CN114976166A - Oxidation-resistant cation exchange membrane, preparation method thereof and oxidation-resistant membrane electrode - Google Patents
Oxidation-resistant cation exchange membrane, preparation method thereof and oxidation-resistant membrane electrode Download PDFInfo
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- CN114976166A CN114976166A CN202210695770.7A CN202210695770A CN114976166A CN 114976166 A CN114976166 A CN 114976166A CN 202210695770 A CN202210695770 A CN 202210695770A CN 114976166 A CN114976166 A CN 114976166A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 239000000243 solution Substances 0.000 claims abstract description 66
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- 238000011065 in-situ storage Methods 0.000 claims abstract description 24
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- 238000002156 mixing Methods 0.000 claims abstract description 6
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- 238000000034 method Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
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- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000003254 radicals Chemical class 0.000 abstract description 61
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- -1 hydrogen ions Chemical class 0.000 abstract description 13
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- 238000012546 transfer Methods 0.000 abstract description 3
- 210000004379 membrane Anatomy 0.000 description 55
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- 229910052737 gold Inorganic materials 0.000 description 2
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- 239000011572 manganese Substances 0.000 description 2
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a preparation method of an oxidation-resistant cation exchange membrane, which comprises the following steps: A) under the ultrasonic condition, mixing a conductive polymer monomer with a hydrochloric acid solution to obtain a polymer monomer solution; B) adding potassium permanganate into the polymer solution to obtain a mixed solution; C) and B) respectively adding the mixed solution and the hydrochloric acid solution with the same concentration as that in the step A) to both sides of the cation exchange membrane, and carrying out in-situ growth to obtain the oxidation-resistant cation exchange membrane. The loose porous structure of the free radical quenching layer can have a larger contact area with the loose structure of the catalyst layer, so that the two layers are combined more tightly, the mass transfer resistance of hydrogen ions is reduced, and the efficiency of the battery is improved; meanwhile, the existence of the free radical quenching layer can achieve a good free radical scavenging effect, and the stability of the fuel cell is improved. The invention also provides an oxidation-resistant cation exchange membrane and an oxidation-resistant membrane electrode.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to an oxidation-resistant cation exchange membrane and a preparation method thereof, namely an oxidation-resistant membrane electrode.
Background
The cation exchange membrane is a membrane with selective action on cations, most of ion exchange groups of the cation exchange membrane adopt sulfonic acid groups, and corresponding dissociable ions exist, so that the cation exchange membrane can be regarded as a polymer electrolyte. The positive ion exchange groups in the positive membrane are negatively charged, so that the positive ions with positive charges can pass through the positive membrane under the action of an external electric field, and the negative ions cannot pass through the positive membrane due to the isotropic repulsion, so that the membrane has selective permeability. The cation exchange membrane has wide application prospect in a plurality of fields such as fuel cells, electrodialysis, wastewater treatment and the like.
However, in the application of the fuel cell, the fuel cell may generate radicals in different forms at the two electrodes due to incomplete four-electron reaction at the electrodes during operation, wherein incomplete reaction of oxygen and protons at the cathode side generates hydrogen peroxide, the hydrogen peroxide further reacts to generate hydroxyl radicals and hydrogen peroxide radicals, and hydrogen gas at the anode side generates hydrogen radicals in the catalyst layer, and the hydrogen radicals partially pass through the membrane layer to combine with oxygen at the cathode to generate hydrogen peroxide radicals, wherein part of the hydrogen peroxide radicals react with hydrogen ions to generate hydrogen peroxide, and further react with the same at the anode side to generate hydroxyl radicals and hydrogen peroxide radicals, and the radicals attack some fragile sites in the cation exchange membrane to cause degradation of the membrane. The current low membrane stability requires frequent replacement and the high price of the high stability membrane is also one of the reasons for the high cost of the fuel cell. A relatively inexpensive and highly stable membrane electrode may be a solution to the high cost of fuel cells.
Disclosure of Invention
The invention aims to provide an oxidation-resistant cation exchange membrane and a preparation method thereof, namely an oxidation-resistant membrane electrode. The oxidation-resistant cation exchange membrane disclosed by the invention is low in preparation cost and good in stability.
The invention provides a preparation method of an oxidation-resistant cation exchange membrane, which comprises the following steps:
A) under the ultrasonic condition, mixing a conductive polymer monomer with a hydrochloric acid solution to obtain a polymer monomer solution;
B) adding potassium permanganate into the polymer solution to obtain a mixed solution;
C) and B) respectively adding the mixed solution and the hydrochloric acid solution with the same concentration as that in the step A) to both sides of the cation exchange membrane, and carrying out in-situ growth to obtain the oxidation-resistant cation exchange membrane.
Preferably, the conductive polymer monomer includes pyrrole and/or aniline;
the concentration of the conductive polymer monomer in the polymer monomer solution is 10-50 mg/mL.
Preferably, the concentration of the hydrochloric acid solution is 30-50 mg/mL.
Preferably, the molar ratio of the conductive polymer monomer to potassium permanganate is 1: (1-3).
Preferably, the conductive polymer monomer and the hydrochloric acid solution in the step A) are mixed for 30-60 min under the ultrasonic condition.
Preferably, the cation exchange membrane is a sulfonic acid type cation exchange membrane.
Preferably, the temperature of the in-situ growth is 4-8 ℃; the in-situ growth time is 3-20 hours.
The invention provides an oxidation-resistant cation exchange membrane prepared by the preparation method, which comprises a cation exchange membrane and a polymer layer growing on the surface of the cation exchange membrane in situ;
the polymer layer includes a polymer and manganese dioxide particles encapsulated within the polymer.
Preferably, the thickness of the polymer layer is 0.5 to 1.5 μm.
The present invention provides an oxidation-resistant membrane electrode comprising an oxidation-resistant cation exchange membrane as hereinbefore described.
The invention provides a preparation method of an oxidation-resistant cation exchange membrane, which comprises the following steps: A) under the ultrasonic condition, mixing a conductive polymer monomer with a hydrochloric acid solution to obtain a polymer monomer solution; B) adding potassium permanganate into the polymer solution to obtain a mixed solution; C) and B) respectively adding the mixed solution and the hydrochloric acid solution with the same concentration as that in the step A) to both sides of the cation exchange membrane, and carrying out in-situ growth to obtain the oxidation-resistant cation exchange membrane. The method comprises the steps of respectively adding a prepared mixed hydrochloric acid solution of a conductive polymer monomer and potassium permanganate and a hydrochloric acid solution with the same concentration to two sides of a cation exchange membrane, and standing at a low temperature; due to the interaction of electrostatic attraction between the protonated conductive polymer and the sulfonate group, the polypyrrole layer grows in situ on the surface of one side of the cation exchange membrane, the grown polypyrrole chain layer can wrap the manganese oxide particles in the polypyrrole chain layer, and a free radical quenching layer is formed on the surface of the cation exchange membrane through growth; meanwhile, due to the loose porous structure of the free radical quenching layer, the contact area between the free radical quenching layer and the loose structure of the catalyst layer is larger, so that the free radical quenching layer and the catalyst layer are combined more tightly, the mass transfer resistance of hydrogen ions is reduced, and the efficiency of the battery is improved; meanwhile, the existence of the free radical quenching layer can achieve a good free radical scavenging effect, and the stability of the fuel cell is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of a base film in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a conductive polymer layer with a radical scavenger according to example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of a cross section of a cation exchange membrane comprising a radical quenching layer according to example 1 of the present invention;
FIG. 4 is a graph of current vs. voltage for a cation exchange membrane containing a radical quenching layer in example 1 of the present invention;
FIG. 5 is an infrared spectrum of a cation exchange membrane containing a radical quenching layer in example 1 of the present invention;
FIG. 6 is a graph comparing the conductance of a cation exchange membrane comprising a radical quenching layer and a base membrane in example 1 of the present invention;
FIG. 7 is a graph of the voltage drop after prolonged operation in a fuel cell of a cation exchange membrane containing a radical quenching layer and a base membrane in example 1 of the present invention;
in FIGS. 5 to 7, SBPI stands for cation exchange membrane (base membrane), SPBI-PPy/MnO2 for oxidation-resistant cation exchange membrane for growing free radical quenching layer; the thickness of the growing radical quenching layer, denoted by SPBI-0.8-PPy/MnO2, was 800nm of an oxidation-resistant cation exchange membrane.
Detailed Description
The invention provides a preparation method of an oxidation-resistant cation exchange membrane, which comprises the following steps:
A) under the ultrasonic condition, mixing a conductive polymer monomer with a hydrochloric acid solution to obtain a polymer monomer solution;
B) adding potassium permanganate into the polymer solution to obtain a mixed solution;
C) and B) respectively adding the mixed solution and the hydrochloric acid solution with the same concentration as that in the step A) to both sides of the cation exchange membrane, and carrying out in-situ growth to obtain the oxidation-resistant cation exchange membrane.
In the invention, preferably under the ultrasonic condition, the conductive polymer monomer is dropwise added into a hydrochloric acid solution and is subjected to ultrasonic treatment for a period of time to obtain a polymer monomer solution.
In the present invention, the conductive polymer monomer is preferably pyrrole and/or aniline; the concentration of the hydrochloric acid solution is preferably 30-50 mg/mL, such as 30mg/mL, 35mg/mL, 40mg/mL, 45mg/mL, 50mg/mL, and preferably ranges with any value as an upper limit or a lower limit; the concentration of the polymer monomer in the polymer monomer solution is preferably 10 to 50mg/mL, more preferably 20 to 40mg/mL, such as 10mg/mL, 15mg/mL, 20mg/mL, 25mg/mL, 30mg/mL, 35mg/mL, 40mg/mL, 45mg/mL, 50mg/mL, and preferably ranges from any of the above values as upper or lower limits.
In the invention, the hydrochloric acid solution provides hydrogen ions to replace proton exchange groups in the proton exchange membrane from sodium sulfonate type to sulfonic acid type, thereby improving the adsorption effect with conductive polymer monomers and achieving the effect of in-situ growth.
In the invention, the time of ultrasonic treatment is preferably 30-60 min, and more preferably 40-50 min; the frequency of the ultrasonic waves is preferably 50-100 Hz, and more preferably 60-80 Hz.
After the polymer monomer solution is obtained, the potassium permanganate is rapidly added and uniformly stirred to obtain a mixed solution.
In the present invention, the molar ratio of the conductive polymer monomer to potassium permanganate is preferably 1: (1-3) such as 1:1, 1: 1.5,1: 2,1: 2.5,1: 3, a range value having any of the above values as an upper limit or a lower limit is preferable.
Then, vertically placing the cation exchange membrane into a reaction container, enabling one side of the cation exchange membrane to contact the mixed solution, enabling the other side of the cation exchange membrane to contact the hydrochloric acid solution with the same concentration, standing at low temperature, and reacting to enable the conductive polymer monomer to grow in situ on the surface of the cation exchange membrane, so as to obtain a polymer layer containing manganese dioxide particles.
In the present invention, the cation exchange membrane is preferably a sulfonic acid type cation exchange membrane, and is preferably a sulfonic acid type cation exchange membrane polymer with high stability prepared by using a super acid catalysis method, and the preparation of the sulfonic acid type cation exchange membrane polymer by using the super acid catalysis method is a common method for those skilled in the art, and the details of the present invention are not repeated herein.
In the in-situ growth process, the surface of the sulfonic acid type cation exchange membrane is provided with an ion exchange group, the protonized conductive polymer monomer and the sulfonate group can be embedded into the cation exchange membrane through electrostatic attraction, and the in-situ growth stable structure is formed by in-situ polymerization, the potassium permanganate can be reduced into manganese oxide particles (used as a radical quencher) which are uniformly attached to the conductive polymer chain layer and are wrapped by the conductive polymer while the conductive polymer chain layer grows, the distribution is uniform, and the potassium permanganate is not easy to fall off, so that the cation exchange membrane containing the radical quencher layer has excellent stability and higher ionic conductivity, and as the conductive polymer is in chain polymerization, a plurality of chains can be grafted with each other, and the chains are interwoven or form a conveying porous structure, due to the existence of the loose structure, the catalyst layer can have larger contact area with a loose structure of the catalyst layer, thereby achieving better proton transmission effect and reducing transmission resistance; the preparation of the integrated membrane electrode can increase the contact area, improve the performance of the cell and stabilize the free radical scavenger through the loose structure of the catalyst and the free radical quenching layer on the surface of the membrane, thereby achieving good free radical scavenging effect and improving the stability of the fuel cell.
In the invention, the temperature of the in-situ growth is preferably 4-8 ℃, more preferably 5-7 ℃, such as 4 ℃, 5 ℃, 6 ℃, 7 ℃ and 8 ℃, and is preferably a range value taking any value as an upper limit or a lower limit; the in-situ growth time is preferably 3 to 20 hours, more preferably 5 to 15 hours, such as 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, and preferably ranges with any of the above values as the upper limit or the lower limit.
The invention also provides an oxidation-resistant cation exchange membrane, which comprises a cation exchange membrane and a polymer layer in-situ grown on the surface of the cation exchange membrane;
the polymer layer includes a polymer and free radical quencher manganese dioxide particles encapsulated within the polymer.
The invention also provides an oxidation-resistant membrane electrode comprising an oxidation-resistant cation-exchange membrane as described above.
In the present invention, preferably, the oxidation-resistant membrane electrode is obtained by placing catalyst layers on both sides of the oxidation-resistant cation-exchange membrane and pressing the catalyst layers to adhere the catalyst layers to the oxidation-resistant cation-exchange membrane.
In the invention, the pressing pressure is preferably 1 to 5kPa, and more preferably 2 to 4 kPa. The pressing time is preferably 6 to 12 hours, and more preferably 8 to 10 hours.
The invention provides a preparation method of an oxidation-resistant cation exchange membrane, which comprises the following steps: A) under the ultrasonic condition, mixing a conductive polymer monomer with a hydrochloric acid solution to obtain a polymer monomer solution; B) adding potassium permanganate into the polymer solution to obtain a mixed solution; C) and B) respectively adding the mixed solution and the hydrochloric acid solution with the same concentration as that in the step A) to both sides of the cation exchange membrane, and carrying out in-situ growth to obtain the oxidation-resistant cation exchange membrane. The method comprises the steps of respectively adding a prepared mixed hydrochloric acid solution of a conductive polymer monomer and potassium permanganate and a hydrochloric acid solution with the same concentration to two sides of a cation exchange membrane, and standing at a low temperature; due to the interaction of electrostatic attraction between the protonated conductive polymer and the sulfonate group, the polypyrrole layer grows in situ on the surface of one side of the cation exchange membrane, the grown polypyrrole chain layer can wrap the manganese oxide particles in the polypyrrole chain layer, and a free radical quenching layer is formed on the surface of the cation exchange membrane through growth; meanwhile, due to the loose porous structure of the free radical quenching layer, the contact area between the free radical quenching layer and the loose structure of the catalyst layer is larger, so that the free radical quenching layer and the catalyst layer are combined more tightly, the mass transfer resistance of hydrogen ions is reduced, and the efficiency of the battery is improved; meanwhile, the existence of the free radical quenching layer can achieve a good free radical scavenging effect, and the stability of the fuel cell is improved.
In order to further illustrate the present invention, the following detailed description of an oxidation-resistant cation exchange membrane and a method for preparing the same, i.e., an oxidation-resistant membrane electrode, is provided in connection with the examples, which should not be construed as limiting the scope of the present invention.
Example 1
Preparing a hydrochloric acid solution of 0.0365g/mL, dropwise adding pyrrole into the hydrochloric acid solution under an ultrasonic environment, continuously carrying out ultrasonic treatment for 30min to obtain a pyrrole hydrochloric acid solution with the pyrrole concentration of 0.02g/mL, rapidly adding potassium permanganate, and uniformly stirring to prepare a mixed hydrochloric acid solution containing 0.03g/mL of potassium permanganate.
Preparing a sulfonic acid type cation exchange membrane polymer by a superacid catalysis method, dissolving sulfonic acid type polyphenyl ether (SPBI) in N-methylpyrrolidone to form a membrane liquid with the mass concentration of 2.5%, dropwise adding the membrane liquid on a smooth glass plate, placing a substrate on a heating plate, heating at 80 ℃ for 6 hours to crosslink part of sulfonic acid groups in the sulfonic acid type polyphenyl ether cation exchange membrane liquid, soaking the glass plate in a container filled with water after heating, standing, and allowing a cation exchange membrane to fall off from the substrate to obtain the sulfonic acid type cation exchange membrane.
And respectively adding 200mL of mixed hydrochloric acid solution and 200mL of 0.0365g/mL hydrochloric acid solution at two sides of the sulfonic acid type cation membrane, standing for 4h at 4 ℃, taking out the soaked membrane, and washing by using flowing deionized water to obtain the cation exchange membrane containing the free radical quenching layer, wherein the thickness of the free radical quenching layer is about 800 nm.
Adopting the cation exchange membrane containing the free radical quenching layer, and placing a load of 0.5mg/cm on two sides of the cation exchange membrane 2 And (3) a catalyst layer of a platinum carbon catalyst, padding filter paper and loading 1Kg of weight, and standing at room temperature for 12 hours to obtain the oxidation-resistant membrane electrode.
The experimental results show that: the stable operation time of the fuel cell is improved by 100 percent compared with that of a basal membrane; the voltage reaches 150h in the stability test without attenuation; the power density during the operation of the fuel cell is reduced by 20% compared with that of the basement membrane; electrochemical workstation test the membrane conductivity was reduced by 20mS/cm compared to the base membrane.
Example 2
Preparing 0.045g/mL hydrochloric acid solution, dropwise adding aniline into the hydrochloric acid solution under an ultrasonic environment, continuously performing ultrasonic treatment for 30min to obtain pyrrole hydrochloric acid solution with aniline concentration of 0.02g/mL, and then rapidly adding potassium permanganate and uniformly stirring to prepare mixed hydrochloric acid solution containing 0.09g/mL potassium permanganate.
Preparing a sulfonic acid type cation exchange membrane polymer by a superacid catalysis method, dissolving sulfonic acid type polyphenyl ether in N-methylpyrrolidone to form a membrane solution with the mass concentration of 4%, dropwise adding the membrane solution on a smooth glass plate, placing a substrate on a heating plate, heating for 8 hours at 60 ℃, enabling part of sulfonic acid groups in the sulfonic acid type polyphenyl ether cation exchange membrane solution to be crosslinked, soaking the glass plate in a container filled with water after heating is completed, standing, and enabling a cation exchange membrane to fall off from the substrate to obtain the sulfonic acid type cation exchange membrane.
And respectively adding 200mL of mixed hydrochloric acid solution and 200mL of 0.045g/mL hydrochloric acid solution on two sides of the sulfonic acid type cation membrane, standing for 4 hours at 4 ℃, taking out the soaked membrane, and washing by using flowing deionized water to obtain the cation exchange membrane containing the free radical quenching layer, wherein the thickness of the free radical quenching layer is about 1 mu m.
And (3) tightly connecting the cation exchange membrane containing the free radical quenching layer with the catalyst layer through a gasket, clamping the cation exchange membrane on two sides for 12 hours by using a gas diffusion layer, and attaching polar plates on two sides to obtain the oxidation-resistant membrane electrode.
The experimental result shows that the cation exchange membrane structure prepared based on the embodiment is similar to the cation exchange membrane structure prepared based on the embodiment 1, has a thicker free radical quenching layer, can effectively reduce the chemical degradation of the membrane in the fuel cell, and improves the stability performance in the operation process of the fuel cell, and the stability test curve is only reduced by 1% in 100h in the fuel cell environment with 30% RH and 90 ℃ when the oxidation-resistant membrane electrode is prepared according to the embodiment.
Topography detection
Taking out the cation exchange membrane subjected to the cation exchange membrane growth and the radical quenching layer from deionized water, drying the cation exchange membrane in an oven at the temperature of 40 ℃, cutting off a part of the membrane, attaching the cut membrane to a conductive adhesive, carrying out gold spraying treatment on the conductive adhesive, and finally placing the conductive adhesive into a scanning electron microscope device for testing to obtain the surface topography of the cation exchange membrane and the cation exchange membrane subjected to the radical quenching layer growth, as shown in fig. 1 and fig. 2. Wherein, FIG. 1 is a scanning electron microscope image of the cation exchange membrane layer, and FIG. 2 is a scanning electron microscope image of the cation exchange membrane growing the free radical quenching layer.
By comparing the scanning electron microscope images in fig. 1 and fig. 2, it can be seen that polypyrrole spontaneously grows on the surface of the film through the processes of electrostatic self-assembly, in-situ polymerization growth and the like, and the generated manganese oxide particles are wrapped in the polypyrrole to form a radical quenching layer, and the radical quenching layer can be uniformly distributed through the scanning electron microscope image in fig. 2, which is beneficial to defense against radical random attack.
Taking the cation exchange membrane subjected to the cation exchange membrane growth and the radical quenching layer from deionized water, drying the cation exchange membrane in an oven at the temperature of 40 ℃, then carrying out freeze fracture treatment on the cation exchange membrane by using liquid nitrogen, pasting the obtained section sample on conductive gel, carrying out gold spraying treatment on the conductive gel, and finally placing the section sample of the cation exchange membrane subjected to the radical quenching layer growth into a device of a scanning electron microscope for testing to obtain a section scanning electron microscope morphology image of the modified cation exchange membrane, wherein the section scanning electron microscope morphology image is shown in figure 3.
Referring to fig. 3, it can be seen from fig. 3 that the cation exchange membrane having the radical quenching layer grown thereon has a uniform thickness of about 800nm and contains a large amount of radical scavenger manganese oxide particles, which can effectively protect the cation exchange membrane from radical attack and improve the chemical stability of the membrane in the fuel cell.
Infrared spectroscopy
The cation exchange membrane of example 1 and the cation exchange membrane with the grown radical quenching layer were taken out of deionized water, dried in an oven at 40 ℃, cut out to a size of 2 × 2cm, and placed in an infrared spectrometer for testing to obtain infrared spectrograms of the cation exchange membranes with and without the grown radical quenching layer, as shown in fig. 5.
As shown in fig. 5, when the cation exchange membrane on which the radical quenching layer was grown is compared with the cation exchange membrane on which the radical quenching layer was not grown, it can be seen that the infrared spectrum of the cation exchange membrane on which the radical quenching layer was grown shows a characteristic peak of N — H bond contained in polypyrrole and a characteristic peak of Mn ═ O bond contained in manganese oxide, and the X-ray photoelectron spectroscopy also confirms the presence of Mn and N elements, confirming the successful growth of the radical quenching layer.
Electrochemical performance test
The cation exchange membrane used in example 1 and the cation exchange membrane on which the radical quenching layer was grown were cut out to a size of 1 × 4cm, immersed in 1M sulfuric acid solution, the sulfuric acid solution was changed every 1h, deionized water was changed after immersion for about 24h, deionized water was changed every 1h, immersed for about 24h and then taken out, the length and width thereof were measured again, the membrane was sandwiched between conductivity measuring instruments, and a test current was set to 10uA for measurement.
As shown in fig. 6, after being soaked in sulfuric acid, the sulfonate type cation exchange membrane is converted into hydrogen form, and then the excess acid solution is washed with deionized water, and the conductivity of the proton membrane of the radical quenching layer growing on the surface is reduced to some extent compared with that of the base membrane, because there is interaction between the protonated pyrrole groups and the sulfonate groups, the pyrrole groups occupy part of the sulfonate groups, and the presence of polypyrrole affects the ion transport rate, resulting in a reduction in the conductivity.
The cation exchange membrane used in example 1 and the cation exchange membrane on which the radical quenching layer was grown were cut into 5 × 5cm, soaked in 1M sulfuric acid solution, the sulfuric acid solution was changed every 1h, the deionized water was changed after soaking for about 24h, the deionized water was changed every 1h, the deionized water was taken out after soaking for about 24h, the solutions were added to a fuel cell test instrument, and the fuel cell power density and I-V curve were tested under conditions of 100% RH and 80 ℃ to obtain a comparative graph of the power density and I-V curve of the fuel cell, as shown in fig. 4.
Fig. 4 shows that the cation exchange membrane with the radical quenching layer grown thereon has a significantly improved performance compared to the base membrane cell, which indicates that the presence of the radical quenching layer can improve the fuel cell performance of the membrane, and the cation conduction efficiency is significantly improved due to the good conduction and even attraction of the radical quenching layer to ions.
The cation exchange membrane used in example 1 and the cation exchange membrane on which the radical quenching layer was grown were cut into 5 × 5cm, soaked in 1M sulfuric acid solution, the sulfuric acid solution was changed every 1h, the deionized water was changed after soaking for about 24h, the deionized water was changed every 1h, the membrane was taken out after soaking for about 24h, the length and width thereof were measured again, the membrane was sandwiched between conductivity measuring instruments, a test current was set to 10uA for measurement, the membrane after measurement was treated in 80 ℃ fenton's reagent for 12h, the above steps were repeated to measure conductivity, and pre-and post-treatment comparative graphs were prepared.
As shown in fig. 7, after soaking, the conductivity of the base film without the radical quenching layer decreases greatly, and the polymer structure of the film is degraded by the attack of the radicals, so that the conductivity decreases.
In combination with the above tests, the cation exchange membrane containing the radical quenching layer of the present invention is used, manganese oxide particles are used as a radical scavenger, and the polypyrrole layer grows in situ on the single-side surface of the cation exchange membrane through the interaction of electrostatic attraction between the protonated conductive polymer and the sulfonate group, and the grown polypyrrole chain layer can wrap the manganese oxide particles therein. Through the phase diagram, the conductivity and the fuel cell test in a scanning electron microscope, an infrared spectrum, an atomic force microscope of the two membranes, the results show that the free radical quenching layer containing manganese oxide has been successfully grown, and the existence of the free radical quenching layer enables the power performance and the durability of the fuel cell to be improved, namely under the same condition, compared with a base membrane, the cation exchange membrane growing the free radical quenching layer has more excellent performance and stability in the fuel cell.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of an oxidation-resistant cation exchange membrane comprises the following steps:
A) under the ultrasonic condition, mixing a conductive polymer monomer with a hydrochloric acid solution to obtain a polymer monomer solution;
B) adding potassium permanganate into the polymer solution to obtain a mixed solution;
C) and B) respectively adding the mixed solution and the hydrochloric acid solution with the same concentration as that in the step A) to both sides of the cation exchange membrane, and carrying out in-situ growth to obtain the oxidation-resistant cation exchange membrane.
2. The production method according to claim 1, wherein the conductive polymer monomer comprises pyrrole and/or aniline;
the concentration of the conductive polymer monomer in the polymer monomer solution is 10-50 mg/mL.
3. The method according to claim 1, wherein the concentration of the hydrochloric acid solution is 30 to 50 mg/mL.
4. The preparation method according to claim 1, wherein the molar ratio of the conductive polymer monomer to potassium permanganate is 1: (1-3).
5. The preparation method according to claim 1, wherein the conductive polymer monomer in the step A) is mixed with the hydrochloric acid solution under ultrasonic conditions for 30-60 min.
6. The production method according to claim 1, wherein the cation exchange membrane is a sulfonic acid type cation exchange membrane.
7. The preparation method according to claim 1, wherein the temperature of the in-situ growth is 4-8 ℃; the in-situ growth time is 3-20 hours.
8. The oxidation-resistant cation exchange membrane prepared by the preparation method of claim 1, which comprises a cation exchange membrane and a polymer layer grown in situ on the surface of the cation exchange membrane;
the polymer layer includes a polymer and manganese dioxide particles encapsulated within the polymer.
9. The oxidation-resistant cation exchange membrane of claim 8, wherein the polymer layer has a thickness of 0.5 to 1.5 μm.
10. An oxidation-resistant membrane electrode comprising the oxidation-resistant cation-exchange membrane of claim 9.
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