CN114497582A - Preparation method of membrane electrode catalyst layer - Google Patents
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- CN114497582A CN114497582A CN202111608142.2A CN202111608142A CN114497582A CN 114497582 A CN114497582 A CN 114497582A CN 202111608142 A CN202111608142 A CN 202111608142A CN 114497582 A CN114497582 A CN 114497582A
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- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 12
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8814—Temporary supports, e.g. decal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a preparation method of a membrane electrode catalyst layer. The membrane electrode comprises an anode catalyst layer, a proton exchange membrane and a cathode catalyst layer; the membrane electrode is stretched by the base of the catalyst layer, so that the catalyst layer has cracks. The catalyst layer with the cracks is transferred to the proton membrane, and the cracks are utilized to improve the water vapor transmission efficiency of the catalyst layer. The method can reduce mass transfer polarization of the battery and optimize the performance of the battery.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of a membrane electrode catalyst layer.
Background
The membrane electrode is composed of a diffusion layer, a catalyst layer and a proton exchange membrane, is an electrochemical generation place of the proton exchange membrane fuel cell and is a core component for chemical energy and electric energy conversion. Fuel cell performance suffers from three losses, namely electrochemical polarization, ohmic polarization, and mass transfer polarization. The catalyst layer has low porosity and few through holes, and is a main component for mass transfer polarization of the membrane electrode. Therefore, the mass transfer efficiency of the catalyst layer is improved, and the method has important significance for improving the performance of the battery. At present, the mass transfer efficiency of the catalyst layer is improved by the following methods. Firstly, slurry for preparing the catalyst layer is adjusted through a solvent and an additive, and a large number of secondary holes are formed in the preparation and forming process of the catalyst layer, so that a convenient oxygen channel is formed. The method needs to study the compatibility and adaptability of various materials in a large amount, has low flexibility of the materials, and is not beneficial to quickly manufacturing the membrane electrode suitable for different requirements. Second, platinum was supported on ordered nanoarrays as catalytic layer. The catalyst layer has a large number of straight-through pore channels, and the pore channels have high through-hole rate and low tortuosity and are the most ideal oxygen mass transfer path. However, the preparation process is relatively expensive, and there are few mass producers except the NSTF series proposed by 3M company. The NSTF series also has many problems. Third, the catalytic layer is prepared from fibrous materials. By using a platinum-carbon catalyst or an ionic resin in a fibrous form, it is possible to form large-sized secondary pores by overlapping them in a loose structure by their length. However, the formation of fibers requires the addition of polymers, and the influence of these polymers on the catalyst activity and the battery durability needs to be further examined.
The prior patent with the application number of 201910136626.8 provides a method for continuously preparing an ordered catalyst layer of a membrane electrode on a large scale, wherein the catalyst layer is prepared by modifying polytetrafluoroethylene fibers by a nano catalyst, then mixing, melting, extruding and calendering the polytetrafluoroethylene fibers, perfluorinated sulfonic acid resin and carbon fibers to prepare a catalyst membrane blank, and finally heating and longitudinally stretching the catalyst membrane blank. The carbon fiber and the catalyst are arranged in a fibrous order, so that a channel is provided for electron and proton transmission, and a micro-channel beneficial to gas and water transmission is reserved after the carbon fiber and the catalyst are attached to a proton exchange membrane, so that a catalyst layer is provided with a micro-channel, the gas is conveniently transported, water is conveniently discharged, and the catalytic activity and the durability are improved. However, the addition of polytetrafluoroethylene greatly improves the hydrophobicity of the catalyst layer, and is not favorable for the working condition of 30% -40% humidity commonly used in the industry at present. In addition, although the bulk phase mass transfer efficiency after stretching is enhanced, polytetrafluoroethylene is attached to the surface of the catalyst, and in turn, local mass transfer resistance is increased, which is not favorable for the low-platinum design of the membrane electrode in the future. For the most commonly used platinum-carbon catalysts supported on carbon black, it is difficult to form a continuous, uniform catalytic layer even with the addition of polytetrafluoroethylene.
In order to improve the performance of the membrane electrode and the fuel cell, it is necessary to provide a method for preparing a membrane electrode catalyst layer, thereby promoting the technical development in the field of fuel cells.
Disclosure of Invention
The invention aims to provide a preparation method of a membrane electrode catalyst layer aiming at the defects in the prior art. The invention utilizes a simplified preparation method to introduce a large-scale oxygen transmission channel into the catalyst layer.
The membrane electrode comprises an anode catalyst layer, a proton exchange membrane and a cathode catalyst layer; the membrane electrode is stretched by the base of the catalyst layer, so that the catalyst layer has cracks. The catalyst layer with the cracks is transferred to the proton membrane, and the cracks are utilized to improve the water vapor transmission efficiency of the catalyst layer. The method can reduce mass transfer polarization of the battery and optimize the performance of the battery.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a membrane electrode catalyst layer, which comprises the following steps:
s1, selecting a material easy to deform to prepare a stretchable substrate;
s2, adding a platinum-carbon catalyst and an ionic resin solution into a solvent and stirring to obtain catalyst layer slurry;
s3, coating the catalytic layer slurry prepared in the step S2 on the stretchable substrate prepared in the step S1, drying the slurry, stretching the substrate, and generating the required deformation amount to obtain the membrane electrode catalytic layer coated on the stretchable substrate.
As one embodiment of the invention, gas transmission channels formed by stretching are distributed in the membrane electrode catalyst layer. Compared with the original secondary pore channels of the catalyst layer, the pore channels have larger size and more ordered direction, so that the transmission efficiency of oxygen is greatly improved. The invention provides a method for stretching a substrate after preparing a catalytic layer on a deformable substrate. Because the catalytic layer is similar in strength and state to dry soil, and is not strong, stretching can cause cracking of the catalytic layer. Finally, the catalytic layer with the cracks is thermally compounded on the proton exchange membrane. Under the condition that the material and the catalytic layer preparation process are determined, the sizes and the densities of generated cracks are basically the same, and the oxygen mass transfer efficiency is improved.
As an embodiment of the present invention, the gas transmission channel has a length of 0.8mm to 1.2mm and a width of 0nm to 200 nm. The crack direction generated by the catalyst layer after stretching is vertical to the stretching direction, the length distribution is about 1mm, the maximum width reaches 100-200nm, and is far larger than secondary pore channels in the unstretched catalyst layer (in the conventional catalyst layer without stretching, gaps accumulated by spherical catalysts are secondary pore channels, the pore diameter is generally distributed at 30-60nm), and large-size cracks are favorable for water and gas leakage. By controlling the deformation amount of the substrate, the crack size and density of the catalyst layer can be controlled so as to adapt to different battery working condition characteristics.
As an embodiment of the invention, the catalytic layer has a Pt loading of 0.25-0.3 mg-cm-2。
As an embodiment of the present invention, the easily deformable material in step S1 includes one of PTFE, PI, ETFE, PE, and PET.
As an embodiment of the present invention, the mass ratio of the ionic resin to carbon in the platinum-carbon catalyst described in step S2 is 0.6 to 1: 1.
As one embodiment of the present invention, the ionic resin solution in step S2 is a 20 wt% Nafion solution.
As an embodiment of the present invention, in step S2, the solvent includes a binary or ternary solvent of isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, water, DMF.
As an embodiment of the present invention, the amount of deformation in step S3 is 5% to 15%.
As an embodiment of the present invention, the stretching rate of the stretching in the step S3 is 1 to 2 μm/S.
As an embodiment of the present invention, the stretching in step S3 is stretching using a universal tester.
As one embodiment of the present invention, the stretching of the base in step S3 is followed by secondary stretching. The secondary stretching is a secondary stretching in the width direction to restore the width. The substrate is stretched along the length direction under the action of the tensile force, the stretched substrate can shrink along the width direction to a certain extent, and the width of the stretched substrate is restored through secondary stretching.
The invention also provides a membrane electrode which comprises a proton exchange membrane, an anode catalyst layer and the cathode catalyst layer, wherein the anode catalyst layer and the cathode catalyst layer are arranged on two sides of the proton exchange membrane.
The invention also provides a preparation method of the membrane electrode, which comprises the following steps:
a1, adding a platinum-carbon catalyst and an ionic resin solution into a solvent, stirring to obtain catalyst layer slurry, coating the catalyst layer slurry on a substrate, and drying to obtain an anode catalyst layer;
a2, thermally combining the anode catalyst layer prepared in the step A1 and the membrane electrode catalyst layer of claim 1 on two sides of the proton exchange membrane, and peeling off the substrate to obtain the membrane electrode.
In step a1, the Pt loading of the anode catalytic layer is 0.05-0.1 mg-cm-2。
The invention utilizes mechanical stretching to manufacture cracks on the catalyst layer of the fuel cell and utilizes the cracks to improve the water vapor transmission efficiency. The invention focuses on the construction mode of the catalyst layer, realizes the improvement of oxygen mass transfer performance, but does not adopt the measure of changing the catalyst, but improves the distribution mode of the ionic resin, and improves the electrochemical reaction efficiency in the catalyst layer, which is attributed to the construction method of the catalyst layer.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, a high-efficiency gas transmission channel is manufactured in the catalyst layer by using a simple physical method, so that the gas transmission efficiency is improved, the mass transfer polarization of the battery can be obviously reduced, and the battery performance is improved;
2. the invention only uses the conventional materials such as platinum-carbon catalyst, ionic resin and the like, does not need chemical additives such as pore-forming agent and the like, and avoids the preparation of ordered arrays or complex materials such as carbon fiber and the like.
3. The invention utilizes a universal test machine to accurately stretch the sample based on the mechanical characteristics of the materials (the substrate and the catalyst layer), and can effectively control the size of the crack, thereby adjusting the performance of the battery.
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 graph showing the results of the battery performance tests of examples 1 to 3 and comparative example 4;
FIG. 2 is the results of the mass transfer resistance test of examples 1 to 3 and comparative example 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. 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 variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
The invention utilizes mechanical stretching to enable the catalyst layer of the fuel cell to generate cracks, and the cracks are utilized to improve the water vapor transmission efficiency. The appearance of the large-size cracks provides a smooth channel for water and gas transmission, so that the mass transfer polarization of the catalyst layer can be effectively reduced, and the performance of the battery is improved. In the invention, the temperature and humidity for testing the battery performance are 80 ℃ and 40% or 100%. The test backpressure was 150 KPaabs. The flow channels selected by the cell are 5cm by 5cm 5-channel serpentine flow fields, and the metering ratio of the test gas is H2: Air: 2. The temperature and the humidity of the mass transfer resistance test of the battery are respectively 80 ℃ and 67 percent. The test backpressure was 150 KPaabs. The flow channel selected by the cell is a 5-channel straight flow field with 2cm x 1cm, and the tested hydrogen gas amount is 800cc min-1The amount of the oxygen-nitrogen mixed gas is 1500cc min-1. The oxygen partial pressure in the oxygen-nitrogen mixture was 4%.
To optimize the performance characteristics of the present invention, the present invention is implemented in the following manner.
Example 1
The embodiment provides a preparation method of a membrane electrode, which comprises the following specific steps:
s1, adding a platinum-carbon catalyst and an ionic resin solution (Nafion, 20% by wt.) into a solvent, and stirring for 24 hours to obtain a catalyst layer slurry; wherein the mass ratio (I/C) of carbon contained in the ionic resin and the platinum-carbon catalyst is controlled to be 0.7: 1. The solvent is a mixed solvent (1: 1by vol.) of isopropanol and water, and the concentration of the platinum-carbon catalyst in the solvent is 10 mg/ml-1。
S2, coating the cathode catalyst layer slurry of S1 on a PTFE substrate by using a spraying machine, drying, and controlling the platinum loading of the catalyst layer on the substrate to be 0.25 mg-cm-2. And (3) placing the substrate loaded with the catalyst layer on a universal testing machine, setting a tensile force to stretch the substrate by 3 percent along the length direction, stretching the substrate to a certain extent along the width direction, and stretching the substrate for a second time in the width direction to recover the width of the substrate to obtain the stretched cathode catalyst layer coated on the stretchable substrate.
S3, coating the catalytic layer slurry in the step S1 on a PTFE substrate by using a spraying machine, and drying, wherein the platinum loading capacity of the substrate is 0.07 mg-cm-2. And drying and then not stretching to obtain the anode catalyst layer coated on the substrate.
S4, thermally compounding the cathode and anode catalyst layers of S2 and S3 on two sides of the proton exchange membrane, and peeling off the substrate to obtain the membrane electrode.
Example 2
Example 2 was prepared in the same manner as in example 1, except that the amount of tensile deformation in step S2 was 10%.
Example 3
Example 3 is the same as the preparation method of example 1 except that the amount of tensile deformation in step S2 is 20%.
Comparative example 1
Comparative example 1 was prepared in the same manner as in example 1, except that stretching was not performed in step S2.
Fig. 1 shows the cell test performance of each example and comparative example. As shown in fig. 1, when the substrate was stretched by 3% (example 1), the battery performance was substantially consistent with that of the unstretched comparative example, indicating that the degree of stretching of 3% was small enough not to substantially affect the battery performance. When the stretching degree reaches 10% (example 2), the performance of the battery in a large current region is remarkably improved, which shows that example 2 has excellent mass transfer efficiency. The mass transfer advantage of example 2 is related to the cracks formed by stretching. The crack can be used as a large-scale water-gas transmission channel, so that water generated by reaction can be discharged in time, and the water flooding of the battery is effectively prevented. When the stretching degree reached 20% (example 3), it was found that the catalytic layer was sufficiently fractured and the proton and electron transport channels inside thereof were not effectively connected, and thus example 3 exhibited poor battery performance. At the same time, the excessive stretching of the area significantly reduces the platinum loading per unit area, which is also an important reason for the poor performance of example 3.
Fig. 2 shows the mass transfer resistance of each example and comparative example. The test results show that example 1 stretches to a lesser degree and fails to form effective fissures, thus presenting a similar, higher mass transfer resistance as the comparative example. And in the embodiments 2 and 3, after the full stretching, a plurality of cracks are formed, and high-efficiency water-gas transmission can be realized, so that the mass transfer resistance is obviously reduced. It can also be demonstrated that the too low performance of the cell of example 3 is not due to mass transfer polarization, but to electrochemical polarization and ohmic polarization.
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 preparation method of a membrane electrode catalyst layer is characterized by comprising the following steps:
s1, selecting a material easy to deform to prepare a stretchable substrate;
s2, adding a platinum-carbon catalyst and an ionic resin solution into a solvent and stirring to obtain catalyst layer slurry;
s3, coating the catalytic layer slurry prepared in the step S2 on the stretchable substrate prepared in the step S1, drying the slurry, stretching the substrate, and generating the required deformation amount to obtain the membrane electrode catalytic layer coated on the stretchable substrate.
2. The method for producing a membrane electrode catalyst layer according to claim 1, wherein gas transmission channels formed by stretching are distributed in the membrane electrode catalyst layer.
3. The method of producing a membrane-electrode catalytic layer according to claim 2, wherein the gas transmission channel has a length of 0.8mm to 1.2mm and a width of 0nm to 200 nm.
4. The method for preparing a membrane-electrode catalytic layer according to claim 1, wherein the easily deformable material in step S1 comprises one of PTFE, PI, ETFE, PE and PET.
5. The method for producing a membrane electrode catalytic layer according to claim 1, wherein the mass ratio of the ionic resin to carbon in the platinum-carbon catalyst in step S2 is 0.6 to 1: 1.
6. The method for producing a membrane electrode catalyst layer according to claim 1, wherein the solvent in step S2 includes a binary or ternary solvent of isopropyl alcohol, n-propyl alcohol, tert-butyl alcohol, water, DMF.
7. The method for producing a membrane electrode catalytic layer according to claim 1, wherein the amount of deformation in step S3 is 5% to 15%.
8. The method for producing a membrane-electrode catalytic layer according to claim 1, wherein the stretching rate of the stretching in step S3 is 1 to 2 μm/S.
9. A membrane electrode comprising a proton exchange membrane and anode catalytic layers on both sides of the proton exchange membrane and a membrane electrode catalytic layer according to claim 1.
10. A method of preparing a membrane electrode according to claim 9, comprising the steps of:
a1, adding a platinum-carbon catalyst and an ionic resin solution into a solvent, stirring to obtain catalyst layer slurry, coating the catalyst layer slurry on a substrate, and drying to obtain an anode catalyst layer;
a2, thermally combining the anode catalyst layer prepared in the step A1 and the membrane electrode catalyst layer of claim 1 on two sides of the proton exchange membrane, and peeling off the substrate to obtain the membrane electrode.
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| CN113745612A (en) * | 2021-07-30 | 2021-12-03 | 上海唐锋能源科技有限公司 | Membrane electrode with high-efficiency proton transmission network and preparation method thereof |
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