CN116231019A - Vinyl phosphonic acid-based modified high-temperature polymer electrolyte membrane and preparation method and application thereof - Google Patents
Vinyl phosphonic acid-based modified high-temperature polymer electrolyte membrane and preparation method and application thereof Download PDFInfo
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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- H01M8/1018—Polymeric electrolyte materials
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Abstract
The invention discloses a vinyl phosphonic acid-based modified high-temperature polymer electrolyte membrane, and a preparation method and application thereof. The preparation process comprises the following steps: (1) Preparing a vinyl imidazole-vinyl phosphoric acid copolymer by adopting a solution polymerization method, and dissolving the copolymer in a solvent to obtain a copolymer solution; (2) dissolving a polymer in a solvent to obtain a film forming liquid; (3) And (3) blending the copolymer solution and the film forming liquid to form uniform slurry, and casting the slurry into a film. The method has simple process, and the prepared polymer electrolyte membrane has excellent proton conductivity.
Description
Technical Field
The invention belongs to the technical field of polymer electrolyte membranes, and particularly relates to a vinyl phosphonic acid-based modified high-temperature polymer electrolyte membrane, and a preparation method and application thereof.
Background
Currently, polymer electrolyte membranes used in medium and high temperature systems are mainly based on polybenzimidazole/inorganic phosphoric acid (PBI/H) 3 PO 4 ) The membrane is represented by the film, the service temperature is 120-160 ℃, and the proton conduction is mainly dependent onIn the phosphoric acid medium, the film has poor mechanical properties due to the severe plasticizing effect of excessive phosphoric acid, and the electrochemical performance is reduced due to acid loss.
Patent CN03805310.1 discloses a mixture comprising vinyl-containing phosphonic acid, a polymer electrolyte membrane comprising polyvinyl phosphonic acid and its use in fuel cells. This patent increases the proton conductivity of the vinylphosphonic acid monomer polymer by introducing it, but it does not relate to the mechanical strength parameters. Patent CN03810598.5 discloses an improved polymer electrolyte membrane, a preparation method and application thereof in fuel cells, which prepares a conductive polymer electrolyte membrane by introducing a monomer containing vinylphosphonic acid and/or vinylsulfonic acid for polymerization, but the prepared conductive polymer electrolyte membrane itself is poor in film forming property, poor in compatibility with other polymers and poor in overall mechanical strength.
For the above reasons, the present application is presented.
Disclosure of Invention
For the above reasons, the present invention aims to solve or at least partially solve the above technical drawbacks of the prior art, and to provide a vinyl phosphonic acid-based modified high temperature polymer electrolyte membrane, and a preparation method and application thereof.
In order to achieve the first object of the present invention, the present invention adopts the following technical scheme:
a polymer electrolyte membrane based on vinyl phosphonic acid modified high temperature is prepared by dissolving a vinyl imidazole-vinyl phosphonic acid copolymer and then blending the dissolved copolymer with polymer film forming liquid.
Specifically, according to the technical scheme, the vinyl phosphonic acid-based modified high-temperature polymer electrolyte membrane is applicable to the polymer electrolyte membrane within the temperature range of 100-200 ℃.
Further, according to the technical scheme, the polymer in the polymer film forming liquid is one or a mixture of more of polyvinyl alcohol, polyvinylpyrrolidone, polyvinylidene fluoride, polyarylene piperidine, polysulfone, polyimide, polybenzimidazole and the like.
Further, according to the technical scheme, the vinyl imidazole-vinyl phosphonic acid copolymer is prepared by adopting a solution polymerization method, and the specific preparation steps are as follows:
sequentially dissolving 1-vinylimidazole, vinylphosphonic acid and an initiator in a solvent for polymerization reaction, and washing, purifying and drying the product after the reaction is finished.
Furthermore, according to the technical scheme, the molar ratio of the 1-vinylimidazole to the vinylphosphonic acid is 1:2-2:1.
Further, according to the technical scheme, the initiator is one or more of azodiisobutyronitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate and the like.
Furthermore, according to the technical scheme, the dosage of the initiator is 0.1-5% of the total mass of the two reaction monomers of the 1-vinylimidazole and the vinylphosphonic acid.
Furthermore, according to the technical scheme, the temperature of the polymerization reaction is 50-100 ℃, and the reaction time is 6-12 h.
Furthermore, according to the technical scheme, the drying is preferably carried out in a vacuum drying oven, wherein the temperature adopted by the drying is 50-120 ℃, and the drying time is 1-48 hours.
Specifically, the synthetic reaction formula related to the polymerization reaction is shown in the following formula one:
a second object of the present invention is to provide the above-mentioned method for preparing a vinyl phosphonic acid-based modified high temperature polymer electrolyte membrane, comprising the steps of:
(1) Preparing a vinyl imidazole-vinyl phosphoric acid copolymer by adopting a solution polymerization method, and then dissolving the vinyl imidazole-vinyl phosphoric acid copolymer in a solvent to obtain a copolymer solution;
(2) Dissolving a polymer in a solvent to obtain a film forming liquid;
(3) And (3) blending the copolymer solution in the step (1) and the film forming liquid in the step (2) to form an integrated slurry, and then casting the slurry into a film.
Further, according to the technical scheme, the solvent used for preparing the copolymer solution in the step (1) and the solvent used for preparing the film forming solution in the step (2) can be one or more of deionized water, methanol, ethanol, isopropanol, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.
Further, according to the technical scheme, the solid content of the copolymer solution in the step (1) and the solid content of the film forming solution in the step (2) are 5-70 wt%.
It is a third object of the present invention to provide the use of the above-mentioned vinyl phosphonic acid-based modified high temperature polymer electrolyte membrane for hydrogen fuel cells.
A hydrogen fuel cell comprising the above-described vinylphosphonic acid-based modified high temperature polymer electrolyte membrane.
The mechanism involved in the invention is as follows:
the introduction of the 1-vinyl imidazole in the invention increases the alkaline adsorption site on the polymer chain, and simultaneously the imidazole ring provides a good proton transmission channel; the introduction of the vinyl phosphonic acid enables the electrolyte membrane to have high proton conductivity under the condition of low phosphoric acid adsorption, and reduces the plasticization of inorganic phosphoric acid to the membrane, thereby improving the mechanical strength of the membrane.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a solution polymerization method to prepare the vinyl imidazole-vinyl phosphonic acid copolymer, and the vinyl imidazole-vinyl phosphonic acid copolymer is dissolved and then is blended with polymer film forming liquid to form a uniform system, and then is cast into a film. According to the method, the phosphonic acid group with high proton transmission is introduced to partially replace plasticized phosphoric acid, and meanwhile, the alkaline active site of the imidazole group is reserved, so that the mechanical strength of the polymer electrolyte membrane is improved, the acid loss is reduced, and the high-temperature polymer electrolyte membrane with excellent comprehensive performance is obtained.
(2) The high-temperature polymer electrolyte membrane prepared by the invention has high proton conductivity under the condition of low phosphoric acid adsorption, reduces the plasticizing effect of inorganic phosphoric acid on the membrane, and further improves the mechanical strength of the membrane.
Drawings
FIGS. 1 (a) and (b) are respectively pictorial representations of a vinyl phosphonic acid-based modified high temperature polymer electrolyte membrane prepared in example 3 of the present invention; wherein: (a): black and white drawings; (b) a color map;
FIG. 2 is a proton conductivity diagram of a vinyl phosphonic acid-based modified high temperature polymer electrolyte membrane prepared in application examples 1-3 of the present invention;
FIG. 3 is a graph showing the power density of a hydrogen fuel cell based on a vinyl phosphonic acid modified high temperature polymer electrolyte membrane prepared in example 3 of the present invention;
FIG. 4 is a Stress-Strain (Stress-Strain) graph of a high temperature polymer electrolyte membrane based on vinyl phosphonic acid modification prepared in example 3 of the present invention;
fig. 5 is a schematic view of a hydrogen fuel cell according to application example 3 of the present invention.
Detailed Description
The invention discloses a vinyl phosphonic acid-based modified high-temperature polymer electrolyte membrane, and a preparation method and application thereof. The preparation process comprises the following steps: (1) Preparing a vinyl imidazole-vinyl phosphoric acid copolymer by adopting a solution polymerization method, and dissolving the copolymer in a solvent to obtain a copolymer solution; (2) dissolving a polymer in a solvent to obtain a film forming liquid; (3) And (3) blending the copolymer solution and the film forming liquid to form uniform slurry, and casting the slurry into a film. The method has simple process, and the prepared polymer electrolyte membrane has excellent proton conductivity.
The invention is described in further detail below by way of examples.
For a better understanding of the present invention, and not to limit its scope, all numbers expressing quantities, percentages, and other values used in the present application are to be understood as being modified in all instances by the term "about". Accordingly, unless specifically indicated otherwise, the numerical parameters set forth in the specification are approximations that may vary depending upon the desired properties sought to be obtained. Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The equipment and materials used in the present invention are commercially available or are commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
The preparation method of the vinyl phosphonic acid-based modified high-temperature polymer electrolyte membrane comprises the following steps:
1) 0.1mol of 1-vinylimidazole, 0.1mol of vinylphosphonic acid and 1mmol of azobisisobutyronitrile are taken and dissolved in 20ml of N, N-dimethylformamide in sequence; transferring the obtained mixture into a constant temperature oil bath pot, controlling the reaction temperature to be 60 ℃ and the reaction time to be 12 hours; after the reaction is finished, the reaction product is washed and purified by methanol and then is placed in a vacuum drying oven to be dried for 24 hours at 80 ℃ to obtain a vinylimidazole-vinylphosphonic acid copolymer product.
2) 1g of the copolymer product was dissolved in 5mL of N, N-dimethylformamide to obtain a copolymer solution having a solid content of 20%.
3) 10g of polyarylene piperidine was dissolved in 50mL of N, N-dimethylformamide, and the solution was stirred at a constant temperature of 80℃for 4 hours to obtain a film-forming solution having a solid content of 20%.
4) And (3) blending the film forming liquid with the copolymer solution, stirring at the constant temperature of 60 ℃ for 2 hours to form a uniform system, and casting to obtain the vinyl phosphonic acid-based modified high-temperature polymer electrolyte film with the thickness of 40 mu m.
Example 2
The preparation method of the vinyl phosphonic acid-based modified high-temperature polymer electrolyte membrane comprises the following steps:
1) 0.2mol of 1-vinylimidazole, 0.1mol of vinylphosphonic acid and 1.5mmol of azobisisobutyronitrile were taken in sequence and dissolved in 20ml of N, N-dimethylacetamide; transferring the obtained mixture into a constant-temperature oil bath pot, controlling the reaction temperature to be 80 ℃ and the reaction time to be 8 hours; after the reaction is finished, the reaction product is washed and purified by methanol and then is placed in a vacuum drying oven for drying at 100 ℃ for 12 hours, and the vinylimidazole-vinylphosphonic acid copolymer product is obtained.
2) 1g of the copolymer product was dissolved in 5mL of N, N-dimethylacetamide to obtain a copolymer solution having a solid content of 20%.
3) 5g of polybenzimidazole is taken and dissolved in 50mL of N, N-dimethylacetamide, and the solution is heated to 100 ℃ and stirred for 12 hours at constant temperature to obtain the film forming solution with the mass volume concentration of 10 percent.
4) And (3) blending the film forming liquid and the copolymer solution, stirring at the constant temperature of 80 ℃ for 1h, forming a uniform system, and casting to obtain the vinyl phosphonic acid-based modified high-temperature polymer electrolyte film with the thickness of 40 mu m.
Example 3
The preparation method of the vinyl phosphonic acid-based modified high-temperature polymer electrolyte membrane comprises the following steps:
1) 0.1mol of 1-vinylimidazole, 0.2mol of vinylphosphonic acid and 0.6mmol of azobisisobutyronitrile are taken and dissolved in 20ml of N-methylpyrrolidone; transferring the obtained mixture into a constant temperature oil bath pot, controlling the reaction temperature to be 100 ℃ and the reaction time to be 6 hours; after the reaction is finished, the reaction product is washed and purified by methanol and then is placed in a vacuum drying oven to be dried for 24 hours at 80 ℃ to obtain a vinylimidazole-vinylphosphonic acid copolymer product.
2) 1g of the copolymer product was dissolved in 5mL of N-methylpyrrolidone to obtain a copolymer solution having a solid content of 20%.
3) Respectively dissolving 5g of polybenzimidazole and polyarylene piperidine with the mass ratio of 1:1 in 50mL of N-methylpyrrolidone, heating to 100 ℃, and stirring for 2 hours at constant temperature to obtain the polymer film-forming solution with the mass volume concentration of 20%.
4) And (3) blending the film forming liquid and the copolymer solution, stirring at the constant temperature of 80 ℃ for 2 hours, forming a uniform system, and casting to obtain the vinyl phosphonic acid-based modified high-temperature polymer electrolyte film with the thickness of 40 mu m.
Performance test:
the vinyl phosphonic acid modified high temperature polymer electrolyte membranes prepared in examples 1-3 were subjected to mechanical properties, proton conductivity, and cell power density tests, wherein:
the mechanical property test method specifically comprises the following steps:
(1) the sample thickness was rapidly measured at a constant temperature and humidity at 25 ℃ ± 2 ℃ and a relative humidity of 50% ± 5%. The thickness and width of each sample should be measured at three points within the gauge length and averaged. The thickness measurement accuracy was + -0.2%, and the width measurement accuracy was + -0.5%.
(2) Placing the sample in a test clamp of a tensile testing machine, enabling the longitudinal axis of the sample to coincide with the central connecting line of the upper clamp and the lower clamp, and clamping the sample. The pressure value of the pneumatic clamp is selected within the range of 0.3MPa to 0.7 MPa.
(3) The stretching speed of the stretching tester is selected within the range of 50 mm/min-200 mm/min.
(4) After the sample breaks, the corresponding load value is read. If the sample breaks at a location outside the reticle, the test is not effective.
And (4) reading the required load, the corresponding film thickness and the corresponding width according to the measured stretching curve, and calculating the maximum stretching strength of the film according to a formula (4).
σ＝p/(b×d)......................................................(4)
Wherein:
sigma, the maximum tensile strength of the film in megapascals (MPa);
p-maximum load in bovine (N);
b-sample width in millimeters (mm);
d-sample thickness in millimeters (mm).
The average value was calculated as the test result by taking 3 samples as a group.
The proton conductivity test method is specifically as follows:
the proton conductivity test method according to the present invention in application example 1 is described in section 3 of GB/T20042.3-2009: proton exchange Membrane test method section 5 proton conductivity test, detailed test method is as follows:
a film of a certain size was taken as a sample, advantageously at a temperature of 25.+ -. 2 ℃ and a relative humidity of 50.+ -. 5%The thickness of the sample was measured with a thickness gauge, and the average value of three points was taken as the value of the calculated thickness d. The sample was fixed in a conductivity measuring jig, and the bolt was tightened with a torque wrench at a torque of 3n·m. Then the conductivity measuring clamp is placed in different constant humidity environments with different temperatures, and the conductivity measuring clamp is tested after being kept constant for 30 minutes under each temperature and humidity condition. In the frequency range of (1-2 x 10) 6 ) And (5) measuring the impedance spectrogram of the sample by using an electrochemical impedance tester under the conditions of Hz and disturbance voltage of 10 mV. In the measured impedance spectrum, the impedance value (R) of the sample is read from the intersection of the high frequency portion of the spectrum line and the real axis, and the proton conductivity of the sample is calculated according to the following formula:
wherein:
sigma—proton conductivity of the sample in siemens per centimeter (S/cm);
a-the distance between two electrodes in centimeters (cm);
r-the measured impedance of the sample in European (omega);
b-the effective length of the membrane in centimeters (cm) perpendicular to the electrodes;
d-the thickness of the sample in centimeters (cm).
The average value was calculated as the test result by taking 3 samples as a group.
The power density testing method of the single cell is specifically as follows:
the single cells are mounted to a fuel cell test platform. Under specified battery operating conditions, the cell output current and voltage are tested in a constant current manner. Every 50mA/cm increase in current density from the open cell 2 ～100mA/cm 2 The voltage value was recorded and the test was terminated when the battery operating voltage was below 0.25V. And drawing a relation curve of discharge voltage and current density according to the voltage and current results recorded in the polarization curve test.
The cell power density was calculated according to the following formula.
Wherein:
p-cell Power Density in watts per centimeter squared (W/cm) 2 )；
I-current in amperes (A);
v-voltage in volts (V);
s, the effective area of the membrane electrode is expressed as square centimeters (cm) 2 )；
And drawing a relation curve of the power density and the current density of the single cell.
Analysis of test results:
FIG. 4 is a Stress-Strain (Stress-Strain) graph of a high temperature polymer electrolyte membrane based on vinylphosphonic acid modification prepared in example 3 of the present invention. As can be seen from fig. 4, the mechanical strength of the wide temperature range polymer electrolyte membrane prepared in example 3 of the present invention reaches 120MPa, the elongation at break is 36%, and the use requirement is satisfied.
Application examples
A hydrogen fuel cell prepared using the vinylphosphonic acid-modified high temperature polymer electrolyte membrane-based polymer electrolyte membrane of the present invention, the hydrogen fuel cell having a structure as shown in fig. 5, the components comprising: end plates, insulating gaskets, bipolar plates, diffusion layers, films and sealing gaskets; assembling the parts and materials into a structure shown in fig. 5; wherein: the membrane was a vinyl phosphonic acid-based modified high temperature polymer electrolyte membrane prepared in example 3.
It is well known to those skilled in the art that the high temperature electrolyte membrane in the conventional high temperature hydrogen fuel cell needs to be soaked with a large amount of inorganic phosphoric acid to conduct proton conduction, resulting in serious plasticization of the membrane and significant decrease of mechanical properties. The high-temperature hydrogen fuel cell prepared by using the high-temperature polymer electrolyte membrane based on the vinyl phosphonic acid modification has high proton conductivity under the condition of low phosphoric acid adsorption, reduces the plasticizing effect of inorganic phosphoric acid on the membrane, and further improves the mechanical strength of the membrane.
FIG. 2 is a proton conductivity diagram of hydrogen fuel cells based on vinyl phosphonic acid modified high temperature polymer electrolyte membranes prepared in application examples 1-3 of the present invention. As can be seen from fig. 2, the membrane of the present invention has proton conductivity at 120-220 ℃; wherein the proton conductivity of the membrane prepared in example 3 under the same conditions is optimal, and the proton conductivity is up to 0.1S/cm.
FIG. 3 is a graph showing the power density of a hydrogen fuel cell based on a vinyl phosphonic acid modified high temperature polymer electrolyte membrane prepared in example 3 of the present invention; as can be seen from FIG. 3, the film of the present invention has a maximum power density of 698mW/cm at 200 ℃ 2 。
The embodiments described above and features of the embodiments herein may be combined with each other without conflict.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A vinyl phosphonic acid-based modified high temperature polymer electrolyte membrane characterized by: the polymer electrolyte membrane is prepared by dissolving a vinyl imidazole-vinyl phosphonic acid copolymer and then blending the dissolved vinyl imidazole-vinyl phosphonic acid copolymer with polymer film forming liquid.
2. The vinylphosphonic acid-modified high temperature polymer electrolyte membrane based according to claim 1, wherein: the polymer in the polymer film forming liquid is one or a mixture of more of polyvinyl alcohol, polyvinylpyrrolidone, polyvinylidene fluoride, polyarylene piperidine, polysulfone, polyimide and polybenzimidazole.
3. The vinylphosphonic acid-modified high temperature polymer electrolyte membrane based according to claim 1, wherein: the vinyl imidazole-vinyl phosphonic acid copolymer is prepared by a solution polymerization method, and the specific preparation steps are as follows:
sequentially dissolving 1-vinylimidazole, vinylphosphonic acid and an initiator in a solvent for polymerization reaction, and washing, purifying and drying the product after the reaction is finished.
4. The vinylphosphonic acid-modified high temperature polymer electrolyte membrane according to claim 3, wherein: the molar ratio of the 1-vinylimidazole to the vinylphosphonic acid is 1:2-2:1.
5. The vinylphosphonic acid-modified high temperature polymer electrolyte membrane according to claim 3, wherein: the dosage of the initiator is 0.1-5% of the total mass of the two reaction monomers of 1-vinylimidazole and vinylphosphonic acid.
6. The vinylphosphonic acid-modified high temperature polymer electrolyte membrane according to claim 3, wherein: the temperature of the polymerization reaction is 50-100 ℃ and the reaction time is 6-12 h.
7. The method for producing a vinyl phosphonic acid-based modified high temperature polymer electrolyte membrane according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
(1) Preparing a vinyl imidazole-vinyl phosphoric acid copolymer by adopting a solution polymerization method, and then dissolving the vinyl imidazole-vinyl phosphoric acid copolymer in a solvent to obtain a copolymer solution;
(2) Dissolving a polymer in a solvent to obtain a film forming liquid;
(3) And (3) blending the copolymer solution in the step (1) and the film forming liquid in the step (2) to form an integrated slurry, and then casting the slurry into a film.
8. The method of manufacturing according to claim 7, wherein: the solid content of the copolymer solution in the step (1) and the film forming solution in the step (2) is 5-70 wt%.
9. Use of the vinyl phosphonic acid-based modified high temperature polymer electrolyte membrane according to any of claims 1 to 6 in hydrogen fuel cells.
10. A hydrogen fuel cell characterized by: comprising the vinylphosphonic acid-based modified high temperature polymer electrolyte membrane according to any one of claims 1 to 6.
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| CN108777314A (en) * | 2018-05-29 | 2018-11-09 | 中国科学院上海有机化学研究所 | A kind of compound organic phospho acid high temperature proton exchange film and preparation method thereof |
| CN113694903A (en) * | 2021-08-30 | 2021-11-26 | 重庆市化工研究院有限公司 | Phosphorus-containing polymer hydrogel and preparation method and application thereof |
| CN114108006A (en) * | 2022-01-19 | 2022-03-01 | 深圳市通用氢能科技有限公司 | Proton exchange membrane for hydrogen production by water electrolysis and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108777314A (en) * | 2018-05-29 | 2018-11-09 | 中国科学院上海有机化学研究所 | A kind of compound organic phospho acid high temperature proton exchange film and preparation method thereof |
| CN113694903A (en) * | 2021-08-30 | 2021-11-26 | 重庆市化工研究院有限公司 | Phosphorus-containing polymer hydrogel and preparation method and application thereof |
| CN114108006A (en) * | 2022-01-19 | 2022-03-01 | 深圳市通用氢能科技有限公司 | Proton exchange membrane for hydrogen production by water electrolysis and preparation method thereof |
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| 韩帅元等: "基于膦酸基的高温质子交换膜的研究进展", 物理化学学报, vol. 30, no. 1, pages 8 - 21 * |
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