CN101787141B - Method for preparing proton exchange membrane with polyvinylidene fluoride grafted and grafting copolymerized with 2-acrylamido-2-methylpropanesulfonic acid - Google Patents
Method for preparing proton exchange membrane with polyvinylidene fluoride grafted and grafting copolymerized with 2-acrylamido-2-methylpropanesulfonic acid Download PDFInfo
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- CN101787141B CN101787141B CN200910216867XA CN200910216867A CN101787141B CN 101787141 B CN101787141 B CN 101787141B CN 200910216867X A CN200910216867X A CN 200910216867XA CN 200910216867 A CN200910216867 A CN 200910216867A CN 101787141 B CN101787141 B CN 101787141B
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- acrylamido
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a method for preparing proton exchange membrane with polyvinylidene fluoride grafted and grafting copolymerized with 2-acrylamido-2-methylpropanesulfonic acid, which belongs to the field of battery electrolyte material. The method comprises: dissolving a silicon compound in water-containing N-methyl pyrrolidone solution; adding polyvinylidene fluoride PVDF and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) to the solution; adding initiator; heating and stirring; casting the solution onto a clean glass plate; drying the obtained product; and removing membrane to obtain graft copolymer membrane with modified PVDF and 2-acrylamido-2-methylpropanesulfonic acid. The proton exchange membrane prepared by the method not only has good proton-conducting pieces, but also is convenient for mass production.
Description
Technical field
The present invention relates to the preparation method of the poly-2-acrylamido of a kind of polymetafluoethyene grafted blend-2-methyl propane sulfonic acid proton exchange membrane, belong to battery electrolyte material field.
Background technology
In Proton Exchange Membrane Fuel Cells and direct methanol fuel cell, the proton exchange membrane ionogen is the critical material in the battery, and the performance of proton exchange membrane will directly influence the performance of battery, and therefore, proton exchange membrane is the emphasis problem of fuel cell research and development always.At present, widely used proton exchange membrane mainly is the perfluorinated sulfonic acid ion exchange membrane of being produced by du pont company (Nafion film).This proton exchange membrane has good proton conductive, but owing to be perfluorinated ion-exchange membrane, so production cost is more expensive, particularly this proton exchange membrane is poor to the barrier of liquid fuels such as methyl alcohol, swelling ratio is big, is unfavorable for making the fuel cell of organic-fuel.In order to address this problem, developed some new proton exchange membrane, as polyvinylidene difluoride (PVDF) sulfonic acid proton exchange film film, this film not only has good proton conductive, also having lower methanol permeability simultaneously, is a kind of ideal direct methanol fuel cell proton exchange membrane therefore.
The key issue of preparation polyvinylidene difluoride (PVDF) sulfonate film is how to make polyvinylidene difluoride (PVDF) slough HF to produce active site, currently used method is, utilize methyl-2-pyrrolidone to make solvent earlier, method with solution casting is made film with polyvinylidene difluoride (PVDF), utilize the high energy electron irradiation irradiation again, make it produce free radical, after free-radical generating, film is put in the cinnamic solution of being furnished with initiator immediately and carried out scion grafting, will be behind the certain hour film of scion grafting carry out sulfonation and handle, thereby obtained the proton exchange membrane of polymetafluoethyene grafted polystyrene sulfonate.According to the difference of radiation exposure time and scion grafting time, the proton conductive of film and the methanol permeability of film are all different.Under an appropriate condition, this scion grafting film has very high proton conductive performance.Therefore this film is considered to a kind of electrolyte of ideal Proton Exchange Membrane Fuel Cells.
In the above-mentioned Proton Exchange Membrane Fuel Cells, proton exchange membrane is the critical material that influences fuel cell always, and proton exchange membrane not only plays a part conducting ion, also plays a part to isolate fuel simultaneously.Yet, in direct methanol fuel cell, use methyl alcohol to act as a fuel, therefore the proton exchange membrane in the battery requires not only have very high proton conductive, should possess very low methanol permeability simultaneously, and this just makes present widely used perfluorinated sulfonic acid proton exchange membrane no longer suitable.In order to obtain being applicable to the proton exchange membrane of direct methanol fuel cell, people propose to use the polymetafluoethyene grafted polystyrene sulfonate film, but this film is owing to must use ray to excite free radical, the polystyrene that is grafted on the other hand on the polyvinylidene fluoride film also needs sulfonation, and this method complex process is unfavorable for scale operation.
Summary of the invention
The object of the present invention is to provide a kind of silicon compound that utilizes to make polyvinylidene difluoride (PVDF) produce free radical, 2-acrylamido-2-the methyl propane sulfonic acid of direct graft-blending, the production process of film is simplified, simultaneously the preparation method of the poly-2-acrylamido of the polymetafluoethyene grafted blend-2-methyl propane sulfonic acid proton exchange membrane that also can control scion grafting amount and specific conductivity.
Technical solution: raw material of the present invention comprises: sodium orthosilicate, 2-acrylamido-2-methyl propane sulfonic acid, ammonium persulphate and polyvinylidene difluoride (PVDF), and each component concentration sum of raw material is 100%;
The preparation method is as follows: the preparation method is as follows: (1) is dissolved in the N-Methyl pyrrolidone solution of moisture 3wt%～5wt% by the sodium orthosilicate of raw material weight per-cent with 5wt%～12wt%, stir and got solution A in 1～3 hour, wherein: every gram polyvinylidene difluoride (PVDF) needs liquid N-Methyl pyrrolidone 5～6mL; (2) by raw material weight per-cent again 53wt%～72wt% polyvinylidene difluoride (PVDF) PVDF is poured in the solution A stirred 1-2 hour mixing solutions B; (3) claim 1wt%～2wt% ammonium persulphate by raw material weight per-cent, measure 2-acrylamido-2-methyl propane sulfonic acid AMPS of 20wt%～30wt% by raw material weight per-cent, join among the mixing solutions B and in 80 ℃～90 ℃ water-baths of nitrogen atmosphere, proceed electronic stirring 1～2h, leave standstill 3h, get solution C, (4) solution C is cast on the clean sheet glass, the gauge control of casting film is to 0.08mm～0.1mm, after volatilizing 5～7 hours under 80 ℃～90 ℃ temperature, dry, demoulding gets modified polyvinilidene fluoride and poly-2-acrylamido-2-methyl propane sulfonic acid graft copolymer membrane; (5) the gained film more than 24 hours, is removed 2-acrylamido-2-methyl propane sulfonic acid homopolymer with the deionized water extracting fully.
Before use film was carried out soaking in deionized water 6～12 hours.
The present invention makes and forms free radical on the polyvinylidene difluoride (PVDF) at polymetafluoethyene grafted poly-2-acrylamido-2-methyl propane sulfonic acid, uses radical initiator then.Its effect: the proton exchange membrane that the present invention makes has lower methanol permeability (10
-7Cm
2/ the number of minutes magnitude), (specific conductivity reaches 10 to have good proton conductive simultaneously
-2The S/cm order of magnitude), swelling ratio is lower, compares with the Nafion117 film of du pont company, and methanol permeation has been reduced by 1 order of magnitude (10
-7Cm
2/ the number of minutes magnitude), swelling ratio has reduced by 10%, and specific conductivity has improved 1 to 2 times.Simultaneously, production cost is low, is convenient to carry out scale operation.
Embodiment
Embodiment:
The pulverous sodium orthosilicate of 0.4g is dissolved in moisture 3%～5% N-Methyl pyrrolidone 16mL, stirs and got solution A in 1 hour, solution A is homogeneous shape solution; Again 3.1g polyvinylidene difluoride (PVDF) PVDF powder is poured in the solution A that stirs and to be stirred 2h and get solution B; Take by weighing the 0.08g ammonium persulphate, 2-acrylamido-2-methyl propane sulfonic acid AMPS of 1.5g is got in weighing, join in the solution B and in 80 ℃ of water-baths of nitrogen atmosphere, proceed electronic stirring 1h, leave standstill 3h and get solution C, be cast on the clean sheet glass getting solution C, after 5 hours, dry, demoulding get modified polyvinilidene fluoride and poly-2-acrylamido-2-methyl propane sulfonic acid graft copolymer membrane in volatilization under 90 ℃ of temperature; The gained film more than 24 hours, is removed 2-acrylamido-2-methyl propane sulfonic acid homopolymer with the deionized water extracting fully.Need before use film was carried out soaking in deionized water 6～12 hours.Survey its specific conductivity by two electrode AC impedance methods, (SD) comes the swelling behavior of characterization of membrane with swelling capacity, and (area is S for the rectangle diaphragm of about 3cm * 4cm earlier dry film to be cut into size
d), immerse 1molL
-1Methanol aqueous solution in, fully take out behind the swelling 48h, measure the size of wet film, obtain area S
W, calculate the swelling capacity SD of film by following formula:
Measure the methanol permeability of film with the barrier film method of diffusion.
Comparative example as a comparison, we utilize the Nafion117 film, and its methanol permeation, swelling ratio and specific conductivity are compared, and the Nafion117 film is soaked a few hours in deionized water, survey its specific conductivity by two electrode AC impedance methods; (SD) comes the swelling behavior of characterization of membrane with swelling capacity, and (area is S for the rectangle diaphragm of about 3cm * 4cm earlier dry film to be cut into size
d), immerse 1molL
-1Methanol aqueous solution in, fully take out behind the swelling 48h, measure the size of wet film, obtain area S
W, calculate the swelling capacity SD of film by following formula:
Measure the methanol permeability of film with the barrier film method of diffusion.
The table 1 modified polyvinilidene fluoride graft-blending 2-acrylamido-performance of 2-methyl propane sulfonic acid (AMPS) proton exchange membrane under 25 ℃ and comparison of Nafion film
| Sample number | Specific conductivity (10 -2S/cm) | Swelling ratio in water (%) | Methanol permeability (10 -6cm 2/ minute) |
| Nafion117 | 1.76 | 33.4 | 2.0 |
| Sample | 4.274 | 20.4 | 0.6 |
Claims (2)
1. polymetafluoethyene grafted blend gathers the preparation method of 2-acrylamido-2-methyl propane sulfonic acid proton exchange membrane, it is characterized in that, raw material of the present invention comprises: sodium orthosilicate, 2-acrylamido-2-methyl propane sulfonic acid, ammonium persulphate and polyvinylidene difluoride (PVDF), and each component concentration sum of raw material is 100%;
The preparation method is as follows: (1) is dissolved in the N-Methyl pyrrolidone solution of moisture 3wt%～5wt% by the sodium orthosilicate of raw material weight per-cent with 5wt%～12wt%, stir and got solution A in 1～3 hour, wherein: every gram polyvinylidene difluoride (PVDF) needs liquid N-Methyl pyrrolidone 5～6mL; (2) by raw material weight per-cent again 53wt%～72wt% polyvinylidene difluoride (PVDF) PVDF is poured in the solution A stirred 1-2 hour mixing solutions B; (3) claim 1wt%～2wt% ammonium persulphate by raw material weight per-cent, measure 2-acrylamido-2-methyl propane sulfonic acid AMPS of 20wt%～30wt% by raw material weight per-cent, join among the mixing solutions B and in 80 ℃～90 ℃ water-baths of nitrogen atmosphere, proceed electronic stirring 1～2h, leave standstill 3h, get solution C, (4) solution C is cast on the clean sheet glass, the gauge control of casting film is to 0.08mm～0.1mm, after volatilizing 5～7 hours under 80 ℃～90 ℃ temperature, dry, demoulding gets modified polyvinilidene fluoride and poly-2-acrylamido-2-methyl propane sulfonic acid graft copolymer membrane; (5) the gained film more than 24 hours, is removed 2-acrylamido-2-methyl propane sulfonic acid homopolymer with the deionized water extracting fully.
2. polymetafluoethyene grafted blend according to claim 1 gathers the preparation method of 2-acrylamido-2-methyl propane sulfonic acid proton exchange membrane, it is characterized in that, before use film is carried out soaking in deionized water 6～12 hours.
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|---|---|---|---|
| CN200910216867XA CN101787141B (en) | 2009-12-25 | 2009-12-25 | Method for preparing proton exchange membrane with polyvinylidene fluoride grafted and grafting copolymerized with 2-acrylamido-2-methylpropanesulfonic acid |
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|---|---|---|---|
| CN200910216867XA CN101787141B (en) | 2009-12-25 | 2009-12-25 | Method for preparing proton exchange membrane with polyvinylidene fluoride grafted and grafting copolymerized with 2-acrylamido-2-methylpropanesulfonic acid |
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| CN101787141B true CN101787141B (en) | 2011-12-28 |
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| CN102847449B (en) * | 2012-09-25 | 2014-12-10 | 内蒙古科技大学 | Preparation method of phosphotungstic acid/polyvinyl alcohol composite proton exchange membrane |
| CN103627014B (en) * | 2013-11-29 | 2016-03-16 | 内蒙古科技大学 | A kind of preparation method of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane |
| CN103626922A (en) * | 2013-11-29 | 2014-03-12 | 内蒙古科技大学 | Method for preparing modified polyvinylidene fluoride one-step grafted 3-sulfonic acid propyl methacrylate (SPMA) proton exchange membrane |
| CN104059240B (en) * | 2013-11-29 | 2017-01-11 | 内蒙古科技大学 | Preparation method of polyvinylidene fluoride grafted styrene sulfonate electrolyte membrane |
| CN105013355B (en) * | 2015-06-30 | 2017-06-16 | 四川大学 | Heparan polyether sulphone hollow fibre film and preparation method thereof and purposes |
| CN107293681B (en) * | 2016-03-30 | 2019-08-20 | 中南大学 | A kind of preparation method of novel lithium sulphur battery functi on diaphragm |
| CN108520970A (en) * | 2018-04-19 | 2018-09-11 | 长春工业大学 | One kind is based on 2- acrylamide-2-methyl propane sulfonic proton exchange membrane and preparation method thereof |
| CN114426643A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method and application of copolymer film material |
| CN113363542B (en) * | 2021-06-09 | 2023-02-14 | 深圳市通用氢能科技有限公司 | Proton exchange membrane, preparation method thereof and fuel cell |
| CN115403710A (en) * | 2022-09-27 | 2022-11-29 | 龙岩学院 | Preparation method and application of fuel cell diaphragm material |
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