CN109054064A - A kind of sulfonated polyimide-phosphoric acid wolframic acid composite membrane and preparation method thereof - Google Patents
A kind of sulfonated polyimide-phosphoric acid wolframic acid composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of sulfonated polyimide-phosphoric acid wolframic acid composite membranes and preparation method thereof.Phosphotungstic acid is added by the way that sulfonated polyimide film to be dissolved in m-cresol in the present invention, and 11~13h is mixed, and by polymer fiber that mixed solution is obtained by filtration after washing, drying, obtains sulfonated polyimide-phosphoric acid tungsten composite membrane；Sulfonated polyimide-phosphoric acid tungsten composite membrane is dissolved in and is prepared into the casting solution that mass concentration is 5% in m-cresol, liquid stream is extended down on clean glass plate, after drying, drying, cooling, film is isolated from glass plate, by the film successively after past residual solvent, deprotonation processing, rinsing, drying, sulfonated polyimide-phosphoric acid wolframic acid composite membrane is obtained.Composite membrane homogeneity prepared by the present invention is fine, has the characteristics that good dispersion performance, strong mechanical degrees, excellent catalytic activity and low vanadium ion exchange rate, can be applied to all-vanadium flow battery.
Description
Technical field
The invention belongs to battery material technical field more particularly to a kind of sulfonated polyimide-phosphoric acid wolframic acid composite membrane and
Preparation method.
Background technique
Since the renewable energy such as wind energy, solar energy, tide energy can not be able to satisfy people and hold to electric energy with seasonal variations
Continuous, stable, controllable demand, this results in electricity storage technology to seem especially most important.All-vanadium flow battery (i.e. VRB) is made
It can be used for solving the problems, such as the energy storage in energy development process for a kind of big static energy storage device.Since 1985, by
The vanadium redox flow battery system (i.e. VRB) that Skyllaska-zacos team is put forward for the first time, because it is responded faster, longer circulation
Service life, the technical advantages such as flexible design receive comparable concern, as vanadium redox flow battery system in the past few years
(VRB) key components, amberplex (IEM) have not only separated two electrolytic cells, to prevent the mixed of electrolytic solution
It closes, but also allows selectively to transport proton (H+).One ideal VRB film should have high proton electric conductivity, and low vanadium seeps
Permeability and good oxidisability.Currently, perfluorinated sulfonic acid polymer is most common ion exchange membrane material such as Du Pont Nafion,
However, there is also the other shortcomings that high vanadium ion permeability and serious water shift for Nafion membrane, to reduce VRB system
Coulombic efficiency and energy efficiency.Therefore, finding novel ion exchange membrane becomes the key of vanadium cell development.
Summary of the invention
The purpose of the present invention is to provide a kind of sulfonated polyimide-phosphoric acid wolframic acid composite membranes and preparation method thereof, it is intended to
Solve the problems, such as vanadium redox flow battery amberplex selectivity.
The invention is realized in this way a kind of sulfonated polyimide-phosphoric acid wolframic acid composite membrane preparation method, this method packet
Include following steps:
(1) sulfonated polyimide film is dissolved in m-cresol, obtain sulfonated polyimide film mass concentration be 8%~
12% solution 1, phosphoric acid tungsten is dissolved in solution 1, obtains the solution 2 that phosphoric acid tungsten mass concentration is 6%~8%, solution 2 is mixed
It is filtered after closing 11~13h of stirring, after the polymer fiber being obtained by filtration washing, drying, obtains sulfonated polyimide-phosphorus
Sour tungsten composite membrane；
(2) sulfonated polyimide-phosphoric acid tungsten composite membrane is dissolved in m-cresol, obtaining composite membrane mass concentration is 5%
Casting solution, casting solution is cast on clean glass plate, drying, drying, it is cooling after, isolated from glass plate thin
The film is successively obtained sulfonated polyimide-phosphoric acid after past residual solvent, deprotonation processing, rinsing, drying by film
Wolframic acid composite membrane.
Preferably, in step (1), the washing, drying specifically: the remaining reagent of acetone washing is used, at 120 DEG C
Vacuum drying 24 hours.
Preferably, in step (2), the drying, dry, cooling specifically: it is small that 12 are dried at a temperature of 80~85 DEG C
When, dry 15h, cools down at room temperature at a temperature of 110 DEG C.
Preferably, described to remove residual solvent in step (2) specifically: under room temperature, film is soaked in 24 in methanol
Hour；The deprotonation processing specifically: under room temperature, film is impregnated 48 hours in 2.0M HCl, then by film 50
It is impregnated 12 hours in DEG C triethanolamine solution；It is described to rinse to be rinsed well film with distilled water；The drying is in 120 DEG C of temperature
It is 12 hours dry under degree, vacuum environment.
Preferably, in step (1), the preparation of the sulfonated polyimide film the following steps are included:
A, it is added in distiller after mixing 4,4- diamino -2,2'- disulfonic acid benzidine, m-cresol, distiller
In be passed through nitrogen, be added dropwise at room temperature triethanolamine and magnetic agitation it is uniform, be warming up to 70 DEG C, return stirring to 4,4- diamino
Base -2,2'- disulfonic acid benzidine is completely dissolved；Wherein, 4,4- diamino -2,2'- disulfonic acid benzidine, m-cresol,
The mass volume ratio of triethanolamine is 2.96g:68mL:2.5mL；
B, 30 DEG C are cooled to, dimethylaminobenzoic acid, Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydrides and benzene first are added into distiller
Acid is warming up to 80 DEG C, return stirring 4 hours, is warming up to 180 DEG C, continues return stirring and reacts 24 hours, obtains viscous solution；
Wherein, the dimethylaminobenzoic acid, Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydrides, benzoic acid mass ratio be 2.76g:4.3g:
3.90g；
C, m-cresol is added into distiller to be diluted, is cooled to 80 DEG C, the viscous solution after dilution is poured into third
In ketone solution, mechanical stirring 1 hour, acetone soln is filtered, by the polymer fiber being obtained by filtration by washing, drying
Afterwards, sulfonated polyimide film is obtained；Wherein, the viscous solution, m-cresol, acetone soln volume ratio be (80~
100ml): 50mL:800mL.
Preferably, in step C, the washing, drying specifically: washed using acetone, in 120 DEG C of vacuum environments
Middle drying is for 24 hours.
Compared with the prior art the shortcomings that and deficiency, the invention has the following advantages:
(1) sulfonated polyimide of the present invention-phosphoric acid wolframic acid composite membrane have strong mechanical degrees, excellent catalytic activity and low vanadium from
The features such as sub- exchange rate, can be applied to all-vanadium flow battery (VRB)；
(2) composite membrane homogeneity prepared by the present invention is fine, has good dispersion performance.
Detailed description of the invention
Fig. 1 is sulfonated polyimide (SPI) film and the scanning of sulfonated polyimide-phosphoric acid wolframic acid (SPI-PWA) composite membrane
Electron microscope；Wherein, Fig. 1 a is SPI film；Fig. 1 b is SPI-PWA composite membrane；
Fig. 2 is the measuring device of vanadium permeability.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Embodiment 1
(1) by 2.96g 4, distillation is added to after 4- diamino -2,2'- disulfonic acid benzidine, the mixing of 68mL m-cresol
In device, it is passed through nitrogen in distiller, 2.5mL triethanolamine is added dropwise at room temperature and magnetic agitation is uniform, is warming up to 70 DEG C, times
Stream stirring to 4,4- diamino -2,2'- disulfonic acid benzidine is completely dissolved；
(2) 30 DEG C are cooled to, 2.76g dimethylaminobenzoic acid, 4.3g Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics are added into distiller
Dianhydride and 3.90g benzoic acid are warming up to 80 DEG C, return stirring 4 hours, are warming up to 180 DEG C, and it is small to continue return stirring reaction 24
When, obtain viscous solution；
(3) 50mL m-cresol is added into distiller 80~100ml viscous solution to be diluted, is cooled to 80 DEG C, it will
Viscous solution after dilution pours into 800mL acetone soln, mechanical stirring 1 hour, is filtered, will filter to acetone soln
To polymer fiber washed using acetone, in 120 DEG C of vacuum environments it is dry for 24 hours, obtain sulfonated polyimide film 1.
Embodiment 2
(1) by 30g 4, distiller is added to after 4- diamino -2,2'- disulfonic acid benzidine, the mixing of 70mL m-cresol
In, it is passed through nitrogen in distiller, 3mL triethanolamine is added dropwise at room temperature and magnetic agitation is uniform, is warming up to 70 DEG C, flows back and stir
It mixes to 4,4- diamino -2,2'- disulfonic acid benzidine and is completely dissolved；
(2) 30 DEG C are cooled to, 2.80g dimethylaminobenzoic acid, 4.5g Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics are added into distiller
Dianhydride and 4.00g benzoic acid are warming up to 80 DEG C, return stirring 4 hours, are warming up to 180 DEG C, and it is small to continue return stirring reaction 24
When, obtain viscous solution；
(3) 50mL m-cresol is added into distiller 90ml viscous solution to be diluted, 80 DEG C is cooled to, after dilution
Viscous solution pour into 800mL acetone soln, mechanical stirring 1 hour, acetone soln is filtered, it is poly- by what is be obtained by filtration
It closes fibres to be washed using acetone, drying for 24 hours, obtains sulfonated polyimide film 2 in 120 DEG C of vacuum environments.
Embodiment 3
(1) sulfonated polyimide film 1 that embodiment 1 is prepared is dissolved in m-cresol, it is sub- obtains sulfonation polyamides
The solution 1 that amine film quality concentration is 8%, phosphoric acid tungsten is dissolved in solution 1, obtains the solution 2 that phosphoric acid tungsten mass concentration is 8%,
It is filtered after 13h is mixed in solution 2, the remaining reagent of polymer fiber acetone washing that will be obtained by filtration will produce
Object is dried in vacuo 24 hours at 120 DEG C, obtains sulfonated polyimide-phosphoric acid tungsten composite membrane；
(2) sulfonated polyimide-phosphoric acid tungsten composite membrane is dissolved in m-cresol, obtaining composite membrane mass concentration is 5%
Casting solution, casting solution is cast on clean glass plate, glass plate is dried into 12 hours, 110 DEG C of temperature at a temperature of 80 DEG C
The lower dry 15h of degree, after cooling down at room temperature, film is isolated from glass plate, under room temperature, it is small that film is soaked in methanol 24
When, it takes the film out to be put into 2.0M HCl and impregnate 48 hours, then film is impregnated 12 hours in 50 DEG C of triethanolamine solutions, by film
It is 12 hours dry under 120 DEG C of temperature, vacuum environments, obtain sulfonated polyimide-phosphoric acid wolframic acid composite membrane 1.
Embodiment 4
(1) sulfonated polyimide film 1 that embodiment 1 is prepared is dissolved in m-cresol, it is sub- obtains sulfonation polyamides
The solution 1 that amine film quality concentration is 12%, phosphoric acid tungsten is dissolved in solution 1, obtains the solution that phosphoric acid tungsten mass concentration is 6%%
2, it is filtered after 11h is mixed in solution 2, the remaining reagent of polymer fiber acetone washing that will be obtained by filtration, it will
Product is dried in vacuo 24 hours at 120 DEG C, obtains sulfonated polyimide-phosphoric acid tungsten composite membrane；
(2) sulfonated polyimide-phosphoric acid tungsten composite membrane is dissolved in m-cresol, obtaining composite membrane mass concentration is 5%
Casting solution, casting solution is cast on clean glass plate, glass plate is dried into 12 hours, 110 DEG C of temperature at a temperature of 85 DEG C
The lower dry 15h of degree, after cooling down at room temperature, film is isolated from glass plate, under room temperature, it is small that film is soaked in methanol 24
When, it takes the film out to be put into 2.0M HCl and impregnate 48 hours, then film is impregnated 12 hours in 50 DEG C of triethanolamine solutions, by film
It is 12 hours dry under 120 DEG C of temperature, vacuum environments, obtain sulfonated polyimide-phosphoric acid wolframic acid composite membrane 2.
Embodiment 5
(1) sulfonated polyimide film 1 that embodiment 1 is prepared is dissolved in m-cresol, it is sub- obtains sulfonation polyamides
The solution 1 that amine film quality concentration is 10%, phosphoric acid tungsten is dissolved in solution 1, obtains the solution 2 that phosphoric acid tungsten mass concentration is 7%,
It is filtered after 12h is mixed in solution 2, the remaining reagent of polymer fiber acetone washing that will be obtained by filtration will produce
Object is dried in vacuo 24 hours at 120 DEG C, obtains sulfonated polyimide-phosphoric acid tungsten composite membrane；
(2) sulfonated polyimide-phosphoric acid tungsten composite membrane is dissolved in m-cresol, obtaining composite membrane mass concentration is 5%
Casting solution, casting solution is cast on clean glass plate, glass plate is dried into 12 hours, 110 at a temperature of 80~85 DEG C
After drying 15h at a temperature of DEG C, cooling down at room temperature, film is isolated from glass plate, under room temperature, film is soaked in methanol
It 24 hours, takes the film out to be put into 2.0M HCl and impregnate 48 hours, then film is impregnated 12 hours in 50 DEG C of triethanolamine solutions,
Film is 12 hours dry under 120 DEG C of temperature, vacuum environments, obtain sulfonated polyimide-phosphoric acid wolframic acid composite membrane 3.
Effect example
Sulfonated polyimide obtained in above-described embodiment 5-phosphoric acid tungsten composite membrane 3 pattern and battery performance are surveyed
Examination experiment, the specific test method is as follows:
1, pattern test
The surface texture of the polymer film of preparation is investigated with SEM.By sulfonated polyimide-phosphoric acid tungsten composite films 80
It is dried 2 hours at DEG C, except the moisture content on striping surface layer, is then covered in golden watch layer and is allowed to conductive.It is observed under different magnifying powers
The microscope figure of SEM, as shown in Figure 1.Fig. 1 b shows sulfonated polyimide-phosphoric acid tungsten composite membrane homogeneous texture, and PWA is not sent out
Raw to reunite, showing good compatibility between heteropoly acid inorganic particulate and polymeric matrix can only because PWA is wrapped up by SPI
PWA is observed in the crack of polymer substrate, it can be seen that is that PWA is embedded in SPI polymer, size is in nanoscale
On.
2, the test of water absorption rate
For 24 hours in 100 DEG C of vacuum drying by sample film, weighing obtains sample dry weight Wdry；Then, film is immersed at room temperature
In deionized water for 24 hours, the water of film surface is quickly blotted in taking-up with filter paper, and weighing obtains sample weight in wet base Ws, can calculate film by following formula
Water absorption rate:
WsAnd WdryWeight respectively after water suction with dry film.
3, film thickness is tested
The rectangle of dry membrane sample shearing 2.5cm × 2cm size is with micrometer respectively to membrane sample rectangle four
Angle and quadrangle and center thickness detect and average.
4, ion exchange capacity (IEC) test of film
Using conventional determination of acid-basetitration.Film is immersed in 1M NaCl solution 24 hours, proton is handed over by sodium ion
It changes, acid is converted into sodium salt, the NaOH titration that the proton exchanged in solution (hydrogen ion) is titrated as 0.05mol/L.Ion exchange
The calculation formula of capacity is as follows:
In above formula, VNaOHAnd CNaOHIt is the volume and concentration of the NaOH standard solution of consumption, WdIt is the matter of membrane sample after drying
Amount.
According to document sulfonation degree DS can be calculated with following formula:
Above-mentioned 1~4 gained test result, as shown in table 1 below:
The main performance of 1 film of table
5, vanadium performance test is hindered
The permeability of vanadium ion (IV) by with the diffusion battery measuring device of UF membrane as shown in Fig. 2, device mainly has
Two and half electrolytic cells, centre are separated by diaphragm.Equipped in solution in the electrolytic cell of right side, cause to reduce left side because of concentration difference
Osmotic pressure variation, be equipped in the electrolytic cell on the left side, liquor capacity is 45ml in each half electrolytic cell, and the area of film is
3.14cm2.Both ends electrolytic cell is constantly recycled with magnetic agitation pump in order to avoid there is concentration polarization.A left side is taken at regular intervals
Side Adlerika measures its absorbance (λ by ultraviolet-visible spectrophotometermax=765nm), VO2+Permeability P can lead to
It crosses Fick's law of diffusion to be fitted to obtain, be shown below:
In formula, VLFor left side electrolyte volume, cm3；L is the thickness of sample film, μm；A is effective product of sample film, cm2；P
It is the permeability of V (IV)；CRFor the concentration of V (IV) in the solution of right side, mol/L；CL(t) for V (IV) in solution on the left of t moment from
Sub- concentration.The ion selectivity of film is determined by the ratio of conductivity and permeability.Test result is as follows shown in table 2:
2 vanadium redox flow battery performance test of table
| Sample | Charge efficiency (%) | Voltage (%) | Energy efficiency (%) |
| Nafion117 | 85.7 | 92.5 | 79.3 |
| SPI | 84.8 | 89.2 | 75.6 |
| SPI-PWA | 93.6 | 89.7 | 83.9 |
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (6)
1. a kind of sulfonated polyimide-phosphoric acid wolframic acid composite membrane preparation method, which is characterized in that this method includes following step
It is rapid:
(1) sulfonated polyimide film is dissolved in m-cresol, obtaining sulfonated polyimide film mass concentration is 8%~12%
Solution 1, phosphoric acid tungsten is dissolved in solution 1, obtain phosphoric acid tungsten mass concentration be 6%~8% solution 2, by solution 2 mix stir
It is filtered after mixing 11~13h, after the polymer fiber being obtained by filtration washing, drying, obtains sulfonated polyimide-phosphoric acid tungsten
Composite membrane；
(2) sulfonated polyimide-phosphoric acid tungsten composite membrane is dissolved in m-cresol, obtains the casting that composite membrane mass concentration is 5%
Casting solution is cast on clean glass plate by film liquid, and after drying, drying, cooling, film is isolated from glass plate, will
After past residual solvent, deprotonation processing, rinsing, drying, it is multiple successively to obtain sulfonated polyimide-phosphoric acid wolframic acid for the film
Close film.
2. sulfonated polyimide as described in claim 1-phosphoric acid wolframic acid composite membrane preparation method, which is characterized in that in step
Suddenly in (1), the washing, drying specifically: use the remaining reagent of acetone washing, be dried in vacuo 24 hours at 120 DEG C.
3. sulfonated polyimide as described in claim 1-phosphoric acid wolframic acid composite membrane preparation method, which is characterized in that in step
Suddenly in (2), the drying, dry, cooling specifically: it is dried 12 hours at a temperature of 80~85 DEG C, it is dry at a temperature of 110 DEG C
15h is cooled down at room temperature.
4. sulfonated polyimide as described in claim 1-phosphoric acid wolframic acid composite membrane preparation method, which is characterized in that in step
Suddenly described to remove residual solvent in (2) specifically: under room temperature, film is soaked in methanol 24 hours；At the deprotonation
Reason specifically: under room temperature, film is impregnated 48 hours in 2.0M HCl, then film is impregnated in 50 DEG C of triethanolamine solutions
12 hours；It is described to rinse to be rinsed well film with distilled water；The drying is dry 12 under 120 DEG C of temperature, vacuum environments
Hour.
5. sulfonated polyimide as described in claim 1-phosphoric acid wolframic acid composite membrane preparation method, which is characterized in that in step
Suddenly in (1), the preparation of the sulfonated polyimide film the following steps are included:
A, it is added in distiller after mixing 4,4- diamino -2,2'- disulfonic acid benzidine, m-cresol, leads in distiller
Enter nitrogen, triethanolamine is added dropwise at room temperature and magnetic agitation is uniform, is warming up to 70 DEG C, return stirring to 4,4- diamino-
2,2'- disulfonic acid benzidine are completely dissolved；Wherein, 4,4- diamino -2,2'- disulfonic acid benzidine, m-cresol, three second
The mass volume ratio of hydramine is 2.96g:68mL:2.5mL；
B, 30 DEG C are cooled to, dimethylaminobenzoic acid, Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydrides and benzoic acid are added into distiller, is risen
Temperature was warming up to 180 DEG C, continues return stirring and react 24 hours, obtain viscous solution to 80 DEG C, return stirring 4 hours；Wherein,
The dimethylaminobenzoic acid, Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydrides, benzoic acid mass ratio be 2.76g:4.3g:3.90g；
C, m-cresol is added into distiller to be diluted, is cooled to 80 DEG C, it is molten that the viscous solution after dilution is poured into acetone
In liquid, mechanical stirring 1 hour, acetone soln is filtered, by the polymer fiber being obtained by filtration after washing, drying,
Obtain sulfonated polyimide film；Wherein, the viscous solution, m-cresol, acetone soln volume ratio be (80~100ml):
50mL:800mL.
6. sulfonated polyimide as claimed in claim 5-phosphoric acid wolframic acid composite membrane preparation method, which is characterized in that in step
In rapid C, the washing, drying specifically: washed using acetone, dried for 24 hours in 120 DEG C of vacuum environments.
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|---|---|---|---|---|
| WO2002025764A1 (en) * | 2000-09-20 | 2002-03-28 | Virginia Tech Intellectual Properties, Inc. | Ion-conducting sulfonated polymeric materials |
| CN104852003A (en) * | 2014-02-17 | 2015-08-19 | 三星Sdi株式会社 | Polymer electrolyte membrane, membrane electrode assembly and fuel cell including the same |
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2018
- 2018-07-06 CN CN201810733916.6A patent/CN109054064A/en active Pending
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|---|---|---|---|---|
| WO2002025764A1 (en) * | 2000-09-20 | 2002-03-28 | Virginia Tech Intellectual Properties, Inc. | Ion-conducting sulfonated polymeric materials |
| CN104852003A (en) * | 2014-02-17 | 2015-08-19 | 三星Sdi株式会社 | Polymer electrolyte membrane, membrane electrode assembly and fuel cell including the same |
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