CN103980511A - Preparation method for cross-linking type polyvinyl butyral composite proton exchange membrane - Google Patents
Preparation method for cross-linking type polyvinyl butyral composite proton exchange membrane Download PDFInfo
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- CN103980511A CN103980511A CN201410187283.5A CN201410187283A CN103980511A CN 103980511 A CN103980511 A CN 103980511A CN 201410187283 A CN201410187283 A CN 201410187283A CN 103980511 A CN103980511 A CN 103980511A
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a preparation method for a cross-linking type polyvinyl butyral composite proton exchange membrane. The method comprises the following steps: dissolving polyvinyl butyral in an alcoholic solution to prepare a polymer solution; adding a cross-linking agent, controlling reaction conditions and carrying out heating and stirring so as to obtain a solution; casting the solution on a glass plate and carrying out drying and cross-linking so as to obtain a membrane; and subjecting the prepared cross-linking type polyvinyl butyral composite membrane to soaking and oxidation in a hydrogen peroxide solution at room temperature so as to obtain the cross-linking type polyvinyl butyral composite proton exchange membrane. The composite proton exchange membrane prepared in the invention has excellent proton conductivity and good stability, the proton conduction rate of the membrane is greater than proton conductivity of a Nafion membrane, and swellbility of the membrane is smaller than swellbility of the Nafion membrane; the preparation method has the advantages of simple process, convenient operation, lower membrane preparation cost compared with cost for preparation of the Nafion membrane and easy industrialization.
Description
Technical field
The present invention relates to the preparation method of a kind of fuel cell proton exchange membrane used, be specifically related to a kind of preparation method of cross-linked type polyethylene butyral compound proton exchange membrane.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is directly by fuel and oxygenant (O
2) chemical energy be converted into electric energy, be a kind of novel power generation assembly.Because its high energy efficiency and the advantage such as pollution-free and be considered to one of the most rising clean energy.
Proton Exchange Membrane Fuel Cells Proton Exchange Membrane Fuel Cells volume is little, weight is lighter, use safe ready, be enough to replace the traditional rechargeable battery using on present portable electric device, as mobile telephone, notebook computer, digital camera, pick up camera, electric bicycle etc.High-power Proton Exchange Membrane Fuel Cells even can also be used for automobile, and Proton Exchange Membrane Fuel Cells has become an important research direction of following novel energy.
As the core material of fuel cell, proton exchange membrane has played and has made proton (H
+) being optionally transmitted to the effect of negative electrode from anode, it has intercepted fuel and oxygenant simultaneously.The performance of proton exchange membrane is determining fuel battery performance.
The proton exchange membrane being applied at present in fuel cell is perfluoro sulfonic acid membrane, the Nafion film that for example du pont company produces.The chemistry of Nafion film and good mechanical stability, proton conductivity of phosphoric acid is good, but its while existing the high and temperature of cost to exceed 100 DEG C proton conductivity descend rapidly degradation shortcoming, limited its commercial applications.Therefore cost of development proton exchange membrane low, good stability becomes study hotspot.
Summary of the invention
The present invention, in order to solve existing proton exchange membrane production cost height and the low problem of stability, provides a kind of preparation method of cross-linked type polyethylene butyral compound proton exchange membrane.
The present invention adopts following technical scheme to realize:
A preparation method for cross-linked type polyethylene butyral compound proton exchange membrane, comprises the following steps:
(1) be that the polyvinyl butyral acetal of 50-100 part is dissolved in the alcoholic solution that mass parts is 100-3000 part by mass parts, make polyvinyl butyral acetal solution, wherein, the condensation degree of polyvinyl butyral acetal is 20%-45%, and selected alcohol is any one or several in methyl alcohol, ethanol, propyl alcohol or Virahol;
(2) polyvinyl butyral acetal solution is heated to 45 DEG C-100 DEG C, stirs 1-12 hour;
(3) above-mentioned solution being cooled to 20 DEG C-50 DEG C, is then the linking agent of 5-60 part to adding mass parts in solution, and solution is heated to 30 DEG C-100 DEG C, stirs 1-8 hour, and naturally cooling, obtains pouring into a mould solution;
Selected linking agent is one or both in gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane;
(4) will pour into a mould solution casting on sheet glass, controlling the film thickness being cast on sheet glass is 80-200 micron, vacuum drying 5-24h, and temperature is controlled at 40 DEG C-80 DEG C, obtains cross-linked type polyethylene butyral composite membrane;
(5) cross-linked type polyethylene butyral composite membrane is at room temperature placed in to hydrogen peroxide solution and soaks 3-10 hour, obtain cross-linked type polyethylene butyral compound proton exchange membrane; Selected hydrogen peroxide solution concentration is 1%-50%.
As above-mentioned preferred preparation method, comprise the following steps:
(1) be that the polyvinyl butyral acetal of 60-80 part is dissolved in the alcoholic solution that mass parts is 600-1800 part by mass parts, make polyvinyl butyral acetal solution, wherein, the condensation degree of polyvinyl butyral acetal is 20-45%;
(2) polyvinyl butyral acetal solution is heated to 70 DEG C, stirs 3-8 hour;
(3) above-mentioned solution being cooled to 20 DEG C-50 DEG C, is then the linking agent of 5-30 part to adding mass parts in solution, and solution is heated to 40 DEG C-80 DEG C, stirs 1-6 hour, and naturally cooling, obtains pouring into a mould solution;
(4) will pour into a mould solution casting on sheet glass, controlling the film thickness being cast on sheet glass is 80-200 micron, vacuum drying 10-24h, and temperature is controlled at 40 DEG C-80 DEG C, obtains cross-linked type polyethylene butyral composite membrane;
(5) cross-linked type polyethylene butyral composite membrane is at room temperature placed in to hydrogen peroxide solution and soaks 5-10 hour, obtain cross-linked type polyethylene butyral compound proton exchange membrane.
Polyvinyl butyral acetal is a kind of good film forming material, there is higher intensity, rigidity and hardness, and there are good agglutinating value(of coal) and a chemical stability, now polyvinyl butyral acetal is configured to solution, in the solution being configured to, add the linking agent that contains sulfydryl, sulfydryl is with becoming sulfonic group after hydrogen peroxide oxidation, and sulfonic acid group can provide proton on the one hand, improves the conductive capability of film; On the other hand, the gamma-mercaptopropyltriethoxysilane adding or γ-mercaptopropyl trimethoxysilane can be cross-linked the antioxidant property that improves film with polyvinyl butyral acetal.The cross-linked type polyethylene butyral compound proton exchange membrane finally making has satisfactory stability and proton conductivity, and manufacture craft of the present invention is simple, and molding cost is lower than the cost of Nafion film processed.
The present invention compare with technology with current material have advantages of as follows:
The proton conduction property excellence of the proton exchange membrane that 1, the present invention makes, its proton conduction speed is greater than the proton conductivity of Nafion film;
The stability of the proton exchange membrane of 2, making in prior art is mostly in 20h, more than the stability of the proton exchange membrane that the present invention makes generally reaches as high as 48h more than 30h;
3, the proton exchange membrane swelling capacity that the present invention makes is less than the swelling capacity of Nafion film;
4, simple, easy to operate, the masking cost of preparation technology of the present invention, lower than Nafion film cost processed, is easy to industrialization.
Embodiment
Further illustrate the present invention below by embodiment, but be not limited to following examples.
Embodiment 1:
A preparation method for cross-linked type polyethylene butyral compound proton exchange membrane, comprises the following steps:
(1) polyvinyl butyral acetal that is 20% by the condensation degree of 5 grams is dissolved in 100 grams of methanol solutions, makes polyvinyl butyral acetal solution;
(2) polyvinyl butyral acetal solution is heated to 100 DEG C, and stirs 12 hours;
(3) above-mentioned solution is cooled to 30 DEG C, to the gamma-mercaptopropyltriethoxysilane that adds 0.5 gram in solution, then solution is heated to 100 DEG C, and stirs 8 hours, then naturally cooling, obtain pouring into a mould solution;
(4) cast solution casting is on sheet glass, and to control the film thickness that is cast on sheet glass be 200 microns, vacuum drying 24h, and the temperature of vacuum drying is 70 DEG C, obtains cross-linked type polyethylene butyral composite membrane;
(5) cross-linked type polyethylene butyral composite membrane soaking at room temperature in 50% hydrogen peroxide solution 3 hours, obtains cross-linked type polyethylene butyral compound proton exchange membrane.
Survey the proton exchange membrane that makes and the specific conductivity of Nafion117 by four electrode AC impedance methods, the proton exchange membrane that makes of test and the swelling ratio of Nafion117 again, the concrete steps of surveying swelling ratio are: the dry proton exchange membrane making and Nafion117 are cut into the rectangle diaphragm that size is 2cm × 4cm, and (establishing area is S
d), immerse in the aqueous solution, after abundant swelling 24h, take out, measure wet proton exchange membrane and the size of Nafion117, obtain area S
w, calculate the swelling ratio SD:SD=(S of film by following formula
w-S
d)/S
d× 100%, result is as shown in the table:
| Sample number | Specific conductivity (10 -2 S/cm） | Swelling ratio (%) | Chemical stability (h) |
| Nafion117 | 1.54 | 35.8 | ＞48 |
| The proton exchange membrane making | 2.67 | 17.3 | 30 |
By finding out in table, the specific conductivity of the proton exchange membrane making is higher than the specific conductivity of Nafion117, and swelling ratio is also lower than the swelling ratio of Nafion117.The proton exchange membrane test chemical stability that the present embodiment makes is 30h, and stability is better.
Embodiment 2:
A preparation method for cross-linked type polyethylene butyral compound proton exchange membrane, comprises the following steps:
(1) polyvinyl butyral acetal that is 20% by the condensation degree of 10 grams is dissolved in 300 grams of propanol solution, makes polyvinyl butyral acetal solution;
(2) polyvinyl butyral acetal solution is heated to 100 DEG C, and stirs 8 hours;
(3) above-mentioned solution is cooled to 25 DEG C, to the gamma-mercaptopropyltriethoxysilane that adds 6 grams in solution, then solution is heated to 80 DEG C, and stirs 8 hours, then naturally cooling, obtain pouring into a mould solution;
(4) cast solution casting is on sheet glass, and to control the film thickness that is cast on sheet glass be 160 microns, vacuum drying 24h, and the temperature of vacuum drying is 70 DEG C, obtains cross-linked type polyethylene butyral composite membrane;
(5) cross-linked type polyethylene butyral composite membrane soaking at room temperature in 50% hydrogen peroxide solution 3 hours, obtains cross-linked type polyethylene butyral compound proton exchange membrane.
According to the method test performance of embodiment 1, result is as shown in the table:
| Sample number | Specific conductivity (10 -2 S/cm） | Swelling ratio (%) | Chemical stability (h) |
| Nafion117 | 1.54 | 35.8 | ＞48 |
| The proton exchange membrane making | 5.19 | 8.3 | ＞48 |
By finding out in table, the specific conductivity of the proton exchange membrane making is higher than the specific conductivity of Nafion117, and swelling ratio is also lower than the swelling ratio of Nafion117.The proton exchange membrane test chemical stability that the present embodiment makes is good.
Embodiment 3:
A preparation method for cross-linked type polyethylene butyral compound proton exchange membrane, comprises the following steps:
(1) polyvinyl butyral acetal that is 45% by the condensation degree of 10 grams is dissolved in 300 grams of ethanolic solns, makes polyvinyl butyral acetal solution;
(2) polyvinyl butyral acetal solution is heated to 45 DEG C, and stirs 12 hours;
(3) above-mentioned solution is cooled to 50 DEG C, to the gamma-mercaptopropyltriethoxysilane that adds 3 grams in solution, then solution is heated to 100 DEG C, and stirs 4 hours, then naturally cooling, obtain pouring into a mould solution;
(4) cast solution casting is on sheet glass, and to control the film thickness that is cast on sheet glass be 80 microns, vacuum drying 15h, and the temperature of vacuum drying is 70 DEG C, obtains cross-linked type polyethylene butyral composite membrane;
(5) cross-linked type polyethylene butyral composite membrane soaking at room temperature in 30% hydrogen peroxide solution 5 hours, obtains cross-linked type polyethylene butyral compound proton exchange membrane.
According to the method test performance of embodiment 1, result is as shown in the table:
| Sample number | Specific conductivity (10 -2 S/cm） | Swelling ratio (%) | Chemical stability (h) |
| Nafion117 | 1.54 | 35.8 | ＞48 |
| The proton exchange membrane making | 3.52 | 12.9 | 38 |
By finding out in table, the specific conductivity of the proton exchange membrane making is higher than the specific conductivity of Nafion117, and swelling ratio is also lower than the swelling ratio of Nafion117.The proton exchange membrane test chemical stability that the present embodiment makes is better.
Embodiment 4:
A preparation method for cross-linked type polyethylene butyral compound proton exchange membrane, comprises the following steps:
(1) polyvinyl butyral acetal that is 40% by the condensation degree of 8 grams is dissolved in 200 grams of aqueous isopropanols, makes polyvinyl butyral acetal solution;
(2) polyvinyl butyral acetal solution is heated to 45 DEG C, and stirs 10 hours;
(3) above-mentioned solution is cooled to 25 DEG C, to the gamma-mercaptopropyltriethoxysilane that adds 5 grams in solution, then solution is heated to 80 DEG C, and stirs 6 hours, then naturally cooling, obtain pouring into a mould solution;
(4) cast solution casting is on sheet glass, and to control the film thickness that is cast on sheet glass be 100 microns, vacuum drying 12h, and the temperature of vacuum drying is 80 DEG C, obtains cross-linked type polyethylene butyral composite membrane;
(5) cross-linked type polyethylene butyral composite membrane soaking at room temperature in 20% hydrogen peroxide solution 8 hours, obtains cross-linked type polyethylene butyral compound proton exchange membrane.
According to the method test performance of embodiment 1, result is as shown in the table:
| Sample number | Specific conductivity (10 -2 S/cm） | Swelling ratio (%) | Chemical stability (h) |
| Nafion117 | 1.54 | 35.8 | ＞48 |
| The proton exchange membrane making | 4.77 | 6.4 | ＞48 |
By finding out in table, the specific conductivity of the proton exchange membrane making is higher than the specific conductivity of Nafion117, and swelling ratio is also lower than the swelling ratio of Nafion117.The proton exchange membrane test chemical stability that the present embodiment makes is good.
Embodiment 5:
A preparation method for cross-linked type polyethylene butyral compound proton exchange membrane, comprises the following steps:
(1) polyvinyl butyral acetal that is 30% by the condensation degree of 6 grams is dissolved in 100 grams of methanol solutions, makes polyvinyl butyral acetal solution;
(2) polyvinyl butyral acetal solution is heated to 80 DEG C, and stirs 3 hours;
(3) above-mentioned solution is cooled to 28 DEG C, to the gamma-mercaptopropyltriethoxysilane that adds 4 grams in solution, then solution is heated to 50 DEG C, and stirs 8 hours, then naturally cooling, obtain pouring into a mould solution;
(4) cast solution casting is on sheet glass, and to control the film thickness that is cast on sheet glass be 80 microns, vacuum drying 8h, and the temperature of vacuum drying is 40 DEG C, obtains cross-linked type polyethylene butyral composite membrane;
(5) cross-linked type polyethylene butyral composite membrane soaking at room temperature in 5% hydrogen peroxide solution 10 hours, obtains cross-linked type polyethylene butyral compound proton exchange membrane.
According to the method test performance of embodiment 1, result is as shown in the table:
| Sample number | Specific conductivity (10 -2 S/cm） | Swelling ratio (%) | Chemical stability (h) |
| Nafion117 | 1.54 | 35.8 | ＞48 |
| The proton exchange membrane making | 4.15 | 5.7 | ＞48 |
By finding out in table, the specific conductivity of the proton exchange membrane making is higher than the specific conductivity of Nafion117, and swelling ratio is also lower than the swelling ratio of Nafion117.The proton exchange membrane test chemical stability that the present embodiment makes is good.
Embodiment 6:
A preparation method for cross-linked type polyethylene butyral compound proton exchange membrane, comprises the following steps:
(1) polyvinyl butyral acetal that is 45% by the condensation degree of 10 grams is dissolved in 225 grams of methanol solutions, makes polyvinyl butyral acetal solution;
(2) polyvinyl butyral acetal solution is heated to 70 DEG C, and stirs 5 hours;
(3) above-mentioned solution is cooled to 20 DEG C, to the gamma-mercaptopropyltriethoxysilane that adds 3 grams in solution, then solution is heated to 40 DEG C, and stirs 6 hours, then naturally cooling, obtain pouring into a mould solution;
(4) cast solution casting is on sheet glass, and to control the film thickness that is cast on sheet glass be 150 microns, vacuum drying 24h, and the temperature of vacuum drying is 40 DEG C, obtains cross-linked type polyethylene butyral composite membrane;
(5) cross-linked type polyethylene butyral composite membrane soaking at room temperature in 30% hydrogen peroxide solution 10 hours, obtains cross-linked type polyethylene butyral compound proton exchange membrane.
According to the method test performance of embodiment 1, result is as shown in the table:
| Sample number | Specific conductivity (10 -2 S/cm） | Swelling ratio (%) | Chemical stability (h) |
| Nafion117 | 1.54 | 35.8 | ＞48 |
| The proton exchange membrane making | 4.29 | 9.1 | ＞48 |
By finding out in table, the specific conductivity of the proton exchange membrane making is higher than the specific conductivity of Nafion117, and swelling ratio is also lower than the swelling ratio of Nafion117.The proton exchange membrane test chemical stability that the present embodiment makes is good.
Claims (5)
1. a preparation method for cross-linked type polyethylene butyral compound proton exchange membrane, is characterized in that: comprise the following steps:
(1) be that the polyvinyl butyral acetal of 50-100 part is dissolved in the alcoholic solution that mass parts is 100-3000 part by mass parts, make polyvinyl butyral acetal solution, wherein, the condensation degree of polyvinyl butyral acetal is 20%-45%;
(2) polyvinyl butyral acetal solution is heated to 45 DEG C-100 DEG C, stirs 1-12 hour;
(3) above-mentioned solution being cooled to 20 DEG C-50 DEG C, is then the linking agent of 5-60 part to adding mass parts in solution, and solution is heated to 30 DEG C-100 DEG C, stirs 1-8 hour, and naturally cooling, obtains pouring into a mould solution;
(4) will pour into a mould solution casting on sheet glass, controlling the film thickness being cast on sheet glass is 80-200 micron, vacuum drying 5-24h, and temperature is controlled at 40 DEG C-80 DEG C, obtains cross-linked type polyethylene butyral composite membrane;
(5) cross-linked type polyethylene butyral composite membrane is at room temperature placed in to hydrogen peroxide solution and soaks 3-10 hour, obtain cross-linked type polyethylene butyral compound proton exchange membrane.
2. the preparation method of cross-linked type polyethylene butyral compound proton exchange membrane according to claim 1, is characterized in that: comprise the following steps:
(1) be that the polyvinyl butyral acetal of 60-80 part is dissolved in the alcoholic solution that mass parts is 600-1800 part by mass parts, make polyvinyl butyral acetal solution, wherein, the condensation degree of polyvinyl butyral acetal is 20-45%;
(2) polyvinyl butyral acetal solution is heated to 70 DEG C, stirs 3-8 hour;
(3) above-mentioned solution being cooled to 20 DEG C-50 DEG C, is then the linking agent of 5-30 part to adding mass parts in solution, and solution is heated to 40 DEG C-80 DEG C, stirs 1-6 hour, and naturally cooling, obtains pouring into a mould solution;
(4) will pour into a mould solution casting on sheet glass, controlling the film thickness being cast on sheet glass is 80-200 micron, vacuum drying 10-24h, and temperature is controlled at 40 DEG C-80 DEG C, obtains cross-linked type polyethylene butyral composite membrane;
(5) cross-linked type polyethylene butyral composite membrane is at room temperature placed in to hydrogen peroxide solution and soaks 5-10 hour, obtain cross-linked type polyethylene butyral compound proton exchange membrane.
3. the preparation method of cross-linked type polyethylene butyral compound proton exchange membrane according to claim 1 and 2, is characterized in that: described alcohol is any one or several in methyl alcohol, ethanol, propyl alcohol or Virahol.
4. the preparation method of cross-linked type polyethylene butyral compound proton exchange membrane according to claim 1 and 2, is characterized in that: described linking agent is any in gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane.
5. the preparation method of cross-linked type polyethylene butyral compound proton exchange membrane according to claim 1 and 2, is characterized in that: the concentration of described hydrogen peroxide solution is 1%-50%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582326A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Antibacterial composite nano-filtration membrane and preparation method and application thereof |
| CN110204757A (en) * | 2019-06-18 | 2019-09-06 | 中北大学 | Polyvinyl butyral-carbon dots nano composite membrane preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172609A (en) * | 2007-10-25 | 2008-05-07 | 同济大学 | Method of producing hollow silicon dioxide microsphere with mercapto on internal and external surfaces |
| CN103627012A (en) * | 2013-12-01 | 2014-03-12 | 太原理工大学 | Preparation method of phosphotungstic acid-polyvinyl formal composite proton exchange membrane |
-
2014
- 2014-05-06 CN CN201410187283.5A patent/CN103980511A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172609A (en) * | 2007-10-25 | 2008-05-07 | 同济大学 | Method of producing hollow silicon dioxide microsphere with mercapto on internal and external surfaces |
| CN103627012A (en) * | 2013-12-01 | 2014-03-12 | 太原理工大学 | Preparation method of phosphotungstic acid-polyvinyl formal composite proton exchange membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582326A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Antibacterial composite nano-filtration membrane and preparation method and application thereof |
| CN110204757A (en) * | 2019-06-18 | 2019-09-06 | 中北大学 | Polyvinyl butyral-carbon dots nano composite membrane preparation method |
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Application publication date: 20140813 |