CN103627012B - A kind of preparation method of phosphotungstic acid-polyvinyl formal composite proton exchange membrane - Google Patents
A kind of preparation method of phosphotungstic acid-polyvinyl formal composite proton exchange membrane Download PDFInfo
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- CN103627012B CN103627012B CN201310624530.9A CN201310624530A CN103627012B CN 103627012 B CN103627012 B CN 103627012B CN 201310624530 A CN201310624530 A CN 201310624530A CN 103627012 B CN103627012 B CN 103627012B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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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 present invention relates to the preparation method of fuel cell proton exchange membrane used, be specially a kind of preparation method of phosphotungstic acid-polyvinyl formal composite proton exchange membrane, first polyvinyl formal is dissolved in alcohol water mixed solution and makes macromolecular solution by the method, add strong phosphoric acid and sodium wolframate or phospho-wolframic acid, be heated, stir, form solution, by solution casting on a glass and dry film forming, namely phosphotungstic acid-polyvinyl formal composite proton exchange membrane is obtained, the proton conduction property of compound proton exchange membrane prepared by the present invention is excellent, its proton conduction speed is greater than the proton conductivity of Nafion film, and there is satisfactory stability, swelling capacity is less than the swelling capacity of Nafion film, and preparation technology of the present invention is simple, masking cost, lower than Nafion film cost processed, is easy to industrialization.
Description
Technical field
The present invention relates to the preparation method of fuel cell proton exchange membrane used, be specially a kind of preparation method of phosphotungstic acid-polyvinyl formal composite proton exchange membrane.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is considered to one of the most rising clean energy because of its high energy efficiency and the advantage such as pollution-free, Proton Exchange Membrane Fuel Cells is directly by fuel and oxygenant (O
2) chemical energy be electric energy, be a kind of novel power generation assembly.Simultaneously, Proton Exchange Membrane Fuel Cells volume is little, lighter in weight, use safe ready, be enough to the conventional rechargeable cells replacing present portable electric device uses, as mobile telephone, notebook computer, digital camera, pick up camera, electric bicycle etc.High-power Proton Exchange Membrane Fuel Cells even can also 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 serves and makes proton (H
+) effect of negative electrode is optionally transmitted to from anode, it has intercepted fuel and oxygenant simultaneously.The performance of proton exchange membrane decides fuel battery performance.
The proton exchange membrane be applied at present in fuel cell is perfluoro sulfonic acid membrane, the Nafion film that such as du pont company produces.The chemistry of Nafion film and good mechanical stability, proton conductivity of phosphoric acid is excellent, but when it exists the high and temperature of cost more than 100 DEG C, proton conductivity descends degradation shortcoming rapidly, limits its commercial applications.Therefore, cost of development proton exchange membrane that is low, good stability becomes study hotspot.
Summary of the invention
The present invention, in order to solve the problem that existing proton exchange membrane production cost is high and stability is low, provides a kind of preparation method of phosphotungstic acid-polyvinyl formal composite proton exchange membrane.
The present invention adopts following technical scheme to realize: a kind of preparation method of phosphotungstic acid-polyvinyl formal composite proton exchange membrane, comprises the following steps:
Be that the polyvinyl formal of 50-80 part is dissolved in the alcohol water mixed solution that mass parts is 100-2400 part by mass parts, obtained polyvinyl formal solution, wherein, the condensation degree of polyvinyl formal is 30%-45%, in alcohol water mixed solution, the volume ratio of alcohol and water is 1:10-10:1, and selected alcohol is the one in methyl alcohol, ethanol, propyl alcohol or Virahol;
Polyvinyl formal solution is heated to 45 DEG C-100 DEG C, and stirs 1-10 hour;
Above-mentioned solution is cooled to 20 DEG C-40 DEG C, then in solution, add the phospho-wolframic acid that mass parts is 5-50 part or mass parts be respectively the mixture that the sodium wolframate of 5-35 part and 5-15 part and mass percent concentration are the strong phosphoric acid of 60%-85%, solution is heated to 60 DEG C-100 DEG C, and stir 1-5 hour, naturally cooling again, obtains pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 80-200 micron, vacuum drying 3-24h, the temperature of vacuum drying is 40 DEG C-70 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Polyvinyl formal is a kind of good film forming material, there is higher intensity, rigidity and hardness, and have good agglutinating value(of coal) and chemical stability, now polyvinyl formal is configured to solution, raw material sodium wolframate and the strong phosphoric acid of the phospho-wolframic acid with proton conducting ability or generation phospho-wolframic acid is added in the solution be configured to, the phospho-wolframic acid added or the proton conductivity of polyvinyl formal can be improved by the phospho-wolframic acid of Material synthesis, finally obtained phospho-wolframic acid-polyvinyl formal compound proton exchange membrane has satisfactory stability and proton conductivity, manufacture craft of the present invention is simple, molding cost is lower than the cost of Nafion film processed, processing parameter in present method is all preferably drawn by scientific research personnel, particularly the thickness of the condensation degree of polyvinyl formal, polyvinyl formal and phospho-wolframic acid or the proportioning generated between the raw material sodium wolframate of phospho-wolframic acid and strong phosphoric acid and last film forming is all optimized through great many of experiments by scientific research personnel, and scientific research personnel has paid performing creative labour for this reason.
The present invention and current material are compared with technology has following advantage:
1. the proton conduction property of proton exchange membrane made of the present invention is excellent, and its proton conduction speed is greater than the proton conductivity of Nafion film, and has satisfactory stability;
2. the proton exchange membrane swelling capacity that the present invention makes is less than the swelling capacity of Nafion film;
3. preparation technology of the present invention is simple, and masking cost, lower than Nafion film cost processed, is easy to industrialization.
Embodiment
Embodiment one:
A preparation method for phosphotungstic acid-polyvinyl formal composite proton exchange membrane, comprises the following steps:
By the condensation degree of 5 grams be 45% polyvinyl formal be dissolved in the mixing solutions of the first alcohol and water of 100 grams, obtained polyvinyl formal solution, the volume ratio of first alcohol and water is 1:9;
Polyvinyl formal solution is heated to 100 DEG C, and stirs 10 hours;
Above-mentioned solution is cooled to 40 DEG C, in solution, adds the sodium wolframate of 3.5 grams and the mass percent concentration of 1.5 grams is the strong phosphoric acid of 85%, then solution is heated to 100 DEG C, and stirs 5 hours, then naturally cooling, obtain pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 200 microns, vacuum drying 24h, the temperature of vacuum drying is 70 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Obtained proton exchange membrane and the specific conductivity of Nafion117 is surveyed by four electrode AC impedance methods, test obtained proton exchange membrane and the swelling ratio of Nafion117 again, the concrete steps surveying swelling ratio are: dry obtained proton exchange membrane and Nafion117 are all cut into the rectangle diaphragm that size is 2cm × 4cm and (set area as S
d), immerse in the aqueous solution, take out after abundant swelling 24h, measure wet proton exchange membrane and the size of Nafion117, obtain area S
w, the swelling ratio SD:SD=(S of film is calculated 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 (%) |
| Nafion117 | 1.54 | 35.8 |
| Obtained proton exchange membrane | 3.79 | 22.6 |
As can be seen from table, the specific conductivity of obtained proton exchange membrane is that the twice of the specific conductivity of Nafion117 is many, and swelling ratio is also lower than the swelling ratio of Nafion117.
Embodiment two:
A preparation method for phosphotungstic acid-polyvinyl formal composite proton exchange membrane, comprises the following steps:
By the condensation degree of 5 grams be 45% polyvinyl formal be dissolved in the mixing solutions of 100 grams of first alcohol and waters, obtained polyvinyl formal solution, the volume ratio of first alcohol and water is 1:9;
Polyvinyl formal solution is heated to 100 DEG C, and stirs 10 hours;
Above-mentioned solution is cooled to 40 DEG C, in solution, adds 5 grams of phospho-wolframic acids, then solution is heated to 100 DEG C, stir 5 hours, then naturally cooling, obtain pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 200 microns, vacuum drying 24h, the temperature of vacuum drying is 70 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Survey obtained proton exchange membrane and the specific conductivity of Nafion117 by four electrode AC impedance methods, then test obtained proton exchange membrane and the swelling ratio of Nafion117, result is as following table:
| Sample number | Specific conductivity (10 -2 S/cm） | Swelling ratio (%) |
| Nafion117 | 1.54 | 35.8 |
| Obtained proton exchange membrane | 3.63 | 20.9 |
As can be seen from table, the specific conductivity of obtained proton exchange membrane is that the twice of the specific conductivity of Nafion117 is many, and swelling ratio is also lower than the swelling ratio of Nafion117.
Embodiment three:
A preparation method for phosphotungstic acid-polyvinyl formal composite proton exchange membrane, comprises the following steps:
By the condensation degree of 8 grams be 45% polyvinyl formal be dissolved in the mixing solutions of 100 grams of second alcohol and waters, obtained polyvinyl formal solution, the volume ratio of second alcohol and water is 2:3;
Polyvinyl formal solution is heated to 70 DEG C, and stirs 5 hours;
Above-mentioned solution is cooled to 40 DEG C, in solution, adds 2 grams of phospho-wolframic acids, then solution is heated to 80 DEG C, stir 4 hours, then naturally cooling, obtain pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 150 microns, vacuum drying 12h, the temperature of vacuum drying is 80 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Survey obtained proton exchange membrane and the specific conductivity of Nafion117 by four electrode AC impedance methods, then test obtained proton exchange membrane and the swelling ratio of Nafion117, result is as following table:
| Sample number | Specific conductivity (10 -2 S/cm） | Swelling ratio (%) |
| Nafion117 | 1.54 | 35.8 |
| Obtained proton exchange membrane | 3.10 | 19.5 |
As can be seen from table, the specific conductivity of obtained proton exchange membrane is that the twice of the specific conductivity of Nafion117 is many, and swelling ratio is also lower than the swelling ratio of Nafion117.
Embodiment four:
To be the condensation degree of 10 grams by quality be 30% polyvinyl formal be dissolved in the mixing solutions that quality is the second alcohol and water of 100 grams, obtained polyvinyl formal solution, the volume ratio of second alcohol and water is 1:10;
Polyvinyl formal solution be heated to 45 DEG C and keep, stirring 1 hour;
Above-mentioned solution is cooled to 20 DEG C, in solution, then adds quality be respectively the mixture that the sodium wolframate of 1 gram and 1 gram and mass percent concentration are the strong phosphoric acid of 85%, solution is heated to 60 DEG C, and stirs 1 hour, then naturally cooling, obtain pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 80 microns, vacuum drying 3h film forming, the temperature of vacuum drying is 70 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Embodiment five:
To be the condensation degree of 16 grams by quality be 45% polyvinyl formal be dissolved in the mixing solutions that quality is the first alcohol and water of 800 grams, obtained polyvinyl formal solution, the volume ratio of first alcohol and water is 10:1;
Polyvinyl formal solution be heated to 100 DEG C and keep, stirring 10 hours;
Above-mentioned solution is cooled to 40 DEG C, in solution, then adds quality be respectively the mixture that the sodium wolframate of 7 grams and 3 grams and mass percent concentration are the strong phosphoric acid of 60%, solution is heated to 100 DEG C, and stirs 5 hours, then naturally cooling, obtain pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 200 microns, vacuum drying 24h film forming, the temperature of vacuum drying is 40 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Embodiment six:
To be the condensation degree of 60 grams by quality be 35% polyvinyl formal be dissolved in the mixing solutions that quality is third alcohol and water of 2400 grams, obtained polyvinyl formal solution, the volume ratio of the third alcohol and water is 1:1;
Polyvinyl formal solution be heated to 60 DEG C and keep, stirring 4 hours;
Above-mentioned solution is cooled to 25 DEG C, in solution, then adds quality be respectively the mixture that the sodium wolframate of 15 grams and 8 grams and mass percent concentration are the strong phosphoric acid of 65%, solution is heated to 75 DEG C, and stirs 3 hours, then naturally cooling, obtain pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 120 microns, vacuum drying 10h film forming, the temperature of vacuum drying is 50 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Embodiment seven:
To be the condensation degree of 70 grams by quality be 40% polyvinyl formal be dissolved in the mixing solutions that quality is the isopropyl alcohol and water of 1600 grams, obtained polyvinyl formal solution, the volume ratio of isopropyl alcohol and water is 5:1;
Polyvinyl formal solution be heated to 80 DEG C and keep, stirring 8 hours;
Above-mentioned solution is cooled to 30 DEG C, in solution, then adds quality be respectively the mixture that the sodium wolframate of 25 grams and 12 grams and mass percent concentration are the strong phosphoric acid of 75%, solution is heated to 90 DEG C, and stirs 4 hours, then naturally cooling, obtain pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 160 microns, vacuum drying 17h film forming, the temperature of vacuum drying is 60 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Embodiment eight:
To be the condensation degree of 10 grams by quality be 45% polyvinyl formal be dissolved in the mixing solutions that quality is the second alcohol and water of 100 grams, obtained polyvinyl formal solution, the volume ratio of second alcohol and water is 1:1;
Polyvinyl formal solution be heated to 45 DEG C and keep, stirring 4 hours;
Above-mentioned solution is cooled to 25 DEG C, then in solution, adds the phospho-wolframic acid that quality is 1 gram, solution is heated to 60 DEG C, and stir 1 hour, then naturally cooling, obtain pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 80 microns, vacuum drying 3h film forming, the temperature of vacuum drying is 70 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Embodiment nine:
To be the condensation degree of 80 grams by quality be 40% polyvinyl formal be dissolved in the mixing solutions that quality is the first alcohol and water of 2400 grams, obtained polyvinyl formal solution, the volume ratio of first alcohol and water is 10:1;
Polyvinyl formal solution be heated to 100 DEG C and keep, stirring 10 hours;
Above-mentioned solution is cooled to 40 DEG C, then in solution, adds the phospho-wolframic acid that quality is 50 grams, solution is heated to 100 DEG C, and stir 5 hours, then naturally cooling, obtain pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 200 microns, vacuum drying 24h film forming, the temperature of vacuum drying is 40 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Embodiment ten:
To be the condensation degree of 60 grams by quality be 35% polyvinyl formal be dissolved in the mixing solutions that quality is third alcohol and water of 1000 grams, obtained polyvinyl formal solution, the volume ratio of the third alcohol and water is 1:10;
Polyvinyl formal solution be heated to 60 DEG C and keep, stirring 4 hours;
Above-mentioned solution is cooled to 20 DEG C, then in solution, adds the phospho-wolframic acid that quality is 20 grams, solution is heated to 75 DEG C, and stir 3 hours, then naturally cooling, obtain pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 120 microns, vacuum drying 10h film forming, the temperature of vacuum drying is 50 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Embodiment 11:
To be the condensation degree of 70 grams by quality be 30% polyvinyl formal be dissolved in the mixing solutions that quality is the isopropyl alcohol and water of 1600 grams, obtained polyvinyl formal solution, the volume ratio of isopropyl alcohol and water is 5:1;
Polyvinyl formal solution be heated to 80 DEG C and keep, stirring 8 hours;
Above-mentioned solution is cooled to 30 DEG C, then in solution, adds the phospho-wolframic acid that quality is 35 grams, solution is heated to 90 DEG C, and stir 4 hours, then naturally cooling, obtain pouring into a mould solution;
Pour into a mould solution casting on a glass, and control cast film thickness is on a glass 160 microns, vacuum drying 17h film forming, the temperature of vacuum drying is 60 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
Claims (1)
1. a preparation method for phosphotungstic acid-polyvinyl formal composite proton exchange membrane, is characterized in that comprising the following steps:
Be that the polyvinyl formal of 50-80 part is dissolved in the alcohol water mixed solution that mass parts is 100-2400 part by mass parts, obtained polyvinyl formal solution, wherein, the condensation degree of polyvinyl formal is 30%-45%, in alcohol water mixed solution, the volume ratio of alcohol and water is 1:10-10:1, and selected alcohol is the one in methyl alcohol, ethanol, propyl alcohol or Virahol;
Polyvinyl formal solution is heated to 45 DEG C-100 DEG C, and stirs 1-10 hour;
Above-mentioned solution is cooled to 20 DEG C-40 DEG C, then in solution, add the phospho-wolframic acid that mass parts is 5-50 part or mass parts be respectively the mixture that the sodium wolframate of 5-35 part and 5-15 part and mass percent concentration are the strong phosphoric acid of 60%-85%, solution is heated to 60 DEG C-100 DEG C, and stir 1-5 hour, naturally cooling again, obtains pouring into a mould solution;
By cast solution casting obtained above on a glass, and control cast film thickness is on a glass 80-200 micron, and vacuum drying 3-24h, the temperature of vacuum drying is 40 DEG C-70 DEG C, obtains phospho-wolframic acid-polyvinyl formal compound proton exchange membrane.
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| CN102850564A (en) * | 2012-09-25 | 2013-01-02 | 内蒙古科技大学 | Method for preparing phosphotungstic acid-polyvinylidene fluoride composite proton exchange membrane |
| CN102863637A (en) * | 2012-09-25 | 2013-01-09 | 内蒙古科技大学 | Preparation method of phosphotungstic acid-polyimide composite proton exchange membrane |
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| CN102850564A (en) * | 2012-09-25 | 2013-01-02 | 内蒙古科技大学 | Method for preparing phosphotungstic acid-polyvinylidene fluoride composite proton exchange membrane |
| CN102863637A (en) * | 2012-09-25 | 2013-01-09 | 内蒙古科技大学 | Preparation method of phosphotungstic acid-polyimide composite proton exchange membrane |
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