CN115000437A - Enhanced proton exchange membrane doped with free radical scavenger and preparation method thereof - Google Patents
Enhanced proton exchange membrane doped with free radical scavenger and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a reinforced proton exchange membrane doped with a free radical scavenger and a preparation method thereof. The method specifically comprises the following steps: preparing a perfluorosulfonic acid resin solution doped with a free radical scavenger; then coating a first layer of perfluorinated sulfonic acid resin solution on the substrate, and flatly laying the polymer film on the first layer of perfluorinated sulfonic acid resin solution; then coating a second layer of perfluorinated sulfonic acid resin solution on the surface of the polymer film, and flatly laying the second layer of polymer film on the coated perfluorinated sulfonic acid resin solution; and finally coating a layer of perfluorinated sulfonic acid resin solution. And obtaining the double-layer enhanced proton exchange membrane doped with the free radical scavenger after heat treatment. The method has simple operation steps, and compared with the mainstream single-layer reinforced membrane, the double-layer reinforced process doped with the free radical scavenger further enhances the mechanical durability of the perfluorosulfonic acid membrane, and simultaneously, the introduced free radical scavenger also further enhances the chemical durability of the double-layer reinforced membrane.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a reinforced proton exchange membrane doped with a free radical scavenger and a preparation method thereof.
Background
The proton exchange membrane plays the roles of transferring protons, insulating electrons and isolating reaction gas. Its lifetime directly determines the lifetime of a pem fuel cell. Perfluorosulfonic acid proton exchange membranes (PFSA membranes), such as Nafion membranes, are widely used due to their good proton conductivity. However, in actual conditions, such membranes face severe mechanical and chemical attenuation. Under the dry-wet alternating working condition, the membrane repeatedly swells and shrinks, and the fatigue stress of the membrane body is generated. The accumulated fatigue stress will cause mechanical attenuation of the membrane body (e.g. cracks, wrinkles, pinholes and tears). Meanwhile, in long-term operation, PFSA membranes are also subject to attack by free radicals. Finally, molecular chains of the membrane are continuously lost, so that the membrane body is thinned, the conductivity is reduced, and the gas barrier capability is reduced. Therefore, the development of proton exchange membranes with high mechanical and chemical durability is urgently needed.
In order to improve the mechanical durability of PFSA films, one of the mainstream methods at present is to introduce a microporous expanded polytetrafluoroethylene MEMBRANE (e-PTFE MEMBRANE) as a reinforcement in PFSA films [ ULTRA-THIN INTEGRAL COMPOSITE MEMBRANE, US Patent Number:5,547,551 ]. The introduction of the reinforcement can inhibit the excessive swelling of the membrane body, improve the dimensional stability of the membrane body, improve the mechanical performance of the membrane body, and reduce the hydrogen permeation, thereby slowing down the mechanical attenuation.
However, existing reinforced proton exchange membranes employ a layer of e-PTFE membrane as the reinforcing layer. Due to the limited constraint force of the reinforced layer, the membrane body still has a larger swelling ratio and the mechanical strength is improved in a limited way; and the problem of chemical decay still remains. Therefore, to meet higher lifetime requirements, further improvements in the mechanical and chemical durability of PFSA membranes are needed.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a reinforced proton exchange membrane doped with a free radical scavenger and a preparation method thereof. The invention introduces two layers of ePTFE membranes as reinforced frameworks, and simultaneously dopes a radical scavenger (CeO) in perfluorinated sulfonic acid resin 2 ) To prepare doped CeO 2 The bilayer reinforced membrane of (1). Doping with CeO, in contrast to a single-layer ePTFE-reinforced membrane 2 The double-layer reinforced film has obviously improved mechanical durability and chemical durability.
The technical scheme provided by the invention is as follows:
a preparation method of a double-layer enhanced proton exchange membrane doped with a free radical scavenger comprises the following steps:
(1) doping a free radical scavenger into a perfluorosulfonic acid resin solution to prepare a perfluorosulfonic acid resin solution doped with the free radical scavenger;
(2) coating a first layer of perfluorinated sulfonic acid resin solution on a substrate, and flatly laying a polymer film on the first layer of perfluorinated sulfonic acid resin solution;
(3) coating a second layer of perfluorinated sulfonic acid resin solution on the surface of the polymer film, and flatly laying the second layer of polymer film on the second layer of perfluorinated sulfonic acid resin solution;
(4) coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film;
(5) and obtaining the double-layer enhanced proton exchange membrane doped with the free radical scavenger after heat treatment.
In the step (1), the free radical scavenger is nano cerium oxide CeO 2 The perfluorinated sulfonic acid resin solution is 5-20 wt% of perfluorinated sulfonic acid resin solution.
CeO 2 The amount of (B) is 0.5-2 wt% of the mass of the perfluorosulfonic acid polymer. Wherein, if the addition amount is too high, the conductivity is reduced, and the performance of the battery is reduced; when the amount of the additive is not sufficient, the effective anti-free radical effect cannot be achieved, and the improvement of the chemical durability is limited.
The polymer film is a polytetrafluoroethylene microporous film, the thickness of the polytetrafluoroethylene microporous film is 5-20 mu m, and the porosity is 50-90%.
The preparation is carried out by mechanical stirring and/or ultrasonic stirring. The mechanical stirring time is 0.5-6h, and the ultrasonic stirring time is 10-60 min.
The mechanical stirring is magnetic stirring or blade stirring, and the rotating speed is set to 400-600 rpm.
In the step (2), the substrate is one of a glass plate and a polyethylene terephthalate (PET) film.
The conditions of the heat treatment are as follows: firstly, the temperature is 80-100 ℃, and the time is 0.5-24 h; the second step, the temperature is 120-150 ℃ and the time is 10-120 min.
The heat treatment may be drying.
In the steps (2), (3) and (4), the solution coating method is a blade coating method or a slit coating method.
The double-layer enhanced proton exchange membrane doped with the free radical scavenger prepared by the preparation method also belongs to the protection scope of the invention.
The application of the double-layer enhanced proton exchange membrane doped with the free radical scavenger in the field of fuel cell electrolyte membranes belongs to the protection scope of the invention.
The beneficial technical effects of the invention are embodied in the following aspects:
(1) the present invention improves both the mechanical and chemical durability of PFSA membranes compared to the mainstream single-layer ePTFE reinforcement technology. The introduction of the double-layer ePTFE reinforced framework further improves the mechanical property of the PFSA membrane, and the double-layer reinforced framework enables the PFSA membrane body to have smaller swelling ratio due to the size constraint of one more layer of ePTFE framework, so that smaller hydrogen permeation is shown, and the mechanical durability of the membrane is improved;
(2) at the same time, CeO 2 The introduction of the free radical scavenger effectively reduces the concentration of free radicals in the membrane, thereby reducing the attenuation of Open Circuit Voltage (OCV) and improving the chemical durability of the membrane.
Drawings
Fig. 1 (a): SEM image of a single layer ePTFE reinforced membrane (comparative example 1); fig. 1 (b): CeO-free 2 SEM images of a doped double layer ePTFE reinforced membrane (comparative example 2); fig. 1 (c): 0.5 wt% CeO 2 SEM image of a doped double layer e-PTFE reinforced membrane (example 1); fig. 1 (d): 1 wt% CeO 2 SEM image of a doped dual layer e-PTFE reinforced membrane (example 2); fig. 1 (e): 2 wt% CeO 2 SEM image of a doped double layer e-PTFE reinforced membrane (example 3); fig. 1 (f): 2 wt% CeO 2 Graph of EDS elemental scan results for a doped dual layer e-PTFE reinforced membrane (example 3).
FIG. 2 is a single layer ePTFE reinforced membrane (comparative example 1) without CeO 2 Doped double layer ePTFE reinforced membrane (comparative example 2), 0.5 wt% CeO 2 Doped double layer e-PTFE reinforced Membrane (example 1), 1 wt% CeO 2 Doped bilayer e-PTFE reinforced film (example 2), 2 wt% CeO 2 Doped dual layer e-PTFE reinforcementMechanical property profile of the membrane (example 3).
FIG. 3 is a single layer ePTFE reinforced membrane (comparative example 1) without CeO 2 Doped double layer ePTFE reinforced membrane (comparative example 2), 0.5 wt% CeO 2 Doped bilayer e-PTFE reinforced film (example 1), 1 wt% CeO 2 Doped bilayer e-PTFE reinforced film (example 2), 2 wt% CeO 2 Plot of hydrogen permeation current (LSV) versus doped dual layer e-PTFE reinforced membrane (example 3).
FIG. 4 is a single layer ePTFE reinforced membrane (comparative example 1) without CeO 2 Doped double layer ePTFE reinforced membrane (comparative example 2), 0.5 wt% CeO 2 The OCV decay profile of the doped dual layer e-PTFE reinforced membrane (example 1) is compared to the performance before and after the fuel cell OCV durability test.
FIG. 5 is a single layer ePTFE reinforced membrane (comparative example 1) without CeO 2 Doped double layer ePTFE reinforced membrane (comparative example 2), 0.5 wt% CeO 2 Doped dual layer e-PTFE reinforced membranes (example 1) comparison of hydrogen permeation current (LSV) before and after OCV durability test.
Detailed Description
The present invention will be described in detail with reference to specific 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 obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
In the following examples, materials and instruments used are commercially available without specific reference.
Example 1
The embodiment relates to a double-layer enhanced proton exchange membrane doped with a free radical scavenger and a preparation method thereof, wherein the double-layer enhanced proton exchange membrane is coated by a scraper and comprises the following steps:
(1) according to free radical scavengers (CeO) 2 ) 0.5 wt% of PFSA polymer, CeO 2 Mixing with PFSA solution (20 wt% perfluorosulfonic acid resin solution), stirring by magneton mechanical stirring at 500rpm for 3 hr, and ultrasonic stirring for 15min to obtain the final product doped with PFSAA perfluorosulfonic acid resin solution of a radical scavenger;
(2) coating a first layer of perfluorinated sulfonic acid resin solution on a glass substrate, wherein the gap of a scraper is 80 mu m, and flatly laying an ePTFE (ePTFE film with the thickness of 10 mu m and the porosity of 78%) on the first layer of perfluorinated sulfonic acid resin solution;
(3) coating a second layer of perfluorosulfonic acid resin solution on the surface of the polymer film, wherein the gap of a scraper is 80 mu m, and laying a second layer of ePTFE film (the thickness is 10 mu m, and the porosity is 78%) on the coated perfluorosulfonic acid resin solution;
(4) and coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film, wherein the gap of a scraper is 50 mu m.
(5) The coated film is then placed in an oven and subjected to a heat treatment under the following conditions: the first step, at 80 ℃, the time is 12 h; the second step, 150 ℃, the time is 30 min. Finally obtaining the CeO doped with 0.5 percent 2 The double-layer enhanced proton exchange membrane.
Example 2
The embodiment relates to a double-layer enhanced proton exchange membrane doped with a free radical scavenger and a preparation method thereof, wherein the double-layer enhanced proton exchange membrane is coated by a scraper and comprises the following steps:
(1) as radical scavengers (CeO) 2 ) 1% of the PFSA polymer mass is added with CeO 2 Mixing with PFSA solution (20 wt% perfluorosulfonic acid resin solution), and stirring by magneton mechanical stirring at 500rpm for 3h, and ultrasonically stirring for 15min to obtain perfluorosulfonic acid resin solution doped with free radical scavenger;
(2) coating a first layer of perfluorinated sulfonic acid resin solution on a glass substrate, wherein the gap of a scraper is 80 mu m, and flatly laying an ePTFE (ePTFE film with the thickness of 10 mu m and the porosity of 78%) on the first layer of perfluorinated sulfonic acid resin solution;
(3) coating a second layer of perfluorinated sulfonic acid resin solution on the surface of the polymer film, wherein the gap of a scraper is 80 mu m, and flatly laying a second layer of ePTFE film (the thickness is 10 mu m, and the porosity is 78%) on the coated perfluorinated sulfonic acid resin solution;
(4) and coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film, wherein the gap of a scraper is 50 mu m.
(5) The coated film is then placed in an oven and subjected to a heat treatment under the following conditions: the first step, 80 ℃ and 12 hours; the second step, 150 ℃, the time is 30 min. Finally obtaining the CeO doped with 1 percent 2 The double-layer enhanced proton exchange membrane.
Example 3
The embodiment relates to a double-layer enhanced proton exchange membrane doped with a free radical scavenger and a preparation method thereof, wherein the double-layer enhanced proton exchange membrane is coated by a scraper and comprises the following steps:
(1) according to free radical scavengers (CeO) 2 ) Accounting for 2 percent of the mass of the PFSA polymer, adding CeO 2 Mixing with PFSA solution (20 wt% perfluorosulfonic acid resin solution), and stirring by magneton mechanical stirring at 500rpm for 3h, and ultrasonically stirring for 15min to obtain perfluorosulfonic acid resin solution doped with free radical scavenger;
(2) coating a first layer of perfluorinated sulfonic acid resin solution on a glass substrate, wherein the gap of a scraper is 80 mu m, and flatly laying an ePTFE (ePTFE film with the thickness of 10 mu m and the porosity of 78%) on the first layer of perfluorinated sulfonic acid resin solution;
(3) coating a second layer of perfluorinated sulfonic acid resin solution on the surface of the polymer film, wherein the gap of a scraper is 80 mu m, and flatly laying a second layer of ePTFE film (the thickness is 10 mu m, and the porosity is 78%) on the coated perfluorinated sulfonic acid resin solution;
(4) and coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film, wherein the gap of a scraper is 50 mu m.
(5) The coated film is then placed in an oven and subjected to a heat treatment under the following conditions: the first step, 80 ℃ and 12 hours; the second step, 150 ℃, the time is 30 min. Finally obtaining the CeO doped with 2 percent 2 The double-layer enhanced proton exchange membrane.
Example 4
The embodiment relates to a double-layer enhanced proton exchange membrane doped with a free radical scavenger and a preparation method thereof, wherein the double-layer enhanced proton exchange membrane is coated by a scraper and comprises the following steps:
(1) according to free radical scavengers (CeO) 2 ) Accounts for PF1% of SA Polymer by weight CeO 2 Mixing with PFSA solution (20 wt% perfluorosulfonic acid resin solution), mechanically stirring with a blade at 500rpm for 6h, and ultrasonically stirring for 60min to obtain perfluorosulfonic acid resin solution doped with free radical scavenger;
(2) coating a first layer of perfluorinated sulfonic acid resin solution on a glass substrate, wherein the gap of a scraper is 80 mu m, and flatly laying an ePTFE (ePTFE) film (with the thickness of 20 mu m) on the first layer of perfluorinated sulfonic acid resin solution;
(3) coating a second layer of perfluorosulfonic acid resin solution on the surface of the polymer film, wherein the gap of a scraper is 80 mu m, and laying a second layer of ePTFE film (the thickness is 10 mu m, and the porosity is 78%) on the coated perfluorosulfonic acid resin solution;
(4) and coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film, wherein the gap of a scraper is 50 mu m.
(5) The coated film is then placed in an oven and subjected to a heat treatment under the following conditions: the first step, the temperature is 80 ℃, and the time is 24 hours; the second step, 120 ℃, the time is 120 min. Finally obtaining the CeO doped with 1 percent 2 The double-layer enhanced proton exchange membrane.
Example 5
The embodiment relates to a double-layer enhanced proton exchange membrane doped with a free radical scavenger and a preparation method thereof, which adopt slit coating and comprise the following steps:
(1) according to free radical scavengers (CeO) 2 ) 1% of the PFSA polymer by mass of CeO 2 Mixing with PFSA solution (5 wt% perfluorosulfonic acid resin solution), mechanically stirring with a blade at 500rpm for 0.5h, and ultrasonically stirring for 10min to obtain perfluorosulfonic acid resin solution doped with free radical scavenger;
(2) coating a first layer of perfluorosulfonic acid resin solution on a glass substrate, wherein the gap of a slit is 150 mu m, and flatly laying an ePTFE (ePTFE) film (with the thickness of 5 mu m) on the first layer of perfluorosulfonic acid resin solution;
(3) coating a second layer of perfluorosulfonic acid resin solution on the surface of the polymer film, wherein the gap of a slit is 150 mu m, and laying a second layer of ePTFE film (the thickness is 10 mu m, and the porosity is 78%) flat on the coated perfluorosulfonic acid resin solution;
(4) and coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film, wherein the gap of the slit is 100 mu m.
(5) The coated film is then placed in an oven and subjected to a heat treatment under the following conditions: the first step, 100 ℃ and 0.5 h; the second step, 150 ℃, the time is 10 min. Finally obtaining the CeO doped with 1 percent 2 The double-layer enhanced proton exchange membrane.
Comparative example 1
In this comparative example, the preparation method of the single-layer ePTFE matrix reinforced proton exchange membrane comprises the following steps:
the 20 wt% perfluorosulfonic acid resin solution was cast onto a glass substrate using a doctor blade with a blade gap of 120 μm. An ePTFE film (10 μm thick, 78% porosity) was then immediately overlaid on the perfluorosulfonic acid resin solution. After the ePTFE backbone was wetted, a second layer of perfluorosulfonic acid resin solution was cast onto the membrane surface with a 100 μm blade gap. The coated film is then placed in an oven and subjected to a heat treatment under the following conditions: the first step, 80 ℃ and 12 hours; and the second step, at 150 deg.C for 30 min. Finally obtaining the composite proton exchange membrane based on the single-layer ePTFE reinforced framework.
Comparative example 2
In this comparative example, doctor blade coating was used without CeO 2 The preparation method of the doped double-layer ePTFE matrix enhanced proton exchange membrane comprises the following steps:
(1) a perfluorosulfonic acid resin solution (20 wt% perfluorosulfonic acid resin solution) is adopted;
(2) a first layer of perfluorosulfonic acid resin solution was applied to the glass substrate with a doctor blade gap of 80 μm. An ePTFE film (with the thickness of 10 mu m and the porosity of 78 percent) is flatly laid on the first layer of the perfluorinated sulfonic acid resin solution;
(3) and coating a second layer of perfluorinated sulfonic acid resin solution on the surface of the polymer film, wherein the gap of a scraper is 80 mu m. A second layer of ePTFE film (10 μm thick, 78% porosity) was laid flat on the coated perfluorosulfonic acid resin solution;
(4) and coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film, wherein the gap of a scraper is 50 mu m.
(5) The coated film is then placed in an oven and subjected to a heat treatment under the following conditions: the first step, at 80 ℃, the time is 12 h; the second step, 150 ℃, the time is 30 min. Finally obtaining CeO-free 2 Doped double-layer ePTFE matrix reinforced proton exchange membrane.
Comparative example 3
The comparative example relates to a double-layer enhanced proton exchange membrane doped with a free radical scavenger and a preparation method thereof, and the preparation method adopts scraper coating and comprises the following steps:
(1) according to free radical scavengers (CeO) 2 ) 5% of the PFSA polymer mass, CeO 2 Mixing with PFSA solution (20 wt% perfluorosulfonic acid resin solution), and stirring by magneton mechanical stirring at 500rpm for 3h, and ultrasonically stirring for 15min to obtain perfluorosulfonic acid resin solution doped with free radical scavenger;
(2) a first layer of perfluorosulfonic acid resin solution was applied to the glass substrate with a doctor blade gap of 80 μm. An ePTFE film (with the thickness of 10 mu m and the porosity of 78 percent) is flatly laid on the first layer of the perfluorinated sulfonic acid resin solution;
(3) and coating a second layer of perfluorinated sulfonic acid resin solution on the surface of the polymer film, wherein the gap of a scraper is 80 mu m. A second layer of ePTFE film (10 μm thick, 78% porosity) was laid flat on the coated perfluorosulfonic acid resin solution;
(4) and coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film, wherein the gap of a scraper is 50 mu m.
(5) The coated film is then placed in an oven and subjected to a heat treatment under the following conditions: the first step, 80 ℃ and 12 hours; the second step, 150 ℃, the time is 30 min. Finally obtaining the CeO doped with 5 percent 2 The double-layer enhanced proton exchange membrane.
Comparative example 4
The comparative example relates to a double-layer enhanced proton exchange membrane doped with a free radical scavenger and a preparation method thereof, and the preparation method adopts scraper coating and comprises the following steps:
(1) according to the antioxidant (ZrO) 2 ) ZrO 0.5% by mass based on the PFSA polymer 2 Mixing with PFSA solution (20 wt% perfluorosulfonic acid resin solution), and stirring by magneton mechanical stirring at 500rpm for 3h, and ultrasonically stirring for 15min to obtain perfluorosulfonic acid resin solution doped with free radical scavenger;
(2) a first layer of perfluorosulfonic acid resin solution was applied to the glass substrate with a doctor blade gap of 80 μm. An ePTFE film (with the thickness of 10 mu m and the porosity of 78 percent) is flatly laid on the first layer of the perfluorinated sulfonic acid resin solution;
(3) and coating a second layer of perfluorinated sulfonic acid resin solution on the surface of the polymer film, wherein the gap of a scraper is 80 mu m. A second layer of ePTFE film (10 μm thick, 78% porosity) was laid flat on the coated perfluorosulfonic acid resin solution;
(4) and coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film, wherein the gap of a scraper is 50 mu m.
(5) The coated film is then placed in an oven and subjected to a heat treatment under the following conditions: the first step, 80 ℃ and 12 hours; the second step, 150 ℃, the time is 30 min. Finally obtaining the product doped with 0.5 percent of ZrO 2 The double-layer enhanced proton exchange membrane.
Comparative example 5
The comparative example relates to a double-layer enhanced proton exchange membrane doped with a free radical scavenger and a preparation method thereof, and the preparation method adopts scraper coating and comprises the following steps:
(1) according to oxide (Al) 2 O 3 ) 0.5% by mass of PFSA polymer, adding Al 2 O 3 Mixing with PFSA solution (20 wt% perfluorosulfonic acid resin solution), and stirring by magneton mechanical stirring at 500rpm for 3h, and ultrasonically stirring for 15min to obtain perfluorosulfonic acid resin solution doped with free radical scavenger;
(2) a first layer of perfluorosulfonic acid resin solution was applied to the glass substrate with a doctor blade gap of 80 μm. An ePTFE film (with the thickness of 10 mu m and the porosity of 78 percent) is flatly laid on the first layer of the perfluorinated sulfonic acid resin solution;
(3) and coating a second layer of perfluorinated sulfonic acid resin solution on the surface of the polymer film, wherein the gap of a scraper is 80 mu m. A second layer of ePTFE film (10 μm thick, 78% porosity) was laid flat on the coated perfluorosulfonic acid resin solution;
(4) and coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film, wherein the gap of a scraper is 50 mu m.
(5) The coated film is then placed in an oven and subjected to a heat treatment under the following conditions: the first step, 80 ℃ and 12 hours; the second step, 150 ℃, the time is 30 min. Finally obtaining the Al doped with 0.5 percent 2 O 3 The double-layer enhanced proton exchange membrane.
Comparative example 6
The comparative example relates to a double-layer enhanced proton exchange membrane doped with a free radical scavenger and a preparation method thereof, and the preparation method adopts scraper coating and comprises the following steps:
(1) according to oxide (SiO) 2 ) Taking up 0.5 percent of the mass of the PFSA polymer, adding SiO 2 Mixing with PFSA solution (20 wt% perfluorosulfonic acid resin solution), and stirring by magneton mechanical stirring at 500rpm for 3h, and ultrasonically stirring for 15min to obtain perfluorosulfonic acid resin solution doped with free radical scavenger;
(2) a first layer of perfluorosulfonic acid resin solution was applied to the glass substrate with a doctor blade gap of 80 μm. An ePTFE film (with the thickness of 10 mu m and the porosity of 78 percent) is flatly laid on the first layer of the perfluorinated sulfonic acid resin solution;
(3) and coating a second layer of perfluorinated sulfonic acid resin solution on the surface of the polymer film, wherein the gap of a scraper is 80 mu m. A second layer of ePTFE film (10 μm thick, 78% porosity) was laid flat on the coated perfluorosulfonic acid resin solution;
(4) and coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film, wherein the gap of a scraper is 50 mu m.
(5) The coated film is then placed in an oven and subjected to a heat treatment under the following conditions: the first step, 80 ℃ and 12 hours; the second step, 150 ℃, the time is 30 min. Finally obtaining the product doped with 0.5 percent SiO 2 The double-layer enhanced proton exchange membrane.
Performance testing of examples and comparative examples
The mechanical properties of each reinforced composite membrane were analyzed using a dynamic mechanical analyzer (Q800). The test sample size is 30mm multiplied by 3mm, and the test speed is 10mm min -1 . The activation area of the assembled single cell was 10cm 2 The temperature of the fuel cell is 80 ℃, the back pressure is 0.1MPa, and the fuel gas is hydrogen and air. Fuel cell performance at 100% RH was tested. To evaluate the chemical durability of the modified reinforced membrane, an OCV durability test was performed to compare the change in the hydrogen permeation current before and after the durability.
FIG. 1 shows a single layer ePTFE reinforced membrane (comparative example 1), CeO free 2 Doped double layer ePTFE reinforced membrane (comparative example 2), 0.5 wt% CeO 2 Doped bilayer e-PTFE reinforced film (example 1), 1 wt% CeO 2 Doped bilayer e-PTFE reinforced film (example 2), 2 wt% CeO 2 The cross-sectional morphology of the doped bilayer e-PTFE reinforced membrane (example 3). The cross-sectional morphology of a single-layer ePTFE reinforced membrane (comparative example 1) is shown in fig. 1(a), and after introducing one layer of ePTFE reinforced membrane in the middle of PFSA polymer, a typical three-layer structure is presented. CeO-free 2 The cross-section of a doped double-layer ePTFE reinforced membrane (comparative example 2), as shown in fig. 1(b), has a clear five-layer structure, i.e., two layers of ePTFE and three layers of PFSA polymer are alternately arranged. 0.5 wt% CeO 2 Example 1), 0.5 wt% CeO 2 Example 2) 0.5 wt% CeO 2 Example 3 a doped double layer e-PTFE reinforced membrane, as shown in fig. 1(c), (d), (e), also has a clear five-layer structure. All films had a uniform thickness, with an average film thickness of around 19 μm. FIG. 1(f) is 2 wt% CeO 2 EDS elemental scan of a doped bilayer e-PTFE reinforced membrane (example 3) confirmed doped CeO 2 The nanoparticles are uniformly distributed in the PFSA membrane body.
FIG. 2 is a single layer ePTFE reinforced membrane (comparative example 1) without CeO 2 Doped double layer ePTFE reinforced membrane (comparative example 2), 0.5 wt% CeO 2 Doped bilayer e-PTFE reinforced film (example 1), 1 wt% CeO 2 Doped bilayer e-PTFE reinforced film (example 2), 2 wt% CeO 2 Mechanical performance plot of the doped dual layer e-PTFE reinforced membrane (example 3). The introduction of double-layer ePTFE can be seen to a large extentImproves the mechanical properties of PFSA films, and CeO 2 The tensile strength of the doped dual-layer e-PTFE reinforced membranes (examples 1, 2, 3) was higher than that of CeO-free membranes 2 A double layer e-PTFE reinforced membrane was doped (comparative example 2).
FIG. 3 is a single layer ePTFE reinforced membrane (comparative example 1) without CeO 2 Doped double layer ePTFE reinforced membrane (comparative example 2), 0.5 wt% CeO 2 Doped bilayer e-PTFE reinforced film (example 1), 1 wt% CeO 2 Doped bilayer e-PTFE reinforced film (example 2), 2 wt% CeO 2 Plot of the hydrogen permeation current of a doped dual layer e-PTFE reinforced membrane (example 3). The introduction of double-layer ePTFE can be seen, and the hydrogen resistance of the PFSA membrane is improved. This is due to the reduced swelling ratio of the PFSA membrane by the bilayer reinforced scaffold (as shown by the results in table 1). And, CeO 2 The tensile strength of the doped dual-layer e-PTFE reinforced membranes (examples 1, 2, 3) was higher than that of CeO-free membranes 2 A double layer e-PTFE reinforced membrane was doped (comparative example 2). The reduction in the hydrogen permeation current contributes to the improvement in the durability of the PFSA membrane.
FIG. 4 is a single layer ePTFE reinforced membrane (comparative example 1) without CeO 2 Doped double layer ePTFE reinforced membrane (comparative example 2), 0.5 wt% CeO 2 OCV decay plots for the doped dual layer e-PTFE reinforced membrane (example 1) were compared to the cell performance before and after. Thus, CeO was observed 2 OCV decay Rate ratio of doped Dual-layer E-PTFE reinforced film to Single-layer reinforced film, and CeO-free 2 The doped double-layer e-PTFE reinforced membrane is smaller, thereby representing higher chemical durability. At the same time, the fuel cell performance attenuation amplitude is minimal.
FIG. 5 is a single layer ePTFE reinforced membrane (comparative example 1) without CeO 2 Doped double layer ePTFE reinforced membrane (comparative example 2), 0.5 wt% CeO 2 Comparison of LSVs before and after OCV durability for the doped dual layer e-PTFE reinforced membrane (example 1). Doping with 0.5% CeO 2 The attack of free radicals on the membrane body is then slowed down, thereby resulting in a reduction in the chemical decay experienced by the PFSA membrane, exhibiting minimal change in the hydrogen permeation current.
The structure, doping composition and main properties of the reinforced films prepared in the examples and comparative examples are summarized in table 1. It can be seen that in comparative example 3, excess CeO was added to the double layer enhanced proton exchange membrane 2 Will leadThe proton conductivity is reduced, the internal resistance of the proton exchange membrane is increased, and the output performance of the fuel cell is influenced. Comparative examples 4, 5 and 6, in which the same amount of ZrO as that of example 1 was added to the double-layer reinforced proton exchange membrane 2 、Al 2 O 3 、SiO 2 Table 1 performance comparison shows that the durability of the hydrogen permeation current and OCV is lower than that of the example, indicating that the addition of the radical scavenger in example 1 is effective in improving the chemical durability of the dual reinforced proton exchange membrane.
TABLE 1 Structure, doping composition and Main Properties of the reinforced films prepared in the examples and comparative examples
In conclusion, the method has simple steps, and the skeleton is increased and the free radical scavenger CeO is doped by introducing double layers of ePTFE 2 The perfluorosulfonic acid membrane has improved mechanical durability and chemical durability, i.e., mechanical and chemical combined durability, while maintaining good fuel cell output performance. 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 (10)
1. A preparation method of a double-layer enhanced proton exchange membrane doped with a free radical scavenger is characterized by comprising the following steps:
(1) doping a free radical scavenger into a perfluorinated sulfonic acid resin solution to prepare a perfluorinated sulfonic acid resin solution doped with the free radical scavenger;
(2) coating a first layer of perfluorinated sulfonic acid resin solution on a substrate, and flatly laying a polymer film on the first layer of perfluorinated sulfonic acid resin solution;
(3) coating a second layer of perfluorinated sulfonic acid resin solution on the surface of the polymer film, and flatly laying the second layer of polymer film on the second layer of perfluorinated sulfonic acid resin solution;
(4) coating a third layer of perfluorinated sulfonic acid resin solution on the surface of the second layer of polymer film;
(5) and performing heat treatment to obtain the double-layer enhanced proton exchange membrane doped with the free radical scavenger.
2. The method of claim 1 for preparing a radical scavenger doped double layer reinforced proton exchange membrane, wherein: in the step (1), the free radical scavenger is nano cerium oxide CeO 2 The perfluorinated sulfonic acid resin solution is 5-20 wt% of perfluorinated sulfonic acid resin solution.
3. The method for preparing the radical scavenger doped double-layer reinforced proton exchange membrane according to claim 2, wherein the method comprises the following steps: in step (1), CeO 2 In an amount of 0.5 to 2 wt% based on the mass of the perfluorosulfonic acid polymer.
4. The method for preparing the radical scavenger doped double-layer reinforced proton exchange membrane according to claim 1, wherein the method comprises the following steps: the polymer film is a polytetrafluoroethylene microporous film, the thickness of the polytetrafluoroethylene microporous film is 5-20 mu m, and the porosity is 50% -90%.
5. The method for preparing the radical scavenger doped double-layer reinforced proton exchange membrane according to claim 1, wherein the method comprises the following steps: in the step (1), the preparation is carried out by mechanical stirring and/or ultrasonic stirring, wherein the mechanical stirring time is 0.5-6h, and the ultrasonic stirring time is 10-60 min.
6. The preparation method of the free radical scavenger doped double-layer reinforced proton exchange membrane according to claim 1, wherein the preparation method comprises the following steps: in the step (2), the substrate is one of a glass plate and a polyethylene terephthalate (PET) film.
7. The method for preparing the radical scavenger doped double-layer reinforced proton exchange membrane according to claim 1, wherein the method comprises the following steps: in the step (5), the heat treatment conditions are as follows: the first step, the temperature is 80-100 ℃, and the time is 0.5-24 h; the second step, the temperature is 120 ℃ and 150 ℃, and the time is 10-120 min.
8. The preparation method of the free radical scavenger doped double-layer reinforced proton exchange membrane according to claim 1, wherein the preparation method comprises the following steps: in the steps (2), (3) and (4), the solution coating method is a blade coating method or a slit coating method.
9. A radical scavenger doped double-layer reinforced proton exchange membrane prepared by the preparation method of any one of claims 1 to 8.
10. The use of the radical scavenger doped double-layer reinforced proton exchange membrane of claim 9 in the field of fuel cell electrolyte membranes.
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