process, otherwise the prepared AEM generates defects; and (3) putting the mould into a blast oven at 80 ℃ for drying for 24h, taking out the mould, and soaking and stripping the mould in water to obtain complete AEMs. Immersing the obtained anion membrane in 1M NaOH solution for 48h, and Br on the membrane-Replacement by OH-. And then cleaning the prepared polymer film to be neutral by using de-aerated deionized water to obtain the PEEK-QA-0.5 anionic membrane.
Example 4
(1) 2g of 4, 4-difluorobenzophenone (9.166mmol), 0.796g of methylhydroquinone (9.166mmol) and 2.534g of anhydrous potassium carbonate (18.322mmol) are placed in a 100mL three-necked flask, 40mL of DMAc and 10mL of toluene are added to the three-necked flask, and a magnetic stirrer is added. A gas inlet and outlet, a water separator and a condenser pipe are arranged on a three-mouth flask, the three-mouth flask is stirred at room temperature to uniformly mix the system, and the reaction system is protected by nitrogen. Reacting at 140 ℃ for 4 h; then continuously heating to 170 ℃, observing the reaction along with the increase of the viscosity of the system, finishing the reaction after 24h, and cooling the reaction liquid to room temperatureThe solution was slowly poured into deionized water at 0 ℃ and a light purple aggregate precipitate appeared in the water. Filtering to remove inorganic salt dissolved in water, washing precipitate with methanol solution for three times, and drying the obtained precipitate in a vacuum drying oven at 80 deg.C for 24 hr to obtain light purple polymer PEEK-CH3-1.0。
(2) 1g of the above PEEK-CH was taken3After-1.0 (3.311mmol) was completely dissolved in 40ml of chlorobenzene solution, 0.589g of NBS (3.311mmol) and 0.033g of AIBN (0.199mmol) were added as initiators to a three-necked flask, the reaction was warmed to 75 ℃ and N was continuously introduced during the reaction2And keeping away from light, stopping reaction after 24h, slowly pouring the reaction solution into an ethanol solution after the reaction solution is cooled to room temperature to obtain white powder precipitate, performing suction filtration, and vacuum drying at 80 ℃ for 24h to finally obtain the white polymer PEEK-CH2Br-0.7。
(3) 1g of the above brominated product PEEK-CH was taken2Br-1.0 was completely dissolved in 20ml of NMP solution, insoluble matter was removed by filtration through 400 mesh filter cloth, 0.249g of 1, 2-bis (4-pyridyl) ethane was added thereto and stirred at normal temperature, followed by filtration again to obtain a quaternized polymer solution PEEK-QA-1.0. Pouring the filtered polymer solution into a clean and dry polytetrafluoroethylene mold, taking care not to generate bubbles in the solution during the process, otherwise the prepared AEM generates defects; and (3) putting the mould into a blast oven at 80 ℃ for drying for 24h, taking out the mould, and soaking and stripping the mould in water to obtain complete AEMs. Immersing the obtained anion membrane in 1M NaOH solution for 48h, and Br on the membrane-Replacement by OH-. And then cleaning the prepared polymer film to be neutral by using de-aerated deionized water to obtain the PEEK-QA-0.5 anionic membrane.
Based on the method, the invention provides a cross-linked polyether-ether-ketone anion-exchange membrane which is prepared by adopting the preparation method. The cross-linked anion exchange membrane has excellent performances of good ionic conductivity, good alkali resistance stability and the like.
The properties of PEEK-QA-0.3, PEEK-QA-0.5, PEEK-QA-0.7 and PEEK-QA-1.0 of examples 1-4 were analyzed by comparison.
(1) Infrared characterization of films
FIG. 1 is an infrared spectrum of PEEK-QA-x film obtained in examples 1 to 4, 1222cm-1Is characterized by the characteristic peak of stretching vibration of ether bond, 1188cm-1The peak is a characteristic peak of C-N stretching vibration, and thus indicates the successful progress of the crosslinking reaction.
(2) Morphology of the film
FIG. 2 is a scanning electron microscope image of the surface and cross-section of PEEK-QA-x films obtained in examples 1-4, which have good light transmittance and flexibility, and can be bent freely without damage. As can be seen from the SEM surface image, the surface of the film is dense and smooth and has no defects. And the SEM sectional view has no obvious holes, which shows that the internal structure of the membrane is also uniform and compact.
(3) Mechanical properties of the film
Table 1 shows the stress-strain curves of the PEEK-QA-x films obtained in examples 1 to 4, in which the tensile strength of the films increased and then decreased as the degree of crosslinking increased. The tensile strength of PEEK-QA-0.5 films is highest. The decrease in tensile strength is also related to the water absorbed in the membrane when the cationic functional groups are increased to some extent. Water may act as a plasticizer in the film, reducing the force between the polymer chains, thereby reducing tensile strength; the membrane prepared provides sufficient mechanical strength for fuel cell applications.
TABLE 1
(4) Ionic conductivity of the membrane
FIG. 3 is a temperature change curve of the ion conductivity of PEEK-QA-x films obtained in examples 1-4, wherein the ion conductivity increases with increasing temperature. On the one hand, the polymer chain spacing becomes larger, the free volume becomes larger, and the ion transport channel becomes wider due to the temperature rise, which reduces the ion diffusion resistance through the chains, thereby increasing the conductivity of the membrane. On the other hand due to OH-The mobility in water increases with increasing temperature. The ionic conductivity of the PEEK-QA-0.5 anion exchange membrane is highest at 80 ℃. With degree of crosslinkingThe ionic conductivity of the membrane increases and then decreases.
(5) Alkali-resistant stability of membranes
FIG. 4 is a graph showing the change of the ion conductivity of the PEEK-QA-x films obtained in examples 1 to 4 with time, and the conductivity of the PEEK-QA-x films was slightly decreased after 1440h of the test. But the anionic membrane remains intact, has no rupture phenomenon and still has excellent flexibility.
(6) Thermal stability of the film
FIG. 5 shows the weight loss of PEEK-QA-x films obtained in examples 1 to 4 during temperature rise. The weight loss at 100-350 ℃ comes from decomposition of side chain functional groups, and the thermal weight loss at more than 350 ℃ comes from thermal decomposition of a polyether-ether-ketone main chain. The fuel cell generally operates at 50-80 ℃, and the PEEK-QA-n membrane does not thermally decompose before 100 ℃, which shows that the membrane has excellent thermal stability and can be suitable for the operating temperature of the fuel cell.
In summary, the preparation method of the cross-linked polyetheretherketone anion-exchange membrane for the fuel cell provided by the invention comprises the steps of firstly preparing the polyetheretherketone polymer main chain of the membrane, and then attaching the 1, 2-bis (4-pyridyl) ethane cross-linking agent through NBS bromine attachment. Finally, drying by air blast to form the film. The crosslinking can improve the ionic conductivity of the membrane and improve the mechanical stability and chemical stability of the membrane. However, the degree of crosslinking is so high that the flexibility of the membrane is deteriorated, and when x is 0.5, the highest ionic conductivity is obtained under the condition that the use requirement of the fuel cell is ensured.
The above description of the embodiments is only for the purpose of helping understanding the method of the present invention and the core idea thereof, and it should be noted that it is possible for those skilled in the art to make modifications and modifications to the present invention without departing from the principle of the present invention, and these modifications and modifications also fall within the protection scope of the claims of the present invention.
Claims (8)
1. A cross-linking polyether-ether-ketone anion exchange membrane for a fuel cell is characterized in that the anion exchange membrane is prepared by polymerizing methyl hydroquinone, hexafluorobisphenol A and 4, 4-difluorobenzophenone, and the structural formula of the membrane is as follows:
wherein x represents the molar ratio of the methyl hydroquinone to the 4, 4-difluorobenzophenone, and is 0.3, 0.5, 0.7 and 1.0 respectively.
2. The cross-linked polyetheretherketone anion-exchange membrane for a fuel cell according to claim 1, wherein: the crosslinking agent is 1, 2-bis (4-pyridyl) ethane, and the larger the molar ratio of the methyl hydroquinone is, the more the functional sites are, and the number of the crosslinking agents is increased.
3. A preparation method of a cross-linking polyether-ether-ketone anion exchange membrane for a fuel cell is characterized by comprising the following steps:
the method comprises the following steps: preparing a polyether-ether-ketone main chain;
step two: carrying out bromination reaction on the methyl on the polyether-ether-ketone main chain obtained in the step one, wherein the bromination reaction needs nitrogen protection and light-proof treatment to obtain a brominated polyether-ether-ketone main chain;
step three: adding 1, 2-bis (4-pyridyl) ethane into the brominated polyether-ether-ketone solution obtained in the second step to obtain a mixed solution;
step four: and filtering the mixed solution obtained in the third step, pouring the filtered mixed solution into a polytetrafluoroethylene mold, standing for 2 hours, and carrying out forced air drying to obtain the cross-linked polyether-ether-ketone anion exchange membrane for the fuel cell.
4. The preparation method of the cross-linking polyether-ether-ketone anion-exchange membrane for the fuel cell according to claim 3, wherein the step one is as follows: methyl hydroquinone, 4-difluorobenzophenone, hexafluorobisphenol A and salt forming agent K are added into a 100ml three-necked bottle2CO3Toluene as a water-carrying agent and DMAC as a solvent; vacuumizing and filling nitrogen into the reaction system for three times of circulation; heating to 140 ℃, refluxing at constant temperature for 4h, and heating to 170 ℃ for reaction for 24 h; reacting the reaction solutionPouring into deionized water, allowing flocculent precipitate to appear, filtering the precipitate, washing with methanol solution for three times, and vacuum drying at 80 deg.C for 24 hr to obtain polyether ether ketone main chain.
5. The preparation method of the cross-linking polyether-ether-ketone anion-exchange membrane for the fuel cell according to claim 3, wherein the second step comprises the following specific steps: completely dissolving a polyether-ether-ketone main chain in a chlorobenzene solution, and then adding an NBS brominating agent and an AIBN initiator, wherein the molar ratio of the polyether-ether-ketone main chain to the NBS is 1: 1.1; reacting for 24h at 75 ℃ to obtain the brominated polyether-ether-ketone main chain.
6. The preparation method of the cross-linking polyether-ether-ketone anion-exchange membrane for the fuel cell according to claim 3, wherein the three specific steps are as follows: and (2) dissolving the brominated polyether ether ketone obtained in the step two in NMP, stirring for 2 hours, and adding 1, 2-bis (4-pyridyl) ethane to obtain a mixed solution.
7. The method for preparing the cross-linked polyether-ether-ketone anion-exchange membrane for the fuel cell according to claim 3, wherein the forced air drying in the fourth step is drying in a forced air oven at 60-80 ℃ for 12-24 h.
8. The method for preparing a cross-linked PEEK anion exchange membrane for a fuel cell as claimed in claim 3, wherein the membrane dried in the fourth step is subjected to alkalization treatment, and Br on the membrane is removed-Replacement by OH-And then the surface is cleaned by deionized water.
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