CN113604817A - PEM water electrolysis membrane electrode, preparation method and application thereof - Google Patents

PEM water electrolysis membrane electrode, preparation method and application thereof Download PDF

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CN113604817A
CN113604817A CN202110901093.5A CN202110901093A CN113604817A CN 113604817 A CN113604817 A CN 113604817A CN 202110901093 A CN202110901093 A CN 202110901093A CN 113604817 A CN113604817 A CN 113604817A
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CN113604817B (en
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马腾飞
刘永浩
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Sunshine Hydrogen Energy Technology Co Ltd
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Sungrow Power Supply Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention provides a preparation method of a PEM water electrolysis membrane electrode, which comprises the following steps: A) respectively preparing cathode catalyst layer slurry, anode catalyst layer slurry, surface coating layer slurry and proton exchange layer slurry; B) respectively preparing a cathode catalyst layer and an anode catalyst layer; C) and sequentially placing the cathode catalyst layer and the anode catalyst layer and performing hot pressing to obtain the PEM water electrolysis membrane electrode. The application provides a preparation method of a PEM water electrolysis membrane electrode, which is characterized in that nanocellulose is added into slurry of each layer of the membrane electrode, so that the strength and the dimensional stability of a proton exchange layer, the bonding force and the structural strength between the proton exchange layer and a catalytic layer and the structural strength of the catalytic layer are enhanced by the nanocellulose, the catalytic layer is not easy to peel off in the water electrolysis process, and the service life of the membrane electrode is prolonged.

Description

PEM water electrolysis membrane electrode, preparation method and application thereof
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to a PEM water electrolysis membrane electrode, a preparation method and application thereof.
Background
When the proton exchange membrane electrode is used, the cathode and anode catalyst layers fall off from the membrane electrode due to the impact of water electrolysis bubbles and circulating water flow, so that the performance of the membrane electrode is attenuated, and the service life of the membrane electrode is shortened. Therefore, in order to avoid the drop of the cathode and anode catalyst layers, an improved preparation technology is required to enhance the bonding force between the catalyst layer and the proton exchange membrane and improve the stability of the catalyst layer.
Chinese patent publication No. CN105742652A discloses a membrane electrode with a double metal layer anode for electrolyzing water and a method for manufacturing the same, which employs an ion exchange-reduction deposition method to sequentially reduce and deposit metal ions on a proton exchange membrane, so that a catalyst layer and the proton exchange membrane are tightly combined, and the impact of water flow and gas in an electrolysis process can be well resisted. Chinese patent publication No. CN1581548 discloses a unit-combined fuel cell membrane electrode and a method for preparing the same, in which a catalyst slurry is coated on a gas diffusion layer to obtain a catalyst layer, a proton exchange resin solution is continuously cast to obtain a proton exchange layer, and then a catalyst slurry is coated to obtain a membrane electrode. Therefore, it is very important to provide a preparation method of a membrane electrode which can enhance the anti-bubble and circulating water impact performance of the catalyst layer and prolong the service life.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a PEM water electrolysis membrane electrode, and the membrane electrode prepared by the method can effectively prevent a catalyst layer from peeling off and prolong the service life of the membrane electrode.
In view of the above, the present application provides a method for preparing a PEM water electrolysis membrane electrode, comprising the following steps:
A) mixing a platinum-based catalyst, water, a Nafion solution, a nano-cellulose solution and a solvent to obtain cathode catalyst layer slurry;
mixing an iridium-based catalyst, water, a Nafion solution, a nano cellulose solution and a solvent to obtain anode catalyst layer slurry;
mixing the Nafion solution and the nano-cellulose solution to obtain surface coating slurry;
mixing the Nafion solution and the nano-cellulose solution to obtain proton exchange layer slurry;
B) precoating surface coating slurry on the cathode diffusion layer, drying, spraying cathode catalyst layer slurry, and drying to obtain a cathode catalyst layer;
precoating surface coating slurry on the anode diffusion layer, drying, spraying anode catalyst layer slurry, and spraying proton exchange layer slurry to obtain an anode catalyst layer;
C) and carrying out hot pressing on the cathode catalyst layer and the anode catalyst layer to obtain the PEM water electrolysis membrane electrode.
Preferably, in the process of preparing the cathode catalyst layer slurry, the platinum-based catalyst is selected from Pt/C catalysts, the concentration of the Nafion solution is 5-10 wt%, and the concentration of the nano cellulose solution is 1-5 wt%; the content of Pt in the Pt/C catalyst is 50-70 wt%, the mass ratio of Pt in the Pt/C catalyst to Nafion in the Nafion solution is 1 (0.5-10), and the nano-cellulose in the nano-cellulose solution is 0.05-1 wt% of the solid content of the cathode catalyst layer slurry.
Preferably, in the preparation of the anode catalyst layer slurry, the iridium-based catalyst is Ir black or IrO2The concentration of the Nafion solution is 5-10 wt%, and the concentration of the nano cellulose solution is 1-5 wt%; the mass ratio of Ir in the iridium-based catalyst to Nafion in the Nafion solution is (0.5-10): 1, the nano-cellulose in the nano-cellulose solution accounts for 0.05-1 wt% of the solid content of the anode catalyst layer slurry.
Preferably, in the preparation process of the surface coating slurry, the concentration of the Nafion solution is 5-10 wt%, the concentration of the nano-cellulose solution is 1-5 wt%, and the nano-cellulose in the nano-cellulose solution is 1-10 wt% of the solid content of the surface coating slurry; in the preparation process of the proton exchange layer slurry, the concentration of the Nafion solution is 15-25 wt%, the concentration of the nano-cellulose solution is 1-5 wt%, and the nano-cellulose in the nano-cellulose solution is 1-10 wt% of the solid content of the proton exchange layer slurry.
Preferably, a cathode is obtainedIn the step of the catalyst layer, the thickness of the surface coating slurry is 1-10 mu m, and the catalyst loading amount is 0.3-2.0 mg/cm2。
Preferably, in the step of obtaining the anode catalyst layer, the thickness of the surface coating slurry is 1 to 10 μm, and the catalyst supporting amount is 1 to 8mg/cm2The thickness of the proton exchange layer slurry is 100 to 200 μm.
Preferably, the hot pressing pressure is 1-10 MPa, the temperature is 100-200 ℃, and the time is 60-300 s.
Preferably, the diameters of the nanocellulose in the cathode catalyst layer slurry, the nanocellulose in the anode catalyst layer slurry, the nanocellulose in the surface coating layer slurry and the nanocellulose in the proton exchange layer slurry are independently 10-100 nm, and the lengths of the nanocellulose in the cathode catalyst layer slurry, the nanocellulose in the anode catalyst layer slurry and the nanocellulose in the proton exchange layer slurry are independently 100-500 nm.
The application also provides the PEM water electrolysis membrane electrode prepared by the preparation method, which comprises an anode catalyst layer and a cathode catalyst layer which are sequentially arranged, wherein the surfaces of the anode catalyst layer and the cathode catalyst layer both contain nano-cellulose.
The application also provides the PEM water electrolysis membrane electrode prepared by the preparation method or the application of the PEM water electrolysis membrane electrode in an electrolytic cell.
The application provides a preparation method of a PEM water electrolysis membrane electrode, which is characterized in that nanocellulose is added into slurry of each layer of the membrane electrode, and the nanocellulose enhances the strength and dimensional stability of a proton exchange layer, the bonding force and structural strength between the proton exchange layer and a catalytic layer and the structural strength of the catalytic layer, so that the catalytic layer is not easy to peel off in the water electrolysis process, and the service life of the membrane electrode is prolonged; furthermore, the method adopts a hot-pressing mode to enhance the binding force of each layer, and simultaneously, the proton exchange layer is partially crystallized, so that the mechanical strength and the stability of the membrane electrode are enhanced.
Drawings
FIG. 1 is a schematic diagram of an electrolytic cell test system for membrane electrodes prepared in example 1 and comparative example 1;
fig. 2 is a constant current test graph of the membrane electrodes prepared in example 1 of the present invention and comparative example 1.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the problem of poor bonding strength and anti-foaming impact performance of the membrane electrode in the prior art, the embodiment of the invention discloses a preparation method of a PEM water electrolysis membrane electrode, which greatly improves the mechanical strength and stability of the PEM water electrolysis membrane electrode finally by introducing nano-cellulose and adopting a hot-pressing mode. Specifically, the application provides a preparation method of a PEM water electrolysis membrane electrode, which comprises the following steps:
A) mixing a platinum-based catalyst, water, a Nafion solution, a nano-cellulose solution and a solvent to obtain cathode catalyst layer slurry;
mixing an iridium-based catalyst, water, a Nafion solution, a nano cellulose solution and a solvent to obtain anode catalyst layer slurry;
mixing the Nafion solution and the nano-cellulose solution to obtain surface coating slurry;
mixing the Nafion solution and the nano-cellulose solution to obtain proton exchange layer slurry;
B) precoating surface coating slurry on the cathode diffusion layer, drying, spraying cathode catalyst layer slurry, and drying to obtain a cathode catalyst layer;
precoating surface coating slurry on the anode diffusion layer, drying, spraying anode catalyst layer slurry, and spraying proton exchange layer slurry to obtain an anode catalyst layer;
C) and sequentially placing and hot-pressing the first polyimide sheet, the cathode catalyst layer, the anode catalyst layer and the second polyimide sheet to obtain the PEM water electrolysis membrane electrode.
In the preparation process of the PEM hydrolyzed membrane electrode, cathode catalyst layer slurry, anode catalyst layer slurry, surface coating layer slurry and proton exchange layer slurry are prepared firstly; in the process of preparing the cathode catalyst layer slurry, mixing a platinum-based catalyst, water, a Nafion solution, a nano-cellulose solution and a solvent to obtain the cathode catalyst layer slurry; in the present application, the platinum-based catalyst is selected from Pt/C catalysts, wherein the content of Pt is 50 to 70 wt%, more specifically, the content of Pt is 55 to 65 wt%. The concentration of the Nafion solution is 5-10 wt%, and the concentration of the nano cellulose solution is 1-5 wt%; more specifically, the concentration of the Nafion solution is 5-8 wt%, and the concentration of the nano-cellulose solution is 1-3 wt%. The mass ratio of Pt in the Pt/C catalyst to Nafion in the Nafion solution is (0.5-10): 1, the nano-cellulose in the nano-cellulose solution accounts for 0.05-1 wt% of the solid content of the cathode catalyst layer slurry.
Similarly, the preparation process of the anode catalyst layer slurry specifically comprises the following steps: mixing an iridium-based catalyst, water, a Nafion solution, a nano cellulose solution and a solvent to obtain anode catalyst layer slurry; in the process, the iridium-based catalyst is Ir black or IrO2The catalyst comprises 5-10 wt% of Nafion solution, 1-5 wt% of nanocellulose solution, more specifically 6-8 wt% of Nafion solution and 2-4 wt% of nanocellulose solution; the mass ratio of Ir in the iridium-based catalyst to Nafion in the Nafion solution is (0.5-10): 1, the nano-cellulose in the nano-cellulose solution accounts for 0.05-1 wt% of the solid content of the anode catalyst layer slurry, and more specifically, the nano-cellulose in the nano-cellulose solution accounts for 0.2-0.8 wt% of the solid content of the anode catalyst layer slurry.
The bonding force of the catalyst layer, the proton exchange membrane and the porous diffusion layer is enhanced through the addition of the nano-cellulose, and the damage of circulating water impact on the MEA structure is reduced.
Mixing a Nafion solution and a nano cellulose solution to obtain surface coating slurry; mixing the Nafion solution and the nano-cellulose solution to obtain proton exchange layer slurry; in the preparation process of the surface coating slurry, the concentration of a Nafion solution is 5-10 wt%, the concentration of a nanocellulose solution is 1-5 wt%, the concentration of nanocellulose in the nanocellulose solution is 1-10 wt% of the solid content of the surface coating slurry, more specifically, the concentration of the Nafion solution is 6-8 wt%, the concentration of the nanocellulose solution is 2-4 wt%, and the concentration of nanocellulose in the nanocellulose solution is 3-8 wt% of the solid content of the surface coating slurry. In the preparation process of the proton exchange layer slurry, the concentration of the Nafion solution is 15-25 wt%, the concentration of the nano-cellulose solution is 1-5 wt%, and the nano-cellulose in the nano-cellulose solution is 1-10 wt% of the solid content of the proton exchange layer slurry; more specifically, the concentration of the Nafion solution is 18-23 wt%, the concentration of the nano-cellulose solution is 2-4 wt%, and the nano-cellulose in the nano-cellulose solution is 2-8 wt% of the solid content of the proton exchange layer slurry.
In the preparation process, the diameter of the nano-cellulose is independently selected from 10-100 nm, and the length of the nano-cellulose is independently selected from 100-500 nm.
After the raw materials are prepared, the surface coating layer slurry is pre-coated on the cathode diffusion layer, the cathode catalyst layer slurry is sprayed after drying, and the cathode catalyst layer slurry is dried to obtain a cathode catalyst layer; precoating surface coating slurry on the anode diffusion layer, drying, spraying anode catalyst layer slurry, and spraying proton exchange layer slurry to obtain an anode catalyst layer; in the present application, the material of the cathode diffusion layer and the material of the anode diffusion layer are well known to those skilled in the art, and there is no particular limitation in the present application; specifically, the cathode diffusion layer can be selected from carbon paper or carbon felt, and the anode diffusion layer can be selected from porous titanium or carbon felt. In the step of obtaining the cathode catalyst layer, the thickness of the surface coating slurry is 1-10 μm, and the catalyst loading amount is 0.3-2.0 mg/cm2(ii) a More specifically, the thickness of the surface coating slurry is 3-8 μm, and the catalyst loading amount is 0.8-1.5 mg/cm2. In the step of obtaining the anode catalyst layer, the thickness of the surface coating slurry is 1-10 μm, and the catalyst loading amount is 1-8 mg/cm2The thickness of the proton exchange layer slurry is 100-200 μm; more specifically, the thickness of the surface coating slurry is 3-8 μm, and the catalyst loading amount is 2-6 mg/cm2。
According to the invention, finally, hot-pressing crystallization is carried out, namely, the cathode catalyst layer and the anode catalyst layer are hot-pressed to obtain the PEM water electrolysis membrane electrode; the hot pressing pressure is 1-10 MPa, the temperature is 100-200 ℃, and the time is 60-300 s; more specifically, the pressure of hot pressing is 2-5 MPa, the temperature is 120-180 ℃, and the time is 100-200 s. The bonding force of each layer is enhanced, and simultaneously, the Nafion membrane layer is partially crystallized, so that the PEM water electrolysis five-in-one membrane electrode assembly is obtained. The application enhances the mechanical strength of the membrane electrode through hot-pressing crystallization, and improves the service durability of the membrane electrode.
For further understanding of the present invention, the following detailed description will be made on the method for preparing the PEM water electrolysis membrane electrode according to the present invention with reference to the following embodiments, and the scope of the present invention is not limited by the following embodiments.
Example 1 cathode Pt loading 0.5mg/cm2Anode IrO2The carrying capacity is 3mg/cm2Membrane electrode preparation
(1) Preparing slurry:
taking a quantitative 60% Pt/C catalyst, adding a small amount of water, carrying out ultrasonic wetting, adding a 5% Nafion solution (Nafion: Pt solid content mass ratio is 3:1) and a 1% nanocellulose solution (adding amount is 10% of the solid content of the catalyst layer), then supplementing an isopropanol solution to enable the solid content of the slurry to be 2%, and carrying out high-speed shearing dispersion after ultrasonic dispersion to obtain cathode catalyst layer slurry A;
quantitative determination of IrO2Adding a small amount of water, ultrasonic wetting, adding 5% Nafion solution (Nafion: IrO)2Solid content mass ratio is 3:1), 1% of nano-cellulose solution (the addition amount is 10% of the solid content of the catalyst layer), then adding isopropanol solution to make the solid content of the slurry be 2%, and performing ultrasonic dispersion and high-speed shearing to obtain cathode catalyst layer slurry B;
mixing 5% of Nafion and 1% of nano cellulose solution according to a mass ratio of 10:1, shearing at a high speed for 2h to obtain surface coating slurry C;
mixing 20% Nafion and 1% nano cellulose solution according to a mass ratio of 5: 1, shearing at a high speed for 2 hours to obtain a proton exchange layer-by-layer castable D;
(2) spraying a cathode catalyst layer: precoating a layer of slurry C with the thickness of 1 μm on the carbon paper, drying, and continuing ultrasonic sprayingCoating cathode catalyst layer slurry A to ensure that the catalyst loading capacity is 0.5mg/cm2Drying for later use;
(3) spraying an anode catalyst layer: pre-coating a layer of slurry C on the porous titanium with the thickness of 1 mu m, and continuously carrying out ultrasonic spraying on the anode catalyst layer slurry B after drying to ensure that the catalyst loading is 3mg/cm2(ii) a Continuously spraying proton exchange layer slurry D to make the thickness of the Nafion layer reach 100 μm, drying for backup
(4) Hot-pressing crystallization: and (3) attaching the catalytic layer surfaces of the cathode and anode porous diffusion layers after being sprayed with the slurry, placing the cathode and anode porous diffusion layers between two flat polyimide sheets, placing the polyimide sheets on a workbench of a hot press, hot-pressing the polyimide sheets at 150 ℃ for 120s under 5MPa, and partially crystallizing the Nafion film layer while enhancing the bonding force of each layer to obtain the PEM water electrolysis five-in-one membrane electrode assembly.
Comparative example 1 cathode Pt loading 0.5mg/cm2Anode IrO2The carrying capacity is 3mg/cm2Membrane electrode preparation
(1) Preparing slurry:
taking a quantitative 60% Pt/C catalyst, adding a small amount of water, carrying out ultrasonic wetting, adding a 5% Nafion solution (the mass ratio of Nafion to Pt solid content is 3:1), then supplementing an isopropanol solution to enable the solid content of the slurry to be 2%, and carrying out high-speed shearing dispersion after ultrasonic dispersion to obtain cathode catalyst layer slurry A;
quantitative determination of IrO2Adding a small amount of water, ultrasonic wetting, adding 5% Nafion solution (Nafion: IrO)2Solid content mass ratio of 3:1), then supplementing isopropanol solution to enable the solid content of the slurry to be 2%, and performing ultrasonic dispersion and high-speed shearing to obtain cathode catalyst layer slurry B;
taking 5% Nafion as surface coating slurry C;
taking 20% Nafion as a proton exchange layer-by-layer castable D;
(2) spraying a cathode catalyst layer: precoating a layer of slurry C on the carbon paper, wherein the thickness is 1 mu m, and continuing to ultrasonically spray the cathode catalyst layer slurry A after drying to ensure that the catalyst loading is 0.5mg/cm2Drying for later use;
(3) spraying an anode catalyst layer: pre-coating a layer of slurry C with the thickness of 1 mu m on the porous titanium, and continuously performing ultrasonic spraying on the slurry of the anode catalyst layer after dryingB, making the catalyst loading amount to be 3mg/cm2(ii) a Continuously spraying proton exchange layer slurry D to ensure that the thickness of the Nafion layer reaches 100 mu m, and drying for later use;
(4) hot-pressing crystallization: and (3) attaching the catalytic layer surfaces of the cathode and anode porous diffusion layers after being sprayed with the slurry, placing the cathode and anode porous diffusion layers between two flat polyimide sheets, placing the polyimide sheets on a workbench of a hot press, hot-pressing the polyimide sheets at 150 ℃ for 120s under 5MPa, and partially crystallizing the Nafion film layer while enhancing the bonding force of each layer to obtain the PEM water electrolysis five-in-one membrane electrode assembly.
Referring to fig. 2, fig. 2 is a constant current test of the membrane electrode of example 1 and comparative example 1 in an electrolytic cell test system (fig. 1) under the following test conditions: constant current 2A/cm2The temperature of the electrolytic cell is 80 ℃, the water flow at the anode side is 5L/min, and the area of the membrane electrode is 100cm2And the operation is carried out at normal pressure. As shown in the figure, the test voltage of the comparative example membrane electrode assembly was suddenly increased after 30h to 715mv at 40h due to strong water flow impact, whereas the test voltage of the membrane electrode assembly of example 1 was increased only 82mv at 30h to 40 h. The circulating water of the comparative example electrolytic cell was found to have significant particulates, whereas example 1 was found to have no particulates. The test result shows that the addition of the nano-cellulose obviously improves the bonding strength of each component of the membrane electrode in the embodiment 1, and avoids the performance attenuation of the membrane electrode caused by the falling-off of the catalyst layer. In the figure 1, 1 is a direct current stabilized voltage power supply, 2 is an ammeter, 3 is a voltmeter, 4 is an electrolytic cell, 5 is a circulating pump, 6 and 7 are magnetic control valves, 8 is a constant temperature water bath, and 9 is a polytetrafluoroethylene tank with air outlets.
Example 2 cathode Pt Loading 0.3mg/cm2Anode Ir supporting amount of 1mg/cm2Membrane electrode preparation
(1) Preparing slurry:
taking a quantitative 60% Pt/C catalyst, adding a small amount of water, carrying out ultrasonic wetting, adding a 5% Nafion solution (Nafion: Pt solid content mass ratio is 1:2) and a 1% nanocellulose solution (adding amount is 50% of the solid content of the catalyst layer), then supplementing an isopropanol solution to enable the solid content of the slurry to be 1%, and carrying out high-speed shearing dispersion after ultrasonic dispersion to obtain cathode catalyst layer slurry A;
quantitative determination of IrO2Catalyst, after ultrasonic wetting with a small amount of water, 5% Nafion solution (Nafion:IrO2solid content mass ratio is 1:2), 1% of nano-cellulose solution (the addition amount is 50% of the solid content of the catalyst layer), then adding isopropanol solution to make the solid content of the slurry be 1%, and performing ultrasonic dispersion and high-speed shearing to obtain cathode catalyst layer slurry B;
mixing 5% Nafion and 1% nano cellulose solution according to a mass ratio of 5: 1, shearing at a high speed for 2h to obtain surface coating slurry C;
mixing 20% Nafion and 1% nano cellulose solution according to the mass ratio of 1: 1, shearing at a high speed for 2 hours to obtain a proton exchange layer-by-layer castable D;
(2) spraying a cathode catalyst layer: precoating a layer of slurry C on the carbon paper, wherein the thickness is 1 mu m, and continuing to ultrasonically spray the cathode catalyst layer slurry A after drying to ensure that the catalyst loading is 0.3mg/cm2Drying for later use;
(3) spraying an anode catalyst layer: pre-coating a layer of slurry C on the porous titanium with the thickness of 1 mu m, and continuously carrying out ultrasonic spraying on the anode catalyst layer slurry B after drying to ensure that the catalyst loading is 1mg/cm2(ii) a Continuously spraying proton exchange layer slurry D to ensure that the thickness of the Nafion layer reaches 100 mu m, and drying for later use;
(4) hot-pressing crystallization: and (3) attaching the catalytic layers of the carbon paper and the porous titanium after being sprayed with the slurry, placing the carbon paper and the porous titanium between two flat polyimide sheets, placing the polyimide sheets on a workbench of a hot press, hot-pressing the polyimide sheets at the temperature of 120 ℃ for 180s under the pressure of 2MPa, and partially crystallizing the Nafion film layer while enhancing the bonding force of each layer to obtain the PEM water electrolysis five-in-one membrane electrode assembly.
Example 3 cathode Pt Loading 1mg/cm2Anode Ir supporting capacity 2mg/cm2Membrane electrode preparation
(1) Preparing slurry:
taking a quantitative 60% Pt/C catalyst, adding a small amount of water, carrying out ultrasonic wetting, adding a 5% Nafion solution (Nafion: Pt solid content mass ratio is 1:2) and a 1% nanocellulose solution (adding amount is 100% of the solid content of the catalyst layer), then supplementing an isopropanol solution to enable the solid content of the slurry to be 1.5%, and carrying out high-speed shearing dispersion after ultrasonic dispersion to obtain cathode catalyst layer slurry A;
quantitative determination of IrO2Adding a small amount of water, ultrasonic wetting, adding 5% Nafion solution (Nafion: IrO)2Solid contentThe weight ratio is 1:2), 1% of nano-cellulose solution (the addition amount is 100% of the solid content of the catalyst layer), then isopropyl alcohol solution is supplemented to make the solid content of the slurry be 1.5%, and the slurry B of the cathode catalyst layer is obtained by high-speed shearing after ultrasonic dispersion;
mixing 5% Nafion and 1% nano cellulose solution according to a mass ratio of 20: 1, shearing at a high speed for 2h to obtain surface coating slurry C;
mixing 20% Nafion and 1% nano cellulose solution according to the mass ratio of 10:1, shearing at a high speed for 2 hours to obtain a proton exchange layer-by-layer castable D;
(2) spraying a cathode catalyst layer: precoating a layer of slurry C on the carbon paper, wherein the thickness is 1 mu m, and continuing to ultrasonically spray the cathode catalyst layer slurry A after drying to ensure that the catalyst loading is 1mg/cm2Drying for later use;
(3) spraying an anode catalyst layer: pre-coating a layer of slurry C on the porous titanium with the thickness of 1 mu m, and continuously carrying out ultrasonic spraying on the anode catalyst layer slurry B after drying to ensure that the catalyst loading amount is 2mg/cm2(ii) a Continuously spraying proton exchange layer slurry D to make the thickness of the Nafion layer reach 100 μm, drying for backup
(4) Hot-pressing crystallization: and (3) attaching the catalytic layer surfaces of the cathode and anode porous diffusion layers after being sprayed with the slurry, placing the cathode and anode porous diffusion layers between two flat polyimide sheets, placing the polyimide sheets on a workbench of a hot press, hot-pressing the polyimide sheets at 150 ℃ for 300s under 3MPa, and partially crystallizing the Nafion film layer while enhancing the bonding force of each layer to obtain the PEM water electrolysis five-in-one membrane electrode assembly.
Example 4 cathode Pt Loading 1.5mg/cm2Anode Ir supporting capacity 4mg/cm2Membrane electrode preparation
(1) Preparing slurry:
taking a quantitative 60% Pt/C catalyst, adding a small amount of water, carrying out ultrasonic wetting, adding a 5% Nafion solution (Nafion: Pt solid content mass ratio is 10:1) and a 1% nanocellulose solution (adding amount is 1.5 times of the solid content of the catalyst layer), then supplementing an isopropanol solution to enable the solid content of the slurry to be 2.5%, and carrying out high-speed shearing dispersion after ultrasonic dispersion to obtain cathode catalyst layer slurry A;
quantitative determination of IrO2Adding a small amount of water, ultrasonic wetting, adding 5% Nafion solution (Nafion: IrO)2Solid content mass ratio of 10:1), 1% nano-cellulose solution (the addition amount is 1.5 times of the solid content of the catalyst layer), then adding isopropanol solution to make the solid content of the slurry be 2.5%, and performing high-speed shearing after ultrasonic dispersion to obtain cathode catalyst layer slurry B;
mixing 5% of Nafion and 1% of nano cellulose solution according to a mass ratio of 15: 1, shearing at a high speed for 2h to obtain surface coating slurry C;
mixing 20% Nafion and 1% nano cellulose solution according to a mass ratio of 15: 1, shearing at a high speed for 2 hours to obtain a proton exchange layer-by-layer castable D;
(2) spraying a cathode catalyst layer: precoating a layer of slurry C on the carbon paper, wherein the thickness is 1 mu m, and continuing to ultrasonically spray the cathode catalyst layer slurry A after drying to ensure that the catalyst loading is 1.5mg/cm2Drying for later use;
(3) spraying an anode catalyst layer: pre-coating a layer of slurry C on the porous titanium with the thickness of 1 mu m, and continuously carrying out ultrasonic spraying on the anode catalyst layer slurry B after drying to ensure that the catalyst loading is 4mg/cm2(ii) a Continuously spraying proton exchange layer slurry D to make the thickness of the Nafion layer reach 100 μm, drying for backup
(4) Hot-pressing crystallization: and (3) attaching the catalytic layer surfaces of the cathode and anode porous diffusion layers after being sprayed with the slurry, placing the cathode and anode porous diffusion layers between two flat polyimide sheets, placing the polyimide sheets on a workbench of a hot press, hot-pressing the polyimide sheets at the temperature of 180 ℃ for 300s under the pressure of 5MPa, and partially crystallizing the Nafion film layer while enhancing the bonding force of each layer to obtain the PEM water electrolysis five-in-one membrane electrode assembly.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A preparation method of a PEM water electrolysis membrane electrode comprises the following steps:
A) mixing a platinum-based catalyst, water, a Nafion solution, a nano-cellulose solution and a solvent to obtain cathode catalyst layer slurry;
mixing an iridium-based catalyst, water, a Nafion solution, a nano cellulose solution and a solvent to obtain anode catalyst layer slurry;
mixing the Nafion solution and the nano-cellulose solution to obtain surface coating slurry;
mixing the Nafion solution and the nano-cellulose solution to obtain proton exchange layer slurry;
B) precoating surface coating slurry on the cathode diffusion layer, drying, spraying cathode catalyst layer slurry, and drying to obtain a cathode catalyst layer;
precoating surface coating slurry on the anode diffusion layer, drying, spraying anode catalyst layer slurry, and spraying proton exchange layer slurry to obtain an anode catalyst layer;
C) and carrying out hot pressing on the cathode catalyst layer and the anode catalyst layer to obtain the PEM water electrolysis membrane electrode.
2. The preparation method according to claim 1, wherein in the process of preparing the cathode catalyst layer slurry, the platinum-based catalyst is selected from Pt/C catalysts, the concentration of the Nafion solution is 5 to 10 wt%, and the concentration of the nanocellulose solution is 1 to 5 wt%; the content of Pt in the Pt/C catalyst is 50-70 wt%, the mass ratio of Pt in the Pt/C catalyst to Nafion in the Nafion solution is 1 (0.5-10), and the nano-cellulose in the nano-cellulose solution is 0.05-1 wt% of the solid content of the cathode catalyst layer slurry.
3. The method of claim 1, wherein the anode is prepared by catalysisIn the process of layer sizing agent, the iridium-based catalyst is Ir black or IrO2The concentration of the Nafion solution is 5-10 wt%, and the concentration of the nano cellulose solution is 1-5 wt%; the mass ratio of Ir in the iridium-based catalyst to Nafion in the Nafion solution is (0.5-10): 1, the nano-cellulose in the nano-cellulose solution accounts for 0.05-1 wt% of the solid content of the anode catalyst layer slurry.
4. The preparation method according to claim 1, wherein during the preparation of the surface coating slurry, the concentration of the Nafion solution is 5-10 wt%, the concentration of the nanocellulose solution is 1-5 wt%, and the nanocellulose in the nanocellulose solution is 1-10 wt% of the solid content of the surface coating slurry; in the preparation process of the proton exchange layer slurry, the concentration of the Nafion solution is 15-25 wt%, the concentration of the nano-cellulose solution is 1-5 wt%, and the nano-cellulose in the nano-cellulose solution is 1-10 wt% of the solid content of the proton exchange layer slurry.
5. The method according to claim 1, wherein in the step of obtaining the cathode catalyst layer, the thickness of the surface coating layer slurry is 1 to 10 μm, and the catalyst supporting amount is 0.3 to 2.0mg/cm2。
6. The method according to claim 1, wherein in the step of obtaining the anode catalyst layer, the thickness of the surface coating slurry is 1 to 10 μm, and the catalyst supporting amount is 1 to 8mg/cm2The thickness of the proton exchange layer slurry is 100 to 200 μm.
7. The method according to claim 1, wherein the hot pressing is performed under a pressure of 1 to 10MPa at a temperature of 100 to 200 ℃ for 60 to 300 seconds.
8. The production method according to any one of claims 1 to 7, wherein the diameter of the nanocellulose in the cathode catalyst layer slurry, the diameter of the nanocellulose in the anode catalyst layer slurry, the diameter of the nanocellulose in the surface coating layer slurry, and the diameter of the nanocellulose in the proton exchange layer slurry are independently 10 to 100nm, and the length of the nanocellulose is independently 100 to 500 nm.
9. The PEM water electrolysis membrane electrode prepared by the preparation method of any one of claims 1-8, which comprises an anode catalyst layer and a cathode catalyst layer which are arranged in sequence, wherein the surfaces of the anode catalyst layer and the cathode catalyst layer both contain nano-cellulose.
10. The use of a PEM water electrolysis membrane electrode prepared by the preparation method of any one of claims 1-8 or the PEM water electrolysis membrane electrode of claim 9 in an electrolytic cell.
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