CN113594521A - Preparation method and system of proton exchange membrane - Google Patents

Preparation method and system of proton exchange membrane Download PDF

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Publication number
CN113594521A
CN113594521A CN202110786729.6A CN202110786729A CN113594521A CN 113594521 A CN113594521 A CN 113594521A CN 202110786729 A CN202110786729 A CN 202110786729A CN 113594521 A CN113594521 A CN 113594521A
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proton exchange
layer
exchange membrane
coating
heating
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CN113594521B (en
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樊建涛
李辉
徐少轶
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Hydrogen Energy Shenzhen Co ltd
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Southwest University of Science and Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • B32B38/145—Printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/18—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
    • 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

In order to overcome the problem that the existing proton exchange membrane cannot meet the requirements of thickness and strength at the same time, the invention provides a preparation method of a proton exchange membrane, which comprises the following operation steps: providing a release film; coating first proton exchange resin slurry on the release film to form a first proton exchange layer; covering one surface of the reinforced net layer on the first proton exchange layer, enabling the proton exchange resin slurry of the first proton exchange layer to enter the reinforced net layer, and heating and drying to obtain a composite layer of the reinforced net layer, the first proton exchange layer and the release film; and coating the second proton exchange resin slurry on the other surface of the reinforced net layer to form a second proton exchange layer, heating, drying and rolling to obtain the proton exchange membrane and release membrane composite material. Meanwhile, the invention also discloses a preparation system of the proton exchange membrane. The preparation method provided by the invention can realize the purpose of large-scale continuous preparation of the proton exchange membrane, and the prepared proton exchange membrane has higher mechanical strength and dimensional stability.

Description

Preparation method and system of proton exchange membrane
Technical Field
The invention belongs to the technical field of proton exchange membranes, and particularly relates to a preparation method and a system of a proton exchange membrane.
Background
Hydrogen energy is the main melody of sustainable development of the twenty-first century, and the hydrogen energy technology is an indispensable clean energy technology for realizing carbon peak reaching and carbon neutralization. Water electrolysis is a hydrogen production technology in the hydrogen energy field, and a fuel cell is a hydrogen utilization technology in the hydrogen energy field, so that the application of hydrogen energy is realized in a head-to-tail manner.
The proton exchange membrane electrolytic water and the proton exchange membrane fuel cell are two technologies with the widest application range, relatively mature technology and the largest market potential. The proton exchange membrane is a key material in the two key technologies.
A Proton Exchange Membrane (PEM) is an ion-conducting membrane that provides a pathway for the migration and transport of protons, while blocking the anode and cathode gases from mixing. The proton exchange membrane is one of the core components of hydrogen production by water electrolysis and hydrogen-oxygen fuel cells, and the performance of the proton exchange membrane is closely related to the performance of the cells. In the process of operating the battery, the influence of the proton exchange membrane on the performance of the battery is mainly reflected on the surface resistance, and the size of the surface resistance is determined by the ionic conductivity of the proton exchange membrane and the thickness of the proton exchange membrane, so that for the proton exchange membrane used in the fuel battery, the current ultra-thinning and high-strength are the inevitable trend of the development of the proton membrane.
The prior proton exchange membrane preparation technology is that perfluorosulfonic acid resin before hydrolysis is heated and melted, then extruded to a base membrane, and subjected to hydrolysis treatment after preparation and membrane formation to obtain the proton exchange membrane. However, this method has two disadvantages, one is that the proton exchange membrane prepared by melt extrusion has a relatively thick thickness, typically over 100 μm; secondly, the method is difficult to add a reinforcing layer in the middle of the proton exchange membrane to improve the mechanical property of the membrane. Another common method at present is to disperse the perfluorosulfonic acid resin in a solvent system of water and alcohol, directly coat the polymer solution on a base film such as PET, and form the proton exchange membrane after drying and heat treatment. Although this method can produce a proton exchange membrane with a small thickness, it is difficult to withstand the pressure difference between the anode and the cathode during the operation of an electrolytic cell or a fuel cell and the dimensional change due to water absorption and swelling.
Disclosure of Invention
Aiming at the problem that the existing proton exchange membrane can not meet the requirements of thickness and strength at the same time, the invention provides a preparation method and a system of the proton exchange membrane.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a preparation method of a proton exchange membrane, which comprises the following operation steps:
providing a release film;
coating first proton exchange resin slurry on the release film to form a first proton exchange layer;
covering one surface of the reinforced net layer on the first proton exchange layer, enabling the proton exchange resin slurry of the first proton exchange layer to enter the reinforced net layer, and heating and drying to obtain a composite layer of the reinforced net layer, the first proton exchange layer and the release film;
and coating the second proton exchange resin slurry on the other surface of the reinforced net layer to form a second proton exchange layer, heating, drying and rolling to obtain the proton exchange membrane and release membrane composite material.
Optionally, the release force of the proton exchange membrane and the release film is 1-100 g/mm.
Optionally, the release film and the reinforced mesh layer are both supplied by a coil, a material compounded by a proton exchange film and the release film is rolled to obtain a coil, the coating modes of the first proton exchange layer and the second proton exchange layer are respectively and independently selected from one or more of slit coating, gravure coating, comma scraper coating and screen printing, and the coating thickness is 100-1000 um.
Optionally, the first proton exchange resin slurry and the second proton exchange resin slurry both include a proton exchange resin and a solvent, and the proton exchange resin is independently selected from one or more of perfluorinated sulfonic acid resin, partially fluorinated sulfonic acid resin, sulfonated polyether ether ketone, sulfonated polysulfone, sulfonated polyether sulfone, quaternary ammonium salt anion exchange resin, and imidazole anion exchange resin; the solid content of the first proton exchange resin slurry and the solid content of the second proton exchange resin slurry are 5-50%.
Optionally, an inorganic particle filler is further added into the first proton exchange resin slurry and the second proton exchange resin slurry, the added mass content of the inorganic particle filler is 0.1-10%, and the inorganic particle filler is selected from SiO2、CeO2、MnO2、MnSO4And one or more of Pt and Pt/C.
Optionally, the thickness of the reinforced net layer is 5-200 um, the aperture is 0.1-1 mm, and the strength is 10-100 MPa.
Optionally, the reinforcing mesh layer is selected from one or more of expanded PTFE, a woven mesh of Polyetheretherketone (PEEK) and a woven mesh of polyester.
Optionally, the step of forming the second proton exchange layer and heating and drying further includes the operation of heat treatment and temperature reduction.
On the other hand, the invention provides a preparation system of a proton exchange membrane, which comprises a first unwinding roller for unwinding a release membrane, a second unwinding roller for unwinding a reinforced net layer, and a first coating roller, a first heating and drying device, a second coating roller and a second heating and drying device which are sequentially arranged along the feeding direction of the first unwinding roller, wherein the reinforced net layer unwound by the second unwinding roller and the unwinding of the first coating roller enter the first heating and drying device for compounding.
Optionally, the first heating and drying device includes a composite roller, a heating device is arranged in the composite roller, and the reinforced mesh layer discharged by the second unwinding roller and the discharged material of the first coating roller are combined on the composite roller and are subjected to heating and drying treatment at the same time.
According to the preparation method of the proton exchange membrane, the release membrane is used as a forming matrix, the thickness of the formed proton exchange membrane can be effectively controlled by coating the first proton exchange resin slurry on the release membrane, applying the subsequent reinforced net layer and coating the second proton resin slurry on the release membrane, the excessive thickness of the proton exchange membrane is avoided, and meanwhile, the addition of the reinforced net layer improves the overall mechanical strength of the proton exchange membrane, so that the proton exchange membrane meets the pressure difference bearing requirement when an electrolytic cell or a fuel cell is applied, and the dimensional stability of the proton exchange membrane is ensured; the filling degree of the first proton exchange resin slurry and the second proton exchange resin to the reinforced net layer is improved by the double-sided coating of the reinforced net layer, and the integral forming effect of the reinforced net layer, the first proton exchange layer and the second proton exchange layer is ensured. Meanwhile, the release film can be used as a protective layer after the proton exchange membrane is formed so as to form a coiled material, and the purpose of large-scale continuous preparation of the proton exchange membrane is realized.
Drawings
FIG. 1 is a schematic structural diagram of a system for preparing a proton exchange membrane according to the present invention;
FIG. 2 is another schematic structural diagram of a proton exchange membrane manufacturing system provided by the present invention.
The reference numbers in the drawings of the specification are as follows:
1-a first unwinding roller; 2-a first applicator roll; 21-a first coating head; 3-a second unwinding roller; 4 a-a compound roller; 4 b-a compound roller; 5-drying device; 6-a second coating roll; 61-a second coating head; 7-a second heating and drying device; 8-a heat treatment device; 9-cooling device.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of a proton exchange membrane, which comprises the following operation steps:
providing a release film;
coating first proton exchange resin slurry on the release film to form a first proton exchange layer;
covering one surface of the reinforced net layer on the first proton exchange layer, enabling the proton exchange resin slurry of the first proton exchange layer to enter the reinforced net layer, and heating and drying to obtain a composite layer of the reinforced net layer, the first proton exchange layer and the release film;
and coating the second proton exchange resin slurry on the other surface of the reinforced net layer to form a second proton exchange layer, heating, drying and rolling to obtain the proton exchange membrane and release membrane composite material.
The release film is used as a forming matrix, the first proton exchange resin slurry is coated on the release film, the subsequent reinforcing mesh layer application and the second proton resin slurry coating are carried out on the release film, the thickness of the formed proton exchange film can be effectively controlled, the proton exchange film is prevented from being too thick, meanwhile, the reinforcing mesh layer is added, the overall mechanical strength of the proton exchange film is improved, the proton exchange film meets the pressure difference bearing requirement when an electrolytic cell or a fuel cell is applied, and the dimensional stability of the proton exchange film is ensured; the filling degree of the first proton exchange resin slurry and the second proton exchange resin to the reinforced net layer is improved by the double-sided coating of the reinforced net layer, and the integral forming effect of the reinforced net layer, the first proton exchange layer and the second proton exchange layer is ensured. Meanwhile, the release film can be used as a protective layer after the proton exchange membrane is formed so as to form a coiled material, and the purpose of large-scale continuous preparation of the proton exchange membrane is realized.
In some embodiments, the release force of the proton exchange membrane and the release film is 1-100 g/mm.
Proton exchange membrane can cut to required size when specific application after, get rid of from the type membrane, can regard as electrolytic cell or fuel cell's proton exchange membrane to use, consequently, from the type membrane with need have between the proton exchange membrane suitable from type power, guarantee from the type membrane with separation between the proton exchange membrane, also avoid simultaneously as the coiled material when saving, from the type membrane with the mutual adhesion of proton exchange membrane surface.
In some embodiments, the first proton exchange layer and the second proton exchange layer are heated to a drying temperature of 40 to 100 ℃.
In some embodiments, the release film and the reinforcing mesh layer are both supplied by a coil, the material compounded by the proton exchange film and the release film is wound to obtain a coil, the first proton exchange layer and the second proton exchange layer are coated in a manner of being independently selected from one or more of slit coating, gravure coating, comma knife coating and screen printing, and the coating thickness is 100-1000 um.
In some embodiments, the first proton exchange resin slurry and the second proton exchange resin slurry each comprise a proton exchange resin and a solvent, and the proton exchange resins are each independently selected from one or more of perfluorinated sulfonic acid resins, partially fluorinated sulfonic acid resins, sulfonated polyethers, sulfonated polyether ether ketones, sulfonated polysulfones, sulfonated polyether sulfones, quaternary ammonium salt based anion exchange resins, and imidazole based anion exchange resins; the solid content of the first proton exchange resin slurry and the solid content of the second proton exchange resin slurry are 5-25%. The solvent may be selected from water or other organic solvents.
In some embodiments, the first proton exchange resin slurry and the second proton exchange resin slurry are further added with an inorganic particulate filler, the inorganic particulate filler is added in an amount of 0.1-10% by mass, and the inorganic particulate filler is selected from SiO2、CeO2、MnO2、MnSO4And one or more of Pt and Pt/C.
The added inorganic particle filler has the functions of moisturizing and resisting oxidation on the proton exchange membrane.
In some embodiments, the thickness of the reinforced net layer is 5-200 um, the aperture is 0.1-1 mm, and the strength is 10-100 MPa.
In some embodiments, the reinforcing mesh layer is selected from one or more of expanded PTFE, Polyetheretherketone (PEEK) woven mesh, and polyester woven mesh.
In some embodiments, the "forming the second proton exchange layer, heating and drying" further includes the operations of heat treatment and temperature reduction.
In some embodiments, the heat treatment temperature is 140-250 ℃ and the treatment time is 10 min-2 h, so that the proton exchange resin in the proton exchange membrane is crosslinked. After heat treatment and cooling operation, the thickness of first proton exchange layer with second proton exchange layer is 3 ~ 40 um.
In some embodiments, the treatment temperature of the temperature reduction operation is 40-100 ℃.
In some embodiments, the thickness of the proton exchange membrane is 5-100 um.
As shown in fig. 1 and fig. 2, the invention provides a proton exchange membrane preparation system, which comprises a first unwinding roller 1 for unwinding a release film, a second unwinding roller 3 for unwinding a reinforced mesh layer, and a first coating roller 2, a first heating and drying device, a second coating roller 6 and a second heating and drying device 7 which are sequentially arranged along the feeding direction of the first unwinding roller 1, wherein the reinforced mesh layer unwound by the second unwinding roller 3 and the unwinding of the first coating roller 2 enter the first heating and drying device for compounding.
The preparation system of the proton exchange membrane is used for implementing the preparation method of the proton exchange membrane.
Releasing a release film through the first unwinding roller 1, allowing the release film released by the first unwinding roller 1 to enter the first coating roller 2 to coat a first proton exchange layer, allowing the release film coated with the first proton exchange layer and an enhanced mesh layer released by the second unwinding roller 3 to enter the first heating and drying device together, attaching the enhanced mesh layer to the first proton exchange layer, heating through the first heating and drying device to remove a solvent, coating the second proton exchange layer at the second coating roller 6, and heating and drying the second proton exchange layer at the second heating and drying device 7 to obtain the composite material of the proton exchange film and the release film.
In some embodiments, a first applicator head 21 is provided at the first applicator roll 2 and a second applicator head 61 is provided at the second applicator roll 6.
In an embodiment, the proton exchange membrane preparation system further includes a heat treatment device 8 and a temperature reduction device 9, the heat treatment device 8 and the temperature reduction device 9 are disposed at intervals in the downstream of the feeding direction of the second heating and drying device 7, the heat treatment device 8 is configured to perform further heat treatment on the dried proton exchange membrane, and the temperature reduction device 9 is configured to cool the heat-treated proton exchange membrane.
As shown in fig. 1, in an embodiment, the first heating and drying device includes a composite roll 4a and a drying device 5, the reinforced web layer discharged from the second unwinding roll 3 and the release film with the first proton exchange layer discharged from the first coating roll 2 are combined on the composite roll 4a, and the combined material is conveyed to the drying device 5 for heating and drying treatment.
In the preparation system of the proton exchange membrane shown in fig. 1, the compounding operation and the drying operation of the enhanced mesh layer and the first proton exchange layer are divided into two discontinuous steps, so that the shrinkage degrees of the enhanced mesh layer, the first proton exchange layer and the release membrane are different due to the drying shrinkage of the first proton exchange layer, and further the problem of membrane material curling or membrane layer separation occurs.
In order to solve the above technical problem, as shown in fig. 2, in a preferred embodiment, the first heating and drying device includes a composite roll 4b, a heating device is disposed in the composite roll 4b, and the reinforced web layer discharged from the second unwinding roll 3 and the discharged material from the first coating roll 2 are combined on the composite roll 4 and subjected to a heating and drying process at the same time.
In this embodiment, the reinforced mesh layer discharged from the second unwinding roller 3 and the release film with the first proton exchange layer discharged from the first coating roller 2 are simultaneously placed on the composite roller 4b, a certain tension is generated on the release film, the first proton exchange layer and the reinforced mesh layer by the composite roller 4b, and the composite roller 4b is heated by the heating device, so that the first proton exchange layer is dried and formed under the condition of the tension, and the problem of membrane layer separation or membrane material curling caused by the shrinkage of the first proton exchange layer can be avoided.
In some embodiments, the second heating and drying device 7 has the same structure as the first heating and drying device.
The present invention will be further illustrated by the following examples.
Example 1
This example is used to illustrate the preparation method of the proton exchange membrane disclosed in the present invention, which is performed by using the system shown in fig. 2, and includes the following steps:
(1) respectively adding a certain amount of perfluorinated sulfonic acid resin solution into the volumetric flasks, adjusting the solid content to be 10% by adding water and alcohols, and taking the perfluorinated sulfonic acid resin solution as perfluorinated sulfonic acid resin slurry of the first coating head and the second coating head.
(2) The wet film coating thickness was controlled at the first coating head at a thickness of 200 microns.
(3) And compounding the reinforced net layer with the thickness of 5 microns and perfluoro sulfonic resin slurry discharged from the second unwinding roller at the compounding roller, and allowing the perfluoro sulfonic resin slurry to penetrate into the reinforced net layer.
(4) Drying and heat treating at 40 deg.C for 10 min.
(5) The second coating head applied a wet film thickness of 200 microns.
(6) Firstly, drying heat treatment is carried out at 40 ℃ in a coating machine, then heat treatment is carried out at 140 ℃, and then cooling treatment is carried out at 60 ℃, and finally the transparent enhanced proton exchange membrane is obtained, wherein the thickness of the proton exchange membrane is 10 microns.
Example 2
This example is used to illustrate the preparation method of the proton exchange membrane disclosed in the present invention, which is performed by using the system shown in fig. 2, and includes the following steps:
(1) respectively adding a certain amount of perfluorinated sulfonic acid resin solution into the volumetric flasks, adjusting the solid content to be 10% by adding water and alcohols, and taking the perfluorinated sulfonic acid resin solution as perfluorinated sulfonic acid resin slurry of the first coating head and the second coating head.
(2) The wet film coating thickness was controlled at the first coating head at a thickness of 200 microns.
(3) And compounding the reinforced net layer with the thickness of 5 microns and perfluoro sulfonic resin slurry discharged from the second unwinding roller at the compounding roller, and allowing the perfluoro sulfonic resin slurry to penetrate into the reinforced net layer.
(4) Drying and heat treating at 60 deg.C for 10 min.
(5) The second coating head applied a wet film thickness of 200 microns.
(6) Firstly, drying heat treatment is carried out at 40 ℃ in a coating machine, then heat treatment is carried out at 250 ℃, and then cooling treatment is carried out at 100 ℃, and finally the transparent enhanced proton exchange membrane is obtained, wherein the thickness of the proton exchange membrane is 10 microns.
Example 3
This example is used to illustrate the preparation method of the proton exchange membrane disclosed in the present invention, which is performed by using the system shown in fig. 2, and includes the following steps:
(1) respectively adding a certain amount of perfluorinated sulfonic acid resin solution into the volumetric flasks, adjusting the solid content to be 10% by adding water and alcohols, and taking the perfluorinated sulfonic acid resin solution as perfluorinated sulfonic acid resin slurry of the first coating head and the second coating head.
(2) The wet film coating thickness was controlled at the first coating head at a thickness of 300 microns.
(3) And compounding the reinforced net layer with the thickness of 5 microns and perfluoro sulfonic resin slurry discharged from the second unwinding roller at the compounding roller, and allowing the perfluoro sulfonic resin slurry to penetrate into the reinforced net layer.
(4) Drying and heat treating at 60 deg.C for 10 min.
(5) The second coating head applied a wet film thickness of 300 microns.
(6) Firstly, drying and heat treating at 40 ℃ in a coating machine, then performing heat treatment at 250 ℃, and then performing cooling treatment at 100 ℃ to finally obtain the transparent enhanced proton exchange membrane with the thickness of 15 microns.
Example 4
This example is used to illustrate the preparation method of the proton exchange membrane disclosed in the present invention, which is performed by using the system shown in fig. 2, and includes the following steps:
(1) respectively adding a certain amount of perfluorinated sulfonic acid resin solution into the volumetric flasks, adjusting the solid content to be 15% by adding water and alcohols, and taking the perfluorinated sulfonic acid resin solution as perfluorinated sulfonic acid resin slurry of the first coating head and the second coating head.
(2) The wet film coating thickness was controlled at the first coating head at a thickness of 200 microns.
(3) And compounding the reinforced net layer with the thickness of 5 microns and perfluoro sulfonic resin slurry discharged from the second unwinding roller at the compounding roller, and allowing the perfluoro sulfonic resin slurry to penetrate into the reinforced net layer.
(4) Drying and heat treating at 60 deg.C for 10 min.
(5) The second coating head applied a wet film thickness of 200 microns.
(6) Firstly, drying and heat treating at 40 ℃ in a coating machine, then performing heat treatment at 250 ℃, and then performing cooling treatment at 100 ℃ to finally obtain the transparent enhanced proton exchange membrane with the thickness of 15 microns.
Example 5
This example is used to illustrate the preparation method of the proton exchange membrane disclosed in the present invention, which is performed by using the system shown in fig. 2, and includes the following steps:
(1) respectively adding a certain amount of perfluorinated sulfonic acid resin solution into the volumetric flasks, adjusting the solid content to be 20% by adding water and alcohols, and taking the perfluorinated sulfonic acid resin solution as perfluorinated sulfonic acid resin slurry of the first coating head and the second coating head.
(2) The wet film coating thickness was controlled at the first coating head at a thickness of 1000 microns.
(3) And compounding the reinforced net layer with the thickness of 80 microns and perfluorinated sulfonic acid resin slurry discharged from the second unwinding roller at the compounding roller, wherein the perfluorinated sulfonic acid resin slurry permeates into the reinforced net layer.
(4) Drying and heat treating at 60 deg.C for 10 min.
(5) The second coating head applied a wet film thickness of 1000 microns.
(6) Firstly, drying and heat treating at 60 ℃, then performing heat treatment at 250 ℃ in a coating machine, and then performing cooling treatment at 100 ℃ to finally obtain the transparent enhanced proton exchange membrane with the thickness of 100 microns.
Comparative example 1
This comparative example is used for comparative illustration of the preparation method of the proton exchange membrane disclosed in the present invention, comprising most of the operating steps of example 1, with the following differences:
the reinforcing mesh layer is not provided.
Performance testing
The proton exchange membrane prepared above was subjected to the following performance tests:
and (3) testing mechanical strength: the proton membrane was cut into a dumbbell shape by a standard cutter by the ASTM D638 test method, and was mounted on a tensile tester, and one end of the membrane was pulled at a speed of 5mm per minute until the membrane was broken, and the tensile strength was calculated from the change in tensile force and the amount of deformation detected during the tensile test.
And (3) testing the swelling degree: cutting the proton membrane into a rectangle of 3 multiplied by 4cm, placing the proton membrane in hot water of 80 ℃ for soaking for 1 hour, taking out, testing the change of the length and the width of the proton membrane, and determining the size change rate of the proton membrane in the length and the width directions as the swelling degree of the proton membrane.
And (3) conductivity test: the proton Membrane was cut into a 1X 2cm rectangle, which was placed in a Membrane Test System apparatus of Scribner, and tested for ionic conductivity at 70% humidity 80 degrees Celsius.
The test results obtained are filled in Table 1.
TABLE 1
Figure BDA0003159229780000091
Figure BDA0003159229780000101
As can be seen from the test results in table 1, compared with the proton exchange membrane provided in comparative example 1, the proton exchange membrane prepared by the preparation method provided by the present invention has higher mechanical strength and lower swelling degree at the same thickness.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. The preparation method of the proton exchange membrane is characterized by comprising the following operation steps:
providing a release film;
coating first proton exchange resin slurry on the release film to form a first proton exchange layer;
covering one surface of the reinforced net layer on the first proton exchange layer, enabling the proton exchange resin slurry of the first proton exchange layer to enter the reinforced net layer, and heating and drying to obtain a composite layer of the reinforced net layer, the first proton exchange layer and the release film;
and coating the second proton exchange resin slurry on the other surface of the reinforced net layer to form a second proton exchange layer, and heating and drying to obtain the proton exchange membrane and release membrane composite material.
2. The method for preparing the proton exchange membrane according to claim 1, wherein the release force of the proton exchange membrane and the release film is 1-100 g/mm.
3. The method for preparing the proton exchange membrane according to claim 1, wherein the release membrane and the reinforced mesh layer are both supplied as a coil, the material compounded by the proton exchange membrane and the release membrane is rolled to obtain a coil, the first proton exchange layer and the second proton exchange layer are coated in a manner of independently selecting one or more of slit coating, gravure coating, comma knife coating and screen printing, and the coating thickness is 100-1000 um.
4. The method for preparing a proton exchange membrane according to claim 1, wherein the first proton exchange resin slurry and the second proton exchange resin slurry each comprise a proton exchange resin and a solvent, and the proton exchange resins are each independently selected from one or more of perfluorinated sulfonic acid resin, partially fluorinated sulfonic acid resin, sulfonated polyether ether ketone, sulfonated polysulfone, sulfonated polyether sulfone, quaternary ammonium salt type anion exchange resin, and imidazole type anion exchange resin; the solid content of the first proton exchange resin slurry and the solid content of the second proton exchange resin slurry are 5-50%.
5. The preparation method of the proton exchange membrane according to claim 4, wherein an inorganic particulate filler is further added into the first proton exchange resin slurry and the second proton exchange resin slurry, the inorganic particulate filler is added in an amount of 0.1 to 10% by mass, and the inorganic particulate filler is selected from SiO2、CeO2、MnO2、MnSO4And one or more of Pt and Pt/C.
6. The method for preparing a proton exchange membrane according to claim 1, wherein the thickness of the reinforced mesh layer is 5 to 200um, the pore diameter is 0.1 to 1mm, and the strength is 10 to 100 MPa.
7. The method for preparing the proton exchange membrane according to claim 1, wherein the reinforcing mesh layer is selected from one or more of expanded PTFE, a woven mesh of polyether ether ketone (PEEK) and a woven mesh of polyester.
8. The method for preparing the proton exchange membrane according to claim 1, wherein the step of forming the second proton exchange layer and heating and drying further comprises the steps of heat treatment and temperature reduction.
9. The preparation system of the proton exchange membrane is characterized by comprising a first unwinding roller for releasing membrane discharge, a second unwinding roller for reinforcing mesh layer discharge, a first coating roller, a first heating and drying device, a second coating roller and a second heating and drying device, wherein the first coating roller, the first heating and drying device, the second coating roller and the second heating and drying device are sequentially arranged along the feeding direction of the first unwinding roller, and the reinforcing mesh layer discharged by the second unwinding roller and the discharge of the first coating roller enter the first heating and drying device for compounding.
10. The system for preparing the proton exchange membrane according to claim 9, wherein the first heating and drying device comprises a composite roller, a heating device is arranged in the composite roller, and the reinforced mesh layer discharged by the second unwinding roller and the discharged by the first coating roller are composited on the composite roller and are subjected to heating and drying treatment simultaneously.
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