CN112687927B - High-durability fuel cell composite proton exchange membrane and preparation method and application thereof - Google Patents
High-durability fuel cell composite proton exchange membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-durability fuel cell composite proton exchange membrane and a preparation method and application thereof. Compared with the common DuPont Nafion membrane, the durability of the composite membrane coated with the polydopamine is greatly improved. The invention has simple and safe manufacturing process and low cost, and can be used for the industrial production of the composite proton exchange membrane.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a proton exchange membrane and a preparation method and application thereof.
Background
Hydrogen fuel cells are known as the next generation of clean energy carriers for portable and automotive applications due to their high energy density, high efficiency, low pollutant emissions, quiet operation, and short start-up and shut-down times. However, hydrogen fuel cells have poor durability and high cost, primarily associated with Proton Exchange Membranes (PEM). A proton exchange membrane, which plays a critical role in hydrogen fuel cells, separates hydrogen and oxygen while allowing protons to pass through. Nafion from dupont is considered a standard PEM because of its high proton conductivity, low hydrogen permeation and good chemical and mechanical stability.
Disclosure of Invention
The invention aims to: the invention aims to provide a high-durability fuel cell composite proton exchange membrane, which improves the stability and the utilization rate of a free radical quencher and has high durability; the second purpose of the invention is to provide a preparation method of the composite proton exchange membrane of the high-durability fuel cell; the invention also aims to provide application of the high-durability fuel cell composite proton exchange membrane.
The technical scheme is as follows: the invention relates to a high-durability fuel cell composite proton exchange membrane, which comprises a membrane matrix and a metal oxide radical quencher dispersed in the membrane matrix, wherein the surface of the radical quencher is provided with an organic matter coating layer; the inside of the metal oxide is formed, and the outside of the metal oxide is coated with organic matters for improving the stability.
Preferably, the thickness of the coating layer is 0.5-5 nm.
The metal oxide free radical quencher is cerium oxide, manganese oxide, chromium oxide or cobalt oxide, and the organic coating layer is polydopamine.
The invention also provides a preparation method of the high-durability fuel cell composite proton exchange membrane, which comprises the following steps:
(1) dissolving a metal oxide free radical quencher, dopamine hydrochloride and Tris (hydroxymethyl) aminomethane (Tris) in a solvent, mixing to obtain a mixed solution, adjusting the pH value of the solution to 8-10, stirring at normal temperature for 0.5-2 h for coating reaction, then carrying out suction filtration and drying on the mixed solution, and obtaining the metal oxide free radical quencher with a coating layer;
(2) mixing the organic matter-coated metal oxide free radical quencher prepared in the step (1) with a polymer resin solution according to a certain proportion, and magnetically stirring to obtain a uniform dispersion liquid;
(3) pouring the dispersion liquid into a mould, drying under a vacuum condition, and performing post heat treatment to obtain a composite membrane;
(4) and respectively soaking the composite membrane in an acid solution and water to obtain the proton exchange membrane.
In the step (1), metal oxide, organic matter for coating the surface of the metal oxide, deionized water and Tris (hydroxymethyl) aminomethane (Tris) are mixed according to a certain proportion and stirred until the mixture is dissolved, a certain amount of NaOH solution is dripped to adjust the pH value of the mixed solution to be alkalescent, magnetic stirring is carried out in air for a period of time at room temperature to obtain the organic matter coated on the surface of metal oxide particles, and the mixed solution after coating reaction is subjected to suction filtration and drying for 12 hours to obtain the organic matter coated metal oxide radical quencher.
The method comprises the steps of mixing a metal oxide free radical quencher, an organic matter, ultrapure water and Tris (hydroxymethyl) aminomethane (Tris) according to a certain proportion, and if the addition amount of the organic matter is too much, forming a thick coating layer on the surface of the metal oxide to be not beneficial to the formation and migration of metal cations, so that the free radical removal effect is reduced, and in order to ensure that the polymerization reaction occurs, a proper amount of the organic matter needs to be added under the alkalescent condition. The coating time is controlled within a reasonable range, and the use effect of the free radical quencher is influenced due to the fact that the coating layer is too thick due to too long coating time. Preferably, in the step (1), the adding mass of the dopamine hydrochloride is 1-4 times that of the free radical quencher; in the mixed solution, the concentration of the dopamine hydrochloride is 0.1-8 mg/mL, and the concentration of the metal oxide free radical quencher is 0.1-4 mg/mL. Preferably, the metal oxide radical quencher is cerium oxide.
In the step (2), the addition amount of the free radical quenching agent in the dispersion liquid accounts for 0.5-1.2 wt% of the addition amount of the polymer resin; the equivalent mass of the polymer resin is 700 g/mol-1200 g/mol, the solvent of the polymer resin solution is dimethyl sulfoxide or N, N-dimethylformamide, and the solute of the polymer resin solution can be DuPont Nafion resin or 3M PFSR resin. If too much free radical quencher is added, the free radical quencher can coordinate with the sulfonate group to reduce proton transmission sites, thereby greatly reducing the electrochemical performance of the battery.
In the step (3), the drying treatment temperature is 40-80 ℃, the drying time is 8-16 h, and the heat treatment temperature is 125-180 ℃. The heat treatment time is 3-6 h.
In the step (4), soaking for 1-2 hours by using a sulfuric acid solution with the temperature of 70-90 ℃ and the concentration of 0.5-2M, and then soaking for 1-2 hours by using deionized water with the temperature of 70-90 ℃ to finally obtain the composite proton exchange membrane.
The preparation method comprises the following steps of (1) mixing cerium oxide, dopamine, ultrapure water and Tris according to a certain proportion, adding dopamine hydrochloride under an alkaline condition, and carrying out oxidative autopolymerization reaction on the dopamine to obtain the polydopamine-coated cerium oxide nanoparticles. In the step (2), the selection of the solvent can directly influence the dispersion state of the free radical quencher in the ion exchange resin and the subsequent film-forming quality, and the selection of the proper high-boiling point solvent is favorable for obtaining a compact and uniform proton exchange membrane. In the step (3), the drying temperature can significantly affect the film-forming quality, if the temperature is too low, the volume cannot be completely volatilized, if the temperature is too high, the formed film can crack, if the annealing temperature can affect the crystallinity of the proton exchange film, if the crystallinity is too low, the phase separation of the proton exchange film is insufficient, the mechanical property is poor, and the proton conductivity is low. In the step (4), the residual metal cations in the proton exchange membrane can be replaced by protons by sulfuric acid soaking so as to improve the proton conductivity, and the proton exchange membrane is cleaned by water soaking.
The method comprises the steps of uniformly dispersing cerium oxide in a Tris buffer solution, adding dopamine hydrochloride in an alkaline environment, oxidizing the dopamine into a quinoid structure, performing intramolecular cyclization and rearrangement on primary amine in molecules, generating polydopamine aggregates which are subjected to Brownian motion in the solution, wherein the polydopamine has strong adhesion due to the fact that the polydopamine contains a catechol structure and amino groups, and the aggregates are attached to the surface of cerium oxide serving as a free radical quencher by virtue of strong adhesion, so that PD @ CeO2And (3) nanoparticles. By the method, the problem that the traditional spherical metal oxide free radical quencher is easy to migrate is remarkably solved, the aggregation of metal ions on a catalyst layer is effectively avoided, and the performance decay rate of the hydrogen fuel cell is greatly reduced.
The durability of the proton exchange membrane is improved by introducing a method of coating a polymer for the first time, and the poly-dopamine is adopted to coat the metal oxide radical quencher, the poly-dopamine molecular structure contains a plurality of active sites, a linear structure can be formed through radical polymerization, the poly-dopamine is favorably combined with a reaction group in a resin solution, and meanwhile, the poly-dopamine-coated metal oxide radical quencher further improves the dispersibility to achieve the technical effect of synergy, so that the durability of the proton exchange membrane of the fuel cell is greatly improved.
Has the advantages that:
(1) the invention prepares uniformly coated PD @ CeO by regulating and controlling the proportion of cerium oxide and dopamine hydrochloride, the pH value of a reaction system, the polymerization reaction temperature, the polymerization reaction time and the like2Introducing the prepared dopamine-coated cerium oxide into a proton exchange membrane to prepare a composite proton exchange membrane; compared with the traditional high-durability proton exchange membrane, the chemical corrosion resistance is further improved, the membrane can adapt to various different fuel cell working conditions, and can be applied to various different use scenes; the preparation process of the invention is highly controllableThe process is safe and can be used for industrial continuous production.
(2) According to the invention, the stability of the free radical quencher can be effectively improved by coating the cerium oxide with dopamine, the problems of dissolution and migration of cerium ions in an acidic proton exchange membrane environment are reduced, the utilization rate of the cerium oxide is improved, and the durability of the battery is further improved.
(3) The method provided by the invention prepares Nafion/PD @ CeO2The composite proton exchange membrane of the fuel cell has good thermal stability and mechanical property, and meanwhile, the composite membrane has stable single cell performance, low hydrogen permeation current density and long service life.
(4) The performance attenuation of the high-durability proton exchange membrane is only 9.49 percent in 10000 circles accelerated aging test, and is far lower than that of a commercial Nafion211 membrane. Compared with a commercial Nafion211 membrane, the high-durability proton exchange membrane prepared by the invention has no obvious performance attenuation, and is a proton exchange membrane with great application prospect.
Drawings
FIG. 1 is a flow chart of the preparation of the composite proton exchange membrane of the present invention.
FIG. 2 is a schematic diagram of the preparation of dopamine-coated cerium oxide.
FIG. 3 is a graph of the decay in performance of example 1 of the present invention versus comparative example 1; wherein, (a) the square point line graph of the graph is the initial polarization curve of the embodiment 1, and the triangular point line graph is the polarization curve of the embodiment 1 after 10000 circles; (b) the square point line graph is the initial polarization curve of comparative example 1, and the circular point line graph is the polarization curve of comparative example 1 after 10000 circles; (a) and (b) the ordinate of the two groups of curves in the graph is shown by the arrow in the graph.
FIG. 4 is a graph showing hydrogen permeation changes of example 1 and comparative example 1, wherein a circle is plotted as Nafion/PD @ CeO composite membrane2The graph of hydrogen permeation change of (1) is a graph of Nafion/CeO in comparative example 12Hydrogen permeation profile of the membrane.
Detailed Description
The present invention will be described in further detail with reference to examples.
The reagents and starting materials used in the following examples and comparative examples were all purchased directly.
Wherein the commercial cerium oxide and manganese oxide are purchased from Shanghai Maxin Biochemical technology, Inc., and the particle size of the cerium oxide is 30 nm-50 nm.
Fig. 1 is a flow chart of the preparation of the composite proton exchange membrane of the present invention, and fig. 2 is a schematic diagram of the preparation of the dopamine-coated cerium oxide of the present invention.
The invention provides a high-durability hydrogen fuel cell proton exchange membrane, which comprises the following steps:
step (1): dissolving cerium oxide, Tris and dopamine hydrochloride in deionized water, performing magnetic stirring until a transparent uniform solution is formed, and slowly dripping a proper amount of NaOH solution while stirring until the pH value of the mixed solution is 8.5. Stirring the alkaline mixed solution at normal temperature for 2 hours, and sequentially carrying out suction filtration and drying on the mixed solution to obtain dopamine-coated cerium oxide;
step (2): mixing the dopamine-coated metal oxide free radical quencher obtained in the step (1) with a polymer resin solution of which the solvent is N, N-dimethyl imide or dimethyl sulfoxide according to a certain proportion, and stirring the mixture until uniform dispersion liquid is formed;
and (3): pouring the uniform dispersion liquid into a pre-leveled glass mold, drying the solvent at 40-80 ℃ under a high vacuum condition, and carrying out heat treatment at 125-180 ℃ to obtain a composite film;
and (4): and (4) removing the composite membrane in the step (3) from the glass mold, soaking the composite membrane in a sulfuric acid solution with the temperature of 70-90 ℃ and the concentration of 0.5-2M for 1-2 hours, and then soaking the composite membrane in deionized water with the temperature of 70-90 ℃ for 1-2 hours to finally obtain the composite proton exchange membrane.
And assembling the prepared proton exchange membrane into a hydrogen fuel cell.
The assembling method of the hydrogen fuel cell comprises the following steps:
(1) stacking the cathode gas diffusion electrode, the proton exchange membrane and the anode gas diffusion electrode in sequence and performing hot pressing to form a membrane electrode assembly;
(2) and clamping the membrane electrode assembly between two graphite flow field plates, stacking a current collecting plate, a stainless steel end plate and an insulating sheet at two ends respectively, and pressurizing and fixing the periphery by using screws to obtain the hydrogen fuel cell.
Example 1:
the preparation method of the proton exchange membrane of the fuel cell in the embodiment comprises the following steps:
(1) 80mg of commercial CeO was weighed on an electronic balance280mg of dopamine hydrochloride and 63mg of Tris are dissolved in 40ml of deionized water and are placed on a magnetic stirrer to be stirred until the dopamine hydrochloride and the Tris are completely dissolved; dropwise adding 1mol/L NaOH solution until the pH value of the solution is 8.5, and placing the solution on a magnetic stirrer to stir for 2 hours; sequentially carrying out suction filtration and drying at 60 ℃ for one night to obtain polydopamine-coated cerium oxide particles; the thickness of polydopamine in this example is about 0.76 nm.
(2) 3g of 10 wt% Nafion/DMSO solution and 3mg of polydopamine-coated cerium oxide were weighed by an electronic balance, and mixed uniformly by shaking with an ultrasonic cleaner to obtain a translucent suspension.
(3) And (3) placing the glass mold for film making on a precise sliding table, transferring the whole into a vacuum drying oven, adjusting the glass mold to be horizontal by using a universal leveling instrument, then pouring the casting film liquid obtained in the step (3) into the glass mold, setting the temperature to be 40 ℃, turning on a vacuum pump, and pumping to a high vacuum state. And after 12 hours, raising the temperature of the vacuum drying oven to 150 ℃, keeping for 5 hours, then taking out the whole glass mold, cooling to room temperature, and then removing the prepared composite membrane from the glass mold to obtain the composite proton exchange membrane with the cerium oxide content of 1 wt%.
(4) Soaking the prepared composite membrane in 1mol/L sulfuric acid solution, heating for 1h at 80 ℃ by using a water bath kettle, soaking the composite membrane in deionized water, heating for 1h at 80 ℃ by using the water bath kettle, and taking out the composite membrane and a beaker filled with the deionized water integrally and placing the composite membrane and the beaker in a dark place for later use.
Comparative example 1:
comparative example 1 Using Nafion/CeO uncoated Polydopamine2A composite membrane.
The preparation method comprises the following steps:
(1) 3g of a 10 wt% Nafion/DMSO solution and 3mg of commercial cerium oxide were weighed by an electronic balance, an appropriate amount of DMSO solution was added, and mixed uniformly by shaking with an ultrasonic cleaner.
(2) And (2) placing the glass mold for film making with a clean surface on a precise sliding table, transferring the whole into a vacuum drying oven, adjusting the glass mold to be horizontal by using a universal leveling instrument, then pouring the casting solution obtained in the step (1) into the glass mold, setting the temperature to be 40 ℃, turning on a vacuum pump, and pumping to a high vacuum state. After 12h, raising the temperature of the vacuum drying oven to 150 ℃, keeping for 5h, then taking out the whole glass mold, cooling to room temperature, and then removing the prepared composite film from the glass mold;
(3) soaking the prepared composite membrane in 1mol/L sulfuric acid solution, heating for 1h at 80 ℃ by using a water bath kettle, soaking the composite membrane in deionized water, heating for 1h at 80 ℃ by using the water bath kettle, and taking out the composite membrane and a beaker filled with the deionized water integrally and placing the composite membrane and the beaker in a dark place for later use.
Performance analysis: the Nafion/PD @ CeO prepared in example 1 and comparative example 1 above was added2Composite proton exchange membrane and Nafion/CeO2And (5) analyzing results of the composite membrane.
FIG. 3(a) is the polarization curve before and after 10000 cycles of accelerated aging test in example 1, wherein the square point line graph is the initial polarization curve of example 1, the triangle point line graph is the polarization curve of example 1 after 10000 cycles, and the performance parameter is the single cell polarization curve at 1000mA/cm2The discharge voltage at (c). Nafion/1 wt% PD @ CeO2At 1000mA/cm2The corresponding voltage is attenuated to 0.524V from 0.579V, and is attenuated by 9.49%, and the figure also shows that the initial maximum power density of the reinforced composite membrane can reach 596mW/cm2After 10000 cycles of accelerated aging circulation, the maximum power density of the composite membrane can still reach 536mW/cm2Attenuation is about 10.06%; fig. b is a polarization curve of comparative example 1 before and after 10000 cycles of accelerated aging test, in which a square dot line graph is an initial polarization curve of comparative example 1, and a circular dot line graph is a polarization curve of comparative example 1 after 10000 cycles. Nafion/CeO2The membrane was at 1000mA/cm2The corresponding voltage is attenuated by 0.573VWhen the voltage reaches 0.5V, the voltage is attenuated by 14.6 percent, and meanwhile, after 10000 circles of accelerated aging experiments, Nafion/CeO2The maximum power density of the membrane is 590mW/cm2Attenuating to 504mW/cm2The attenuation was about 14.5%. This shows that after the dopamine-coated cerium oxide particles are introduced into the Nafion film, the free radical quenching activity is greatly improved, the decay rate of the performance of the monocell is greatly slowed down, and the service life of the monocell is effectively prolonged.
FIG. 4 is a graph showing the hydrogen permeation profile in 10000 cycles of accelerated aging test in example 1, and Nafion/CeO2Compared with membrane hydrogen permeation, the composite proton exchange membrane Nafion/1 wt% PD @ CeO2No significant increase in hydrogen permeation occurred and a smaller value indicated better membrane durability. Therefore, the poly-dopamine coated cerium oxide nanoparticles have better free radical quenching activity. The circle point diagram in the figure is a composite membrane Nafion/1 wt% PD @ CeO2The graph of hydrogen permeation change of (1) is a graph of Nafion/CeO in comparative example 12Hydrogen permeation profile of the membrane.
Example 2:
the metal oxide radical quencher in this example is cerium oxide.
This example is substantially the same as example 1 except that in step (1), the amounts of cerium oxide and polymer resin added were controlled to obtain a composite proton exchange membrane having a cerium oxide content of 0.8 wt%.
In step (1), commercial CeO is used2Dissolving dopamine hydrochloride and Tris in deionized water, and stirring on a magnetic stirrer until the dopamine hydrochloride and the Tris are completely dissolved; dropwise adding 1mol/L NaOH solution until the pH value of the solution is 9, and placing the solution on a magnetic stirrer to stir for 1.5 h; and sequentially carrying out suction filtration and drying at 60 ℃ for one night to obtain the polydopamine-coated cerium oxide particles.
Wherein, in the mixed solution, the concentration of the dopamine hydrochloride is 3mg/mL, and the concentration of the metal oxide free radical quencher is 3 mg/mL. The thickness of polydopamine in this example is about 0.7 nm.
Example 3:
the metal oxide radical quencher in this example is cerium oxide.
This example is substantially the same as example 1 except that in step (1), the amounts of cerium oxide and polymer resin added were controlled to obtain a composite proton exchange membrane having a cerium oxide content of 1.2 wt%.
In step (1), commercial CeO is used2Dissolving dopamine hydrochloride and Tris in deionized water, and stirring on a magnetic stirrer until the dopamine hydrochloride and the Tris are completely dissolved; dropwise adding 1mol/L NaOH solution until the pH value of the solution is 10, and placing the solution on a magnetic stirrer to stir for 2 hours; and sequentially carrying out suction filtration and drying at 60 ℃ for one night to obtain the polydopamine-coated cerium oxide particles.
Wherein, in the mixed solution, the concentration of the dopamine hydrochloride is 8mg/mL, and the concentration of the metal oxide free radical quencher is 4 mg/mL. The thickness of polydopamine in this example is about 0.85 nm.
Example 4:
the metal oxide radical quencher in this example is cerium oxide.
This example is substantially the same as example 1 except that in step (1), the amounts of cerium oxide and polymer resin added were controlled to obtain a composite proton exchange membrane having a manganese oxide content of 0.5 wt%.
Dissolving manganese oxide, dopamine hydrochloride and Tris in deionized water, and stirring the solution on a magnetic stirrer until the solution is completely dissolved; dropwise adding 1mol/L NaOH solution until the pH value of the solution is 9, and placing the solution on a magnetic stirrer to stir for 1.5 h; and sequentially carrying out suction filtration and drying at 60 ℃ for one night to obtain the polydopamine-coated manganese oxide particles.
Wherein, the concentration of the hydrochloric acid dopamine in the mixed solution is 0.1mg/mL, and the concentration of the metal oxide free radical quencher is 0.1 mg/mL.
Comparative example 2:
this comparative example is substantially the same as example 1, except that 6mg of polydopamine-coated cerium oxide was added in step (2) to prepare a composite proton exchange membrane having a cerium oxide content of 2 wt%.
The proton exchange membranes prepared in the examples 2-4 and the comparative example 2 are subjected to performance tests, and the performances of the examples 2-4 are consistent with the performance of the example 1. The poly-dopamine is used for coating the cerium oxide, so that the loss of the free radical quencher cerium oxide in the electrochemical reaction is reduced, the utilization rate of the cerium oxide is improved on one hand, and the service life of the composite proton exchange membrane is prolonged on the other hand. Compared with the common DuPont Nafion membrane, the durability of the dopamine-coated composite membrane is greatly improved. The invention has simple and safe manufacturing process and low cost, and can be used for the industrial production of the composite proton exchange membrane.
While the electrochemical performance of comparative example 2 is much lower than that of example 1; it has been found that excess free radical quencher can coordinate with the sulfonate, lowering proton transport sites and thus reducing the electrochemical performance of the hydrogen fuel cell.
Example 5:
the metal oxide radical quencher in this example is manganese oxide.
This example is substantially the same as example 1 except that in step (1), the amounts of cerium oxide and polymer resin added were controlled to obtain a composite proton exchange membrane having a manganese oxide content of 0.5 wt%.
Dissolving manganese oxide, dopamine hydrochloride and Tris in deionized water, and stirring the solution on a magnetic stirrer until the solution is completely dissolved; dropwise adding 1mol/L NaOH solution until the pH value of the solution is 9, and placing the solution on a magnetic stirrer to stir for 1.5 h; and sequentially carrying out suction filtration and drying at 60 ℃ for one night to obtain the polydopamine-coated manganese oxide particles.
Wherein, the concentration of the hydrochloric acid dopamine in the mixed solution is 0.1mg/mL, and the concentration of the metal oxide free radical quencher is 0.1 mg/mL.
Tests show that the composite proton exchange membrane doped with 0.5wt% of coated polydopamine manganese oxide prepared in the embodiment has greatly improved durability compared with the composite proton exchange membrane doped with 0.5wt% of uncoated polydopamine manganese oxide.
Claims (5)
1. A preparation method of a high-durability fuel cell composite proton exchange membrane is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) dissolving a metal oxide free radical quencher, dopamine hydrochloride and tris (hydroxymethyl) aminomethane in a solvent to obtain a mixed solution, adjusting the pH value of the solution to 8-10, stirring at normal temperature for 0.5-2 h for coating reaction, then carrying out suction filtration and drying on the mixed solution, and obtaining the metal oxide free radical quencher with a coating layer;
(2) mixing the metal oxide free radical quenching agent obtained in the step (1) with a polymer resin solution, and stirring to obtain a uniform dispersion liquid;
(3) pouring the dispersion liquid into a mold, drying under a vacuum condition, and performing post heat treatment to obtain a composite film;
(4) respectively placing the composite membrane in an acid solution and water for soaking treatment to obtain a proton exchange membrane;
in the step (2), in the dispersion liquid, the addition amount of the free radical quenching agent accounts for 0.5-1.2 wt% of the addition amount of the polymer resin;
the composite proton exchange membrane comprises a membrane matrix and a metal oxide radical quencher dispersed in the membrane matrix, wherein an organic matter coating layer is arranged on the surface of the radical quencher; the thickness of the coating layer is 0.5-5 nm; the metal oxide free radical quencher is cerium oxide, manganese oxide, chromium oxide or cobalt oxide, and the organic coating layer is polydopamine.
2. The method of preparing a highly durable fuel cell composite proton exchange membrane according to claim 1, wherein: in the step (1), the adding amount of the dopamine hydrochloride is 1-4 times of the mass of the free radical quencher.
3. The method of preparing a highly durable fuel cell composite proton exchange membrane according to claim 1, wherein: in the step (1), the concentration of the dopamine hydrochloride in the mixed solution is 0.1-8 mg/mL, and the concentration of the metal oxide free radical quencher is 0.1-4 mg/mL.
4. The method of preparing a highly durable fuel cell composite proton exchange membrane according to claim 1, wherein: in the step (2), the equivalent mass of the polymer resin is 700 g/mol-1200 g/mol, and the solvent of the polymer resin solution is dimethyl sulfoxide or N, N-dimethylformamide.
5. The method of preparing a highly durable fuel cell composite proton exchange membrane according to claim 1, wherein: in the step (3), the drying treatment temperature is 40-80 ℃, the drying time is 8-16 h, the heat treatment temperature is 125-180 ℃, and the heat treatment time is 3-6 h.
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| KR20200033630A (en) * | 2018-09-20 | 2020-03-30 | 한국과학기술연구원 | Reinforced composite membrane for fuel cells and method for manufacturing the same |
| CN109755613A (en) * | 2018-12-19 | 2019-05-14 | 湖北工程学院 | A kind of three-dimensional framework and aromatic sulfonated polymer compound proton exchange membrane and preparation method thereof |
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