CN101787140B - Preparation method of silicotungstic acid/silicon dioxide polyvinyl alcohol proton exchange membrane - Google Patents
Preparation method of silicotungstic acid/silicon dioxide polyvinyl alcohol proton exchange membrane Download PDFInfo
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- CN101787140B CN101787140B CN2009102168665A CN200910216866A CN101787140B CN 101787140 B CN101787140 B CN 101787140B CN 2009102168665 A CN2009102168665 A CN 2009102168665A CN 200910216866 A CN200910216866 A CN 200910216866A CN 101787140 B CN101787140 B CN 101787140B
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a preparation method of a silicotungstic acid/silicon dioxide polyvinyl alcohol proton exchange membrane, belonging to the field of battery electrolyte materials. The preparation method comprises the following steps of: firstly solving the polyvinyl alcohol in deionized water to prepare a macromolecular solution, adding silicon compounds and sodium tungstate to the prepared solution, heating and mixing to form a solution, pouring the solution on a polytetrafluoroethylene glass plate and drying to form a membrane, and then obtaining the required silicotungstic acid/silicon dioxide polyvinyl alcohol proton exchange membrane. The prepared proton exchange membrane has great proton conductivity and low methanol permeability and is convenient for the large-scale production.
Description
Technical field
The present invention relates to the preparation method of a kind of silicotungstic acid/silicon-dioxide polyvinyl alcohol proton exchange membrane, belong to battery electrolyte material field.
Background technology
In Proton Exchange Membrane Fuel Cells, generally use proton exchange membrane as ionogen, 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, is unfavorable for making the fuel cell of organic-fuel.
In order to address this problem, developed some new proton exchange membrane, as silicotungstic acid doping composite membrane of polyvinyl alcohol, 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 silicotungstic acid doping composite membrane of polyvinyl alcohol is to reduce the swelling ratio of film and the nano-silicon wolframic acid particulate of interpolation is evenly distributed in polyvinyl alcohol matrix, currently used method is, prepare the silicotungstic acid particulate earlier, it is joined polyvinyl alcohol water solution, method with solution casting behind the certain hour is made film with polyvinyl alcohol, has obtained silicotungstic acid doping polyvinyl alcohol proton exchange membrane.According to the difference of the amount of adding the silicotungstic acid particulate, 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 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 silicotungstic acid doping composite membrane of polyvinyl alcohol, but because silicotungstic acid reunion skewness in film, the swelling ratio of the film that this method makes is big, alcohol-resistant performance is lower.
Summary of the invention
The object of the present invention is to provide a kind of in-situ synthetic method that utilizes in film, to produce silicon-dioxide and silicotungstic acid, the swelling ratio of film is reduced, silicotungstic acid is evenly distributed in film, and specific conductivity and alcohol-resistant performance improve, the preparation method of the silicotungstic acid that cost is low/silicon-dioxide polyvinyl alcohol proton exchange membrane.
Technical solution: raw material of the present invention comprises: polyvinyl alcohol (PVA), sodium wolframate and silicon tetrachloride;
The preparation method is as follows: (1) is by weight percentage with 75wt%～67wt% polyvinyl alcohol solution A of making soluble in water, wherein: every gram PVAC polyvinylalcohol needs water 9～19g; (2) solution A is heated to 80-95 ℃, and under this temperature, stirs and made solution B in 1 to 3 hour; (3) the solution B temperature is reduced to 50～65 ℃, in solution B, add silicon tetrachloride and the 10wt%～13wt% sodium wolframate of 15wt%～20wt%, after stirring 1 to 3 hour under 50-60 ℃ the temperature, be cooled to room temperature, form uniform solution C; (4) solution C is cast on the tetrafluoroethylene sheet glass and dries film forming, film thickness is controlled at 0.1～0.2 millimeter, bake out temperature: 50-60 ℃, promptly obtains required silicotungstic acid/silicon-dioxide polyvinyl alcohol proton exchange membrane.
Need before using film was soaked in deionized water 6～12 hours.
The present invention is owing to add sodium wolframate and silicon tetrachloride in polyvinyl alcohol solution, the silicon tetrachloride hydrolysis generates orthosilicic acid and hydrochloric acid, sodium wolframate generates silicotungstic acid with orthosilicic acid in sour environment simultaneously, utilizes in-situ synthetic method to produce silicon-dioxide and silicotungstic acid like this in film.
Effect of the present invention: the proton exchange membrane that the in-situ synthetic method that the present invention proposes 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, and swelling ratio has reduced by 10%, and specific conductivity has improved 1 to 2 times, and cost is low.This method is convenient to carry out scale operation.
Embodiment
Embodiment:
20 gram polyvinyl alcohol are dissolved in 150 ml waters form macromolecular solution A, this macromolecular solution A is heated to 90 ℃, and stirring got solution B in 2 hours under this temperature, then the solution B temperature is reduced to 60 ℃, in solution B, add 2.5g silicon tetrachloride and 2.5g sodium wolframate, after stirring 2 hours under 60 ℃ the temperature, be cooled to room temperature, form uniform solution C; Be cast in solution C on the polyfluortetraethylene plate and dry film forming, film thickness is controlled at 0.12 millimeter, and bake out temperature promptly obtains silicotungstic acid/silicon-dioxide polyvinyl alcohol proton exchange membrane for 50 ℃.Need before use film was soaked in deionized water 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 performance of table 1 silicotungstic acid/silicon-dioxide polyvinyl alcohol proton exchange membrane under 25 ℃ and the 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 | 3.46 | 23.3 | 0.4 |
Claims (2)
1. the preparation method of silicotungstic acid/silicon-dioxide polyvinyl alcohol proton exchange membrane is characterized in that, raw material of the present invention comprises: PVAC polyvinylalcohol, sodium wolframate, silicon tetrachloride;
The preparation method is as follows: (1) by weight percentage with 75wt%～67wt% polyvinyl alcohol solution A of making soluble in water, wherein every gram PVAC polyvinylalcohol needs water 9～19g; (2) solution A is heated to 80-95 ℃, and under this temperature, stirs and made solution B in 1 to 3 hour; (3) the solution B temperature is reduced to 50-65 ℃, in solution B, add silicon tetrachloride and the 10wt%～13wt% sodium wolframate of 15wt%～20wt%, after stirring 1 to 3 hour under 50-60 ℃ the temperature, be cooled to room temperature, form uniform solution C; (4) solution C is cast on the tetrafluoroethylene sheet glass and dries film forming, film thickness is controlled at 0.1～0.2 millimeter, bake out temperature: 50-60 ℃, promptly obtains required silicotungstic acid/silicon-dioxide polyvinyl alcohol proton exchange membrane.
2. the preparation method of silicotungstic acid according to claim 1/silicon-dioxide polyvinyl alcohol proton exchange membrane is characterized in that, needs film was soaked in deionized water 6～12 hours before using.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102168665A CN101787140B (en) | 2009-12-25 | 2009-12-25 | Preparation method of silicotungstic acid/silicon dioxide polyvinyl alcohol proton exchange membrane |
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| CN2009102168665A CN101787140B (en) | 2009-12-25 | 2009-12-25 | Preparation method of silicotungstic acid/silicon dioxide polyvinyl alcohol proton exchange membrane |
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| CN101787140A CN101787140A (en) | 2010-07-28 |
| CN101787140B true CN101787140B (en) | 2011-10-26 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863637B (en) * | 2012-09-25 | 2014-09-03 | 内蒙古科技大学 | Preparation method of phosphotungstic acid-polyimide composite proton exchange membrane |
| 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 |
| CN103396575A (en) * | 2013-07-19 | 2013-11-20 | 内蒙古科技大学 | Preparation method of polyvinylidene fluoride-polyvinyl alcohol composite proton exchange membrane |
| CN103351472A (en) * | 2013-07-19 | 2013-10-16 | 内蒙古科技大学 | Preparation method for silicotungstic acid-silica dioxide polyimide proton exchange membrane |
| CN103351475A (en) * | 2013-07-19 | 2013-10-16 | 内蒙古科技大学 | Preparation method for silicotungstic acid-silica polyvinylidene fluoride proton exchange membrane |
| JP6163509B2 (en) * | 2015-03-13 | 2017-07-12 | ニッポン高度紙工業株式会社 | Fuel cell |
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