CN113346114A - Integrated membrane electrode and preparation method thereof - Google Patents

Integrated membrane electrode and preparation method thereof Download PDF

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CN113346114A
CN113346114A CN202010135699.8A CN202010135699A CN113346114A CN 113346114 A CN113346114 A CN 113346114A CN 202010135699 A CN202010135699 A CN 202010135699A CN 113346114 A CN113346114 A CN 113346114A
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layer
gas diffusion
electrode
proton exchange
exchange membrane
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李海滨
乔睿
刘磊
刘旻硕
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Shanghai Jiaotong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
    • 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

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  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

The invention relates to the technical field of electrochemistry, in particular to an integrated membrane electrode and a preparation method thereof. The membrane electrode comprises a first gas diffusion layer electrode, a first proton exchange membrane layer, a second proton exchange membrane layer and a second gas diffusion layer electrode which are sequentially stacked; the membrane structure further comprises an insulating airtight frame layer, wherein the insulating airtight frame layer is arranged on the circumferential edge of the first proton exchange membrane layer or the second proton exchange membrane layer. The integrated membrane electrode has a structure that the proton exchange membrane and the gas diffusion electrodes on two sides are integrated, hot pressing or cold pressing is not needed in the preparation process, and the proton exchange membrane and the catalyst layers of the gas diffusion electrodes are integrated, so that the proton transfer resistance between the proton exchange membrane and the catalyst layers is reduced, and the performance of a fuel cell of the membrane electrode is improved.

Description

Integrated membrane electrode and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemistry, in particular to an integrated membrane electrode and a preparation method thereof.
Background
A fuel cell is a power generation device that directly converts chemical energy in fuel into electrical energy through an electrochemical reaction. Among various categories, proton exchange membrane fuel cells are widely concerned, have relatively low working temperature and mature development, and are suitable for being used as power supplies for vehicles, portable and houses.
The Membrane Electrode (MEA) is the core component of a proton exchange membrane fuel cell, is an important place for electrochemical reaction, and mainly consists of a Gas Diffusion Layer (GDL), a Catalyst Layer (CL) and a Proton Exchange Membrane (PEM). The membrane electrode preparation method, assembly process, physical and chemical properties, materials used, operating conditions, etc. all affect the performance of the fuel cell.
Membrane electrode fabrication methods are often divided into two methods, catalyst on substrate (CCS) and catalyst on membrane (CCM), depending on the support substrate of the catalyst layer during the membrane electrode fabrication process. The CCS method is to mix a catalyst and a solvent to prepare a catalyst slurry with a gas diffusion layer as a support substrate of a catalyst layer, then coat the catalyst slurry on pretreated carbon paper or carbon cloth (PTFE hydrophobic treatment, microporous layer coating treatment, etc.) by using different methods (spray coating, screen printing, blade coating, etc.) to prepare a Gas Diffusion Electrode (GDE), and then sandwich a proton exchange membrane between two prepared gas diffusion electrodes to form a sandwich structure, and form a membrane electrode by hot pressing or cold pressing. CCM employs a proton exchange membrane as a support substrate for a catalyst layer, and deposits the catalyst layer on the proton exchange membrane by a direct coating method or a transfer printing method to form a membrane electrode structure with catalyst layers attached to both sides of the membrane, and then presses a carbon paper or carbon cloth subjected to pretreatment (PTFE hydrophobic treatment, microporous layer coating treatment, etc.) on both sides of the membrane electrode. Compared with the CCS method, the CCM method can effectively improve the utilization rate of the catalyst and reduce the proton transfer resistance between the membrane and the catalyst layer, and becomes the mainstream technology for preparing the membrane electrode at present. However, in the manufacturing process, when the catalyst is sprayed, the proton exchange membrane adsorbs the solvent in the catalyst slurry, so that the membrane body of the proton exchange membrane is easy to deform, and the subsequent fuel cell assembly is influenced, so that the membrane electrode is manufactured by the CCM method, and the process difficulty is high.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide an integrated membrane electrode and a method for manufacturing the same, which solve the problems of the prior art.
In order to achieve the above and other related objects, an aspect of the present invention provides a membrane electrode having an integrated structure, the membrane electrode including a first gas diffusion layer electrode, a first proton exchange membrane layer, a second proton exchange membrane layer, and a second gas diffusion layer electrode, which are sequentially stacked; the membrane structure further comprises an insulating airtight frame layer, wherein the insulating airtight frame layer is arranged on the circumferential edge of the first proton exchange membrane layer and/or the second proton exchange membrane layer.
In some embodiments of the invention, the first gas diffusion layer electrode comprises a first gas diffusion layer, a first microporous layer, and a first catalytic layer, which are sequentially stacked; the first catalytic layer is in contact with a first proton exchange membrane layer.
In some embodiments of the invention, the first proton exchange membrane layer is selected from a combination of one or more of a layer of perfluorosulfonic acid resin, a layer of sulfonated polyetheretherketone.
In some embodiments of the present invention, the material of the insulating and airtight rim layer is selected from one or more of polyethylene terephthalate, glass fiber reinforced polytetrafluoroethylene, polyimide, and silicone rubber in combination.
In some embodiments of the invention, the insulating hermetic frame layer has a thickness of 5-100 μm; the insulating airtight frame layer sequentially comprises an outer frame and an inner frame in the radial direction of the membrane electrode, at least part of the outer frame is exposed out of the first proton exchange membrane layer and/or the second proton exchange membrane layer, and the inner frame is embedded into the first proton exchange membrane layer and/or the second proton exchange membrane layer.
In some embodiments of the invention, the second diffusion layer electrode comprises a second gas diffusion layer, a second microporous layer, and a second catalytic layer, which are sequentially stacked; the second catalytic layer is in contact with a second proton exchange membrane layer.
In some embodiments of the invention, the second proton exchange membrane layer is selected from a combination of one or more of a layer of perfluorosulfonic acid resin, a layer of sulfonated polyetheretherketone.
In another aspect, the present invention provides a method for preparing a membrane electrode according to the present invention, comprising the following steps:
1) providing a first gas diffusion electrode layer, coating a proton conducting polymer solution on the first gas diffusion electrode layer, and forming a first proton exchange membrane layer on the first gas diffusion electrode layer after heat treatment;
2) providing a second gas diffusion electrode layer, coating a proton conducting polymer solution on the second gas diffusion electrode layer;
3) arranging an insulating airtight frame at the circumferential edge of the first proton exchange membrane layer obtained in the step 1) to form an insulating airtight frame layer;
4) and 3) placing the surface, coated with the proton conducting polymer solution, of the second gas diffusion electrode layer in the step 2) on the insulating airtight frame layer, forming a second proton exchange membrane layer between the second gas diffusion electrode layer and the insulating airtight frame layer after heat treatment, and obtaining the integrated membrane electrode.
In some embodiments of the invention, the preparing of the first gas diffusion electrode layer in step 1) comprises: a first microporous layer is coated on the first gas diffusion layer, and a catalyst slurry is further coated on the first microporous layer to obtain a first catalyst layer.
In some embodiments of the invention, the preparing of the second gas diffusion electrode layer in step 2) comprises: and coating a second microporous layer on the second gas diffusion layer, and coating the catalyst slurry on the second microporous layer to obtain a second catalyst layer.
In some embodiments of the present invention, the proton-conducting polymer solution is coated on the first catalyst layer in the step 1).
In some embodiments of the present invention, the proton conducting polymer solution in step 1) is selected from a perfluorosulfonic acid solution and a sulfonated polyether ether ketone solution.
In some embodiments of the present invention, the temperature of the heat treatment in the step 1) is 80 to 180 ℃.
In some embodiments of the present invention, the proton-conducting polymer solution is coated on the second catalyst layer in the step 2).
In some embodiments of the present invention, the proton conducting polymer solution in step 2) is selected from a perfluorosulfonic acid solution and a sulfonated polyetheretherketone solution.
In some embodiments of the present invention, the material of the insulating airtight rim in the step 3) is selected from one or more of polyethylene terephthalate, glass fiber reinforced polytetrafluoroethylene, polyimide, and silicone rubber.
In some embodiments of the present invention, the temperature of the heat treatment in the step 4) is 100 to 180 ℃.
In another aspect, the invention provides the use of the membrane electrode preparation method of the invention in a fuel cell.
Drawings
FIG. 1 is an appearance view of a sample of an integral membrane electrode prepared in example 1;
fig. 2 is a schematic view of an integrated membrane electrode.
FIG. 3 is a scanning electron micrograph of a cross section of the integrated membrane electrode prepared in example 2;
fig. 4 is a graph comparing performance curves of the integrated membrane electrode prepared in example 2 and a membrane electrode assembled fuel cell prepared by the CCS process.
FIG. 2 element numbers:
1 first gas diffusion layer electrode
11 first gas diffusion layer
12 first microporous layer
13 first catalytic layer
2 first proton exchange membrane layer
3 insulating airtight frame layer
4 second proton exchange membrane layer
5 second gas diffusion layer electrode
51 second gas diffusion layer
52 second microporous layer
53 second catalytic layer
Detailed Description
The invention provides a structure that a proton exchange membrane and gas diffusion electrodes at two sides are integrated into a whole through a large number of exploration experiments, the integrated membrane electrode and the proton exchange membrane therein are formed simultaneously, hot pressing or cold pressing is not needed in the preparation process, and the proton exchange membrane and the catalyst layers of the gas diffusion electrodes are integrated into a whole, so that the proton transfer resistance between the membrane and the catalyst layers is reduced, and the performance of the fuel cell is improved. Moreover, different from the traditional membrane electrode preparation method which needs to prepare the proton exchange membrane in advance or use the commercially available proton exchange membrane, the invention prepares the proton exchange membrane while preparing the membrane electrode, thereby effectively improving the membrane electrode preparation efficiency. The obtained integrated membrane electrode can be directly assembled with a fuel cell without subsequent operations such as hot pressing, cold pressing and the like.
The invention provides a membrane electrode, which has an integrated structure and comprises a first gas diffusion layer electrode 1, a first proton exchange membrane layer 2, a second proton exchange membrane layer 4 and a second gas diffusion layer electrode 5 which are sequentially stacked; the proton exchange membrane structure further comprises an insulating airtight frame layer 3, wherein the insulating airtight frame layer 3 is arranged on the circumferential edge of the first proton exchange membrane layer 2 or the second proton exchange membrane layer 4.
In the membrane electrode provided by the invention, the first gas diffusion layer electrode comprises a first gas diffusion layer 11, a first microporous layer 12 and a first catalytic layer 13 which are sequentially stacked; the first catalytic layer 11 is in contact with the first proton exchange membrane layer 2. The first gas diffusion layer is selected from carbon paper or carbon cloth, and in some embodiments, the first gas diffusion layer may be first subjected to hydrophobic treatment with polytetrafluoroethylene, and then a first microporous layer is coated on the first gas diffusion layer, and the material of the first microporous layer consists of carbon powder and polytetrafluoroethylene. And then coating the first microporous layer to form a first catalyst layer. The first catalyst layer may be, for example, Pt/C, Pt (Co)/C, Pt, etc., and the size and thickness of the first gas diffusion layer electrode may be adjusted according to the actual membrane electrode requirements in a normal case, for example, the size of the first gas diffusion layer electrode is 3.3 gamma 3.3cm to 50 gamma 50 cm. The size of the first gas diffusion layer is 3.3cm to 50 cm. The first microporous layer has a size of 3.3 gamma 3.3cm to 50 gamma 50 cm. The first catalytic layer is 3.3 cm-50 cm gamma in size. The thickness of the first gas diffusion layer electrode is 100-500 μm. The thickness of the first gas diffusion layer is 50-430 μm. The thickness of the first microporous layer is 5 to 50 μm, and the thickness of the first catalytic layer is 1 to 20 μm.
In the membrane electrode provided by the invention, the first proton exchange membrane layer is selected from one or more of a perfluorinated sulfonic acid resin layer and a sulfonated polyether ether ketone layer. The material of the perfluorosulfonic acid resin layer may be selected from one or more of a Nafion D2020 solution (perfluorosulfonic acid resin content 20 wt%), a Nafion D520 solution (perfluorosulfonic acid resin content 5 wt%) or a Nafion D1020 solution (perfluorosulfonic acid resin content 10 wt%), for example. The material of the sulfonated polyether ether ketone layer is selected from SPEEK (sulfonated polyether ether ketone content 12 wt%), and the like. Generally, the size and thickness of the first proton exchange membrane layer can be adjusted according to the needs of the actual membrane electrode. In some embodiments, the first proton exchange membrane layer is the same size as the first gas diffusion layer electrode. For example, the first proton exchange membrane layer has a size of 3.3 x 3.3cm to 50 x 50 cm. The thickness of the first proton exchange membrane layer is 5-100 μm.
In the membrane electrode provided by the invention, the material of the insulating airtight frame layer is selected from one or more of polyethylene terephthalate, glass fiber reinforced polytetrafluoroethylene, polyimide and silicon rubber. In some embodiments, the insulating hermetic border layer has a thickness of 5-100 μm; the insulating airtight frame layer sequentially comprises an outer frame and an inner frame in the radial direction of the membrane electrode, at least part of the outer frame is exposed out of the first proton exchange membrane layer and/or the second proton exchange membrane layer, and the inner frame is embedded into the first proton exchange membrane layer and/or the second proton exchange membrane layer. The size of the outer frame is larger than that of the first gas diffusion layer electrode, the size of the inner frame is smaller than that of the first gas diffusion layer electrode, for example, the size of the first gas diffusion layer electrode is 3.3 gamma 3.3cm, the size of the outer frame is 4.5 gamma 4.5cm, and the size of the inner frame is 2.7 gamma 2.7 cm. The insulating airtight frame is non-conductive and airtight, can prevent short circuit between the upper and lower layer gas diffusion electrodes, and plays a role in protecting edges, thereby facilitating assembly and gas sealing of the fuel cell.
In the membrane electrode provided by the invention, the second diffusion layer electrode comprises a second gas diffusion layer 51, a second microporous layer 52 and a second catalytic layer 53 which are sequentially stacked; the second catalytic layer 53 is in contact with the second proton exchange membrane layer 4. The second gas diffusion layer is selected from carbon paper or carbon cloth, and in some embodiments, the second gas diffusion layer may be hydrophobic-treated with polytetrafluoroethylene, and then a second microporous layer is coated on the second gas diffusion layer, and the material of the second microporous layer is composed of carbon powder and polytetrafluoroethylene. And coating the second microporous layer to form a second catalyst layer. The second catalyst layer may be, for example, Pt/C, Pt (Co)/C, Pt, etc., and the size of the second gas diffusion layer electrode may be adjusted according to the needs of the actual membrane electrode in a normal case, and the size and thickness of the second gas diffusion layer electrode may be adjusted according to the needs of the actual membrane electrode in a normal case. In some embodiments, the second gas diffusion layer electrode is the same size as the first gas diffusion layer electrode. For example, the second gas diffusion layer electrode has a size of 3.0 x 3.0cm to 50 x 50 cm. The size of the second gas diffusion layer is 3.0 x 3.0 cm-50 x 50 cm. The size of the second microporous layer is 3.0 gamma 3.0 cm-50 gamma 50 cm. The size of the second catalytic layer is 3.0 gamma 3.0 cm-50 gamma 50 cm. For example, the thickness of the second gas diffusion layer electrode is 100 to 500 μm. The thickness of the second gas diffusion layer is 50-430 μm. The thickness of the second microporous layer is 5-50 μm, and the thickness of the second catalytic layer is 1-20 μm.
In the membrane electrode provided by the invention, the second proton exchange membrane layer is selected from one or more of a perfluorinated sulfonic acid resin layer and a sulfonated polyether ether ketone layer. The material of the perfluorosulfonic acid resin layer may be selected from one or more of a Nafion D2020 solution (perfluorosulfonic acid resin content 20 wt%), a Nafion D520 solution (perfluorosulfonic acid resin content 5 wt%) or a Nafion D1020 solution (perfluorosulfonic acid resin content 10 wt%), for example. The material of the sulfonated polyether ether ketone layer is selected from SPEEK (sulfonated polyether ether ketone content 12 wt%), and the like. Generally, the size and thickness of the second proton exchange membrane layer can be adjusted according to the needs of the actual membrane electrode. In some embodiments, the second proton exchange membrane layer is the same size as the first gas diffusion layer electrode. For example, the second proton exchange membrane layer has a size of 3.3 x 3.3cm to 50 x 50 cm. The thickness of the second proton exchange membrane layer is 5-100 μm.
The second aspect of the present invention provides a method for preparing a membrane electrode provided by the first aspect of the present invention, comprising the steps of:
1) providing a first gas diffusion electrode layer, coating a proton conducting polymer solution on the first gas diffusion electrode layer, and forming a first proton exchange membrane layer on the first gas diffusion electrode layer after heat treatment;
2) providing a second gas diffusion electrode layer, coating a proton conducting polymer solution on the second gas diffusion electrode layer;
3) arranging an insulating airtight frame at the circumferential edge of the first proton exchange membrane layer obtained in the step 1) to form an insulating airtight frame layer;
4) and 3) placing the surface, coated with the proton conducting polymer solution, of the second gas diffusion electrode layer in the step 2) on the insulating airtight frame layer, forming a second proton exchange membrane layer between the second gas diffusion electrode layer and the insulating airtight frame layer after heat treatment, and obtaining the integrated membrane electrode.
In the preparation method of the membrane electrode provided by the invention, the step 1) is to provide a first gas diffusion electrode layer, coat proton conducting polymer solution on the first gas diffusion electrode layer, and form a first proton exchange membrane layer on the first gas diffusion electrode layer after heat treatment. Wherein the preparation of the first gas diffusion electrode layer in step 1) comprises: a first microporous layer is coated on the first gas diffusion layer, and a catalyst slurry is further coated on the first microporous layer to obtain a first catalyst layer. In some embodiments, the first gas diffusion layer may be hydrophobic treated with ptfe, and then a first microporous layer made of carbon powder and ptfe is coated on the first gas diffusion layer. A catalyst slurry is then prepared by mixing a catalyst, such as Pt/C, Pt (Co)/C, Pt, a proton conductive polymer, polytetrafluoroethylene powder, and a solvent, such as those known to those skilled in the art to be useful in the present invention. And then, a first catalyst layer is formed on the first microporous layer by adopting methods such as spraying, screen printing, blade coating and the like. Further, the proton-conducting polymer solution is coated on the first catalyst layer.
Further, the proton conducting polymer solution in the step 1) is selected from one or more of a perfluorinated sulfonic acid solution and a sulfonated polyether ether ketone solution. In general, the heat treatment temperature and time in step 1) are not limited, and a single-stage heat treatment or a multi-stage heat treatment may be performed. In some embodiments, the temperature of each heat treatment is 80-150 ℃ and the time of each heat treatment is 5-120 min. The heat treatment in step 1) may be performed in an oven.
In the preparation method of the membrane electrode provided by the invention, the step 2) provides a second gas diffusion electrode layer, and the proton conducting polymer solution is coated on the second gas diffusion electrode layer. Wherein the preparation of the second gas diffusion electrode layer in step 2) comprises: coating a second microporous layer on the second gas diffusion layer, and coating catalyst slurry on the second microporous layer to obtain a second catalyst layer; in some embodiments, the second gas diffusion layer may be hydrophobic treated with ptfe, and then a second microporous layer made of carbon powder and ptfe is coated on the first gas diffusion layer. A catalyst slurry is then prepared by mixing a catalyst, such as Pt/C, Pt (Co)/C, Pt, with a solvent, such as those known to those skilled in the art to be useful in the present invention. And then the first catalyst layer is formed on the second microporous layer by adopting methods such as spraying, screen printing, blade coating and the like. Further, the proton-conducting polymer solution is coated on the second catalyst layer.
Further, the proton conducting polymer solution in the step 2) is selected from a perfluorinated sulfonic acid solution and a sulfonated polyether ether ketone solution. The material of the perfluorosulfonic acid resin layer may be selected from one or more of a Nafion D2020 solution (perfluorosulfonic acid resin content 20 wt%), a Nafion D520 solution (perfluorosulfonic acid resin content 5 wt%) or a Nafion D1020 solution (perfluorosulfonic acid resin content 10 wt%), for example. The material of the sulfonated polyether ether ketone layer is selected from SPEEK (sulfonated polyether ether ketone content 12 wt%), and the like.
In the preparation method of the membrane electrode provided by the invention, in the step 3), an insulating airtight frame is arranged at the circumferential edge of the first proton exchange membrane layer obtained in the step 1) to form an insulating airtight frame layer. Wherein the material of the insulating airtight frame in the step 3) is selected from one or more of polyethylene terephthalate, glass fiber reinforced polytetrafluoroethylene, polyimide and silicon rubber.
In the preparation method of the membrane electrode provided by the invention, in the step 4), one surface of the second gas diffusion electrode layer coated with the proton conducting polymer solution in the step 2) is placed on the insulating airtight frame layer, and a second proton exchange membrane layer is formed between the second gas diffusion electrode layer and the insulating airtight frame layer after heat treatment, so that the integrated membrane electrode is obtained. Specifically, in general, the heat treatment temperature and time in the step 4) are not limited, and a single-stage heat treatment or a multi-stage heat treatment may be performed. In some embodiments, the temperature of each heat treatment is 100 to 180 ℃ and the time of each heat treatment is 5 to 120 min. The heat treatment in step 4) may be performed in an oven.
A third aspect of the invention provides the use of a method of making a membrane electrode as provided in the first aspect of the invention in a fuel cell.
The invention has the beneficial effects that:
the integrated membrane electrode has a structure that the proton exchange membrane and the gas diffusion electrodes on two sides are integrated, hot pressing or cold pressing is not needed in the preparation process, and the proton exchange membrane and the catalyst layers of the gas diffusion electrodes are integrated, so that the proton transfer resistance between the proton exchange membrane and the catalyst layers is reduced, and the performance of a fuel cell of the membrane electrode is improved. Moreover, different from the traditional membrane electrode preparation method which needs to prepare the proton exchange membrane in advance or use the commercially available proton exchange membrane, the invention prepares the proton exchange membrane while preparing the membrane electrode, effectively improves the membrane electrode preparation efficiency, and has simple working procedures and easy operation. The obtained integrated membrane electrode can be directly assembled with a fuel cell without any subsequent operation such as hot pressing, cold pressing and the like.
The following examples are provided to further illustrate the advantageous effects of the present invention.
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is further described in detail below with reference to examples. However, it should be understood that the embodiments of the present invention are only for explaining the present invention and are not for limiting the present invention, and the embodiments of the present invention are not limited to the embodiments given in the specification. The examples were prepared under conventional conditions or conditions recommended by the material suppliers without specifying specific experimental conditions or operating conditions.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified.
Example 1
(1) A piece of gas diffusion electrode (Pt loading 0.4 mg/cm) with a size of 3.3 gamma 3.3cm was taken2) Coating with a scraper, adjusting the gap of the scraper to 400 μm, and coating a perfluorosulfonic acid solution (Nafion D2020 solution, with a perfluorosulfonic acid resin content of 20 wt%) on the catalytic layer of the gas diffusion electrode to obtain a gas diffusion electrode coated with the perfluorosulfonic acid solution;
(2) carrying out single-stage heat treatment at 100 ℃ for 15min to obtain the gas diffusion electrode coated with the perfluorosulfonic acid resin layer;
(3) another gas diffusion electrode with the same size and specification is taken, the step in the step (1) is repeated, and another gas diffusion electrode coated with the perfluorinated sulfonic acid solution is obtained;
(4) using the gas diffusion electrode coated with the perfluorosulfonic acid resin layer obtained in step (2), a glass fiber reinforced polytetrafluoroethylene insulating airtight frame (outer frame size 4.5 x 4.5 cm; inner frame size 2.7 x 2.7 cm; thickness 50 μm) was placed thereon, and another gas diffusion electrode coated with the perfluorosulfonic acid solution prepared in step (3) was coated thereon, followed by two-stage heat treatment at 100 ℃ for 60min followed by 130 ℃ for 30min to form an integrated membrane electrode having an active area of about 7.3cm2(2.7╳2.7cm)。
Fig. 1 is an optical photograph of the integrated type membrane electrode prepared in example 1.
Example 2
(1) A piece of gas diffusion electrode (Pt loading 0.4 mg/cm) with a size of 3.3 gamma 3.3cm was taken2) Coating with a scraper, adjusting the gap of the scraper to 400 μm, and coating a perfluorosulfonic acid solution (Nafion D2020 solution, with a perfluorosulfonic acid resin content of 20 wt%) on the catalytic layer of the gas diffusion electrode to obtain a gas diffusion electrode coated with the perfluorosulfonic acid solution;
(2) carrying out single-stage heat treatment at 100 ℃ for 15min to obtain the gas diffusion electrode coated with the perfluorosulfonic acid resin layer;
(3) another gas diffusion electrode with the same size and specification is taken, the step in the step (1) is repeated, and another gas diffusion electrode coated with the perfluorinated sulfonic acid solution is obtained;
(4) using the gas diffusion electrode coated with the perfluorosulfonic acid resin layer obtained in (2), a polyethylene terephthalate (PET) insulating airtight frame (outer frame size 4.5 x 4.5 cm; inner frame size 2.7 x 2.7 cm; thickness 25 μm) was placed thereon, and another gas diffusion electrode coated with the perfluorosulfonic acid solution prepared in (3) was coated thereon, followed by two-stage heat treatment at 100 ℃ for 60min followed by 130 ℃ for 30min to form an integrated membrane electrode having an activation area of about 7.3cm2(2.7╳2.7cm)。
Fig. 2 is a schematic view of an integrated membrane electrode.
A cross-sectional photograph of the sample was obtained using a JSM-7800F field emission scanning electron microscope. Fig. 3 is a scanning electron micrograph of a cross section of the integrated type membrane electrode prepared in example 2. As can be seen from FIG. 3, the PEM located in the middle of the integrated membrane electrode is dense, complete, uniform, free of defects and cracks, and has a membrane thickness of about 34 μm. And the interface contact between the proton exchange membrane and the catalytic layer of the integrated membrane electrode is good and seamless, so that the proton transfer resistance between the membrane and the catalytic layer is ensured to be reduced.
Example 3
(1) A piece of gas diffusion electrode (Pt loading 0.4 mg/cm) with a size of 3.3 gamma 3.3cm was taken2) Coating with a scraper, adjusting the gap of the scraper to 300 μm, and coating a perfluorosulfonic acid solution (Nafion D2020 solution, with a perfluorosulfonic acid resin content of 20 wt%) on the catalytic layer of the gas diffusion electrode to obtain a gas diffusion electrode coated with the perfluorosulfonic acid solution;
(2) carrying out single-stage heat treatment at 100 ℃ for 15min to obtain the gas diffusion electrode coated with the perfluorosulfonic acid resin layer;
(3 Another gas diffusion electrode with a size of 3.3 gamma 3.3cm (Pt loading 0.1 mg/cm) is taken2) Repeating the step (1) to obtain another gas diffusion electrode coated with the perfluorinated sulfonic acid solution;
(4) using the perfluorosulfonic acid resin layer-coated gas diffusion electrode obtained in (2), a sheet of silicone rubber (outer frame size) was placed thereon4.5 gamma 4.5 cm; inner frame size 2.7 gamma 2.7 cm; 80 μm thick), coating another gas diffusion electrode coated with perfluorosulfonic acid solution prepared in step (3), and performing two-stage heat treatment at 100 deg.C for 60min and 150 deg.C for 30min to obtain an integrated membrane electrode with an active area of about 7.3cm2(2.7╳2.7cm)。
Example 4
(1) A piece of gas diffusion electrode (Pt loading 0.4 mg/cm) with a size of 3.3 gamma 3.3cm was taken2) Spraying a perfluorosulfonic acid solution (Nafion D520 solution, the content of perfluorosulfonic acid resin is 5 wt%) on a catalytic layer of the gas diffusion electrode by adopting a BioSpot workstation with a PipeJet tube to obtain the gas diffusion electrode coated with the perfluorosulfonic acid solution;
(2) carrying out single-stage heat treatment at 100 ℃ for 15min to obtain the gas diffusion electrode coated with the perfluorosulfonic acid resin layer;
(3) another gas diffusion electrode with the same size and specification is taken, the step in the step (1) is repeated, and another gas diffusion electrode coated with the perfluorinated sulfonic acid solution is obtained;
(4) the gas diffusion electrode coated with the perfluorosulfonic acid resin layer obtained in the step (2) is utilized, a polyimide frame (the size of an outer frame is 4.5 x 4.5cm, the size of an inner frame is 2.7 x 2.7cm, the thickness is 80 mu m) is placed on the gas diffusion electrode coated with the perfluorosulfonic acid resin layer, the other gas diffusion electrode coated with the perfluorosulfonic acid solution prepared in the step (3) is covered on the polyimide frame, then two-stage heat treatment is carried out, the temperature is 100 ℃, the temperature is 60min, and then the temperature is 120 ℃, the temperature is 30min, so that an integrated membrane electrode is formed, the activation area of the integrated membrane electrode is about 7.3cm2(2.7╳2.7cm)。
Example 5
(1) A gas diffusion electrode (Pt loading 0.4 mg/cm) of 5 gamma 5cm size was taken2) Coating a perfluorosulfonic acid solution (Nafion D1020 solution, the content of perfluorosulfonic acid resin is 10 wt%) on a catalytic layer of the gas diffusion electrode by adopting a screen printing method to obtain the gas diffusion electrode coated with the perfluorosulfonic acid solution;
(2) carrying out single-stage heat treatment at 100 ℃ for 15min to obtain the gas diffusion electrode coated with the perfluorosulfonic acid resin layer;
(3) another gas diffusion electrode with the same size and specification is taken, the step in the step (1) is repeated, and another gas diffusion electrode coated with the perfluorinated sulfonic acid solution is obtained;
(4) the gas diffusion electrode coated with the perfluorosulfonic acid resin layer obtained in the step (2) is utilized, a glass fiber reinforced polytetrafluoroethylene frame (the size of an outer frame is 6.5 x 6.5cm, the size of an inner frame is 4 x 4cm, the thickness is 100 mu m) is placed on the gas diffusion electrode coated with the perfluorosulfonic acid solution, the other gas diffusion electrode coated with the perfluorosulfonic acid solution prepared in the step (3) is covered on the gas diffusion electrode, then two-stage heat treatment is carried out, the temperature is 100 ℃, the temperature is 60min, the temperature is 180 ℃, the temperature is 30min, and an integrated membrane electrode is formed, and the activation area of the integrated membrane electrode is about 16cm2(4╳4cm)。
Example 6
(1) A piece of gas diffusion electrode (Pt loading 0.4 mg/cm) with a size of 3.3 gamma 3.3cm was taken2) Coating with a scraper, adjusting the gap of the scraper to 500 μm, and coating sulfonated polyether ether ketone solution (SPEEK, sulfonated polyether ether ketone content 12 wt%) on the catalyst layer of the gas diffusion electrode to obtain a gas diffusion electrode coated with the sulfonated polyether ether ketone solution;
(2) carrying out single-stage heat treatment at 80 ℃ for 60min to obtain the gas diffusion electrode coated with the sulfonated polyether-ether-ketone layer;
(3) another gas diffusion electrode with the same size and specification is taken, the step in the step (1) is repeated, and another gas diffusion electrode coated with the sulfonated polyether ether ketone solution is obtained;
(4) using the gas diffusion electrode coated with the sulfonated polyether ether ketone layer obtained in the step (2), placing a polyethylene terephthalate (PET) frame (the outer frame size is 4.5 gamma 4.5cm, the inner frame size is 2.7 gamma 2.7cm, the thickness is 80 mu m), coating another gas diffusion electrode coated with the sulfonated polyether ether ketone solution prepared in the step (3) on the frame, then carrying out single-stage heat treatment, carrying out heat treatment at 100 ℃ for 120min, and forming an integrated membrane electrode, wherein the activation area of the integrated membrane electrode is about 7.3cm2(2.7╳2.7cm)。
Example 7
(1) A piece of gas diffusion electrode (Pt loading 0.4 mg/cm) with a size of 3.3 gamma 3.3cm was taken2) The catalyst layer of the gas diffusion electrode was coated using a BioSpot workstation with a PipeJet tubeSulfonated polyetheretherketone solution (SPEEK, sulfonated polyetheretherketone content 12 wt%) to obtain a gas diffusion electrode coated with sulfonated polyetheretherketone solution;
(2) carrying out single-stage heat treatment at 100 ℃ for 60min to obtain the gas diffusion electrode coated with the sulfonated polyether-ether-ketone layer;
(3) another gas diffusion electrode with the same size and specification is taken, the step in the step (1) is repeated, and another gas diffusion electrode coated with the sulfonated polyether ether ketone solution is obtained;
(4) the gas diffusion electrode coated with the sulfonated polyether ether ketone layer obtained in the step (2) is utilized, a glass fiber reinforced polytetrafluoroethylene frame (the size of an outer frame is 4.5 x 4.5cm, the size of an inner frame is 2.7 x 2.7cm, the thickness is 100 mu m) is placed on the gas diffusion electrode coated with the sulfonated polyether ether ketone solution, another gas diffusion electrode coated with the sulfonated polyether ether ketone solution prepared in the step (3) is covered on the gas diffusion electrode, and then single-stage heat treatment is carried out, the heat treatment is carried out at the temperature of 110 ℃ for 120min, so that an integrated membrane electrode is formed, the activation area of the integrated membrane electrode is about 7.3cm2(2.7╳2.7cm)。
Comparative example 1
Two gas diffusion electrodes (Pt loading 0.4 mg/cm) with a 3.3 gamma 3.3cm size were used2) And a Gore15 μm proton exchange membrane with 4.5 x 4.5cm size, which is clamped between two gas diffusion electrodes to form a sandwich structure, and hot pressing is carried out under the following conditions: and (3) preparing the membrane electrode at 120 ℃ for 2 min.
Performance testing of examples and comparative examples
Single cell performance testing of example 2 and comparative example 1: introducing hydrogen and air into anode and cathode of single cell respectively, wherein the gas flow rate of hydrogen is 500ml min-1The gas flow of air is 1000ml min-1And the humidification humidity of the anode and the cathode are both 100%, the fuel cell temperature is 75 ℃.
As can be seen from FIG. 4, using the integrated type membrane electrode in example 2, the open circuit voltage of the assembled unit cell was 0.918V, and the peak power density was 0.5W cm-2(ii) a Using the membrane electrode prepared by the CCS method in the comparative example, the open-circuit voltage of the assembled unit cell was 0.898V, and the unit peak power was 0.431W cm-2. It is obvious thatCompared with a membrane electrode prepared by a CCS method, the membrane electrode has the advantages that the open-circuit voltage and the peak power density of a single cell are obviously improved. For the integrated membrane electrode, the proton exchange membrane is integrated with the catalyst layer of the gas diffusion electrode, so that the proton transfer resistance between the proton exchange membrane and the catalyst layer is reduced to a great extent, and the performance of the fuel cell of the membrane electrode is improved.
The numbers and main features of the integrated type membrane electrodes prepared in the respective examples, and the performance of the fuel cell assembled using the integrated type membrane electrodes are shown in table 1.
TABLE 1
Figure BDA0002397235150000121
In summary, the integrated membrane electrode and the preparation method thereof provided by the invention have the advantages that the integrated membrane electrode has a structure that the proton exchange membrane and the gas diffusion electrodes on the two sides are integrated, the integrated membrane electrode and the proton exchange membrane therein are formed simultaneously, hot pressing or cold pressing is not needed in the preparation process, the proton exchange membrane and the catalyst layers of the gas diffusion electrodes are integrated, the proton transfer resistance between the proton exchange membrane and the catalyst layers is greatly reduced, and the performance of a fuel cell is improved. Moreover, different from the traditional membrane electrode preparation method which needs to prepare the proton exchange membrane in advance or use the commercially available proton exchange membrane, the invention prepares the proton exchange membrane while preparing the membrane electrode, effectively improves the membrane electrode preparation efficiency, and has simple working procedures and easy operation. The obtained integrated membrane electrode can be directly applied without subsequent operations such as hot pressing, cold pressing, opposite pressing and the like. The invention is expected to be widely applied to the fields of fuel cells, water electrolysis, liquid flow energy storage cells and the like.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (10)

1. The membrane electrode is characterized by having an integrated structure and comprising a first gas diffusion layer electrode, a first proton exchange membrane layer, a second proton exchange membrane layer and a second gas diffusion layer electrode which are sequentially stacked; the membrane structure further comprises an insulating airtight frame layer, wherein the insulating airtight frame layer is arranged on the circumferential edge of the first proton exchange membrane layer and/or the second proton exchange membrane layer.
2. The membrane electrode of claim 1, wherein the first gas diffusion layer electrode comprises a first gas diffusion layer, a first microporous layer, and a first catalytic layer, which are sequentially stacked; the first catalytic layer is in contact with a first proton exchange membrane layer.
3. The membrane electrode of claim 1, wherein the first proton exchange membrane layer is selected from the group consisting of a perfluorosulfonic acid resin layer, a sulfonated polyetheretherketone layer, and combinations thereof.
4. The membrane electrode of claim 1, wherein the insulating, gas-tight border layer is made of a material selected from the group consisting of one or more of polyethylene terephthalate, glass fiber reinforced polytetrafluoroethylene, polyimide, and silicone rubber.
5. The membrane electrode of claim 1, further comprising one or more of the following technical features:
A1) the thickness of the insulating airtight frame layer is 5-100 mu m; the insulating airtight frame layer sequentially comprises an outer frame and an inner frame in the radial direction of the membrane electrode, at least part of the outer frame is exposed out of the first proton exchange membrane layer and/or the second proton exchange membrane layer, and the inner frame is embedded into the first proton exchange membrane layer and/or the second proton exchange membrane layer;
A2) the second diffusion layer electrode comprises a second gas diffusion layer, a second microporous layer and a second catalytic layer which are sequentially stacked; the second catalyst layer is in contact with a second proton exchange membrane layer;
A3) the second proton exchange membrane layer is selected from one or more of a perfluorinated sulfonic acid resin layer and a sulfonated polyether ether ketone layer.
6. The method for producing a membrane electrode according to any one of claims 1 to 5, comprising the steps of:
1) providing a first gas diffusion electrode layer, coating a proton conducting polymer solution on the first gas diffusion electrode layer, and forming a first proton exchange membrane layer on the first gas diffusion electrode layer after heat treatment;
2) providing a second gas diffusion electrode layer, coating a proton conducting polymer solution on the second gas diffusion electrode layer;
3) arranging an insulating airtight frame at the circumferential edge of the first proton exchange membrane layer obtained in the step 1) to form an insulating airtight frame layer;
4) and 3) placing the surface, coated with the proton conducting polymer solution, of the second gas diffusion electrode layer in the step 2) on the insulating airtight frame layer, forming a second proton exchange membrane layer between the second gas diffusion electrode layer and the insulating airtight frame layer after heat treatment, and obtaining the integrated membrane electrode.
7. The method for preparing a membrane electrode according to claim 6, wherein the preparing of the first gas diffusion electrode layer in step 1) comprises: a first microporous layer is coated on the first gas diffusion layer, and a catalyst slurry is further coated on the first microporous layer to obtain a first catalyst layer.
8. The method for preparing a membrane electrode according to claim 6, wherein the preparing of the second gas diffusion electrode layer in step 2) comprises: and coating a second microporous layer on the second gas diffusion layer, and coating the catalyst slurry on the second microporous layer to obtain a second catalyst layer.
9. The method for preparing a membrane electrode according to any one of claims 6 to 8, further comprising one or more of the following technical features:
B1) the proton-conducting polymer solution is coated on the first catalyst layer in the step 1);
B2) the proton conducting polymer solution in the step 1) is selected from a perfluorinated sulfonic acid solution and a sulfonated polyether ether ketone solution;
B3) the temperature of the heat treatment in the step 1) is 80-180 ℃;
B4) the proton-conducting polymer solution is coated on the second catalyst layer in the step 2);
B5) the proton conducting polymer solution in the step 2) is selected from a perfluorinated sulfonic acid solution and a sulfonated polyether ether ketone solution;
B6) the material of the insulating airtight frame in the step 3) is selected from one or more of polyethylene terephthalate, glass fiber reinforced polytetrafluoroethylene, polyimide and silicon rubber;
B7) the temperature of the heat treatment in the step 4) is 100-180 ℃.
10. Use of a method of preparing a membrane electrode according to any one of claims 1 to 5 in a fuel cell.
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