CN108912361B - Method for constructing efficient proton transfer channel in proton exchange membrane - Google Patents
Method for constructing efficient proton transfer channel in proton exchange membrane Download PDFInfo
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- CN108912361B CN108912361B CN201810778209.9A CN201810778209A CN108912361B CN 108912361 B CN108912361 B CN 108912361B CN 201810778209 A CN201810778209 A CN 201810778209A CN 108912361 B CN108912361 B CN 108912361B
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Abstract
The invention discloses a method for constructing a high-efficiency proton transfer channel in a proton exchange membrane, which grafts hydrophobic branched chains on sulfonated aromatic polymers to prepare a sulfonated polymer proton exchange membrane containing the hydrophobic branched chains. The high mobility of the hydrophobic branched chain is utilized to promote the hydrophilic/hydrophobic phase separation in the film forming process, and a high-efficiency proton transfer channel is constructed in the proton exchange membrane, so that the proton conductivity of the membrane is improved. The invention solves the problem of low proton conductivity of sulfonated aromatic polymers. The raw materials used in the invention are cheap, the preparation process of the polymer is simple and convenient, and the commercial application can be realized.
Description
Technical Field
The invention belongs to the technical field of proton exchange membrane fuel cells, and particularly relates to a method for constructing a high-efficiency proton transfer channel in a proton exchange membrane.
Background
The fuel cell is a clean energy device and has the characteristics of high energy exchange rate, cleanness, no pollution and the like. The proton exchange membrane is one of the key parts of the proton exchange membrane fuel cell, but the commercialized Nafion series proton exchange membranes have the defects of high manufacturing cost, serious fuel permeation, great reduction of electrical conductivity in high-temperature and low-humidity environments and the like, and the adoption of the cheap sulfonated aromatic polymer proton exchange membrane to replace Nafion becomes the current research hotspot.
The sulfonated aromatic polymer proton exchange membrane has the advantages of low price, high mechanical property, good thermal stability, excellent performance of preventing fuel from shuttling and the like, but has the defects of unobvious separation of hydrophilic/hydrophobic phases and low proton conductivity.
Disclosure of Invention
In view of the above, embodiments of the present invention provide a method for constructing a high efficiency proton transfer channel in a proton exchange membrane.
In order to solve the technical problems, the technical scheme adopted by the embodiment of the invention is a method for constructing a high-efficiency proton transfer channel in a proton exchange membrane, wherein a hydrophobic branched chain is grafted on a sulfonated aromatic polymer, then the grafted sulfonated aromatic polymer is cast into a membrane, and the membrane is removed and washed to obtain the proton exchange membrane with the high-efficiency proton transfer channel.
Preferably, the method for constructing the high-efficiency proton transfer channel in the proton exchange membrane specifically comprises the following steps:
(1) preparing a sulfonated aromatic polymer;
(2) dissolving the dried sulfonated aromatic polymer in a solvent, adding a catalyst, stirring, adding a compound to be grafted, heating for reaction, washing and filtering after the reaction is finished, and drying a filter cake to obtain the sulfonated aromatic polymer grafted with the hydrophobic branched chain;
(3) dissolving the sulfonated aromatic polymer grafted with the hydrophobic branched chain in a solvent, casting to form a film, heating and drying, immersing the film in an acidic solution for acidification after demoulding, and washing with water after acidification to obtain the proton exchange membrane containing the efficient proton transfer channel.
Preferably, the sulfonated aromatic polymer is sulfonated aromatic polymer such as sulfonated polyether ether ketone, sulfonated polyether sulfone, sulfonated polyamide or sulfonated polyimide.
Preferably, the hydrophobic branches are flexible, rigid or branched hydrophobic branches.
Preferably, the compound to be grafted is a monoamine such as n-hexylamine, aniline, tritylamine or 3, 3-diphenylpropylamine.
Compared with the related art, the technical scheme provided by the embodiment of the invention has the following beneficial effects: the invention relates to a method for constructing a high-efficiency proton transfer channel in a proton exchange membrane, which comprises the steps of grafting a hydrophobic branched chain on a sulfonated aromatic polymer, then casting the grafted sulfonated aromatic polymer into a membrane, and obtaining the proton exchange membrane with the high-efficiency proton transfer channel after membrane removal and washing; and the high mobility of the hydrophobic branched chain is utilized to promote hydrophilic/hydrophobic phase separation in the film forming process, so that the proton conductivity of the film is improved.
Drawings
FIG. 1 is a flow chart of a method for constructing a high efficiency proton transfer channel in a proton exchange membrane according to an embodiment of the present invention;
FIG. 2 is a schematic diagram showing the proton conductivity comparison between the hydrophobic n-hexylamine grafted sulfonated polyether ether ketone membrane and the sulfonated polyether ether ketone membrane without grafted hydrophobic branched chain, wherein the hydrophobic n-hexylamine grafted sulfonated polyether ether ketone membrane is used for constructing the efficient proton transfer channel according to the method of the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings.
Example one
The embodiment of the invention provides a method for constructing a high-efficiency proton transfer channel in a proton exchange membrane, which comprises the steps of grafting a hydrophobic branched chain on a sulfonated aromatic polymer, then casting the grafted sulfonated aromatic polymer into a membrane, and obtaining the proton exchange membrane with the high-efficiency proton transfer channel after membrane removal and washing. The hydrophobic branched chain is flexible, rigid or branched. The proton exchange membrane with the efficient proton transfer channel is prepared by the embodiment of the invention, so that the problem of low proton conductivity of the sulfonated aromatic polymer is solved; the adopted raw materials are low in price, the preparation process of the polymer is simple and convenient, and the commercial application can be realized.
Referring to fig. 1, further, a method for constructing a high efficiency proton transfer channel in a proton exchange membrane specifically includes the following steps:
(1) preparing a sulfonated aromatic polymer; the sulfonated aromatic polymer is sulfonated aromatic polymer such as sulfonated polyether ether ketone, sulfonated polyether sulfone, sulfonated polyamide or sulfonated polyimide;
(2) dissolving the dried sulfonated aromatic polymer in a solvent, adding a catalyst, stirring, adding a compound to be grafted, heating for reaction, washing and filtering after the reaction is finished, and drying a filter cake to obtain the sulfonated aromatic polymer grafted with the hydrophobic branched chain; the solvent, the catalyst, the reaction temperature and the reaction time are determined according to different sulfonated aromatic compounds; the compound to be grafted is monoamine such as n-hexylamine, aniline, triphenylmethylamine or 3, 3-diphenylpropylamine;
(3) dissolving the sulfonated aromatic polymer grafted with the hydrophobic branched chain in a solvent, casting to form a film, heating and drying, immersing the film in an acidic solution for acidification after demoulding, and washing with water after acidification to obtain the proton exchange membrane containing the efficient proton transfer channel.
Further, in the step (2), the grafting degree of the sulfonated aromatic polymer grafted with the hydrophobic branched chain is 10% to 50%.
Example two
The method for constructing the proton exchange membrane of the efficient proton transfer channel comprises the following steps:
(1) preparing sulfonated polyether-ether-ketone;
specifically, adding dried polyether-ether-ketone particles and concentrated sulfuric acid into a flask, mechanically stirring for 6 hours at 30 ℃, then heating to 50 ℃ to continue reacting for 3 hours, pouring a reaction product into ice water to terminate the reaction, washing with ultrapure water until the pH value of the solution is neutral, and drying the product for 24 hours at 100 ℃ to obtain sulfonated polyether-ether-ketone with a certain sulfonation degree; sulfonated polyether ether ketone with different sulfonation degrees can be obtained by adjusting the reaction temperature and the reaction time, wherein the sulfonation degree range is 50-80%;
(2) dissolving dried sulfonated polyether ether ketone in dimethyl sulfoxide (DMSO), adding a proper amount of N, N' -carbonyldiimidazole catalyst, stirring for 3 hours at 60 ℃, adding a proper amount of N-hexylamine, reacting for 3 hours at 60 ℃, reacting amino with a sulfonate group, pouring the solution into water to obtain a precipitate after the reaction is finished, washing with water for multiple times, and drying for 24 hours at 100 ℃ to obtain the sulfonated polyether ether ketone containing N-hexylamine hydrophobic branched chains; the grafting degree of the hydrophobic branched chain can be controlled by adjusting the addition amount of N, N' -carbonyldiimidazole and N-hexylamine;
(3) dissolving sulfonated polyether ether ketone containing n-hexylamine hydrophobic branched chains in DMSO (dimethyl sulfoxide), casting to form a film, drying at 100 ℃ for 24 hours, demoulding, immersing in a 1mol/L sulfuric acid solution for acidification, and washing with ultrapure water for multiple times to obtain the hydrophobic n-hexylamine grafted sulfonated polyether ether ketone proton exchange membrane containing the efficient proton transfer channel. The rest is the same as the first embodiment.
The process for constructing the hydrophobic n-hexylamine grafted sulfonated polyether ether ketone proton exchange membrane containing the efficient proton transfer channel is shown as the following reaction formula;
the ion exchange capacity and proton conductivity of the hydrophobic n-hexylamine grafted sulfonated polyether ether ketone membrane and the sulfonated polyether ether ketone membrane which is not grafted with the hydrophobic branched chain, which are used for constructing the efficient proton transfer channel by the method of the embodiment of the invention, are compared in table 1.
Table 1 comparison of proton exchange membranes of inventive examples with ungrafted sulfonated polyetheretherketone membranes
As shown in Table 1, the invention constructs a high-efficiency proton transfer channel in the proton exchange membrane, and the grafted hydrophobic branched-chain membrane has higher proton conductivity under the similar ion exchange capacity.
Referring to the attached figure 2, as can be seen from comparison between the hydrophobic n-hexylamine grafted sulfonated polyether ether ketone membrane with the efficient proton transfer channel constructed by the method of the embodiment of the present invention and the sulfonated polyether ether ketone membrane without grafted hydrophobic branched chains, the proton conductivity of the hydrophobic n-hexylamine grafted sulfonated polyether ether ketone membrane of the embodiment of the present invention is significantly greater than that of the sulfonated polyether ether ketone membrane without grafted hydrophobic branched chains. The high mobility of the hydrophobic branched chain is utilized to promote the hydrophilic/hydrophobic phase separation in the film forming process, and a high-efficiency proton transfer channel is constructed in the proton exchange membrane, so that the proton conductivity of the membrane is improved.
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A method for constructing a high-efficiency proton transfer channel in a proton exchange membrane is characterized in that a hydrophobic branched chain is grafted on a sulfonated aromatic polymer, then the grafted sulfonated aromatic polymer is cast into a membrane, and the membrane is removed and washed to obtain the proton exchange membrane with the high-efficiency proton transfer channel; the method specifically comprises the following steps:
(1) preparing a sulfonated aromatic polymer;
(2) dissolving the dried sulfonated aromatic polymer in a solvent, adding a catalyst, stirring, adding a compound to be grafted, heating for reaction, washing and filtering after the reaction is finished, and drying a filter cake to obtain the sulfonated aromatic polymer grafted with the hydrophobic branched chain; the compound to be grafted is n-hexylamine, aniline, triphenylmethylamine or 3, 3-diphenylpropylamine;
(3) dissolving the sulfonated aromatic polymer grafted with the hydrophobic branched chain in a solvent, casting to form a film, heating and drying, immersing the film in an acidic solution for acidification after demoulding, and washing with water after acidification to obtain the proton exchange membrane containing the efficient proton transfer channel.
2. The method as claimed in claim 1, wherein the grafting degree of the proton exchange membrane containing the high efficiency proton transfer channels in the step (3) is 10% to 50%.
3. The method as claimed in claim 1, wherein the grafting of the hydrophobic branch chain onto the sulfonated aromatic polymer is performed in the following reaction manner:
4. the method as claimed in claim 1, wherein the sulfonated aromatic polymer is sulfonated polyether ether ketone, sulfonated polyether sulfone, sulfonated polyamide or sulfonated polyimide.
5. The method as claimed in claim 1, wherein the hydrophobic branches are flexible, rigid or branched hydrophobic branches.
6. The method for constructing a high efficiency proton transfer channel in a proton exchange membrane as claimed in claim 1, which comprises the following steps:
(1) preparing sulfonated polyether-ether-ketone; adding dried polyether-ether-ketone particles and concentrated sulfuric acid into a flask, mechanically stirring for 6 hours at 30 ℃, then heating to 50 ℃ to continue reacting for 3 hours, pouring a reaction product into ice water to terminate the reaction, washing with ultrapure water until the pH value of the solution is neutral, and drying the product for 24 hours at 100 ℃ to obtain sulfonated polyether-ether-ketone;
(2) dissolving dried sulfonated polyether ether ketone in dimethyl sulfoxide, adding a proper amount of N, N' -carbonyl diimidazole catalyst, stirring for 3 hours at 60 ℃, adding N-hexylamine, reacting for 3 hours at 60 ℃, pouring the solution into water to obtain a precipitate after the reaction is finished, washing with water, and drying for 24 hours at 100 ℃ to obtain sulfonated polyether ether ketone containing N-hexylamine hydrophobic branched chains;
(3) dissolving sulfonated polyether ether ketone containing n-hexylamine hydrophobic branched chain in dimethyl sulfoxide, casting to form a film, drying for 24 hours at 100 ℃, demoulding, immersing in 1mol/L sulfuric acid solution for acidification, and washing with ultrapure water to obtain the hydrophobic n-hexylamine grafted sulfonated polyether ether ketone proton exchange membrane containing the efficient proton transfer channel.
7. The method as claimed in claim 6, wherein in the step (1), the sulfonation degree of the sulfonated polyether ether ketone is 50% to 80%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101771159A (en) * | 2010-01-26 | 2010-07-07 | 新奥科技发展有限公司 | Proton exchange membrane and preparation method thereof |
| CN106117473A (en) * | 2016-06-30 | 2016-11-16 | 中国科学院上海高等研究院 | A kind of can be as sulfonated polyether-ether-ketone of cross-linked proton exchange membrane material and its production and use |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101771159A (en) * | 2010-01-26 | 2010-07-07 | 新奥科技发展有限公司 | Proton exchange membrane and preparation method thereof |
| CN106117473A (en) * | 2016-06-30 | 2016-11-16 | 中国科学院上海高等研究院 | A kind of can be as sulfonated polyether-ether-ketone of cross-linked proton exchange membrane material and its production and use |
Non-Patent Citations (2)
| Title |
|---|
| "Effect of different ion-aggregating structures on the property of proton conducting membrane based on polyvinyl alcohol";Yi Yang等;《Journal of Membrane Science》;20150915;第490卷;第39页 * |
| "Synthesis, Nanostructures and Properties of Sulfonated Poly(phenylene oxide) Bearing Polyfluorostyrene Side Chains as Proton Conducting Membranes";Mark Ingratta等;《Macromolecules》;20110314;第44卷;第2074-2076页 * |
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Inventor after: Zhang Yunfeng Inventor after: Liu Xupo Inventor after: Cheng Hansong Inventor before: Cheng Hansong Inventor before: Zhang Yunfeng Inventor before: Liu Xupo |