CN113150248B - Ether-bond-free aryl sulfonated non-fluorine ionomer and preparation method and application thereof - Google Patents
Ether-bond-free aryl sulfonated non-fluorine ionomer and preparation method and application thereof Download PDFInfo
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses an ether bond-free aryl sulfonated non-fluorine ionomer as well as a preparation method and application thereof, wherein the ionomer takes 2,2, 2-trichloroacetophenone, Ar and M as raw materials, is dissolved in a reaction medium of a polar solvent, a catalyst is dripped into a reaction system at the temperature of-2 ℃, and the reaction is continued for 18-30h under the condition; after the reaction is finished, adding a solvent into the system for dilution, then pouring the diluted solution into a methanol aqueous solution, mixing and filtering; washing with deionized water, and washing with K 2 CO 3 Soaking the solution, and finally filtering and drying to obtain the target ionomer. The main chain of the ionomer does not contain vulnerable chemical bonds such as 'ether, ketone, sulfone' and the like, so that the ionomer has good chemical stability and is beneficial to prolonging the service life; and a hydrophilic phase and a hydrophobic phase are obtained through copolymerization, and the phase separation capability is adjusted through adjusting the proportion and the polymerization degree of the hydrophilic phase and the hydrophobic phase, so that a proton transmission channel is constructed, and the proton conductivity is improved.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a proton exchange membrane material for fuel cells or hydrogen production by water electrolysis, in particular to an ether bond-free aryl sulfonated non-fluorine ionomer and a preparation method and application thereof.
Background
The proton exchange membrane is a key core component in water electrolysis hydrogen production equipment, plays a role in providing a hydrogen ion channel and isolating two-stage reaction gas, and directly influences the performance, the energy conversion efficiency, the service life and the like of an electrolytic cell. Currently, perfluorosulfonic acid polymer membranes (PFSA) represented by Nafion membranes from DuPont are most widely used. Although the perfluorosulfonic acid membrane has the advantages of excellent chemical stability, high proton conductivity and the like, the further application of the perfluorosulfonic acid membrane in hydrogen production by electrolyzing water is greatly hindered by the expensive price, high gas transmittance and low working temperature (the glass transition temperature of a Nafion dry membrane is about 105 ℃, and the glass transition temperature of the Nafion dry membrane is greatly reduced due to the plasticizing effect of water after the Nafion dry membrane is soaked in water).
Aiming at the problems of the perfluorosulfonic acid proton exchange membrane, the current research mainly focuses on the improvement of the existing perfluorosulfonic acid proton exchange membrane and the development of a novel non-fluorine proton exchange membrane material. The improvement on the basis of the existing perfluorosulfonic acid membrane cannot fundamentally solve the existing problems, such as the electrical property of the membrane still depends on the content of perfluorosulfonic acid resin, and the working temperature is difficult to be greatly improved, so that the development of a novel non-fluorine proton exchange membrane material with high performance and low cost is one of the working hotspots of water electrolysis and fuel cells.
Currently, the developed non-fluorine proton exchange membrane materials are mainly sulfonated aromatic polymers, such as sulfonated phthalazinone polyether sulfone ketone, sulfonated polyether ether ketone, sulfonated polysulfone and the like. However, due to the relatively small degree of phase separation in non-fluorine proton exchange membranes, proton conductivity is mostly low; the swelling degree in water is higher; in addition, the main chain contains more vulnerable chemical bonds such as ether, ketone and sulfone, and the chemical stability is relatively poor.
Disclosure of Invention
The invention provides an ether bond-free aryl sulfonated non-fluorine ionomer as well as a preparation method and application thereof, and the ionomer can be used for preparing a proton exchange membrane with high proton conductivity and high chemical stability.
The invention has the technical scheme that the ether bond-free aryl sulfonated non-fluorine ionomer has a structural formula as follows:
wherein Ar is a biphenyl group; m contains a sulfonic acid group and a carbonyl group.
Further, Ar is biphenyl or terphenyl.
Further, M is 2-acrylamido-2-methylpropanesulfonic acid or levo/dextro/dl camphorsulfonic acid.
The present invention also relates to a method for preparing the ether bond-free arylsulfonic non-fluorine ionomer, comprising the steps of:
s1, dissolving 2,2, 2-trichloroacetophenone, Ar and M serving as raw materials in a reaction medium of a polar solvent, dropwise adding a catalyst solution into a reaction system at the temperature of-2 ℃, and continuously reacting for 18-30 hours under the condition;
s2, after the reaction is finished, adding a solvent into the system for dilution, then pouring the diluted solution into a methanol water solution, mixing and filtering; washing with deionized water, and washing with K 2 CO 3 Soaking the solution, and finally filtering and drying to obtain the target ionomer.
Further, the molar ratio of 2,2, 2-trichloroacetophenone, Ar and M is n:100 (100-n).
Further, the polar solvent is one or more of dichloromethane, trichloromethane, ethyl acetate, glacial acetic acid, DMSO, DMF and NMP.
Further, the catalyst used was trifluoroacetic acid, diluted with trifluoromethanesulfonic acid to form a trifluoroacetic acid solution. The concentration is 0.8 mol/L-1.1 mol/L; the molar ratio of the added amount of the catalyst to M is 1: 1-1: 1.2.
Further, K is used in S2 2 CO 3 When the solution is soaked, the temperature is controlled to be 40-60 ℃, and the time is 10-18h, preferably 12 h; the drying temperature is 50-80 ℃.
The invention also relates to the use of said ionomers in proton exchange membranes.
Further, when the proton exchange membrane is prepared, the ionomer is dissolved by a solvent, then the solution is cast to form a membrane, and finally the membrane is dried in vacuum to obtain the aryl sulfonated non-fluorine proton exchange membrane without ether bonds.
The invention has the following beneficial effects:
1. in the ionomer, the main chain does not contain easily attacked chemical bonds such as 'ether, ketone, sulfone' and the like, so that the chemical stability of the non-fluorine polymer is improved, and the service life is prolonged; and a hydrophilic phase and a hydrophobic phase are obtained through copolymerization, and the phase separation capability is adjusted through adjusting the proportion and the polymerization degree of the hydrophilic phase and the hydrophobic phase, so that a proton transmission channel is constructed, and the proton conductivity is improved.
2. The preparation process and operation of the invention are relatively simple and easy to realize, and the yield can reach more than 80%. The reaction principle is Friedel-crafts reaction, the solution after reaction is slowly poured into methanol solution, and stirring is carried out along with the reaction so as to ensure that the polymer is fully precipitated and the wrapping of other impurities is reduced as much as possible; the washing is to remove impurities dissolved in the methanol solution on the surface of the polymer, and the soaking and washing with the potassium carbonate solution is to remove acidic substances in the reaction system, thereby further improving the purity of the obtained product.
Drawings
FIG. 1 shows the NMR spectrum of the product obtained in example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
Adding 2,2, 2-trichloroacetophenone, biphenyl and 2-acrylamido-2-methylpropanesulfonic acid into a reactor at a molar ratio of 30:100:70, wherein the molar number of the biphenyl is 100mmol, and adding a mixed solvent of dichloromethane/DMF (the mixed volume ratio is 1:1) to stir and dissolve. 6mL of TFA (trifluoroacetic acid) and 75mL of TFSA (trifluoromethanesulfonic acid) are added dropwise into the system at 0 ℃, the two are uniformly mixed before being added dropwise, then the mixed solution is slowly added dropwise into the system through a constant-pressure dropping funnel, the reaction is continued for 18 hours under the condition after the addition, the viscous solution is slowly poured into the methanol aqueous solution, and the methanol aqueous solution is stirred while being poured, fully stirred, washed and filtered. Washing with deionized water, and soaking in 1MK 2 CO 3 In 50 ℃ for 12h, filtered and finally the solid is dried at 60 ℃ for 48h to give the desired polymer in a pale yellow color with a yield of 90% and a molecular weight of about 61.5kg/mol in DMF.
The NMR spectrum of the obtained polymer is shown in FIG. 1, wherein 1 H NMR(DMSO-d 6 ,δ,ppm):7.79-7.32(H 1 ,H 1’ ,H 2 ,H 2’ ),7.20-7.09(H 3 ,H 4 ,H 5 )。
Example 2
Adding 2,2, 2-trichloroacetophenone, terphenyl and 2-acrylamide-2-methyl propanesulfonic acid into a reactor at a molar ratio of 10:100:90 (the molar number of the terphenyl is 100mmol), adding a mixed solvent of dichloromethane/DMF (the mixed volume ratio is 2:3), and stirring for dissolving. 6mL of TFA (trifluoroacetic acid) and 75mL of TFSA (trifluoromethanesulfonic acid) are added dropwise to the system at 0 ℃, the two are uniformly mixed before being added dropwise, then the mixed solution is slowly added dropwise to the system through a constant-pressure dropping funnel, the reaction is continued for 24 hours under the condition after the addition, the viscous solution is slowly poured into the methanol aqueous solution, and the methanol aqueous solution is poured, stirred, fully stirred, washed and filtered. Washing with deionized water, and soaking in 1M K 2 CO 3 Soaking at 50 deg.C for 20h, sonicating for 5h, filtering, and finally drying the solid at 80 deg.C for 60h to give the pale yellow target polymer in 92% yield with a molecular weight of about 59.6kg/mol and DMF as solvent.
Example 3
Adding 2,2, 2-trichloroacetophenone, biphenyl and racemic camphor sulfonic acid into a reactor at a molar ratio of 40:100:60 (the molar number of the biphenyl is 100mmol), adding a mixed solvent of dichloromethane/ethyl acetate (the mixing volume ratio is 3:2), and stirring for dissolving. And (2) dropwise adding 8mL of TFA (trifluoroacetic acid) and 75mL of TFSA (trifluoromethanesulfonic acid) into the system at 0 ℃, uniformly mixing the TFA and TFSA before dropwise adding, slowly dropwise adding the mixed solution into the system through a constant-pressure dropping funnel, continuously reacting for 30 hours under the condition after dropwise adding, slowly pouring the viscous solution into the methanol aqueous solution, and stirring while pouring, fully stirring, washing and filtering. Washing with deionized water, and soaking in 1MK 2 CO 3 Soaking at 50 deg.C for 30h, sonicating for 5h, filtering, and finally drying the solid at 40 deg.C for 60h to give the desired polymer in yellow color in 88% yield and having a molecular weight of about 60.2kg/mol in DMF as solvent.
Example 4
Adding 2,2, 2-trichloroacetophenone, terphenyl and racemic camphor sulfonic acid into a reactor at a molar ratio of 60:100:40 (the mole number of the biphenyl is 100mmol), adding a mixed solvent of dichloromethane/ethyl acetate (the mixing volume ratio is 2:1), and stirring for dissolving. And (2) dropwise adding 8mL of TFA (trifluoroacetic acid) and 80mL of TFSA (trifluoromethanesulfonic acid) into the system at 0 ℃, uniformly mixing the TFA and TFSA before dropwise adding, slowly dropwise adding the mixed solution into the system through a constant-pressure dropping funnel, continuously reacting for 26 hours under the condition after dropwise adding, slowly pouring the viscous solution into the methanol aqueous solution, and stirring while pouring, fully stirring, washing and filtering. Washing with deionized water, and soaking in 1MK 2 CO 3 Soaking at 50 deg.C for 30h, sonicating for 5h, filtering, and finally drying the solid at 40 deg.C for 50h to give the desired polymer in yellow color in 88% yield and a molecular weight of about 63.8kg/mol in DMF as solvent.
Example 5:
the specific steps for preparing the proton exchange membrane by utilizing the ionomer are as follows: 1g of the ionomer prepared in example 1 was uniformly dispersed in a mixed solvent of dichloromethane and N, N-dimethylacetamide (volume ratio of the two is 1:3) with a mass ratio of the ionomer to the solvent of 1:10, and subjected to ultrasonic agitation for 6 hours each. And (3) forming a film from the prepared dispersion liquid by a tape casting method, enabling the dispersion liquid to flow onto a substrate, and forming a wet belt by relative movement of a scraper and the substrate, wherein the thickness of the film is controlled by the distance between the scraper and the substrate. And (3) putting the wet membrane and the substrate together at room temperature to evaporate dichloromethane, then putting the wet membrane and the substrate in an oven, vacuumizing, heating to 80 ℃, and drying for 48 hours to obtain the proton exchange membrane. Proton exchange membranes corresponding to examples 2, 3 and 4 and the comparative sulfonated polyetheretherketone (degree of sulfonation of 0.45) were prepared by the same method, wherein the composition of the solvent and the drying temperature and time were adjusted accordingly.
The performance data of the proton exchange membrane prepared from the materials are shown in table 1.
TABLE 1
Note: the detection method comprises the following steps:
1. proton conductivity test:
the proton conductivity of the proton exchange membrane in-plane direction is measured by an alternating current impedance method, and the test environment is a constant temperature water bath at 25 ℃. In the measured impedance spectrum, the impedance value (R) of the sample is read from the intersection of the high-frequency part of the spectrum and the solid axis, and the proton conductivity of the sample is calculated according to the following formula.
In the formula: l is the distance between the two electrodes, cm; r is membrane resistance, omega; a is the effective cross-sectional area of the film in the direction perpendicular to the electrodes, cm 2 。
Test of Water absorption and swelling Rate
Weighing the mass W of the dry proton exchange membrane d Then the membrane is immersed into deionized water and is kept stand at room temperature for 24 hours to obtain the wet membrane quality W w . The water absorption was calculated from the following formula:
in the formula: w d 、W w The mass of the dry film and the wet film, respectively.
The swelling ratio was measured as follows: measuring the size and thickness L of a square sample cut in advance by a caliper dry (ii) a The sample was placed in a constant temperature deionized water bath at a given temperature of 25 ℃. Keeping for 12 h; taking out the film sample to be measured, spreading the film sample on a measuring platform, and rapidly measuring the size L of the film sample wet . The swelling ratio of the sample was calculated as a linear change ratio by the following formula:
in the formula: SR is swelling ratio,%; l is d Is a sampleInitial size, μm; l is w The size of the sample after immersion in a thermostatic water bath, μm.
In the two tests, three samples are tested on each membrane sample, and the average value is calculated to serve as an experimental result.
3. Tensile strength
The test conditions were carried out according to the standard ISO 1184-1983.
As can be seen from Table 1, the proton exchange membrane prepared from the ionomer obtained by the method of the present invention has high proton conductivity and good chemical stability.
Claims (8)
1. An ether bond-free arylsulfonate non-fluorine ionomer having the formula:
wherein Ar is biphenyl or terphenyl; m contains sulfonic group and carbonyl, specifically M is 2-acrylamide-2-methylpropanesulfonic acid or levo/dextro/racemic camphorsulfonic acid, and n is more than or equal to 40 and more than or equal to 10.
2. A process for preparing the ether linkage free arylsulfonic acid non-fluorine ionomer of claim 1 comprising the steps of:
s1, dissolving 2,2, 2-trichloroacetophenone, Ar and M serving as raw materials in a reaction medium of a polar solvent, dropwise adding a catalyst solution into a reaction system at the temperature of-2 ℃, and continuously reacting for 18-30 hours under the condition;
s2, after the reaction is finished, adding a solvent into the system for dilution, then pouring the diluted solution into a methanol water solution, mixing and filtering; washing with deionized water, and washing with K 2 CO 3 Soaking the solution, and finally filtering and drying to obtain the target ionomer.
3. The method of claim 2, wherein: the molar ratio of the 2,2, 2-trichloroacetophenone, Ar and M is n:100 (100-n).
4. The method of claim 2, wherein: the polar solvent is one or more of dichloromethane, trichloromethane, ethyl acetate, glacial acetic acid, DMSO, DMF and NMP.
5. The method of claim 2, wherein: the catalyst used was trifluoroacetic acid, diluted with trifluoromethanesulfonic acid to form a trifluoroacetic acid solution.
6. The method of claim 2, wherein: k used in S2 2 CO 3 When the solution is soaked, controlling the temperature at 40-60 ℃ for 10-18 h; the drying temperature is 50-80 ℃.
7. Use of the ionomer according to claim 1 or prepared according to any one of claims 3-6 in a proton exchange membrane.
8. Use according to claim 7, characterized in that: when the proton exchange membrane is prepared, the ionomer is dissolved by a solvent, then the solution is cast to form a membrane, and finally the membrane is dried in vacuum to obtain the aryl sulfonated non-fluorine proton exchange membrane without ether bonds.
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| CN112175217A (en) * | 2020-09-01 | 2021-01-05 | 中国科学院山西煤炭化学研究所 | Anion exchange membrane containing arylene piperidine and diketone monomer copolymer and preparation method and application thereof |
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| CN112175217A (en) * | 2020-09-01 | 2021-01-05 | 中国科学院山西煤炭化学研究所 | Anion exchange membrane containing arylene piperidine and diketone monomer copolymer and preparation method and application thereof |
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