CN113314748A - Preparation method of enhanced proton exchange membrane based on surface modified polymer framework - Google Patents
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Abstract
The invention discloses an enhanced proton exchange membrane based on a surface sol-gel modified polymer framework and a preparation method thereof. The method specifically comprises the following steps: soaking the polymer reinforced skeleton in a dopamine solution, cleaning and drying to obtain a dopamine hydrophilic modified polymer skeleton, then soaking the skeleton in a zirconium propanol solution, taking out and cleaning, and drying to obtain an ultrathin zirconium oxide coating modified polymer skeleton; and (3) coating the sulfonic acid resin solution on two sides of the modified polymer skeleton, and drying to obtain the enhanced proton exchange membrane based on the surface modified polymer skeleton. The method has simple operation steps, improves the hydrophilicity and the surface polarity of the polymer framework, and promotes the interface combination between the polymer framework and the sulfonic acid resin. Meanwhile, the zirconium oxide is deposited on the polymer reinforced framework, so that the loss of the antioxidant is inhibited, and the chemical durability of the composite proton exchange membrane is improved. The invention aims to solve the problem of durability in the field of proton exchange membranes and has better popularization prospect.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a surface sol-gel modified polymer skeleton-based enhanced proton exchange membrane and a preparation method thereof.
Background
Proton exchange membranes are one of the key components of proton exchange membrane fuel cells. Plays multiple roles of transferring protons, insulating electrons and isolating reaction gas. The physical and chemical properties of the proton exchange membrane fuel cell directly determine the electrochemical performance and the service life of the proton exchange membrane fuel cell. Perfluorosulfonic acid (PFSA) series membranes (e.g., Nafion membranes) are widely used due to their good electrical conductivity. However, such membranes suffer from severe mechanical and chemical degradation over long periods of battery operation. The mechanical attenuation is mainly caused by repeated shrinkage and swelling of the perfluorosulfonic acid membrane in a dry-wet alternating environment. Mainly embodied in cracks, wrinkles, pinholes and tears of the film body. The chemical attenuation is mainly caused by the fact that free radicals directly attack the chemical structure of the proton exchange membrane to cause loss of carbon-fluorine bonds and sulfonic acid groups, so that the membrane body is thinned, and the proton conductivity and the gas barrier capability are reduced. Therefore, the development of proton exchange membranes with high mechanical and chemical durability is urgently needed.
Embedding a polymeric microporous framework (e.g., ePTFE microporous membrane) and doping with an antioxidant (e.g., CeO)2，ZrO2、Ce2+、Mn2+) Are typical measures for improving the mechanical durability and chemical durability of the proton exchange membrane, respectively. However, these two widely used methods still have drawbacks. Ting-Chu et al (Degradation mechanism study of PTFE/Nafion membrane in MEA degraded Degradation technique [ J]International Journal of Hydrogen Energy, 2012, 37 (18): 13623-. Marta et al (Migration of Ce and Mn Ions in PEMFC and Its Impact on PFSA Membrane Migration [ J ] et al]Journal of The Electrochemical Society, 2018, 165 (6): F3281-F3289) analyzed by Ce2+、Mn2+Radical scavenger stability of ion-doped PFSA composite membranes. The results show that there is significant free radical scavenger loss both in the direction of the membrane face and perpendicular to the membrane face.
Disclosure of Invention
Aiming at the problems of poor interface compatibility of a polymer skeleton and sulfonic acid resin and easy loss of a doped free radical scavenger in the prior art, the invention provides a surface modified polymer skeleton-based enhanced proton exchange membrane and a preparation method thereof.
The preparation operation steps of the enhanced proton exchange membrane based on the surface modified polymer framework are as follows:
(1) adding buffer triaminomethane hydrochloride into deionized water, and then adding dopamine hydrochloride to obtain 0.2wt% dopamine solution;
(2) soaking the polymer porous reinforced skeleton in the dopamine solution, taking out, washing with deionized water, and drying to obtain a dopamine hydrophilic modified polymer reinforced skeleton;
(3) soaking the dopamine hydrophilic modified polymer skeleton in 120mM zirconium n-propoxide Zr (OnPr)4Taking out the solution, washing the solution with normal propyl alcohol, hydrolyzing the solution in deionized water, and drying the solution to obtain zirconium oxide (ZrO)2) A coating-modified polymer-reinforced backbone;
(4) coating a sulfonic acid resin solution with the concentration of 20wt% on two side surfaces of the polymer reinforced skeleton modified by the zirconia coating, drying, thermally annealing, and repeating the operation of the step (3) for more than one time; obtaining a reinforced proton exchange membrane based on a surface modified polymer skeleton and provided with 1-3 coating layers;
the thickness of the enhanced proton exchange membrane is 22-24 μm, the tensile strength is 10-20Mpa, and the water absorption rate is 12-16.5%; no loss of zirconia was monitored after going through the OCV durability test of 63 h.
The specific technical scheme is as follows:
in the step (1), the polymer porous reinforced framework is one of a polytetrafluoroethylene microporous membrane and a polyvinylidene fluoride electrostatic spinning microporous membrane; the film thickness is 5-20 μm, and the porosity is more than 50%.
In the step (2), the soaking time in the dopamine solution is 1-2 h; the cleaning time is 5-30 min; the drying condition is that the temperature is 60-80 ℃ and the time is 12-24 h.
In the step (3), the soaking time in the zirconium n-propoxide solution is 1-5 min; the cleaning time is 2-5 min; the hydrolysis time is 2-5 min; the drying condition is that the temperature is 100 ℃ and 120 ℃ and the time is 10-30 min.
In the step (4), the coating method of the sulfonic acid resin solution is blade coating or slit extrusion coating.
In the step (4), the sulfonic acid resin solution is a perfluorosulfonic acid solution.
In the step (4), the drying condition is that the temperature is 80 ℃ and the time is 12-24 h; the thermal annealing condition is at 150 deg.C for 15-30 min.
The beneficial technical effects of the invention are embodied in the following aspects:
(1) the method of the invention combines dopamine hydrophilic modification technology with surface sol-gel technology to coat ultrathin ZrO on a micropore polymer framework2And (4) coating. The dopamine hydrophilic modification treatment aims to coat a hydrophilic polydopamine layer on the surface of the framework. In zirconium propanol solution, alkoxide molecules are combined with hydroxyl (-OH) and amino groups on the polydopamine layer on the surface of the diaphragm through chemical adsorption. The zirconium oxide (ZrO) deposited by chemical bonding2) The coating and the polymer skeleton have strong binding force, thereby solving the problem of loss of the free radical scavenger brought by the traditional doping technology (namely directly adding free radical scavenger particles or doping through ion exchange), and improving the chemical durability. Example (c): the invention is based on a layer of zirconium oxide (ZrO)2) Zirconia (ZrO) was still not detected after the modified PTFE coated enhanced proton exchange membrane was subjected to an OCV durability test for 63h2) The loss of the free radical eliminating agent is solved by the enhanced proton exchange membrane prepared by the method, and the chemical attenuation resistance of the enhanced proton exchange membrane is enhanced.
(2) The method of the invention prepares the ultrathin zirconium oxide (ZrO) on the surface of the microporous polymer framework2) The coating can improve the hydrophilicity and polarity of the surface of the hydrophobic polymer skeleton, improve the interface combination between the polymer skeleton and the sulfonic acid resin and promote the filling of the resin in polymer micropores.Thereby improving the mechanical durability of the composite reinforced membrane. Example (c): the invention is based on a single, double or triple layer of zirconium oxide (ZrO)2) The reinforced proton exchange membranes coated with the modified PTFE all show higher tensile strength than the unmodified reinforced membranes, and the mechanical properties of the reinforced proton exchange membranes based on the surface sol-gel modification are enhanced.
(3) The method of the invention introduces inorganic zirconium oxide (ZrO)2) Coating by means of zirconium oxide (ZrO)2) The natural properties of hydrophilicity, polarity and the like can enhance the water absorption of the composite membrane, thereby enhancing the proton conductivity and the fuel cell performance of the composite membrane, and particularly showing more obvious performance in a low humidity environment. Example (c): the invention is based on a layer of zirconium oxide (ZrO)2) The conductivity of the modified PTFE-coated enhanced proton exchange membrane at low humidity (80 ℃, 30% RH) is 11.24mS/cm, which is higher than that of the unmodified enhanced membrane (10.85 mScm)-1). The peak power of the power is 97mW/cm under the conditions of 80 ℃ and 20 percent RH2Much higher than the peak power of the unmodified reinforced membrane (34 mW/cm)2）。
Drawings
FIGS. 1 (a) and (b) respectively show the unmodified ePTFE microporous framework (comparative example) and the deposition of a layer of ZrO by the surface sol-gel method2High resolution scanning electron micrograph of the surface of the ePTFE microporous framework of (example 1).
FIGS. 2 (a) and (b) are based on an unmodified ePTFE microporous framework (comparative example) and a layer of ZrO deposited, respectively2High resolution scanning electron micrograph of cross section of composite film prepared from polymer backbone (example 1).
FIGS. 3 (a) and (b) respectively show the unmodified ePTFE microporous framework and the deposition of a layer of ZrO by the surface sol-gel method2Graph of the results of the hydrophilicity angle test of the ePTFE microporous framework of (example 1).
FIG. 4 is a graph showing the results of mechanical tensile tests of composite films prepared in comparative examples, examples 1, 2 and 3.
FIGS. 5 (a) and (b) are graphs showing the results of proton conductivity tests of the composite membranes prepared in comparative example, examples 1, 2 and 3 at 30% RH and 90% RH (80 ℃ C.), respectively.
FIGS. 6 (a) and (b) are graphs showing the results of battery performance tests of composite membranes prepared in comparative example, examples 1, 2, and 3 at 20% RH and 80% RH (80 ℃ C.), respectively.
Fig. 7 is a graph showing the results of OCV durability tests of the composite membranes manufactured in comparative example and example 1.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
In the following examples, materials and instruments used are commercially available unless otherwise specified.
Example 1
The embodiment relates to a reinforced composite proton exchange membrane based on a surface sol-gel modified polymer framework and a preparation method thereof, and the preparation method comprises the following steps:
(1) adding 0.394g of buffer triaminomethane hydrochloride into 250mL of deionized water to prepare a 0.157wt% buffer solution, and then adding 0.5g of dopamine hydrochloride into the buffer solution to prepare a 0.2wt% dopamine solution;
(2) soaking a Polytetrafluoroethylene (PTFE) microporous membrane (with the thickness of 10 micrometers and the porosity of 78%) with the area of 10cm multiplied by 10cm in the dopamine solution prepared in the step (a) for 1h, taking out, washing with deionized water for 5min, and drying at 60 ℃ for 12h to obtain a dopamine hydrophilic modified polymer skeleton;
(3) soaking the hydrophilic modified polymer skeleton prepared in the step (2) in a 120mM zirconium n-propoxide solution, taking out the hydrophilic modified polymer skeleton after 2min, cleaning the hydrophilic modified polymer skeleton with n-propanol, then soaking and hydrolyzing the hydrophilic modified polymer skeleton in deionized water for 2min, taking out the hydrophilic modified polymer skeleton and drying the hydrophilic modified polymer skeleton for 10min at 100 ℃; finally obtaining the zirconium oxide (ZrO) deposited with 1 layer2) A modified polymer backbone of the coating;
(4) the sulfonic acid resin solution was cast on a glass substrate using a doctor blade to a wet film thickness of 120 μm. The modified polymer backbone was then immediately overlaid on the sulfonic acid resin solution. After wetting of the modified polymer backbone, a second layer of sulfonic acid resin solution having a thickness of 100 μm was cast onto the membrane surface. Drying at 80 ℃ for 12h in order to evaporate the solvent and solidify the sulfonic acid resin; and (3) carrying out thermal annealing at 150 ℃ for 15 min. Finally obtaining the enhanced proton exchange membrane based on the surface modified polymer framework.
The physicochemical properties of the enhanced proton exchange membrane based on the surface modified polymer skeleton prepared in example 1 are shown in table 1, the number of zirconia deposition layers is 1, the thickness of the enhanced proton exchange membrane is 22.9 μm, the tensile strength is 19.6Mpa, and the water absorption rate is 12.04%.
Example 2
The embodiment relates to a reinforced composite proton exchange membrane based on a surface sol-gel modified polymer framework and a preparation method thereof, and the preparation method comprises the following steps:
(1) adding 0.394g of buffer triaminomethane hydrochloride into 250mL of deionized water to prepare a 0.157wt% buffer solution, and then adding 0.5g of dopamine hydrochloride into the buffer solution to prepare a 0.2wt% dopamine solution;
(2) soaking a Polytetrafluoroethylene (PTFE) microporous membrane (with the thickness of 10 micrometers and the porosity of 78%) with the area of 10cm multiplied by 10cm in the dopamine solution prepared in the step (a) for 1.5h, taking out, washing with deionized water for 15min, and drying at 70 ℃ for 18h to obtain a dopamine hydrophilic modified polymer skeleton;
(3) soaking the hydrophilic modified polymer skeleton prepared in the step (2) in a 120mM zirconium n-propoxide solution, taking out the hydrophilic modified polymer skeleton after 3min, cleaning the hydrophilic modified polymer skeleton with n-propanol, then soaking and hydrolyzing the hydrophilic modified polymer skeleton in deionized water for 3min, taking out the hydrophilic modified polymer skeleton and drying the hydrophilic modified polymer skeleton for 20min at 110 ℃; and repeating the process for 2 times, namely soaking the dried polymer skeleton in zirconium n-propoxide solution again, and then cleaning, hydrolyzing and drying. Finally obtaining the zirconium oxide (ZrO) deposited with 2 layers2) A modified polymer backbone of the coating;
(4) the sulfonic acid resin solution was cast on a glass substrate using a doctor blade to a wet film thickness of 120 μm. The modified polymer backbone was then immediately overlaid on the sulfonic acid resin solution. After wetting of the modified polymer backbone, a second layer of sulfonic acid resin solution having a thickness of 100 μm was cast onto the membrane surface. Drying at 80 ℃ for 18h in order to evaporate the solvent and solidify the sulfonic acid resin; and (3) carrying out thermal annealing at 150 ℃ for 20 min. Finally obtaining the enhanced proton exchange membrane based on the surface modified polymer framework.
The physicochemical properties of the enhanced proton exchange membrane based on the surface modified polymer skeleton prepared in example 2 are shown in table 1, where the number of zirconia deposition layers is 2, the thickness of the enhanced proton exchange membrane is 23.1 μm, the tensile strength is 18.0Mpa, and the water absorption rate is 13.74%.
Example 3
The embodiment relates to a reinforced composite proton exchange membrane based on a surface sol-gel modified polymer framework and a preparation method thereof, and the preparation method comprises the following steps:
(1) adding 0.394g of buffer triaminomethane hydrochloride into 250mL of deionized water to prepare a 0.157wt% buffer solution, and then adding 0.5g of dopamine hydrochloride into the buffer solution to prepare a 0.2wt% dopamine solution;
(2) soaking a Polytetrafluoroethylene (PTFE) microporous membrane (with the thickness of 10 micrometers and the porosity of 78%) with the area of 10cm multiplied by 10cm in the dopamine solution prepared in the step (1), taking out after soaking for 2 hours, washing with deionized water for 30min, and then drying at 80 ℃ for 24 hours to obtain a dopamine hydrophilic modified polymer skeleton;
(3) soaking the hydrophilic modified polymer skeleton prepared in the step (2) in a 120mM zirconium n-propoxide solution, taking out the hydrophilic modified polymer skeleton after 5min, cleaning the hydrophilic modified polymer skeleton with n-propanol, then soaking and hydrolyzing the hydrophilic modified polymer skeleton in deionized water for 5min, taking out the hydrophilic modified polymer skeleton and drying the hydrophilic modified polymer skeleton for 30min at 120 ℃; and repeating the process for 3 times, namely soaking the dried polymer skeleton in zirconium n-propoxide solution again, and then cleaning, hydrolyzing and drying. Finally obtaining the zirconium oxide (ZrO) deposited with 3 layers2) A modified polymer backbone of the coating;
(4) the sulfonic acid resin solution was cast on a glass substrate using a doctor blade to a wet film thickness of 120 μm. The modified polymer backbone was then immediately overlaid on the sulfonic acid resin solution. After wetting of the modified polymer backbone, a second layer of sulfonic acid resin solution having a thickness of 100 μm was cast onto the membrane surface. Drying for 24h at 80 ℃ in order to evaporate the solvent and solidify the sulfonic acid resin; and (3) carrying out thermal annealing at 150 ℃ for 30 min. Finally obtaining the enhanced proton exchange membrane based on the surface modified polymer framework.
The physicochemical properties of the enhanced proton exchange membrane based on the surface modified polymer skeleton prepared in example 3 are shown in table 1, the number of zirconia deposition layers is 3, the thickness of the enhanced proton exchange membrane is 23.5 μm, the tensile strength is 18.3Mpa, and the water absorption is 16.27%.
Example 4
The embodiment relates to a reinforced composite proton exchange membrane based on a surface sol-gel modified polymer framework and a preparation method thereof, and the preparation method comprises the following steps:
(1) adding 0.394g of buffer triaminomethane hydrochloride into 250mL of deionized water to prepare a 0.157wt% buffer solution, and then adding 0.5g of dopamine hydrochloride into the buffer solution to prepare a 0.2wt% dopamine solution;
(2) soaking a polyvinylidene fluoride (PVDF) electrostatic spinning microporous membrane (10 cm in thickness and 83% in porosity) with the area of 10cm multiplied by 10cm in the dopamine solution prepared in the step (1), taking out after soaking for 1h, washing for 5min by deionized water, and then drying for 12h at 60 ℃ to obtain a dopamine hydrophilic modified polymer skeleton;
(3) soaking the hydrophilic modified polymer skeleton prepared in the step (2) in a 120mM zirconium n-propoxide solution for 2min, taking out, cleaning with n-propanol, soaking in deionized water for hydrolysis for 2min, taking out, and drying at 100 ℃ for 10 min; finally obtaining the zirconium oxide (ZrO) deposited with 1 layer2) A modified polymer backbone of the coating;
(4) the sulfonic acid resin solution was cast on a glass substrate using a doctor blade to a wet film thickness of 120 μm. The modified polymer backbone was then immediately overlaid on the sulfonic acid resin solution. After wetting of the modified polymer backbone, a second layer of sulfonic acid resin solution having a thickness of 100 μm was cast onto the membrane surface. Drying at 80 ℃ for 12h in order to evaporate the solvent and solidify the sulfonic acid resin; and (3) carrying out thermal annealing at 150 ℃ for 15 min. Finally obtaining the enhanced composite proton exchange membrane based on the surface modified polymer framework.
The physicochemical properties of the enhanced proton exchange membrane based on the surface modified polymer skeleton prepared in example 4 are shown in table 1, the number of zirconia deposition layers is 1, the thickness of the enhanced proton exchange membrane is 21.6 μm, the tensile strength is 10.1Mpa, and the water absorption rate is 18.1%.
Comparative example
The sulfonic acid resin solution was cast on a glass substrate using a doctor blade to a wet film thickness of 120 μm. An unmodified ePTFE polymer backbone (10 cm x 10cm area of Polytetrafluoroethylene (PTFE) microporous membrane, 10 μm thick, 78% porosity) was then immediately overlaid on the sulfonic acid resin solution. After wetting of the ePTFE polymer backbone, a second layer of sulfonic acid resin solution with a thickness of 100 μm was cast onto the membrane surface. Drying at 80 ℃ for 12h in order to evaporate the solvent and solidify the sulfonic acid resin; and (3) carrying out thermal annealing at 150 ℃ for 30 min. Finally obtaining the reinforced composite proton exchange membrane based on the unmodified ePTFE microporous framework.
The physicochemical properties of the enhanced proton exchange membrane based on the unmodified polymer skeleton prepared in the comparative example are shown in table 1, the enhanced proton exchange membrane has a thickness of 19.85 μm, a tensile strength of 17.0Mpa and a water absorption of 6.6%.
Performance testing of examples and comparative examples
The hydrophilicity of the modified skeleton was confirmed by testing the water contact angle of each modified polymer skeleton by a contact angle analyzer (DSA 100). The mechanical properties of each reinforced composite membrane were analyzed using a dynamic mechanical analyzer (CMT-4104). The test sample size is 40mm multiplied by 10mm, and the test speed is 20mm min-1. Proton conductivity at 30% and 90% RH based on modified ePTFE backbone reinforced membranes was tested using an electrochemical workstation (ENERGYLAB XM). The activation area of the assembled single cell was 10cm2The battery temperature was 80 ℃. Fuel cell performance was tested at 20% and 80% RH. To evaluate the chemical durability of the modified reinforced film, an OCV durability test was performed.
FIG. 1 (a) and FIG. 1 (b) are respectively an unmodified ePTFE microporous framework and a layer of ZrO deposited by a surface sol-gel process2Comparison of the surface topography of the ePTFE microporous framework of example 1, it can be seen that a layer of ZrO was applied2ePTFE porous skeletonThere was no significant clogging.
FIG. 2 (a) and FIG. 2 (b) are based on an unmodified ePTFE microporous framework (comparative example) and a layer of ZrO deposited, respectively2The cross-sectional morphology of the enhanced proton exchange membrane prepared from the polymer framework of example 1 shows that the prepared enhanced proton exchange membrane has a relatively uniform thickness.
FIG. 3 (a) and FIG. 3 (b) are respectively an unmodified ePTFE microporous framework and a layer of ZrO deposited by surface sol-gel method2Results of the hydrophilic angle test of the ePTFE microporous framework of (example 1). Thus, coating with ZrO2The hydrophilicity of the ePTFE backbone is then significantly increased.
FIG. 4 shows the results of mechanical tensile testing of the reinforced proton exchange membranes prepared in comparative examples, examples 1, 2, and 3. It can be seen that the coating is based on ZrO2The reinforced membrane of the modified ePTFE framework is mechanically stronger.
Fig. 5 (a) and fig. 5 (b) show the proton conductivity test results of the enhanced proton exchange membranes prepared in comparative example, examples 1, 2, and 3 at 30% RH and 90% RH (80 ℃). It can be seen that the zirconium-coated modified reinforced film or the two zirconium-coated modified reinforced films both have higher electrical conductivity at high and low humidity than the comparative examples.
FIG. 6 (a) and FIG. 6 (b) show the cell performance test results of the enhanced proton exchange membranes prepared in the comparative examples, examples 1, 2, and 3 at 20% RH and 80% RH (80 deg.C), respectively. Thus, coating with ZrO2And then, the performance of the fuel cell of the enhanced proton exchange membrane is improved, and is particularly obvious under the condition of low humidity.
Figure 7 is a comparison of OCV durability for the reinforced proton exchange membranes prepared in comparative example and example 1. The results show that the coating with ZrO2Thereafter, the enhanced proton exchange membrane has a higher OCV and a smaller OCV decay rate.
The composition and properties of the reinforced films prepared in the examples and comparative examples are shown in table 1.
TABLE 1
| Numbering | Microporous polymerization Skeleton of article | Zirconium oxide Deposit layer Number of | Enhanced proton Exchange membrane thickness （μm） | Enhanced proton exchange Tensile strength of film change （Mpa） | Enhanced proton Exchange membrane water absorption Percentage (%) | Framework Hydrophilic Property of (2) | Enhanced quality Proton exchange membrane Electrical conductivity of | Enhanced proton Exchange membrane machine Performance of | Fuel Battery with a battery cell Performance of | OCV Durable Property of (2) |
| Practice of Example 1 | Polytetrafluoroethylene
|
1 | 22.9 | 19.6 | 12.04 | Superior food | Superior in quality | Superior in quality | Superior in quality | Superior food |
| Practice of Example 2 | Polytetrafluoroethylene
|
2 | 23.1 | 18.0 | 13.74 | Superior food | Superior food | Superior food | Superior food | Superior food |
| Practice of Example 3 | Polytetrafluoroethylene Microporous olefin membrane | 3 | 23.5 | 18.3 | 16.27 | Superior food | Good wine | Superior food | Good wine | Superior food |
| Practice of Example 4 | Polyvinylidene fluoride
Alkene electrostatic spinning
|
1 | 21.6 | 10.1 | 18.1 | Superior food | Superior in quality | Superior in quality | Superior in quality | Superior food |
| Comparison of Example (b) | Polytetrafluoroethylene
|
0 | 19.85 | 17.0 | 6.6 | Difference (D) | Good wine | Difference (D) | Difference (D) | Difference (D) |
In conclusion, the preparation method has simple operation steps, and the prepared ZrO prepared by the method has the advantages of2The coating thickness is thin and the size is controllable. The enhanced proton exchange membrane prepared based on the modified framework has the characteristics of high proton conductivity, high mechanical strength, excellent battery performance and excellent chemical durability. Has application potential in prolonging the service life of the proton exchange membrane fuel cell.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the application can be combined with one another arbitrarily without conflict.
Claims (7)
1. A preparation method of an enhanced proton exchange membrane based on a surface modified polymer skeleton is characterized by comprising the following operation steps:
(1) adding buffer triaminomethane hydrochloride into deionized water, and then adding dopamine hydrochloride to obtain 0.2wt% dopamine solution;
(2) soaking the polymer porous reinforced skeleton in the dopamine solution, taking out, washing with deionized water, and drying to obtain a dopamine hydrophilic modified polymer reinforced skeleton;
(3) soaking the dopamine hydrophilic modified polymer skeleton in 120mM zirconium n-propoxide Zr (OnPr)4Taking out the solution, washing the solution with normal propyl alcohol, hydrolyzing the solution in deionized water, and drying the solution to obtain zirconium oxide (ZrO)2) A coating-modified polymer-reinforced backbone;
(4) coating a sulfonic acid resin solution with the concentration of 20wt% on two side surfaces of the polymer reinforced skeleton modified by the zirconia coating, drying, thermally annealing, and repeating the operation of the step (3) for more than one time; obtaining a reinforced proton exchange membrane based on a surface modified polymer skeleton and provided with 1-3 coating layers;
the tensile strength of the enhanced proton exchange membrane is 10-20Mpa, and the water absorption rate is 12-16.5%; no loss of zirconia was monitored after going through the OCV durability test of 63 h.
2. The preparation method of the enhanced composite proton exchange membrane based on the surface modified polymer skeleton of claim 1 is characterized in that: in the step (1), the polymer porous reinforced framework is one of a polytetrafluoroethylene microporous membrane and a polyvinylidene fluoride electrostatic spinning microporous membrane; the film thickness is 5-20 μm, and the porosity is more than 50%.
3. The preparation method of the enhanced proton exchange membrane based on the surface modified polymer skeleton of claim 1, which is characterized in that: in the step (2), the soaking time in the dopamine solution is 1-2 h; the cleaning time is 5-30 min; the drying condition is that the temperature is 60-80 ℃ and the time is 12-24 h.
4. The preparation method of the enhanced proton exchange membrane based on the surface modified polymer skeleton of claim 1, which is characterized in that: in the step (3), the soaking time in the zirconium n-propoxide solution is 1-5 min; the cleaning time is 2-5 min; the hydrolysis time is 2-5 min; the drying condition is that the temperature is 100 ℃ and 120 ℃ and the time is 10-30 min.
5. The preparation method of the enhanced proton exchange membrane based on the surface modified polymer skeleton of claim 1, which is characterized in that: in the step (4), the coating method of the sulfonic acid resin solution is blade coating or slit extrusion coating.
6. The preparation method of the enhanced composite proton exchange membrane based on the surface modified polymer skeleton of claim 1 is characterized in that: in the step (4), the sulfonic acid resin solution is a perfluorosulfonic acid solution.
7. The preparation method of the enhanced proton exchange membrane based on the surface modified polymer skeleton of claim 1, which is characterized in that: in the step (4), the drying condition is that the temperature is 80 ℃ and the time is 12-24 h; the thermal annealing condition is at 150 deg.C for 15-30 min.
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| CN117117270A (en) * | 2023-10-23 | 2023-11-24 | 国家电投集团氢能科技发展有限公司 | Modified porous membrane, ion exchange membrane, preparation method and application of modified porous membrane and ion exchange membrane, and fuel cell |
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