CN115000479B - Modified proton exchange membrane and preparation method and application thereof - Google Patents
Modified proton exchange membrane and preparation method and application thereof Download PDFInfo
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Classifications
-
- 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
-
- 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
-
- 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
- H01M8/1076—Micromachining techniques, e.g. masking, etching steps or photolithography
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The application belongs to the technical field of fuel cells, and provides a modified proton exchange membrane and a preparation method and application thereof, wherein the preparation method comprises the following steps: a raw material layer is constructed on one side or two sides of a flat proton exchange membrane through resin solution casting, and the raw material layer is a resin layer with proton conduction capacity; and then carrying out micro-nano imprinting and structure re-imprinting on the raw material layer by using a template, wherein the micro-nano imprinting is low-temperature imprinting below 50 ℃, and carrying out heat curing treatment to obtain the modified proton exchange membrane with the ordered microstructure on the surface. The modified proton exchange membrane has an ordered microstructure layer on the surface, can improve the utilization efficiency of a catalyst applied subsequently, has good mechanical stability, and can be widely applied to ultrathin ordered proton exchange membranes.
Description
Technical Field
The application belongs to the technical field of fuel cells, relates to a method for constructing an ordered microstructure on the surface of a proton exchange membrane, and in particular relates to a modified proton exchange membrane, and a preparation method and application thereof.
Background
The fuel cell is used as a novel energy source technology, has the advantages of high energy density, environmental protection, quick start and the like, and has wide application prospect. The single battery is generally composed of a positive electrode and a negative electrode (a fuel electrode and an oxidant electrode as a cathode) and an electrolyte; fuel cells typically require the use of a noble metal platinum or platinum alloy catalyst. The platinum noble metal is scarce in resources and expensive, so how to reduce the catalyst loading in the fuel cell and improve the utilization efficiency of the catalyst are important links for realizing the commercialization of the fuel cell.
A Proton Exchange Membrane Fuel Cell (PEMFC) is a fuel cell, wherein a single cell mainly comprises an anode, a cathode and a proton exchange membrane, the anode is a place where hydrogen fuel is oxidized, the cathode is a place where oxidant is reduced, and both electrodes contain catalysts for accelerating electrochemical reactions of electrodes. The proton exchange membrane is used as a key component of a membrane electrode in a fuel cell, plays a role in isolating hydrogen and air and providing a proton transmission channel, and simultaneously provides an electrochemical reaction place on the surface. At present, a proton exchange membrane is generally prepared by casting, extrusion and other methods, a planar structure is generally adopted, the contact area of the proton exchange membrane and a catalytic layer is relatively fixed, and the electrochemical reaction interface is very limited. By constructing a microstructure on the surface of the proton exchange membrane or carrying out patterning processing on the surface of the proton exchange membrane, the contact area of the proton exchange membrane and the catalytic layer can be effectively increased, so that the reaction interface of the fuel cell is increased, the utilization efficiency of the catalyst is improved, and the purposes of reducing the noble metal loading and improving the performance of the fuel cell are achieved.
In the prior art, the Chinese patent document with the application publication number of CN 103199268A forms ordered nano-structures complementary with patterns on a hard template on a polymer membrane in a hot stamping mode so as to achieve the purposes of improving the utilization rate of a catalyst and reducing the cost of a battery. However, the method adds higher temperature and pressure on the flat proton exchange membrane, which can cause certain damage to the original proton exchange membrane structure, thus leading to the thinning of the original proton exchange membrane and increasing the risk of hydrogen-oxygen series leakage of the membrane electrode, and the method is not suitable for the application scene of the ultrathin proton exchange membrane with the thickness of less than 10 micrometers.
Disclosure of Invention
Aiming at the defects in the prior art, the application provides the modified proton exchange membrane, the preparation method and the application thereof, and the surface of the modified proton exchange membrane is provided with the ordered microstructure layer, so that the utilization efficiency of a catalyst for subsequent application can be improved, and the mechanical stability of the modified proton exchange membrane is better, so that the modified proton exchange membrane can be widely applied to ultrathin ordered proton exchange membranes.
The application provides a preparation method of a modified proton exchange membrane, which comprises the following steps:
a raw material layer is constructed on one side or two sides of a flat proton exchange membrane through resin solution casting, and the raw material layer is a resin layer with proton conduction capacity;
and then carrying out micro-nano imprinting and structure re-imprinting on the raw material layer by using a template, wherein the micro-nano imprinting is low-temperature imprinting below 50 ℃, and carrying out heat curing treatment to obtain the modified proton exchange membrane with the ordered microstructure on the surface.
In an embodiment of the present application, the raw material layer is cast from a resin solution having a mass percentage concentration of 0.1% -30%, and the resin in the resin solution is independently selected from fluorinated sulfonic acid resins or other aromatic resins.
In an embodiment of the present application, the solvent in the resin solution is selected from one or more of methanol, ethanol, N-propanol, isopropanol, ethylene glycol, water, dimethyl sulfoxide, and N-methyl pyrrolidone.
In an embodiment of the present application, the proton exchange membrane is a membrane material with proton conductivity and a thickness of 8 micrometers-15 micrometers.
In an embodiment of the present application, the proton exchange membrane is a Nafion117, nafion211, nafion212, nafion hp membrane, gore membrane, or dongle membrane.
In an embodiment of the application, the template is a stainless steel mesh screen, a hard plastic mesh screen, a glass template, a silicon oxide template, a silicon carbide template, a polydimethylsiloxane template, or a polymethyl methacrylate template.
In the embodiment of the application, the micro-nano imprinting mode is one or more of point pressing, line pressing, surface pressing and rolling, and the pressure range of the micro-nano imprinting is 0.1-10MPa.
In an embodiment of the present application, the heat curing treatment is a heat treatment at 50 to 150 ℃ for 0.2 to 24 hours.
The application provides a modified proton exchange membrane obtained by the preparation method, and the surface of the modified proton exchange membrane is provided with an ordered microstructure layer with the dimension below 5 micrometers.
The application provides the use of a modified proton exchange membrane as hereinbefore described in a fuel cell.
Compared with the prior art, the application adopts proton conduction resin raw materials, and builds an ordered microstructure layer on one side or two sides of the proton exchange membrane by a casting method and a low-temperature micro-nano processing technology. The application only carries out structure construction on the raw material layer, the formed microstructure is tightly connected with the proton exchange membrane, the proton exchange membrane base material cannot be damaged, and the structural integrity of the original base material can be ensured. The microstructure layer morphology is complementary with the template morphology, the scale can be controlled to be below 5 micrometers or even at the nanometer level, the membrane impedance is not increased, and the microstructure layer morphology and the template morphology can be widely applied to preparation and modification of ultrathin ordered proton exchange membranes. The embodiment of the application can increase the surface area of the proton exchange membrane by 1-5 times, increase the contact area between the proton exchange membrane and the catalytic layer, and reduce ohmic resistance, thereby improving the performance of the applied fuel cell.
Meanwhile, the preparation method has simple flow, does not need post-treatment operations such as acidification and the like, does not cause environmental pollution, is easy for industrial amplification, and has great development value and market potential.
Drawings
FIG. 1 is a flow chart of an embodiment of the present application for preparing a modified proton exchange membrane;
FIG. 2 is an SEM image of a proton exchange membrane with a microstructure layer prepared in example 1 using a stainless steel mesh screen as a template;
FIG. 3 is an SEM image of a proton exchange membrane with a microstructure layer prepared by using a stainless steel mesh screen as a template, after a catalytic layer is sprayed on the surface of the proton exchange membrane;
FIG. 4 is a graph showing the polarization curves measured under the same test conditions for a membrane electrode prepared using a proton exchange membrane with a microstructured layer and a membrane electrode prepared using a planar commercial membrane;
FIG. 5 is an SEM image of a proton exchange membrane with a microstructure layer prepared by using PDMS as a template in example 3;
fig. 6 is an SEM image after spraying a catalytic layer on the surface of a proton exchange membrane with a microstructure layer prepared by using PDMS as a template.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The application provides a preparation method of a modified proton exchange membrane, which comprises the following steps: a raw material layer is constructed on one side or two sides of a flat proton exchange membrane through resin solution casting, and the raw material layer is a resin layer with proton conduction capacity; and then carrying out micro-nano imprinting and structure re-imprinting on the raw material layer by using a template, wherein the micro-nano imprinting is low-temperature imprinting below 50 ℃, and carrying out heat curing treatment to obtain the modified proton exchange membrane with the ordered microstructure on the surface.
The modified proton exchange membrane has an ordered microstructure layer on the surface, can improve the utilization efficiency of a catalyst applied subsequently, has good mechanical stability, and can be widely applied to ultrathin ordered proton exchange membranes.
Referring to fig. 1, fig. 1 is a flow chart of preparing a modified proton exchange membrane according to an embodiment of the present application. In a preferred embodiment of the application, the specific steps of the preparation method are as follows:
s1, dissolving ion exchange resin containing sulfonic groups in a solvent to prepare a resin solution;
s2, spreading the proton exchange membrane on a vacuum adsorption plate, and casting a layer of resin solution on the membrane to obtain a raw material layer;
s3, flatly covering the template material on the raw material layer, and applying a certain pressure to finish the structure re-etching of the template microstructure to the raw material layer;
s4, demolding, and putting the proton exchange membrane with the micro-etched structure into a drying oven for annealing, so that the resin is solidified to form an ordered micro-structure layer.
The embodiment of the application firstly prepares the resin solution, and can mix and dissolve commercial resin raw materials with a solvent according to a certain proportion to obtain the resin solution. The resin in the resin solution is independently selected from fully fluorinated sulfonic acid resins, partially fluorinated sulfonic acid resins or other aromatic resins; the solvent can be water and/or alcohols, etc., preferably one or more selected from methanol, ethanol, N-propanol, isopropanol, ethylene glycol, water, dimethyl sulfoxide and N-methyl pyrrolidone.
The embodiment of the application can prepare the resin solution with the mass percentage concentration of 0.1-30%, and the resin solution is cast to form the raw material layer with proton conductivity. The mass concentration of the resin solution is preferably 1% to 20%, more preferably 5% to 18%, and particularly may be a perfluorosulfonic acid resin solution. However, the specific resin type of the raw material layer is not limited in the embodiment of the application, and the raw material layer can be commercial dupont resin, 3M resin, xu-shi resin, suwei resin, domestic east Yue resin or other aromatic sulfonated resins, and can be made into microstructures to achieve the advantages of improving the surface roughness of the proton membrane and improving the performance of the fuel cell. By way of example, the present example used a commercial DuPont model D2020 resin solution with a resin solids content of 20% by weight and a water content of 34%.
In the embodiment of the application, a flat proton exchange membrane is used as a modified substrate; in an embodiment of the application, the raw material layer is constructed on a single surface or two surfaces of the proton exchange membrane by a casting method. The proton exchange membrane can be Nafion117, nafion211, nafion212, nafion HP membrane, gore membrane, dongyue membrane or other membrane materials with proton conducting capability; the chemical structure of the Nafion membrane is a branched chain with polytetrafluoroethylene as a framework and sulfonic acid groups. The gore membrane is a proton exchange membrane produced by gore company and has the characteristics of ultra-thin property, durability and the like; the Dongyue membrane is a membrane material produced by Dongyue group. In the modified base material with the specific model, compared with the proton membrane with the first three models, the NafionHP membrane has different thickness and structure, and a reinforcing layer is added in the middle; the Nafion series films are thinner than the east Yue film and the gore film is thinner than the east Yue film.
The substrate prepared at present in the embodiment of the application is about 8-14 microns, is suitable for ultrathin proton exchange membranes, and can effectively reduce the resistance of the battery. The basic indexes such as the sulfonation degree, the void ratio and the surface area of the base material are not particularly limited, and the base material can be constructed on the surface of any proton exchange membrane. According to the embodiment of the application, the commercial substrate film can be flatly paved on the vacuum adsorption plate, and a wet film with the thickness of 20-50 microns is constructed on the substrate to form a raw material layer with the thickness of 0.1-5 microns. In the embodiment of the application, the casting method is one or more of a knife coating method, a spraying method, a spin coating method and a casting method, and the conventional operation in the field is adopted. The wet film is coated on the substrate by a knife coating method, a spraying method, a spin coating method and a casting method, and the thickness of the wet film is controllable. In contrast, a dry film is formed after the solution in a wet film is volatilized, and the thickness depends on the solid content and the like. The embodiment of the application does not change the base material, the structure of the raw material layer is changed, the thickness of the raw material layer is adjusted, the thickness of the wet film of the raw material layer is 20-50 microns, and the final dry film is 0.1-5 microns.
After the raw material layer is formed, a template material is flatly paved on the raw material layer, micro-nano imprinting and structure re-engraving are carried out on the raw material layer, and the ordered microstructure layer is obtained after demoulding and heat curing. The template can be a through hole type mesh screen hard template and/or a polymer soft template with an ordered array structure; including but not limited to one or more of stainless steel mesh, glass templates, hard plastic mesh, silica templates, porous silica, silicon carbide templates, polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA), or other polymer soft templates.
In the application, the micro-nano imprinting is low-temperature imprinting below 50 ℃, and the microstructure forming temperature is lower. The micro-nano imprinting mode can be one or more of point pressing, line pressing, surface pressing and rolling; the pressure of the micro-nano imprint is preferably in the range of 0.1 to 10MPa, more preferably 0.1 to 9MPa, for example, the pressure applied above the template is 0.1MPa,1MPa,3MPa, 5MPa, 6MPa, or the like.
And (5) demolding after maintaining for a certain time to obtain the proton exchange membrane with the structure subjected to repeated etching. According to the embodiment of the application, the modified proton exchange membrane with the microstructure layer is obtained through heat curing treatment. The heat curing treatment mainly comprises the steps of placing the proton exchange membrane with the structure subjected to the re-etching in an oven for heat preservation and resin curing; the modified proton exchange membrane can be obtained by heat treatment for 0.2-24h at 50-150 ℃, the temperature is preferably 80-130 ℃ and the time is preferably 0.5-12 h.
The embodiment of the application provides a modified proton exchange membrane obtained by the preparation method, wherein the surface of the modified proton exchange membrane is provided with an ordered microstructure layer complementary with a template, and the microstructure scale can be below 5 micrometers and even reach the nanometer level. In some embodiments of the application, the microstructures are rectangular arrays of projections, and in other embodiments, the microstructures are hexagonal stacked conical arrays.
The application only uses the raw material layer to form the microstructure, the microstructure is tightly connected with the proton exchange membrane, the original proton exchange membrane cannot be damaged in any structure or thinned, and the mechanical stability of the proton exchange membrane is maintained. The application does not increase the membrane impedance, the microstructure scale can be controlled to be below 5 micrometers or even to be at the nanometer level, and the application can be widely applied to the preparation and modification of ultrathin ordered proton exchange membranes. The surface of the modified proton exchange membrane is provided with an ordered array, which is beneficial to water and gas transmission.
In addition, the application does not need post-treatment operations such as acidification and the like, does not cause environmental pollution, and is easy for industrial amplification.
The application provides the use of a modified proton exchange membrane as described hereinbefore in a fuel cell; specifically, the modified proton exchange membrane and the catalytic layer are combined to form a membrane electrode, and the membrane electrode is further assembled into a fuel single cell. The catalyst layer component and the fuel cell assembly are conventional, and the present application is not particularly limited.
According to the application, an ordered microstructure layer is constructed on one side or two sides of the proton exchange membrane by a casting method and a micro-nano processing technology, and the microstructure layer can effectively increase the surface area of the proton exchange membrane (can be increased by 1-5 times), so that the interface contact area between the proton exchange membrane and a catalytic layer is increased, and the purposes of improving the utilization efficiency of a catalyst, reducing the noble metal loading and improving the performance of a fuel cell are achieved.
In order to better understand the technical content of the present application, the following provides specific examples to further illustrate the present application. The concentration of the resin solution prepared in the following examples was between 0.1 and 30%, and commercial products were used for each material.
Example 1
1. Preparing a resin solution: commercial D2020 resin solution was selected according to the resin: n-propanol: the water is 15:51:34 mass ratio, and preparing to obtain resin solution.
2. And (3) ordered microstructure construction: spreading a commercial 15-micrometer film in the east Yue on a vacuum adsorption plate, adjusting the height of a scraper to 45 mu m, scraping the resin solution in the step 1 on the proton exchange film in the east Yue, and standing for 1min to form a raw material layer. Then a stainless steel screen (2000 mesh) was laid flat on the raw material layer, and a pressure of 5MPa was applied above the stainless steel screen at room temperature, and the pressure was maintained for 5 minutes. And demolding to obtain the proton exchange membrane with the microstructure.
3. And (3) curing resin: placing the proton exchange membrane with the microstructure in a baking oven at 120 ℃, and carrying out heat preservation for half an hour to carry out resin curing to obtain a modified proton exchange membrane with a microstructure layer; the SEM (scanning electron microscope) image is shown in fig. 2. The microstructure is a rectangular bulge array, and the surface area of the modified proton exchange membrane with the microstructure is increased by 1.1 times compared with that of a planar membrane.
Comparative example 1
1. Preparing a membrane electrode: cathode and anode catalytic layer slurries are prepared and sprayed on two sides of a commercial east Yue 15 micron membrane (a planar proton exchange membrane) to form a catalytic layer coated membrane (catalyst coated membrane, CCM for short). Catalyst loadings of the membrane electrodes were 0.05mg/cm, respectively 2 (anode), 0.15mg/cm 2 (cathode); the CCM is arranged between two gas diffusion layers, and the CCM is attached by a frame to prepare the membrane electrode.
2. Polarization curve: the prepared membrane electrode is assembled into a single cell, and the effective reaction area is 25cm 2 . The test conditions for the polarization curve were: hydrogen/air, absolute pressure 150kPa, cell temperature 80 ℃, gas metering ratio: anode 2.0, cathode 2.0. Polarization curves were tested at 100% humidification.
Example 2
1. Preparing a membrane electrode:
a proton exchange membrane with a microstructure was prepared in the same way as in example 1.
The same cathode and anode catalyst layer slurries as in comparative example 1 were prepared and sprayed on both sides of the above-described proton exchange membrane with microstructure to prepare CCM. The SEM image of the surface of the CCM is shown in fig. 3, and fig. 3 is an SEM image after a catalytic layer is sprayed on the surface of a proton exchange membrane with a microstructure layer prepared by using a stainless steel mesh screen as a template. Catalyst loading of the membrane electrode was 0.05mg/cm 2 (anode) and 0.15mg/cm 2 (cathode); the CCM is arranged between two gas diffusion layers, and the CCM is attached by a frame to prepare the membrane electrode.
2. Polarization curve: the prepared membrane electrode is assembled into a single cell, and the effective reaction area is 25cm 2 . The test conditions for the polarization curve were: hydrogen/air, absolute pressure 150kPa, cell temperature 80 ℃, gas metering ratio: anode 2.0, cathode 2.0. Test at 100% moisturization conditionsA lower polarization curve.
Fig. 4 shows polarization curves measured under the same test conditions for a membrane electrode prepared using a proton exchange membrane with a microstructured layer and a membrane electrode prepared using a flat commercial membrane. In the polarization curve of fig. 4, sample No. 1 is a control group, and sample No. 2 is an experimental group. Sample No. 1 is a membrane electrode prepared using a planar proton exchange membrane, and sample No. 2 is a membrane electrode prepared using a pattern membrane.
As shown in FIG. 4 (sample No. 1, E-1 represents the voltage at this current density, E-IR-1 represents the voltage after ohmic resistance removal, ASR-1 represents the area specific resistance), the membrane electrode produced in comparative example 1 exhibited good polarization performance. Membrane electrode for 100% humidification condition test, 1600 mA.cm -2 The voltage at this point can reach 0.583V.
As shown in FIG. 4 (sample No. 2, E-2 represents the voltage at this current density, E-IR-2 represents the voltage after ohmic resistance removal, ASR-2 represents the area specific resistance), the membrane electrode produced in example 2 exhibited good polarization performance. Membrane electrode for 100% humidification condition test, 1600 mA.cm -2 The voltage at this point may reach 0.620V. Compared with the control group plane proton exchange membrane sample of comparative example 1, the control group plane proton exchange membrane sample has 37mV improvement, ASR is obviously reduced, and better catalyst utilization efficiency and fuel cell performance are shown under the same catalyst loading.
Example 3
1. Preparing a resin solution: commercial D2020 resin solution was selected according to the resin: ethanol/n-propanol mixture: the water is 15:51:34 mass ratio, preparing to obtain a resin solution; the volume ratio of the ethanol to the n-propanol mixed solution is about 1:1.
2. And (3) ordered microstructure construction: and (3) spreading the commercial gore 8 micrometer film on a vacuum adsorption plate, adjusting the height of a scraper to be 32 mu m, scraping the resin solution in the step (1) on the gore proton exchange film, and standing for 1min to form a raw material layer. The PMDS template was then tiled on top of the stock layer, applying a pressure of 0.1MPa over the PMDS template (4 inch size) for 5min. And demolding to obtain the proton exchange membrane with the microstructure.
3. And (3) curing resin: placing the proton exchange membrane with the microstructure in a baking oven at 120 ℃, and carrying out heat preservation for half an hour to carry out resin curing to obtain a modified proton exchange membrane with a microstructure layer; the SEM image is shown in figure 5. The microstructure is a hexagonal stacked conical array, and the proton exchange membrane with the microstructure has a 1.4-fold increase in surface area compared with a planar membrane.
CCM: the same cathode and anode catalyst layer slurries as in example 2 were prepared and sprayed on both sides of the above-described proton exchange membrane with microstructure to prepare CCM. As shown in the SEM map of the CCM surface, the surface of the CCM is flat and has no obvious fluctuation.
Example 4
1. A resin with a commercial 3MEW value of 800g/mol (E-216669A) was selected according to the following: n-propanol: the water is 20:53:27 mass ratio, and preparing to obtain a resin solution.
2. And (3) ordered microstructure construction: spreading a commercial 15-micrometer film in the east Yue on a vacuum adsorption plate, adjusting the height of a scraper to 35 mu m, scraping the resin solution in the step 1 on the proton exchange film in the east Yue, and standing for 1min to form a raw material layer. Then a stainless steel screen (2000 mesh) was laid flat on the raw material layer, and a pressure of 1MPa was applied above the stainless steel screen at room temperature, and the pressure was maintained for 5 minutes. And demolding to obtain the proton exchange membrane with the microstructure.
3. And (3) curing resin: and (3) placing the proton exchange membrane with the microstructure in a baking oven at 150 ℃, and preserving heat for 15min to perform resin curing to obtain the modified proton exchange membrane with the microstructure layer. The microstructure is a rectangular bulge array, and the surface area of the modified proton exchange membrane with the microstructure is increased by 1.1 times compared with that of a planar membrane.
As can be seen from the above examples, the present application adopts proton conductive resin material to construct an ordered microstructure layer on one side or both sides of the proton exchange membrane by casting method and low temperature micro-nano processing technique. The microstructure layer morphology is complementary with the template morphology, the scale can be controlled to be below 5 micrometers or even at the nanometer level, the membrane impedance is not increased, and the microstructure layer morphology and the template morphology can be widely applied to preparation and modification of ultrathin ordered proton exchange membranes. The embodiment of the application can increase the surface area of the proton exchange membrane by 1-5 times, increase the contact area between the proton exchange membrane and the catalytic layer, and reduce ohmic resistance, thereby improving the performance of the applied fuel cell. Meanwhile, the preparation method is simple in flow, does not need post-treatment operations such as acidification and the like, does not cause environmental pollution, and is easy for industrial amplification.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The principles and embodiments of the present application have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present application and its core ideas. The foregoing is merely illustrative of the preferred embodiments of this application, and it is noted that there is objectively no limit to the specific structure disclosed herein, since numerous modifications, adaptations and variations can be made by those skilled in the art without departing from the principles of the application, and the above-described features can be combined in any suitable manner; such modifications, variations and combinations, or the direct application of the inventive concepts and aspects to other applications without modification, are contemplated as falling within the scope of the present application.
Claims (9)
1. The preparation method of the modified proton exchange membrane is characterized by comprising the following steps of:
a raw material layer is constructed on one side or two sides of a flat proton exchange membrane through resin solution casting, and the raw material layer is a resin layer with proton conduction capacity; and then carrying out micro-nano imprinting and structure re-imprinting on the raw material layer by using a template, wherein the micro-nano imprinting is low-temperature imprinting below 50 ℃, and carrying out heat curing treatment to obtain the modified proton exchange membrane with the ordered microstructure on the surface, wherein the ordered microstructure layer with the dimension below 5 microns is arranged on the surface.
2. The method of claim 1, wherein the feedstock layer is cast from a resin solution having a mass percent concentration of 0.1% -30%, the resin in the resin solution being independently selected from fluorinated sulfonic acid resins or other aromatic resins.
3. The method according to claim 2, wherein the solvent in the resin solution is one or more selected from the group consisting of methanol, ethanol, N-propanol, isopropanol, ethylene glycol, water, dimethyl sulfoxide and N-methyl pyrrolidone.
4. A method according to any one of claims 1 to 3, wherein the proton exchange membrane is a membrane material having proton conductivity with a thickness of 8 to 15 μm.
5. The method of claim 4, wherein the proton exchange membrane is Nafion117, nafion211, nafion212, nafion hp, gore or dongle.
6. A method of preparation according to any one of claims 1 to 3 wherein the template is a stainless steel mesh screen, a hard plastic mesh screen, a glass template, a silica template, a silicon carbide template, a polydimethylsiloxane template or a polymethyl methacrylate template.
7. The preparation method according to any one of claims 1 to 3, wherein the micro-nano imprinting mode is one or more of spot pressing, line pressing, surface pressing and rolling, and the pressure of the micro-nano imprinting is in the range of 0.1 to 10MPa.
8. A production method according to any one of claims 1 to 3, wherein the heat-curing treatment is heat-treatment at 50 to 150 ℃ for 0.2 to 24 hours.
9. Use of a modified proton exchange membrane obtained by the preparation method according to any one of claims 1 to 8 in a fuel cell.
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