CN102850564B - Method for preparing phosphotungstic acid-polyvinylidene fluoride composite proton exchange membrane - Google Patents
Method for preparing phosphotungstic acid-polyvinylidene fluoride composite proton exchange membrane Download PDFInfo
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Abstract
The invention discloses a method for preparing a phosphotungstic acid-polyvinylidene fluoride composite proton exchange membrane and belongs to the field of battery electrolyte materials. Firstly polyvinylidene fluoride is dissolved in a dimethyl sulfoxide to obtain a macromolecular solution, the solution is coated to form a membrane, the membrane is processed in an alkaline liquor and then cleanly washed by deionized water to obtain a modified membrane, the modified membrane is dissolved in a mixed liquor of the dimethyl sulfoxide and water, a strong phosphoric acid and sodium tungstate are added to obtain a mixture, the mixture is heated and stirred to obtain a solution, and the solution is poured on a polytetrafluoroethylene glass pane and dried to obtain the phosphotungstic acid-polyvinylidene fluoride composite proton exchange membrane. The prepared composite proton exchange membrane is good in proton conduction, low in methanol permeability, swelling degree and cost and convenient to massively produce.
Description
Technical field
The preparation method who the present invention relates to a kind of phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane, belongs to battery electrolyte Material Field.
Background technology
Direct methanol fuel cell (DMFC) is as Novel clean renewable energy source,, operating temperature simple in structure owing to having and the feature that pressure requirement is low, energy density is high (being approximately 6000Wh/Kg), can provide than the high 10 times of above electric weight of secondary cell, and have advantages of and do not need reformer, in the field such as automobile and portable electric appts, gather around and have broad application prospects.Having received at present increasing concern, is the green energy resource of most possibly realizing commercial applications.
As the core material of direct methanol fuel cell, proton exchange membrane has played the optionally effect from negative electrode conduction matter to anode, and 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 direct methanol fuel cell is mostly the aquation perfluoro sulfonic acid membranes such as Nafion film, Nafion membrance chemistry and good mechanical stability, proton conductivity of phosphoric acid is good, but it exists high cost, environment for use to require the shortcomings such as high and methanol permeability is high, has limited the commercial applications of DMFC.
The Nafion film that cost of development is low, good stability, methanol permeability are low substitutes proton exchange membrane becomes study hotspot.
In the study on the modification of many proton exchange membrane, organic and inorganic composite membrane is owing to having compared with high machinery and thermostability, being subject to sufficient attention compared with low methanol crossover and suitable proton conductivity.
Polyvinylidene difluoride (PVDF) (PVDF) is the fluoropolymer of a kind of high molecular (400,000-600,000), half hitch crystal, its excellent combination property, there is compact structure, thermostability is high, mechanical property is strong, good, the advantage such as alcohol-resistant performance is high, stable chemical nature of snappiness after film forming, but simple PVDF proton conductivity is very low.
Inorganic proton conductive body is 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.
So investigator proposes the heteropolyacid that adulterates in PVDF and improves its specific conductivity, heteropolyacid is the general name of the condensation oxygen acid that made by different oxygen acid condensations.Be the protonic acid of even intensity, and have redox ability.By changing molecular composition, adjustable strength of acid and redox property.But because heteropolyacid is soluble in water, under the condition of DMFC operation, the water that heteropolyacid is easy to generate with electrode runs off, and the skewness in film of reuniting.
Can therefore, how to solve the reunion of heteropolyacid in film and losing issue becomes this class film and become the key issue that substitutes Nafion film.
Summary of the invention
The technical issues that need to address of the present invention are just to overcome the defect of prior art, a kind of preparation method of phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane is provided, it utilizes in-situ synthetic method in proton exchange membrane, to produce phospho-wolframic acid, the swelling ratio of proton exchange membrane is reduced, phospho-wolframic acid is evenly distributed in proton exchange membrane, specific conductivity and the alcohol-resistant performance of proton exchange membrane are improved, and the cost of proton exchange membrane is low.
For addressing the above problem, the present invention adopts following technical scheme:
The preparation method who the invention provides a kind of phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane, is dissolved in polyvinylidene difluoride (PVDF) in dimethyl sulfoxide (DMSO) and makes macromolecular solution, coats film forming, and this film is put into after alkali lye processing, cleans and obtains modified membrane with deionized water; Modified membrane is dissolved in the mixed solution of dimethyl sulfoxide (DMSO) and water again, adds strong phosphoric acid and sodium wolframate, be heated, stir, form solution, this solution casting on tetrafluoroethylene sheet glass and dry film forming, is obtained to phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane.
Concrete preparation method is:
(1) need the amount of dimethyl sulfoxide (DMSO) 15-19g by every gram of polyvinylidene difluoride (PVDF), weigh polyvinylidene difluoride (PVDF) and be dissolved in dimethyl sulfoxide (DMSO), oil bath is heated to 50 DEG C-70 DEG C, stirs 1-3 hour, makes solution A;
(2) solution A is cast on sheet glass, 60 DEG C of-90 DEG C of vacuum-dryings become polyvinylidene difluoride (PVDF) (PVDF) film, pvdf membrane is put into the sodium hydroxide solution of 6 ~ 8mol/L, in 60 ~ 80 DEG C of oil baths, process 8-10h, water rinses repeatedly to neutrality again, dries and form modification pvdf membrane at 100 ~ 120 DEG C of temperature;
(3) be respectively 15-17 part, 3-2 by the weight part proportioning of modification pvdf membrane, sodium wolframate and strong phosphoric acid, the ratio of part and 2-1 part takes respectively modification pvdf membrane, sodium wolframate and strong phosphoric acid; Modification pvdf membrane is dissolved in the mixed solution of dimethyl sulfoxide (DMSO) and water and makes solution B, in mixed solution, the volume ratio of dimethyl sulfoxide (DMSO) and water is 8-12:1, and it is 15-19g that every gram of modification pvdf membrane needs the amount of mixed solution;
(4) solution B is heated to 80 DEG C-95 DEG C, stirs after 1 to 3 hour, temperature is down to 60 DEG C-75 DEG C, forms solution C;
(5) sodium wolframate and the strong phosphoric acid that step (3) are taken, add in solution C, stirs and be down to room temperature after 1 to 3 hour, and vacuum oil bath is heated to 110-130 DEG C, fully stirs, until after moisture all evaporates in solution, be down to room temperature, forms uniform solution D;
(6) solution D is cast on polyfluortetraethylene plate and vacuum-drying film forming, film thickness is 0.1-0.2 millimeter, and vacuum-drying temperature is 90-100 DEG C, obtains phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane.
The mass percent concentration of strong phosphoric acid is 85.54%.
The present invention is owing to adding sodium wolframate and strong phosphoric acid in the dimethyl sulphoxide solution that is dissolved with modified polyvinilidene fluoride, sodium wolframate and phosphoric acid original position are synthesized phospho-wolframic acid particulate, be evenly distributed in modified polyvinylidene fluoride-based material, continue the dimethyl sulphoxide solution that is dissolved with modified polyvinilidene fluoride that contains phospho-wolframic acid particulate to be cast in and on polyfluortetraethylene plate, to dry film forming, the now hydroxyl in hydroxyl and the phospho-wolframic acid on modified polyvinilidene fluoride, further there is hydroxyl condensation reaction, form a network-like structure, reunion and the loss of phospho-wolframic acid are avoided so on the one hand, swelling ratio and the methanol permeability of film are reduced on the other hand.
The present invention compare with technology with current material have advantages of as follows:
The proton conduction property excellence of the compound proton exchange membrane that 1, prepared by the present invention, its proton conduction speed is greater than the proton conductivity of Nafion film.
2, the prepared compound proton exchange membrane of the present invention, alcohol permeability ratio Nafion film little, methanol permeability has reduced an order of magnitude, features good methanol diffusion resistance.
3, the prepared compound proton exchange membrane swelling capacity of the present invention is 1/2nd of Nafion film, and swelling capacity obviously reduces than Nafion film.
4, preparation technology of the present invention is simple, and the film cost of the compound proton exchange membrane of preparation, lower than Nafion film, is easy to industrialization, can promote the development of direct methanol fuel cell.
Embodiment
embodiment 1
20 grams of polyvinylidene difluoride (PVDF) are dissolved in 380g dimethyl sulfoxide (DMSO) and form solution A; Solution A is heated to 60 DEG C, stirs 2 hours to obtain solution B, solution B is cast to 70 DEG C of vacuum-drying film forming on clean sheet glass; Film is put into the sodium hydroxide solution of 6mol/L, taken out after processing 8h in 60 DEG C of oil baths, water rinses repeatedly to neutrality, dries and form film at 105 DEG C of temperature; 10g dry film is dissolved in to the mixed solution of 190g dimethyl sulfoxide (DMSO) and 21.6mL water, forms solution C; Solution C is heated to 80 DEG C, stirs 2 hours, temperature is down to 70 DEG C, adds 2 g sodium wolframates and 1.25g strong phosphoric acid, stir cooling after 2 hours, vacuum oil bath is warmed up to 130 DEG C, stirs 1.5 hours, until moisture all evaporates in solution, be down to room temperature, form solution D; Solution D is cast on polyfluortetraethylene plate, and 90 DEG C of vacuum-dryings obtain phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane.
Need before use film to be soaked in deionized water 12 hours.Survey its specific conductivity by two electrode AC impedance methods, use swelling capacity (
sD) carrying out the swelling behavior of characterization of membrane, (area is the rectangle diaphragm that first dry film to be cut into size be approximately 3 cm × 4 cm
s d), immerse 1 molL
-1methanol aqueous solution in, fully after swelling 48 h, take out, measure the size of wet film, obtain area
s w , calculate the swelling capacity of film by following formula
sD:
；
Measure the methanol permeability of film with barrier film method of diffusion.
embodiment 2
15 grams of polyvinylidene difluoride (PVDF) are dissolved in 240g dimethyl sulfoxide (DMSO) and form solution A, solution A is heated to 50 DEG C, stir 2 hours to obtain solution B, solution B is cast to 60 DEG C of vacuum-drying film forming on clean sheet glass; Film is put into the sodium hydroxide solution of 7mol/L, taken out after processing 9h in 70 DEG C of oil baths, water rinses repeatedly to neutrality, dries and form film at 110 DEG C of temperature; 8g dry film is dissolved in to the mixed solution of 128g dimethyl sulfoxide (DMSO) and 13mL water, forms solution C; Solution C is heated to 85 DEG C, stirs 2 hours, temperature is down to 60 DEG C, adds 1.25g sodium wolframate and 0.88g strong phosphoric acid, stir cooling after 2 hours, vacuum oil bath is warmed up to 110 DEG C, stirs 1 hour, until moisture all evaporates in solution, be down to room temperature, form solution D; Solution D is cast on polyfluortetraethylene plate, and 95 DEG C of vacuum-dryings obtain phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane.
embodiment 3
10 grams of polyvinylidene difluoride (PVDF) are dissolved in 180g dimethyl sulfoxide (DMSO) and form solution A, solution A is heated to 60 DEG C, stir 2 hours to obtain solution B, solution B is cast to 80 DEG C of vacuum-drying film forming on clean sheet glass; Film is put into the sodium hydroxide solution of 7mol/L, taken out after processing 10h in 80 DEG C of oil baths, water rinses repeatedly to neutrality, dries and form film at 115 DEG C of temperature; 6g dry film is dissolved in to the mixed solution of 108g dimethyl sulfoxide (DMSO) and 10mL water, forms solution C; Solution C is heated to 90 DEG C, stirs 2.5 hours, temperature is down to 65 DEG C, adds 0.71g sodium wolframate and 0.41g strong phosphoric acid, stir cooling after 2 hours, vacuum oil bath is warmed up to 120 DEG C, stirs 2 hours, until moisture all evaporates in solution, be down to room temperature, form solution D; Solution D is cast on polyfluortetraethylene plate, and 95 DEG C of vacuum-dryings obtain phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane.
embodiment 4
25 grams of polyvinylidene difluoride (PVDF) are dissolved in 375g dimethyl sulfoxide (DMSO) and form solution A, solution A is heated to 70 DEG C, stir 2 hours to obtain solution B, solution B is cast to 90 DEG C of vacuum-drying film forming on clean sheet glass; Film is put into the sodium hydroxide solution of 8 mol/L, taken out after processing 8h in 80 DEG C of oil baths, water rinses repeatedly to neutrality, dries and form film at 120 DEG C of temperature; 13g dry film is dissolved in to the mixed solution of 195g dimethyl sulfoxide (DMSO) and 16mL water, forms solution C; Solution C is heated to 95 DEG C, stirs 3 hours, temperature is down to 60 DEG C, adds 2.33g sodium wolframate and 1.55g strong phosphoric acid, stir cooling after 2 hours, vacuum oil bath is warmed up to 125 DEG C, stirs 1.5 hours, until moisture all evaporates in solution, be down to room temperature, form solution D; Solution D is cast on polyfluortetraethylene plate, and 100 DEG C of vacuum-dryings obtain phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane.
comparative example
As a comparison, phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane and Nafion117 film that we utilize embodiment 1 to prepare, perviousness, swelling ratio and specific conductivity to its methyl alcohol compare, two kinds of films are soaked a few hours in deionized water, survey its specific conductivity by two electrode AC impedance methods; With swelling capacity (
sD) carrying out the swelling behavior of characterization of membrane, (area is the rectangle diaphragm that first dry film to be cut into size be approximately 3 cm × 4 cm
s d), immerse 1 molL
-1methanol aqueous solution in, fully after swelling 48 h, take out, measure the size of wet film, obtain area
s w , calculate the swelling capacity of film by following formula
sD:
Measure the methanol permeability of film with barrier film method of diffusion.
The performance of table 1 phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane at 25 DEG C and the comparison of Nafion film, in table, sample is phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane prepared by embodiment 1.
As can be seen from Table 1, utilize the proton conduction property excellence of the prepared compound proton exchange membrane of the present invention, its proton conduction speed is greater than the proton conductivity of Nafion film.The reduction of alcohol permeability ratio Nafion an order of magnitude, features good methanol diffusion resistance.Swelling capacity is 1/2nd of Nafion film.
Finally it should be noted that: obviously, above-described embodiment is only for example of the present invention is clearly described, and the not 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 without also giving exhaustive to all embodiments.And the apparent variation of being amplified out thus or variation are still among protection scope of the present invention.
Claims (3)
1. a preparation method for phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane, is characterized in that, polyvinylidene difluoride (PVDF) is dissolved in dimethyl sulfoxide (DMSO) and makes macromolecular solution, coats film forming, and this film is put into after alkali lye processing, cleans and obtains modified membrane with deionized water; Modified membrane is dissolved in the mixed solution of dimethyl sulfoxide (DMSO) and water again, adds strong phosphoric acid and sodium wolframate, be heated, stir, form solution, this solution casting on tetrafluoroethylene sheet glass and dry film forming, is obtained to phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane.
2. the preparation method of phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane as claimed in claim 1, is characterized in that, concrete preparation method is:
(1) need the amount of dimethyl sulfoxide (DMSO) 15-19g by every gram of polyvinylidene difluoride (PVDF), weigh polyvinylidene difluoride (PVDF) and be dissolved in dimethyl sulfoxide (DMSO), oil bath is heated to 50 DEG C-70 DEG C, stirs 1-3 hour, makes solution A;
(2) solution A is cast on sheet glass, 60 DEG C of-90 DEG C of vacuum-dryings become polyvinylidene difluoride (PVDF) (PVDF) film, pvdf membrane is put into the sodium hydroxide solution of 6 ~ 8mol/L, in 60 ~ 80 DEG C of oil baths, process 8-10h, water rinses repeatedly to neutrality again, dries and form modification pvdf membrane at 100 ~ 120 DEG C of temperature;
(3) ratio that is respectively 15-17 part, 2-5 part and 1-2 part in the weight part proportioning of modification pvdf membrane, sodium wolframate and strong phosphoric acid takes respectively modification pvdf membrane, sodium wolframate and strong phosphoric acid; Modification pvdf membrane is dissolved in the mixed solution of dimethyl sulfoxide (DMSO) and water and makes solution B, in mixed solution, the volume ratio of dimethyl sulfoxide (DMSO) and water is 8-12:1, and it is 15-19g that every gram of modification pvdf membrane needs the amount of mixed solution;
(4) solution B is heated to 80 DEG C-95 DEG C, stirs after 1 to 3 hour, temperature is down to 60 DEG C-75 DEG C, forms solution C;
(5) sodium wolframate and the strong phosphoric acid that step (3) are taken, add in solution C, stirs and be down to room temperature after 1 to 3 hour, and vacuum oil bath is heated to 110-130 DEG C, fully stirs, until after moisture all evaporates in solution, be down to room temperature, forms uniform solution D;
(6) solution D is cast on polyfluortetraethylene plate and vacuum-drying film forming, film thickness is 0.1-0.2 millimeter, and vacuum-drying temperature is 90-100 DEG C, obtains phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane.
3. the preparation method of phospho-wolframic acid-polyvinylidene difluoride (PVDF) compound proton exchange membrane as claimed in claim 2, is characterized in that, the mass percent concentration of strong phosphoric acid is 85.54%.
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| CN104163932B (en) * | 2013-05-16 | 2017-05-31 | 北京航空航天大学 | A kind of shitosan phosphotungstic acid compound proton exchange membrane of meso-hole structure and preparation method thereof |
| 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 |
| 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 |
| CN103360617A (en) * | 2013-07-19 | 2013-10-23 | 内蒙古科技大学 | Preparation method of polyvinylidene fluoride-polyvinyl alcohol composite proton exchange membrane |
| CN103627012B (en) * | 2013-12-01 | 2015-12-09 | 太原理工大学 | A kind of preparation method of phosphotungstic acid-polyvinyl formal composite proton exchange membrane |
| CN105514466B (en) * | 2016-01-13 | 2018-03-09 | 山东星火科学技术研究院 | A kind of preparation method for the methanol fuel cell PEM for loading multicomponent catalyst |
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| Title |
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| 阎新宝."以PVA、PVDF为基材的DMFC用质子交换膜的研究".《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑（月刊）》.2007,(第03期),第46－48页. * |
| 阎新宝."以PVA、PVDF为基材的DMFC用质子交换膜的研究".《中国优秀博硕士学位论文全文数据库(硕士)工程科技I辑(月刊)》.2007,(第03期),第46-48页. * |
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