CN114388858A - Preparation method of fuel cell membrane electrode - Google Patents
Preparation method of fuel cell membrane electrode Download PDFInfo
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- CN114388858A CN114388858A CN202111458948.8A CN202111458948A CN114388858A CN 114388858 A CN114388858 A CN 114388858A CN 202111458948 A CN202111458948 A CN 202111458948A CN 114388858 A CN114388858 A CN 114388858A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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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]
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/109—After-treatment of the membrane other than by polymerisation thermal other than drying, e.g. sintering
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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
- H01M2008/1095—Fuel cells with polymeric electrolytes
Abstract
The invention provides a preparation method of a fuel cell membrane electrode, which is characterized in that dilute solution of proton conducting polymer is sprayed on the surface of a Gas Diffusion Electrode (GDE) in a heating state to form a first coating; coating the concentrated solution of the proton conducting polymer on the surface of the first coating to form a second coating; two GDEs having a second coating and a first (or second) coating, respectively, are placed on both sides of an insulating gas-tight frame to assemble a fuel cell membrane electrode. The method utilizes a direct membrane deposition technology to directly form the proton exchange membrane on the surface of the GDE, so that the good contact between a catalyst layer and the proton exchange membrane can be ensured, and the interface resistance is reduced; the first coating barrier is formed on the surface of the GDE in a heating state, so that excessive permeation of liquid proton conduction polymer solution to a catalyst layer and film forming defects in the direct film deposition process can be reduced, and the catalytic activity of the membrane electrode and the gas blocking capability of a proton exchange membrane are improved.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and relates to a preparation method of a fuel cell membrane electrode.
Background
At present, proton exchange membrane fuel cell technology is mature, and some products are applied. However, low electrical output performance, slow manufacturing speed, and high manufacturing cost remain important obstacles to the widespread commercialization of fuel cells. As an electrochemical reaction site, the membrane electrode is the most central component in a proton exchange membrane fuel cell, and the characteristics of the membrane electrode directly determine the quality and production cost of the fuel cell. The membrane electrode is composed of three functional layers, namely a gas diffusion layer, a cathode and anode catalyst layer (usually containing platinum, carbon and proton conducting polymer) and a Proton Exchange Membrane (PEM). The proton exchange membrane fuel cell can be widely applied to the fields of vehicles (automobiles), distributed power supply (communication base stations) and the like, the demand of the membrane electrode is greatly increased along with the popularization and application of the proton exchange membrane fuel cell in different fields, and the large-scale production of the high-performance membrane electrode is a key for the commercialization of the proton exchange membrane fuel cell.
The manufacturing method of the membrane electrode and the structural design of each functional layer affect the electrical output performance and the production speed of the membrane electrode. In the conventional manufacturing method of the membrane electrode, each functional layer is regarded as an independent unit to be manufactured separately, an obvious interface exists between each functional layer, and a plurality of problems or limitations exist in the manufacturing process, which cause the problems of low electrical output performance, long production period and the like of the membrane electrode, so that a new membrane electrode manufacturing method needs to be developed. Chinese patent CN109638298A adopts slit die head casting technology to coat cathode catalyst, Nafion solution and anode catalyst in sequence to prepare a 3D structure membrane electrode. Chinese patent CN110247062A directly coats a perfluorosulfonic acid resin (PFSA) solution on a gas diffusion electrode, and coats another catalytic layer after drying to form a film to prepare a membrane electrode, wherein the perfluorosulfonic acid resin solution is coated one or more times to make the proton exchange membrane reach a target thickness. The proton-conducting polymer solution is directly coated on the catalyst layer to form the membrane, so that a separate membrane-making process can be omitted, and the interface contact between the catalyst layer and the proton exchange membrane is enhanced. The phenomenon that Nafion solution fills any cracks of The catalytic layer during coating process was observed by The Scanning Electron Microscope (SEM) and The energy dispersive X-ray spectrometer (EDX) by Ding et al (Journal of The Electrochemical Society,159(6) B746-B753(2012)), and that Nafion penetration into The catalytic layer was a big problem. At present, in the proton-conducting polymer coating process, the polymer solution is mainly coated by spraying, blade coating, slit extrusion coating, and the like. The spraying technique requires long spraying time, and repeated spraying operation is needed to obtain sufficient proton conducting polymer loading and thickness, so that the membrane electrode production efficiency is low, and the final membrane forming quality is poor (the membrane surface is rough, and the gas permeability is high); the fast coating technology (such as roll coating, blade coating, slit extrusion coating and the like) can improve the production efficiency, but the proton-conducting polymer solution is easy to permeate into the catalyst layer and excessively fills the catalyst layer, so that the problems of reduction of active components in the catalyst layer, waste of proton-conducting polymer, poor film forming quality and the like are caused, and the performance of the membrane electrode is influenced. Therefore, the direct film deposition technique is difficult to apply to large-scale membrane electrode production.
Disclosure of Invention
The invention provides a membrane electrode preparation method and a preparation method of a proton exchange membrane in a membrane electrode, aiming at the problems that the production cycle of the membrane electrode in the prior art is long, and the proton conduction polymer is easy to permeate into pores of a catalyst layer in the direct membrane deposition process to cause the over filling of the proton conduction polymer and the poor membrane forming quality. The method forms a thin first electrolyte membrane coating on the surface of a catalytic layer by a spraying technology, then coats a second electrolyte membrane coating based on the first electrolyte membrane coating, and finally, two membrane coating electrodes containing the second coating and a first (or second) coating are assembled into a fuel cell membrane electrode by hot pressing. According to the method, the first electrolyte membrane coating prepared by using the spraying technology can quickly form a layer of barrier on the surface of the catalyst layer, effectively prevent the proton-conducting polymer solution from permeating into the catalyst layer in the subsequent coating process, and can ensure that the active component in the catalyst layer is not excessively coated and the second coating has good film forming quality. Meanwhile, the spraying technology only relates to the first coating, and the second coating adopts a rapid coating technology, so that the preparation time of the proton exchange membrane and the membrane electrode can be greatly shortened. The method optimizes the membrane electrode preparation technology, can improve the membrane forming quality and production efficiency of the proton exchange membrane while improving the electrical output performance of the membrane electrode, shortens the membrane electrode manufacturing time, and is expected to realize large-scale industrial application of the membrane electrode.
The invention is realized by the following scheme:
a preparation method of a fuel cell membrane electrode comprises the following steps:
s1, fixing the gas diffusion electrode on a constant-temperature heating table, wherein the catalytic layer is positioned on the upper surface;
s2, after the upper surface temperature of the gas diffusion electrode is consistent with the set temperature of the constant-temperature heating table, coating dilute solution of proton-conducting polymer on a catalyst layer of the gas diffusion electrode by using a coating tool, and forming a first coating after drying, forming and thermal annealing treatment to obtain a membrane coating electrode with the first coating;
s3, coating the concentrated solution of the proton conducting polymer on the first coating of the gas diffusion electrode by using a coating tool, drying, forming and carrying out thermal annealing treatment to form a second coating, and obtaining a membrane coating electrode with the second coating;
and S4, placing two membrane coating electrodes containing the second coating and the first (or second) coating on two sides of the insulating airtight frame, and performing hot-pressing assembly to obtain the fuel cell membrane electrode.
A method for preparing membrane electrode of fuel cell includes combining the second coating and the first (or second) coating on two membrane coating electrodes to form proton exchange membrane layer when membrane electrode is assembled by hot pressing.
In one embodiment of the present invention, the set temperature of the constant temperature heating stage in step S1 is 60 to 100 ℃.
As an embodiment of the present invention, the gas diffusion electrode of step S1 includes a catalytic layer and a gas diffusion layer; the Pt loading capacity in the catalytic layer is 0.1-0.4mg/cm2(ii) a The catalytic layer has flat surface and less cracks.
As an embodiment of the present invention, the dilute solution of the proton-conducting polymer in step S1 is a perfluorosulfonic acid solution, a sulfonated polyetheretherketone solution, or a sulfonated trifluorostyrene solution, and the solid content is 1wt% to 3 wt%.
As an embodiment of the present invention, the concentrated solution of the proton-conducting polymer in step S1 is a perfluorosulfonic acid solution, a sulfonated polyetheretherketone solution, or a sulfonated trifluorostyrene solution, and the solid content is 10 to 30 wt%.
As an embodiment of the present invention, the proton conducting polymer sprayed in the first coating layer in the step S1The amount is 1-5mg/cm2The mass of the proton conducting polymer in the second coating layer is 0.5-10mg/cm2。
As an embodiment of the present invention, the proton-conducting polymer dilute solution of step S1 is applied by: spraying; the coating mode of the proton conducting polymer concentrated solution is as follows: the coating process of the proton-conducting polymer concentrated solution can be performed one or more times according to the required thickness of the proton exchange membrane, and the next coating process is performed after the solution is completely dried to form a membrane after each coating is finished.
As an embodiment of the present invention, the drying treatment temperature in step S1 is 60-100 deg.C, and the time is 1-4 h; the annealing heat treatment temperature is 110-150 ℃, and the time is 5-120 min.
As an embodiment of the present invention, the heat treatment temperature of the hot press molding in the step S1 is 100-150 ℃, the pressure is 0.1-1MPa, and the hot press time is 30-180S.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalytic layer in the gas diffusion layer used in the invention has flat surface and less cracks, and the permeation of proton-conducting polymer solution to the catalytic layer in the direct film deposition process can be reduced to a certain extent;
2. according to the invention, the first electrolyte membrane coating is prepared on the surface of the catalyst layer by using a spraying technology, so that a layer of barrier can be quickly formed on the surface of the catalyst layer, the permeation of proton-conducting polymer solution to the catalyst layer in the subsequent coating process can be effectively blocked, and the active components in the catalyst layer can be prevented from being excessively coated and the good film forming quality of the second coating can be ensured.
3. The spray coating technology of the invention only relates to the thin first coating, and the second coating uses the rapid coating technology, so that the time for preparing the electrolyte membrane and the membrane electrode can be greatly shortened. The method optimizes the membrane electrode preparation technology, can improve the membrane forming quality and production efficiency of the proton exchange membrane while improving the electrical output performance of the membrane electrode, shortens the membrane electrode manufacturing time, and is expected to realize large-scale industrial production of the membrane electrode.
The key technical points of the application are as follows:
1. firstly preparing a thin first electrolyte membrane coating on the surface of the catalytic layer by using a spraying technology, and then preparing a thicker second electrolyte membrane coating by using a quick coating technology based on the first electrolyte membrane coating, wherein the preparation method comprises the following steps:
a) the first electrolyte membrane coating can form a layer of barrier on the surface of the catalyst layer, so that the permeation of proton-conducting polymer solution to the catalyst layer in the subsequent coating process is effectively blocked, and the active components in the catalyst layer can be prevented from being excessively coated and the good film forming quality of the second coating can be ensured;
b) the spraying technology requiring repeated spraying only involves a thin first coating, and the second coating uses a rapid coating technology, so that the time for preparing the electrolyte membrane and the membrane electrode can be greatly shortened, and the production efficiency can be improved.
2. The preparation process of the proton exchange membrane is directly integrated into the preparation process of the membrane electrode, the preparation process is simple, and the time and the production cost are saved;
drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a flow chart of the steps in the fuel cell membrane electrode preparation process of the present invention;
FIG. 2 is a schematic view of a membrane electrode structure prepared by the method of the present invention;
the gas diffusion electrode comprises a gas diffusion electrode 1, a gas diffusion layer 11, a catalyst layer 12, a proton exchange membrane 2, a first electrolyte membrane coating 21, a second electrolyte membrane coating 22 and an insulating airtight frame layer 3, wherein the gas diffusion electrode is arranged on the gas diffusion layer 1;
FIG. 3 is a graph comparing the performance curves of the membrane electrode assembly fuel cell prepared in example 1 with those of the membrane electrode assembly fuel cells prepared in comparative examples 1, 2, and 3;
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Example 1
The structure of the fuel cell membrane electrode according to this embodiment is shown in fig. 2, and includes, from bottom to top, a gas diffusion electrode 1, a proton exchange membrane layer 2, an insulating airtight frame layer 3, a proton exchange membrane layer 2, and a gas diffusion electrode 1; the gas diffusion electrode 1 includes a gas diffusion layer 11 and a catalytic layer 12; the proton exchange membrane layer 2 includes a first electrolyte membrane coating 21 and a second electrolyte membrane coating 22.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
a) a cathode gas diffusion electrode and an anode gas diffusion electrode (available from Yangtze Energy Technologies, Inc., cathode GDE platinum loading of 0.4 mg/cm)2The anode GDE platinum loading is 01mg/cm2) Respectively fixing on 80 deg.C constant temperature heating table, wherein the catalyst layer is arranged on the upper surface;
b) after the upper surface temperature of the gas diffusion electrode is consistent with the set temperature of the constant temperature heating table, 1wt% of Nafion dilute solution is coated on the catalyst layer of the gas diffusion electrode by using a spray gun, and the mass density of Nafion resin is controlled to be 1mg/cm by controlling the spraying time2Drying and forming on a constant-temperature heating table, transferring to a 130 ℃ oven, heating and annealing for 30min to form a first coating, and obtaining a film-coated electrode with the first coating;
c) adjusting the distance between a scraper of a scraper coating tool and the first coating to be 100 mu m, coating a Nafion concentrated solution with the concentration of 20 wt% on the first coating of the gas diffusion electrode, drying and forming on a constant temperature table, transferring to 130 ℃ for heating and annealing for 30min to form a second coating, wherein the Nafion loading capacity of the second coating is 2mg/cm2Obtaining an anode film coating electrode and a cathode film coating with a second coating;
d) and placing the anode film coating electrode and the cathode film coating electrode with the second coating on two sides of the insulating airtight frame, hot-pressing to assemble the fuel cell membrane electrode, setting the hot-pressing temperature to be 120 ℃, the pressure to be 0.3MPa and the time to be 2min, and obtaining the membrane electrode after the hot-pressing is finished.
Example 2
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
a) a cathode gas diffusion electrode and an anode gas diffusion electrode (available from Yangtze Energy Technologies, Inc., cathode GDE platinum loading of 0.4 mg/cm)2The anode GDE platinum loading is 0.1mg/cm2) Respectively fixing on a constant temperature heating table at 60 deg.C, wherein the catalyst layer is arranged on the upper surface;
b) after the upper surface temperature of the gas diffusion electrode is consistent with the set temperature of the constant temperature heating table, 1.6 wt% of Nafion dilute solution is coated on the catalyst layer of the gas diffusion electrode by using a spray gun, and the mass density of Nafion resin is controlled to be 2mg/cm by controlling the spraying time2Drying and forming on a constant-temperature heating table, transferring to a 130 ℃ oven, heating and annealing for 30min to form a first coating, and obtaining an anode film coating and a cathode film coating electrode with the first coating;
c) adjusting the gap between a scraper of a scraper coating tool and the first coating of the anode membrane coating electrode to be 100 mu m, coating 15 wt% of Nafion concentrated solution on the first coating of the gas diffusion electrode, drying and molding on a constant temperature table, coating 100 mu m 15 wt% of Nafion concentrated solution on the membrane coating by using the scraper again, transferring to 130 ℃ after drying and molding, heating and annealing for 30min to form a second coating, wherein the Nafion carrying capacity of the second coating is 3mg/cm2Obtaining an anode film coating electrode with a second coating; d) and placing the cathode membrane coating electrode with the first coating and the membrane coating electrode with the anode second coating on two sides of the insulating airtight frame, hot-pressing to assemble the fuel cell membrane electrode, setting the hot-pressing temperature to be 120 ℃, the pressure to be 0.3MPa and the time to be 2min, and obtaining the membrane electrode after the hot-pressing is finished.
Example 3
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
a) a cathode gas diffusion electrode and an anode gas diffusion electrode (available from Yangtze Energy Technologies, Inc., cathode GDE platinum loading of 0.4 mg/cm)2The anode GDE platinum loading is 0.1mg/cm2) Respectively fixing on a constant temperature heating table at 100 deg.C, wherein the catalyst layer is arranged on the upper surface;
b) after the upper surface temperature of the gas diffusion electrode is consistent with the set temperature of the constant temperature heating table, coating a 3wt% Nafion dilute solution on the catalyst layer of the gas diffusion electrode by using a spray gun, and controlling the mass density of Nafion resin to be 5mg/cm by controlling the spraying time2Drying and forming on a constant-temperature heating table, transferring to a 130 ℃ oven, heating and annealing for 30min to form a first coating, and obtaining an anode film coating electrode and a cathode film coating electrode with the first coating;
c) adjusting the gap between a die head of a slit extrusion coating tool and a first coating of a cathode film coating electrode to be 200 mu m, coating a Nafion concentrated solution with the concentration of 20 wt% on the first coating of the gas diffusion electrode, drying and forming on a constant temperature table, transferring to 130 ℃ for heating and annealing for 30min to form a second coating, wherein the Nafion loading capacity of the second coating is 4mg/cm2Obtaining a cathode film coated electrode with a second coating;
d) and placing the anode film coating electrode with the first coating and the cathode film coating electrode with the second coating on two sides of the insulating airtight frame, hot-pressing to assemble the fuel cell membrane electrode, setting the hot-pressing temperature to be 120 ℃, the pressure to be 0.3MPa and the time to be 2min, and obtaining the membrane electrode after the hot-pressing is finished.
Comparative example 1
The preparation of the membrane electrode of the comparative example specifically comprises the following steps:
commercial CCM membrane electrodes (Yangtze Energy Technologies) were taken with cathode and anode Pt loadings of 0.1 and 0.4mg/cm, respectively2。
Comparative example 2
The preparation of the membrane electrode of the comparative example specifically comprises the following steps:
a) the cathode gasDiffusion electrode and anode gas diffusion electrode (available from Yangtze Energy Technologies, Inc., cathode GDE platinum loading of 0.4 mg/cm)2The anode GDE platinum loading is 0.1mg/cm2) Respectively fixing on 80 deg.C constant temperature heating table, wherein the catalyst layer is arranged on the upper surface;
b) after the upper surface temperature of the gas diffusion electrode is consistent with the set temperature of the constant temperature heating table, 1wt% of Nafion dilute solution is respectively coated on the catalyst layers of the anode and the cathode gas diffusion electrode by using a spray gun, and the mass density of Nafion resin is controlled to be 0.5mg/cm by controlling the spraying time2Drying and forming on a constant-temperature heating table, transferring to a 130 ℃ oven, heating and annealing for 30min to form a first coating, and obtaining an anode and a cathode film coated electrode with the first coating;
c) adjusting the distance between a scraper of a scraper coating tool and the first coating to be 100 mu m, coating a Nafion concentrated solution with the concentration of 20 wt% on the first coating of the gas diffusion electrode, drying and forming on a constant temperature table, transferring to 130 ℃ for heating and annealing for 30min to form a second coating, wherein the Nafion loading capacity of the second coating is 2mg/cm2Obtaining anode and cathode film coated electrodes with a second coating;
d) and placing the anode and cathode film coating electrodes with the second coating on two sides of the insulating airtight frame, hot-pressing to assemble the fuel cell film electrode, setting the hot-pressing temperature to be 120 ℃, the pressure to be 0.3MPa and the time to be 2min, and obtaining the film electrode after the hot-pressing is finished.
Comparative example 3
The preparation of the membrane electrode of the comparative example specifically comprises the following steps:
a) a cathode gas diffusion electrode and an anode gas diffusion electrode (available from Yangtze Energy Technologies, Inc., cathode GDE platinum loading of 0.4 mg/cm)2The anode GDE platinum loading is 0.1mg/cm2) Respectively fixing on a constant temperature heating table at 100 deg.C, wherein the catalyst layer is arranged on the upper surface;
b) after the temperature of the upper surface of the gas diffusion electrode is consistent with the set temperature of the constant temperature heating table, the gap of a scraper coating tool is adjusted to be 100 mu m, and 20 wt% Nafion concentrated solution is respectively coated on the anode and the cathode gas diffusion electrodesAfter drying and forming on a constant temperature table, transferring the catalyst layer to 130 ℃ for heating and annealing for 30min to form an electrolyte membrane coating, wherein the Nafion loading capacity of the coating is 2mg/cm2Obtaining an anode and a cathode film coated electrode with an electrolyte film coating;
d) and respectively placing the anode and cathode film coating electrodes with the electrolyte film coatings on two sides of the insulating airtight frame, hot-pressing to assemble the fuel cell membrane electrode, setting the hot-pressing temperature to be 120 ℃, the pressure to be 0.3MPa and the time to be 2min, and obtaining the membrane electrode after the hot-pressing is finished.
Performance testing of examples and comparative examples
Single cell performance testing of example 1 and comparative examples 1, 2, 3: and respectively introducing hydrogen and air into the anode and the cathode of the single cell, wherein the gas flow of the hydrogen is 400mL/min, the gas flow of the air is 800mL/min, the humidification humidity of the anode and the cathode is 100%, the temperature of the fuel cell is 80 ℃, and no back pressure exists.
As can be seen from FIG. 3, the membrane electrode assembly cell prepared in example 1 measured an open circuit voltage of 0.908V and a peak power density of 523mW/cm2In comparative example 1, a commercially available CCM type membrane electrode assembled cell was measured to have an open circuit voltage of 0.907V and a peak power density of 514mW/cm2(ii) a Comparative example 2 the mass of Nafion in the first electrolyte membrane coating was 0.5mg/cm2Then, the membrane electrode assembly single cell measured open circuit voltage of 0.874V and peak power density of 423mW/cm2Comparative example 3 in which the first electrolyte film layer was not applied to the surface of the gas diffusion electrode, the open circuit voltage of the membrane electrode assembly cell was 0.843V, and the peak power density was 343mW/cm2. The reason is analyzed: the first coating is not applied to the surface of the gas diffusion layer or is too thin to form enough barrier to prevent the permeation of Nafion solution to the catalytic layer in the subsequent coating process, so that the active sites in the catalyst are reduced, the film forming quality is poor, and the electric output performance of the membrane electrode is insufficient. Obviously, the open-circuit voltage and the peak power of the membrane electrode prepared in the embodiment are obviously improved compared with those of the membrane electrode prepared in the comparative example. The first electrolyte membrane coating layer formed on the surface of the catalytic layer by the spray coating technique in this embodiment is then based on the first electrolyte membraneA second electrolyte membrane coating (thickness of more than 80% of the total membrane thickness) applied over the layer. The method can quickly form a layer of barrier on the surface of the catalyst layer, effectively prevent the proton conduction polymer solution from permeating into the catalyst layer in the subsequent coating process, and can ensure that the active component in the catalyst layer is not excessively coated and the film forming quality of the second coating layer. Meanwhile, the spraying technology only relates to an extremely thin first coating, and the second coating uses a rapid coating technology, so that the time for preparing the electrolyte membrane and the membrane electrode can be greatly shortened. The method optimizes the membrane electrode preparation technology, can improve the membrane forming quality and production efficiency of the proton exchange membrane while improving the electrical output performance of the membrane electrode, shortens the membrane electrode manufacturing time, and is expected to realize large-scale industrial application of the membrane electrode.
The numbers and main features of the membrane electrodes prepared in the respective examples and comparative examples, and the performance of the fuel cell assembled using the integrated membrane electrode assembly are shown in table 1.
TABLE 1
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A method of making a membrane electrode, the method comprising:
fixing a gas diffusion electrode on a constant-temperature heating table, wherein a catalytic layer is positioned on the upper surface;
after the upper surface temperature of the gas diffusion electrode is consistent with the set temperature of the constant-temperature heating table, coating dilute solution of proton-conducting polymer on a catalyst layer of the gas diffusion electrode by using a coating tool, and forming a first coating after drying, forming and thermal annealing treatment to obtain a membrane coating electrode with the first coating;
coating the concentrated solution of the proton conducting polymer on the first coating of the gas diffusion electrode by using a coating tool, and forming a second coating after drying, forming and thermal annealing treatment to obtain a membrane coating electrode with the second coating;
and (3) placing two membrane coating electrodes containing a second coating and a first (or second) coating on two sides of the insulating airtight frame, and performing hot-pressing assembly to obtain the fuel cell membrane electrode.
2. The method of producing a membrane electrode according to claim 1, characterized in that: the set temperature of the constant temperature heating table is 60-100 ℃.
3. The method of producing a membrane electrode according to claim 1, characterized in that: the gas diffusion electrode comprises a catalytic layer and a gas diffusion layer; the Pt loading capacity in the catalytic layer is 0.1-0.4mg/cm2(ii) a The catalytic layer has flat surface and less cracks.
4. The method of producing a membrane electrode according to claim 1, characterized in that: the dilute solution of the proton-conducting polymer is a perfluorinated sulfonic acid solution, a sulfonated polyether-ether-ketone solution or a sulfonated trifluorostyrene solution, and the solid content is 1-3 wt%.
5. The method of producing a membrane electrode according to claim 1, characterized in that: the concentrated solution of the proton-conducting polymer is a perfluorinated sulfonic acid solution, a sulfonated polyether-ether-ketone solution or a sulfonated trifluorostyrene solution, and the solid content is 10-30 wt%.
6. The method of producing a membrane electrode according to claim 1, characterized in that: the mass of the proton conducting polymer sprayed in the first coating is 1-5mg/cm2The mass of the proton conducting polymer in the second coating layer is 0.5-10mg/cm2。
7. The method of producing a membrane electrode according to claim 1, characterized in that: the coating mode of the proton conducting polymer dilute solution is as follows: spraying; the coating mode of the proton conducting polymer concentrated solution is as follows: the coating process of the proton-conducting polymer concentrated solution can be performed one or more times according to the required thickness of the proton exchange membrane, and the next coating process is performed after the solution is completely dried to form a membrane after each coating is finished.
8. The method for preparing a membrane electrode according to claim 1, wherein the drying treatment temperature is 60 to 100 ℃ and the time is 1 to 4 hours; the annealing heat treatment temperature is 110-150 ℃, and the time is 5-120 min.
9. The method of producing a membrane electrode according to claim 1, characterized in that: the heat treatment temperature of the hot-press molding is 100-150 ℃, the pressure is 0.1-1MPa, and the hot-press time is 30-180 s.
10. The method of preparing a membrane electrode according to claim 1, wherein the second coating layer and the first (or second) coating layer coated on the two gas diffusion electrodes, respectively, are integrated to form a proton exchange membrane layer when hot-pressed and assembled into a membrane electrode.
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Citations (8)
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