CN103351472A - Preparation method for silicotungstic acid-silica dioxide polyimide proton exchange membrane - Google Patents
Preparation method for silicotungstic acid-silica dioxide polyimide proton exchange membrane Download PDFInfo
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Abstract
The invention discloses a preparation method for a silicotungstic acid-silica dioxide polyimide proton exchange membrane, which comprises the following steps: adding a certain amount of diamine and equal mole amount dianhydride into dimethyl sulfoxide solvent to synthesis polyamide acid solution, adding silicon compound, sodium tungstate and deionized water into the polyamide acid solution, heating and stirring the polyamide acid solution to prepare solution, pouring the solution onto a glass plate, placing the glass plate in a drying oven flat-wise and conducting imidization by raising the temperature in stages, so as to obtain the silicotungstic acid-silica dioxide polyimide proton exchange membrane. The preparation method is simple, the purposes of in situ synthesizing silicotungstic acid and silica dioxide on polyimide substrate are realized by the chemical reaction of polyurethane acyl acid, silicic acid and wolframate radical and imidization, so as to effectively solve the problem that inorganic particle and polymer are poor in consistency and easy to split phase, and enable the inorganic proton conductor to be dispersed on the substrate stably and uniformly. According to the proton exchange membrane prepared by the invention, proton conductivity under intermediate temperature is remarkably improved, methanol permeability is decreased, and the proton exchange membrane is suitable for mass production.
Description
Technical field
The present invention relates to the preparation method of a kind of silicotungstic acid-silicon-dioxide medlin proton exchange film, belong to the battery electrolyte Material Field.
Background technology
Direct methanol fuel cell (DMFC) stores and adds the characteristics such as convenient owing to its energy transformation ratio height, environmental friendliness, fuel source enrich, and is subject to people's attention.
The active low and saturating pure problem of catalyst is two crucial difficult problems that restriction DMFC uses.The effective means that solves these two problems is the working temperature that improves battery.Because temperature improves, but the accelerating electrode reaction kinetics, and the catalytic activity of raising catalyzer reduces CO and poisons; On the other hand, improve methanol oxidation speed, can reduce methyl alcohol and see through.Yet, have the Nafion film that in direct methanol fuel cell, uses now and not only have expensive problem, but also exist the high problem of poor stability, methanol permeability of high temperature membrane, inapplicable aspect middle temperature direct methanol fuel cell.
Therefore, how improving the middle temperature stability of proton exchange membrane, reduce its methanol permeability, develop the novel proton exchange membranes of high-performance and low-cost, is a great technical barrier of warm direct methanol fuel cell in the exploitation.
The researchist concentrates on the research emphasis of this types of fuel cells on the organic-inorganic compoiste proton exchange film at present one after another.
Polyimide (PI) is a kind of nitrogenous heterocyclic alkaline polymer, and its excellent combination property has the advantages such as compact structure, thermostability height, stable chemical nature and becomes one of important body material of temperature proton exchange film in the preparation.And the doping inorganics is to improve at present the under mesophilic condition effective way of proton conductivity in the film, the inorganics that mixes mainly contains two classes: a class is bibulous oxide compound such as silicon-dioxide, titanium dioxide, zirconium dioxide etc., this type oxide has stronger wettability power, thereby guarantee that composite membrane also can have enough water to form the proton transport passage when middle temperature, but because this type oxide itself does not have proton conduction property, therefore the amount that adds can not be too high, otherwise the specific conductivity of film declines by a big margin; Another kind of is inorganic proton conductive body such as heteropolyacid (phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid etc.), and the ionic conductivity of this class proton conduction body is very high, and does not need too much to rely on the existence of moisture, therefore receives publicity.
But because hygroscopic oxide compound is easily reunited, make the film of preparation inhomogeneous, degradation; Heteropolyacid has water-soluble preferably in middle temperature environment, under the condition of DMFC operation, heteropolyacid is easy to run off with the water that electrode generates, and the losing issue that therefore how to solve the reunion of water absorbability oxide compound in film and heteropolyacid has become the key issue of warm proton exchange membrane used for direct methanol fuel cell in the preparation.
Summary of the invention
The technical issues that need to address of the present invention just are to overcome the defective of prior art, the preparation method of a kind of silicotungstic acid-silicon-dioxide medlin proton exchange film is provided, it utilizes in-situ synthetic method to distribute in film and produces even silicon-dioxide and silicotungstic acid, the swelling ratio of film is reduced, specific conductivity and alcohol-resistant performance improve, be the preparation method of temperature proton exchange film in the low silicotungstic acid of a kind of cost-silicon-dioxide polyimide, the film of preparation is middle temperature (100 ℃) direct methanol fuel cell organic-inorganic compoiste proton exchange film.
For addressing the above problem, the present invention adopts following technical scheme:
The invention provides the preparation method of a kind of silicotungstic acid-silicon-dioxide medlin proton exchange film, at first the dianhydride with diamines and equimolar amount adds synthesizing polyamides acid solution in the dimethyl sulfoxide solvent, then add silicon compound, sodium wolframate and deionized water, be heated, stir, form solution, this solution casting on sheet glass, is lain against and carries out the ladder-elevating temperature imidization in the baking oven and namely obtain required organic and inorganic compound proton exchange membrane.
The raw material that the present invention prepares described silicotungstic acid-silicon-dioxide medlin proton exchange film comprises: pyromellitic acid anhydride, phenyl ether diamines, sodium wolframate and silicon tetrachloride;
The preparation method is as follows:
(1) first the pyromellitic acid anhydride of phenyl ether diamines and equimolar amount is added in the dimethyl sulfoxide solvent the synthetic 10wt% polyamic acid solution A of stirring at normal temperature 0.5～1h under nitrogen atmosphere, after wherein every 0.01mol/L phenyl ether diamines needs dimethyl sulfoxide (DMSO) 3.1g(volume to convert);
(2) the weight part proportioning by polyamic acid and sodium wolframate and silicon tetrachloride among the polyamic acid solution A is respectively 80-72 part, the ratio of 10-15 part and 10-13 part, weighing sodium wolframate and silicon tetrachloride, the solution A temperature is risen to 60～75 ℃, add successively sodium wolframate and silicon tetrachloride and ionized water in solution A, the add-on of ionized water is that the volume ratio of water and dimethyl sulfoxide (DMSO) is 1:10; Stirred 1～3 hour, and formed uniform solution B;
(3) the solution B oil bath is heated to 110～130 ℃, and under this temperature, stirred 1～2 hour, until all evaporations of moisture in the solution are cooled to room temperature with the solution that obtains, form uniform solution C;
(4) solution C is cast in lies against in the loft drier on the sheet glass, heat successively 12h, 1h, 1h, 1h and 1h at 120 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃, after cooling comes off, namely obtain required silicotungstic acid-silicon-dioxide medlin proton exchange film.
After (4) step, with film at rare H
2SO
4Middle immersion 24～48h uses H residual in the deionized water wash film again
2SO
4
The present invention adds deionized water after polyamic acid is synthetic, the adding of water is conducive to dissolving and the reaction of inorganics.
The present invention adds silicon tetrachloride and sodium wolframate, and silicon tetrachloride is met the water vigorous reaction and generated silicic acid and hydrochloric acid, and under sour environment, silicic acid and wolframate radical reaction generate silicotungstic acid.
The silicotungstic acid of the present invention's preparation-silicon-dioxide medlin proton exchange film needs film was soaked in deionized water 12 hours before use.
The present invention is owing to add sodium wolframate and silicon tetrachloride in polyamic acid solution, hydrolyzing silicon tetrachloride generates orthosilicic acid and hydrochloric acid, sodium wolframate generates silicotungstic acid with orthosilicic acid in sour environment simultaneously, carboxyl on polyamic acid, silicotungstic acid and the silicic acid, carbonyl and hydroxyl react each other, form stable network-like structure, utilize like this in-situ synthetic method in film, to produce silicon-dioxide and silicotungstic acid.
The present invention compares with technology with current material has following advantage:
1, the proton conduction property of compound proton exchange membrane under middle temperature that utilizes preparation method proposed by the invention to make is excellent, and its proton conduction speed is greater than the proton conductivity of Nafion film.
2, utilize the prepared proton exchange membrane of the present invention, the methanol permeability of 130～180 ℃ of temperature ranges is less than Nafion, features good methanol diffusion resistance.
3, the preparation technology of the proton exchange membrane of the present invention's preparation is simple, and the film cost is lower than the Nafion film, is easy to industrialization, the development of warm direct methanol fuel cell in can promoting.
Embodiment
Embodiment 1
4.78 gram phenyl ether diamines and 5.22 gram pyromellitic acid anhydrides are dissolved in the 90g dimethyl sulfoxide (DMSO) and form macromolecular solution, this macromolecular solution is stirred 1h get solution A in nitrogen atmosphere, then the solution A temperature is risen to 65 ℃, in solution B, add 1.25g silicon tetrachloride, 1.25 g sodium wolframates and 0.82g water, after stirring 2 hours under this temperature, form uniform solution B; The oil bath of solution B vacuum is heated to 120 ℃, continue to stir until in the solution moisture all evaporate, cool to room temperature obtains homogeneous solution C; Solution C is cast on the sheet glass plate lies against in the loft drier, heat successively 12h, 1h, 1h, 1h and 1h at 120 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃, after cooling comes off, namely obtain required silicotungstic acid-silicon-dioxide medlin proton exchange film.
Embodiment 2
4.78 gram phenyl ether diamines and 5.22 gram pyromellitic acid anhydrides are dissolved in the 90g dimethyl sulfoxide (DMSO) and form macromolecular solution, this macromolecular solution is stirred 1h get solution A in nitrogen atmosphere, then the solution A temperature is risen to 65 ℃, in solution B, add 1.41g silicon tetrachloride, 1.41 g sodium wolframates and 0.82g water, after stirring 2 hours under this temperature, form uniform solution B; The oil bath of solution B vacuum is heated to 120 ℃, continue to stir until in the solution moisture all evaporate, cool to room temperature obtains homogeneous solution C; Solution C is cast on the sheet glass plate lies against in the loft drier, heat successively 12h, 1h, 1h, 1h and 1h at 120 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃, after cooling comes off, namely obtain required silicotungstic acid-silicon-dioxide medlin proton exchange film.
Embodiment 3
4.78 gram phenyl ether diamines and 5.22 gram pyromellitic acid anhydrides are dissolved in the 90g dimethyl sulfoxide (DMSO) and form macromolecular solution, this macromolecular solution is stirred 1h get solution A in nitrogen atmosphere, then the solution A temperature is risen to 65 ℃, in solution A, add 1.58g silicon tetrachloride, 1.58 g sodium wolframates and 0.82g water, after stirring 2 hours under this temperature, form uniform solution B; The oil bath of solution B vacuum is heated to 120 ℃, continue to stir until in the solution moisture all evaporate, cool to room temperature obtains homogeneous solution C; Solution C is cast on the sheet glass plate lies against in the loft drier, heat successively 12h, 1h, 1h, 1h and 1h at 120 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃, after cooling comes off, namely obtain required silicotungstic acid-silicon-dioxide medlin proton exchange film.
Embodiment 4
4.78 gram phenyl ether diamines and 5.22 gram pyromellitic acid anhydrides are dissolved in the 90g dimethyl sulfoxide (DMSO) and form macromolecular solution, this macromolecular solution is stirred 1h get solution A in nitrogen atmosphere, then the solution A temperature is risen to 65 ℃, in solution A, add 1.76g silicon tetrachloride, 1.76 g sodium wolframates and 0.82g water, after stirring 2 hours under this temperature, form uniform solution B; The oil bath of solution B vacuum is heated to 120 ℃, continue to stir until in the solution moisture all evaporate, cool to room temperature obtains homogeneous solution C; Solution C is cast on the sheet glass plate lies against in the loft drier, heat successively 12h, 1h, 1h, 1h and 1h at 120 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃, after cooling comes off, namely obtain required silicotungstic acid-silicon-dioxide medlin proton exchange film.
Embodiment 5
4.78 gram phenyl ether diamines and 5.22 gram pyromellitic acid anhydrides are dissolved in the 90g dimethyl sulfoxide (DMSO) and form macromolecular solution, this macromolecular solution is stirred 1h get solution A in nitrogen atmosphere, then the solution A temperature is risen to 65 ℃, in solution A, add 2.10g silicon tetrachloride, 1.80 g sodium wolframates and 0.82g water, after stirring 2 hours under this temperature, form uniform solution B; The oil bath of solution B vacuum is heated to 120 ℃, continue to stir until in the solution moisture all evaporate, cool to room temperature obtains homogeneous solution C; Solution C is cast on the sheet glass plate lies against in the loft drier, heat successively 12h, 1h, 1h, 1h and 1h at 120 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃, after cooling comes off, namely obtain required silicotungstic acid-silicon-dioxide medlin proton exchange film.
Comparative example
As a comparison, we utilize the Nafion117 film, and transmission coefficient, swelling ratio and the specific conductivity of its methyl alcohol compared, and the Nafion117 film is soaked a few hours in deionized water, survey its specific conductivity by two electrode AC impedance methods; Measure the methanol permeability of film with the barrier film method of diffusion.
The table 1 silicotungstic acid/methanol permeability of silicon-dioxide pi proton exchange membrane and the comparison of Nafion film
In the table 1, sample 1 is the silicotungstic acid-silicon-dioxide medlin proton exchange film of embodiment 1 preparation, as can be seen from Table 1:
1, the proton conduction property of compound proton exchange membrane under middle temperature that utilizes preparation method proposed by the invention to make is excellent, and its proton conduction speed is greater than the proton conductivity of Nafion film.
2, utilize the prepared proton exchange membrane of the present invention, the methanol permeability of 130～180 ℃ of temperature ranges is less than Nafion, features good methanol diffusion resistance.
Thereby, preparation method of the present invention and technique are simple, by the chemical reaction between poly-inferior acyl acid, silicic acid and wolframate radical, last imidization has reached the purpose that original position is synthesized silicotungstic acid and silicon-dioxide on polyimide matrix, effectively avoided the problem of the poor easy phase-splitting of consistency between inorganic particulate and the polymkeric substance, made inorganic solid proton conductor can stablize, be scattered in the base material uniformly.Compare with the Nafion film, proton exchange membrane proton conduction property under middle temperature of the present invention's preparation obviously improves, and methanol permeability reduces, and is convenient to carry out scale operation.
It should be noted that at last: obviously, above-described embodiment only is for example of the present invention clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being amplified out thus or change still are among protection scope of the present invention.
Claims (3)
1. the preparation method of silicotungstic acid-silicon-dioxide medlin proton exchange film, it is characterized in that, at first the dianhydride with diamines and equimolar amount adds synthesizing polyamides acid solution in the dimethyl sulfoxide solvent, then add silicon compound, sodium wolframate and deionized water, be heated, stir, form solution, this solution casting on sheet glass, is lain against and carries out the ladder-elevating temperature imidization in the baking oven and namely obtain required organic and inorganic compound proton exchange membrane.
2. the preparation method of silicotungstic acid as claimed in claim 1-silicon-dioxide medlin proton exchange film, it is characterized in that the raw material for preparing described silicotungstic acid-silicon-dioxide medlin proton exchange film comprises: pyromellitic acid anhydride, phenyl ether diamines, sodium wolframate and silicon tetrachloride;
The preparation method is as follows:
(1) first the pyromellitic acid anhydride of phenyl ether diamines and equimolar amount is added in the dimethyl sulfoxide solvent the synthetic 10wt% polyamic acid solution A of stirring at normal temperature 0.5～1h under nitrogen atmosphere, after wherein every 0.01mol/L phenyl ether diamines needs dimethyl sulfoxide (DMSO) 3.1g(volume to convert);
(2) the weight part proportioning by polyamic acid and sodium wolframate and silicon tetrachloride among the polyamic acid solution A is respectively 80-72 part, the ratio of 10-15 part and 10-13 part, weighing sodium wolframate and silicon tetrachloride, the solution A temperature is risen to 60～75 ℃, add successively sodium wolframate and silicon tetrachloride and ionized water in solution A, the add-on of ionized water is that the volume ratio of water and dimethyl sulfoxide (DMSO) is 1:10; Stirred 1～3 hour, and formed uniform solution B;
(3) the solution B oil bath is heated to 110～130 ℃, and under this temperature, stirred 1～2 hour, until all evaporations of moisture in the solution are cooled to room temperature with the solution that obtains, form uniform solution C;
(4) solution C is cast in lies against in the loft drier on the sheet glass, heat successively 12h, 1h, 1h, 1h and 1h at 120 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃, after cooling comes off, namely obtain required silicotungstic acid-silicon-dioxide medlin proton exchange film.
3. the preparation method of silicotungstic acid as claimed in claim 2-silicon-dioxide medlin proton exchange film is characterized in that, after (4) step, with film at rare H
2SO
4Middle immersion 24～48h uses H residual in the deionized water wash film again
2SO
4
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111082112A (en) * | 2019-12-25 | 2020-04-28 | 深圳氢时代新能源科技有限公司 | Proton exchange membrane, preparation method thereof and fuel cell |
| CN114204210A (en) * | 2021-11-05 | 2022-03-18 | 东方电气集团科学技术研究院有限公司 | Preparation method of novel sodium-ion battery diaphragm |
| CN114628751A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of high-temperature polymer electrolyte membrane fuel cell membrane electrode |
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| CN1461070A (en) * | 2003-05-19 | 2003-12-10 | 清华大学 | Method for preparing heat-resisting proton exchange film |
| CN101787140A (en) * | 2009-12-25 | 2010-07-28 | 内蒙古科技大学 | Preparation method of silicotungstic acid/silicon dioxide polyvinyl alcohol 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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Patent Citations (3)
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| CN1461070A (en) * | 2003-05-19 | 2003-12-10 | 清华大学 | Method for preparing heat-resisting proton exchange film |
| CN101787140A (en) * | 2009-12-25 | 2010-07-28 | 内蒙古科技大学 | Preparation method of silicotungstic acid/silicon dioxide polyvinyl alcohol 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111082112A (en) * | 2019-12-25 | 2020-04-28 | 深圳氢时代新能源科技有限公司 | Proton exchange membrane, preparation method thereof and fuel cell |
| CN114628751A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of high-temperature polymer electrolyte membrane fuel cell membrane electrode |
| CN114628751B (en) * | 2020-12-11 | 2023-09-15 | 中国科学院大连化学物理研究所 | Preparation method of high-temperature polymer electrolyte membrane fuel cell membrane electrode |
| CN114204210A (en) * | 2021-11-05 | 2022-03-18 | 东方电气集团科学技术研究院有限公司 | Preparation method of novel sodium-ion battery diaphragm |
| CN114204210B (en) * | 2021-11-05 | 2024-01-05 | 东方电气集团科学技术研究院有限公司 | Preparation method of sodium ion battery diaphragm |
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Application publication date: 20131016 |