CN113604817B - PEM water electrolysis membrane electrode, preparation method and application thereof - Google Patents
PEM water electrolysis membrane electrode, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a PEM water electrolysis membrane electrode, which comprises the following steps: a) Preparing cathode catalytic layer slurry, anode catalytic layer slurry, surface coating slurry and proton exchange layer slurry respectively; b) Respectively preparing a cathode catalytic layer and an anode catalytic layer; c) And placing and hot-pressing the cathode catalytic layer and the anode catalytic layer in sequence 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 dimensional stability of a proton exchange layer, the binding force and structural strength between the proton exchange layer and a catalytic layer and the structural strength of the catalytic layer are enhanced, 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
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
In the use process of the proton exchange membrane electrode, the cathode catalytic layer falls 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 reduced. Therefore, in order to avoid the falling-off of the cathode catalytic layer, the preparation technology needs to be improved so as to enhance the binding force between the catalytic layer and the proton exchange membrane and improve the stability of the catalytic layer.
The Chinese patent with publication number of CN105742652A discloses a membrane electrode with a double metal layer anode for water electrolysis and a preparation method thereof, which adopts an ion exchange-reduction deposition method to sequentially reduce and deposit metal ions on a proton exchange membrane, so that a catalytic layer is tightly combined with the proton exchange membrane, and the impact of water flow and gas in the electrolysis process can be well resisted, but the method has the advantages of low catalyst loading amount, difficult control of the loading amount and adverse influence of residual ions on the performance of the proton exchange membrane. The Chinese patent with publication number of CN1581548 discloses a unit combined fuel cell membrane electrode and a preparation method thereof, wherein 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 the catalyst slurry is coated to obtain the membrane electrode. Therefore, it is extremely important to provide a method for producing a membrane electrode that enhances the bubble and circulating water impact resistance of the catalytic layer and improves the service life.
Disclosure of Invention
The technical problem solved by the invention is to provide a preparation method of a PEM water electrolysis membrane electrode, which can effectively prevent the catalyst layer from peeling off and prolong the service life of the membrane electrode.
In view of this, the present application provides a method for preparing a PEM water electrolysis membrane electrode comprising the steps of:
a) Mixing a platinum-based catalyst, water, a Nafion solution, a nanocellulose solution and a solvent to obtain cathode catalytic layer slurry;
mixing an iridium-based catalyst, water, nafion solution, nano cellulose solution and a solvent to obtain anode catalytic layer slurry;
mixing Nafion solution and nano cellulose solution to obtain surface coating slurry;
mixing Nafion solution and nano cellulose solution to obtain proton exchange layer slurry;
b) Precoating surface coating slurry on the cathode diffusion layer, drying, spraying cathode catalytic layer slurry, and drying to obtain a cathode catalytic layer;
precoating surface coating slurry on the anode diffusion layer, drying, spraying anode catalytic layer slurry, and spraying proton exchange layer slurry to obtain an anode catalytic layer;
c) And hot-pressing the cathode catalytic layer and the anode catalytic layer to obtain the PEM water electrolysis membrane electrode.
Preferably, in the process of preparing the cathode catalytic layer slurry, the platinum-based catalyst is selected from Pt/C catalyst, the concentration of Nafion solution is 5-10wt%, and the concentration of nanocellulose solution is 1-5wt%; the Pt/C catalyst comprises 50-70wt% of Pt, the mass ratio of Pt in the Pt/C catalyst to Nafion in the Nafion solution is 1 (0.5-10), and the nanocellulose in the nanocellulose solution is 0.05-1wt% of the solid content of the cathode catalytic layer slurry.
Preferably, in the process of preparing the anode catalytic layer slurry, the iridium-based catalyst is Ir black or IrO 2 The concentration of the Nafion solution is 5-10wt% and the concentration of the nanocellulose solution is 1-5wt%; the mass ratio of Ir in the iridium-based catalyst to Nafion in the Nafion solution is (0.5-10): 1, wherein the nanocellulose in the nanocellulose solution is 0.05-1 wt% of the solid content of the anode catalytic layer slurry.
Preferably, in the preparation process of the surface coating slurry, the concentration of the Nafion solution is 5-10wt%, the concentration of the nano cellulose solution is 1-5wt%, and the nano cellulose in the nano cellulose solution is 1-10wt% 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 nanocellulose solution is 1-5 wt%, and the nanocellulose in the nanocellulose solution is 1-10 wt% of the solid content of the proton exchange layer slurry.
Preferably, in the step of obtaining the cathode catalytic layer, the thickness of the surface coating slurry is 1 to 10 μm, and the catalyst loading is 0.3 to 2.0mg/cm 2 。
Preferably, in the step of obtaining the anode catalytic layer, the thickness of the surface coating slurry is 1 to 10 μm, and the catalyst loading is 1 to 8mg/cm 2 The thickness of the proton exchange layer slurry is 100-200 mu m.
Preferably, the hot pressing pressure is 1-10 MPa, the temperature is 100-200 ℃, and the time is 60-300 s.
Preferably, the diameter of the nanocellulose in the cathode catalytic layer slurry, the nanocellulose in the anode catalytic layer slurry, the nanocellulose in the surface coating slurry and the nanocellulose in the proton exchange layer slurry are independently 10-100 nm, and the length thereof is independently 100-500 nm.
The application also provides a PEM water electrolysis membrane electrode prepared by the preparation method, which comprises an anode catalytic layer and a cathode catalytic layer which are sequentially arranged, wherein the surfaces of the anode catalytic layer and the cathode catalytic layer all contain nanocellulose.
The application also provides a PEM water electrolysis membrane electrode prepared by the preparation method or 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 each layer of slurry 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 binding force of each layer is enhanced by adopting a hot pressing mode, and meanwhile, 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 view of an electrolytic cell test system of the membrane electrode prepared in example 1 and comparative example 1;
fig. 2 is a constant current test graph of the membrane electrode prepared in example 1 and comparative example 1 of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
In view of the problem of poor bonding strength and bubbling impact resistance 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 leads the mechanical strength and stability of the PEM water electrolysis membrane electrode to be greatly improved by introducing nanocellulose 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 nanocellulose solution and a solvent to obtain cathode catalytic layer slurry;
mixing an iridium-based catalyst, water, nafion solution, nano cellulose solution and a solvent to obtain anode catalytic layer slurry;
mixing Nafion solution and nano cellulose solution to obtain surface coating slurry;
mixing Nafion solution and nano cellulose solution to obtain proton exchange layer slurry;
b) Precoating surface coating slurry on the cathode diffusion layer, drying, spraying cathode catalytic layer slurry, and drying to obtain a cathode catalytic layer;
precoating surface coating slurry on the anode diffusion layer, drying, spraying anode catalytic layer slurry, and spraying proton exchange layer slurry to obtain an anode catalytic layer;
c) And placing and hot-pressing the first polyimide sheet, the cathode catalytic layer, the anode catalytic layer and the second polyimide sheet in sequence to obtain the PEM water electrolysis membrane electrode.
In the preparation process of the PEM hydrolysis membrane electrode, cathode catalytic layer slurry, anode catalytic layer slurry, surface coating slurry and proton exchange layer slurry are firstly prepared; in the process of preparing the cathode catalytic layer slurry, mixing a platinum-based catalyst, water, nafion solution, nanocellulose solution and a solvent to obtain the cathode catalytic layer slurry; in the present application, the platinum-based catalyst is selected from Pt/C catalysts, wherein the content of Pt is 50 to 70wt%, more specifically, the content of Pt is 55 to 65wt%. The concentration of the Nafion solution is 5-10wt% and the concentration of the nanocellulose solution is 1-5wt%; more specifically, the concentration of the Nafion solution is 5-8wt% and the concentration of the nanocellulose solution is 1-3wt%. The mass ratio of Pt in the Pt/C catalyst to Nafion in the Nafion solution is (0.5-10): 1, wherein the nanocellulose in the nanocellulose solution is 0.05-1 wt% of the solid content of the cathode catalytic layer slurry.
Likewise, the preparation process of the anode catalytic layer slurry specifically comprises the following steps: mixing an iridium-based catalyst, water, nafion solution, nano cellulose solution and a solvent to obtain anode catalytic layer slurry; in this process, the iridium-based catalyst is Ir black or IrO 2 The concentration of the Nafion solution is 5-10wt%, the concentration of the nanocellulose solution is 1-5wt%, more specifically, the concentration of the Nafion solution is 6-8wt%, and the concentration of the nanocellulose solution is 2-4wt%; the mass ratio of Ir in the iridium-based catalyst to Nafion in the Nafion solution is (0.5-10): 1, wherein the nanocellulose in the nanocellulose solution is 0.05-1 wt% of the solid content of the anode catalytic layer slurry, and more specifically, the nanocellulose in the nanocellulose solution is 0.2-0.8 wt% of the solid content of the anode catalytic layer slurry.
The binding force of the catalytic layer, the proton exchange membrane and the porous diffusion layer is enhanced through the addition of the nanocellulose, so that the damage of circulating water impact to the MEA structure is reduced.
Mixing Nafion solution and nanocellulose solution to obtain surface coating slurry; mixing Nafion solution and nano cellulose solution to obtain proton exchange layer slurry; in the preparation process of the surface coating slurry, the concentration of the Nafion solution is 5-10wt%, the concentration of the nano cellulose solution is 1-5wt%, the nano cellulose in the nano cellulose solution is 1-10wt% of the solid content of the surface coating slurry, more specifically, the concentration of the Nafion solution is 6-8wt%, the concentration of the nano cellulose solution is 2-4wt%, and the nano cellulose in the nano cellulose solution is 3-8wt% 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 nanocellulose solution is 2-4 wt%, and the nanocellulose in the nanocellulose solution is 2-8 wt% of the solid content of the proton exchange layer slurry.
In the preparation process, the diameter of the nanocellulose is independently selected from 10-100 nm, and the length of the nanocellulose is independently selected from 100-500 nm.
After the preparation of the raw materials is completedThe cathode diffusion layer is precoated with surface coating slurry, and the cathode diffusion layer is dried and then sprayed with cathode catalytic layer slurry, and the cathode catalytic layer is obtained after drying; precoating surface coating slurry on the anode diffusion layer, drying, spraying anode catalytic layer slurry, and spraying proton exchange layer slurry to obtain an anode catalytic layer; in the present application, the materials of the cathode diffusion layer and the anode diffusion layer are materials well known to those skilled in the art, and there is no particular limitation in this application; in particular, the cathode diffusion layer may be selected from carbon paper or carbon felt, and the anode diffusion layer may be selected from porous titanium or carbon felt. In the step of obtaining the cathode catalytic layer, the thickness of the surface coating slurry is 1-10 mu m, and the catalyst loading is 0.3-2.0 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the More specifically, the thickness of the surface coating slurry is 3-8 μm, and the catalyst loading is 0.8-1.5 mg/cm 2 . In the step of obtaining the anode catalytic layer, the thickness of the surface coating slurry is 1-10 mu m, and the catalyst loading is 1-8 mg/cm 2 The thickness of the slurry of the proton exchange layer is 100-200 mu m; more specifically, the thickness of the surface coating slurry is 3-8 μm, and the catalyst loading is 2-6 mg/cm 2 。
According to the invention, finally, carrying out hot-pressing crystallization, namely hot-pressing a cathode catalytic layer and an anode catalytic layer to obtain a PEM water electrolysis membrane electrode; the pressure of the hot pressing is 1-10 MPa, the temperature is 100-200 ℃ and the time is 60-300 s; more specifically, the hot pressing pressure is 2-5 MPa, the temperature is 120-180 ℃ and the time is 100-200 s. And (3) partially crystallizing the Nafion membrane layer while enhancing the binding force of each layer to obtain the PEM water electrolysis five-in-one membrane electrode assembly. The mechanical strength of the membrane electrode is enhanced through hot-pressing crystallization, and the durability of the membrane electrode is improved.
In order to further understand the present invention, the following examples are provided to illustrate the preparation method of the PEM water electrolysis membrane electrode according to the present invention in detail, and the scope of the present invention is not limited by the following examples.
EXAMPLE 1 cathodic Pt loading 0.5mg/cm 2 Anode IrO 2 The loading amount was 3mg/cm 2 Membrane electrode preparation
(1) And (3) preparing slurry:
taking a certain amount of 60% Pt/C catalyst, adding a small amount of water, carrying out ultrasonic wetting, adding 5% Nafion solution (Nafion: pt solid content mass ratio is 3:1) and 1% nano cellulose solution (addition amount is 10% of solid content of the catalytic layer), then adding isopropanol solution to enable the solid content of the slurry to be 2%, and carrying out ultrasonic dispersion and then carrying out high-speed shearing dispersion to obtain cathode catalytic layer slurry A;
taking out the quantitative IrO 2 Adding a small amount of water into the catalyst, adding 5% Nafion solution (Nafion: irO) 2 The mass ratio of the solid content is 3:1), 1% of nano cellulose solution (the addition amount is 10% of the solid content of the catalytic layer), then adding isopropanol solution to make the solid content of the slurry be 2%, and carrying out high-speed shearing after ultrasonic dispersion to obtain cathode catalytic layer slurry B;
5% Nafion and 1% nano cellulose solution are mixed according to the mass ratio of 10:1, shearing for 2 hours at a high speed to obtain surface coating slurry C;
20% Nafion and 1% nano cellulose solution are mixed according to the mass ratio of 5:1, shearing for 2 hours at a high speed to obtain a proton exchange layer-by-layer castable D;
(2) And (3) spraying a cathode catalytic layer: precoating a layer of slurry C on carbon paper with the thickness of 1 mu m, drying, and continuing ultrasonic spraying the cathode catalytic layer slurry A to ensure that the catalyst loading capacity is 0.5mg/cm 2 Drying for later use;
(3) And (3) spraying an anode catalytic layer: precoating a layer of slurry C on porous titanium with the thickness of 1 mu m, drying, and continuing ultrasonic spraying anode catalytic layer slurry B to enable the catalyst loading capacity to be 3mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Continuously spraying the proton exchange layer slurry D to enable the Nafion layer thickness to reach 100 mu m, and drying for later use
(4) And (5) hot pressing crystallization: and (3) attaching the catalytic layers of the anode and cathode porous diffusion layers after spraying the slurry, placing the catalytic layers in the middle of two flat polyimide sheets, placing the polyimide sheets on a workbench of a hot press, and hot-pressing the polyimide sheets at the temperature of 5MPa and 150 ℃ for 120 seconds, so that the binding force of each layer is enhanced, and meanwhile, the Nafion membrane layer is partially crystallized, thus obtaining the PEM water electrolysis five-in-one membrane electrode assembly.
Comparative example 1 cathodic Pt loading 0.5mg/cm 2 Anode IrO 2 The loading amount was 3mg/cm 2 Membrane electrode preparation
(1) And (3) preparing slurry:
taking a certain amount of 60% Pt/C catalyst, adding a small amount of water, carrying out ultrasonic wetting, adding 5% Nafion solution (Nafion: pt solid content mass ratio is 3:1), then adding isopropanol solution to make the solid content of the slurry be 2%, and carrying out ultrasonic dispersion and then carrying out high-speed shearing dispersion to obtain cathode catalytic layer slurry A;
taking out the quantitative IrO 2 Adding a small amount of water into the catalyst, adding 5% Nafion solution (Nafion: irO) 2 The mass ratio of the solid content is 3:1), then adding isopropanol solution to enable the solid content of the slurry to be 2%, and carrying out high-speed shearing after ultrasonic dispersion to obtain cathode catalytic layer slurry B;
5% Nafion as surface coating slurry C;
taking 20% Nafion as a proton exchange layer-by-layer castable D;
(2) And (3) spraying a cathode catalytic layer: precoating a layer of slurry C on carbon paper with the thickness of 1 mu m, drying, and continuing ultrasonic spraying the cathode catalytic layer slurry A to ensure that the catalyst loading capacity is 0.5mg/cm 2 Drying for later use;
(3) And (3) spraying an anode catalytic layer: precoating a layer of slurry C on porous titanium with the thickness of 1 mu m, drying, and continuing ultrasonic spraying anode catalytic layer slurry B to enable the catalyst loading capacity to be 3mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Continuously spraying the proton exchange layer slurry D to enable the thickness of the Nafion layer to reach 100 mu m, and drying for later use;
(4) And (5) hot pressing crystallization: and (3) attaching the catalytic layers of the anode and cathode porous diffusion layers after spraying the slurry, placing the catalytic layers in the middle of two flat polyimide sheets, placing the polyimide sheets on a workbench of a hot press, and hot-pressing the polyimide sheets at the temperature of 5MPa and 150 ℃ for 120 seconds, so that the binding force of each layer is enhanced, and meanwhile, the Nafion membrane layer is partially crystallized, thus obtaining 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 conditions: constant current 2A/cm 2 The temperature of the electrolytic cell is 80 ℃, the water flow rate at the anode side is 5L/min, and the area of the membrane electrode is 100cm 2 And (3) operating at normal pressure. As shown in the figure, the comparative MEA test voltage was suddenly increased after 30h, by 715mv at 40h, due to strong water flow impingement, whereas the MEA test of example 1The voltage is raised by only 82mv after 30h to 40 h. The comparative example cell cycle water had found significant particulate matter whereas example 1 did not. The test result shows that the addition of the nanocellulose obviously improves the bonding strength of each component of the membrane electrode of the embodiment 1, and avoids the performance attenuation of the membrane electrode caused by the falling of the catalytic layer. In fig. 1, 1 is a direct current stabilized 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 force control valves, 8 is a constant temperature water bath, and 9 is a polytetrafluoroethylene tank with an air outlet.
EXAMPLE 2 cathodic Pt loading 0.3mg/cm 2 Anode Ir loading 1mg/cm 2 Membrane electrode preparation
(1) And (3) preparing slurry:
taking a certain amount of 60% Pt/C catalyst, adding a small amount of water, carrying out ultrasonic wetting, adding 5% Nafion solution (Nafion: pt solid content mass ratio is 1:2) and 1% nano cellulose solution (addition amount is 50% of solid content of the catalytic layer), then adding isopropanol solution to make the solid content of the slurry be 1%, and carrying out ultrasonic dispersion and then carrying out high-speed shearing dispersion to obtain cathode catalytic layer slurry A;
taking out the quantitative IrO 2 Adding a small amount of water into the catalyst, adding 5% Nafion solution (Nafion: irO) 2 The mass ratio of the solid content is 1:2), 1% of nano cellulose solution (the addition amount is 50% of the solid content of the catalytic layer), then adding isopropanol solution to make the solid content of the slurry be 1%, and carrying out high-speed shearing after ultrasonic dispersion to obtain cathode catalytic layer slurry B;
5% Nafion and 1% nano cellulose solution are mixed according to the mass ratio of 5:1, shearing for 2 hours at a high speed to obtain surface coating slurry C;
20% Nafion and 1% nano cellulose solution are mixed according to the mass ratio of 1:1, shearing for 2 hours at a high speed to obtain a proton exchange layer-by-layer castable D;
(2) And (3) spraying a cathode catalytic layer: precoating a layer of slurry C on carbon paper with the thickness of 1 mu m, drying, and continuing ultrasonic spraying the cathode catalytic layer slurry A to ensure that the catalyst loading capacity is 0.3mg/cm 2 Drying for later use;
(3) And (3) spraying an anode catalytic layer: precoating a layer of slurry C on porous titanium with the thickness of 1 mu m, drying, and continuing ultrasonic spraying anode catalytic layer slurry B to enable the catalyst loading amount to be 1mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Continuously spraying the proton exchange layer slurry D to enable the thickness of the Nafion layer to reach 100 mu m, and drying for later use;
(4) And (5) hot pressing crystallization: and (3) attaching the catalytic layers of the carbon paper and the porous titanium after spraying the slurry, placing the catalytic layers in the middle of two flat polyimide sheets, placing the polyimide sheets on a workbench of a hot press, and hot-pressing the polyimide sheets at the temperature of 2MPa and 120 ℃ for 180 seconds, so that the binding force of each layer is enhanced, and simultaneously, the Nafion membrane layer is partially crystallized to obtain the PEM water electrolysis five-in-one membrane electrode assembly.
EXAMPLE 3 cathodic Pt loading 1mg/cm 2 Anode Ir loading 2mg/cm 2 Membrane electrode preparation
(1) And (3) preparing slurry:
taking a certain amount of 60% Pt/C catalyst, adding a small amount of water, carrying out ultrasonic wetting, adding 5% Nafion solution (Nafion: pt solid content mass ratio is 1:2) and 1% nano cellulose solution (addition amount is 100% of solid content of a catalytic layer), then adding isopropanol solution to enable the solid content of slurry to be 1.5%, and carrying out ultrasonic dispersion and then carrying out high-speed shearing dispersion to obtain cathode catalytic layer slurry A;
taking out the quantitative IrO 2 Adding a small amount of water into the catalyst, adding 5% Nafion solution (Nafion: irO) 2 The mass ratio of the solid content is 1:2), 1% of nano cellulose solution (the addition amount is 100% of the solid content of the catalytic layer), then adding isopropanol solution to make the solid content of the slurry be 1.5%, and carrying out high-speed shearing after ultrasonic dispersion to obtain cathode catalytic layer slurry B;
5% Nafion and 1% nano cellulose solution are mixed according to the mass ratio of 20:1, shearing for 2 hours at a high speed to obtain surface coating slurry C;
20% of Nafion and 1% of nanocellulose solution are mixed according to the mass ratio of 10:1, shearing for 2 hours at a high speed to obtain a proton exchange layer-by-layer castable D;
(2) And (3) spraying a cathode catalytic layer: precoating a layer of slurry C on carbon paper with the thickness of 1 mu m, drying, and continuing ultrasonic spraying of cathode catalytic layer slurry A to enable the catalyst loading capacity to be 1mg/cm 2 Drying for later use;
(3) And (3) spraying an anode catalytic layer: precoating a layer of slurry C on porous titanium with the thickness of 1 mu m, drying, and continuing ultrasonic spraying anode catalytic layer slurry B to enable the catalyst loading capacity to be 2mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the ContinuingSpraying proton exchange layer slurry D to make Nafion layer thickness reach 100 μm, and oven drying
(4) And (5) hot pressing crystallization: and (3) attaching the catalytic layers of the anode and cathode porous diffusion layers after spraying the slurry, placing the catalytic layers in the middle of two flat polyimide sheets, placing the polyimide sheets on a workbench of a hot press, and hot-pressing the polyimide sheets at the temperature of 3MPa and 150 ℃ for 300 seconds, so that the binding force of each layer is enhanced, and meanwhile, the Nafion membrane layer is partially crystallized, thus obtaining the PEM water electrolysis five-in-one membrane electrode assembly.
EXAMPLE 4 cathodic Pt loading 1.5mg/cm 2 Anode Ir loading 4mg/cm 2 Membrane electrode preparation
(1) And (3) preparing slurry:
taking a certain amount of 60% Pt/C catalyst, adding a small amount of water, carrying out ultrasonic wetting, adding 5% Nafion solution (Nafion: pt solid content mass ratio is 10:1) and 1% nano cellulose solution (the addition amount is 1.5 times of the solid content of the catalytic layer), then adding isopropanol solution to enable the solid content of the slurry to be 2.5%, and carrying out ultrasonic dispersion and high-speed shearing and dispersion to obtain cathode catalytic layer slurry A;
taking out the quantitative IrO 2 Adding a small amount of water into the catalyst, adding 5% Nafion solution (Nafion: irO) 2 The mass ratio of the solid content is 10:1), 1% of nano cellulose solution (the solid content of the catalytic layer is 1.5 times of the addition amount), then adding isopropanol solution to enable the solid content of the slurry to be 2.5%, and carrying out high-speed shearing after ultrasonic dispersion to obtain cathode catalytic layer slurry B;
5% Nafion and 1% nano cellulose solution are mixed according to the mass ratio of 15:1, shearing for 2 hours at a high speed to obtain surface coating slurry C;
20% of Nafion and 1% of nanocellulose solution are mixed according to the mass ratio of 15:1, shearing for 2 hours at a high speed to obtain a proton exchange layer-by-layer castable D;
(2) And (3) spraying a cathode catalytic layer: precoating a layer of slurry C on carbon paper with the thickness of 1 mu m, drying, and continuing ultrasonic spraying of cathode catalytic layer slurry A to ensure that the catalyst loading capacity is 1.5mg/cm 2 Drying for later use;
(3) And (3) spraying an anode catalytic layer: precoating a layer of slurry C on porous titanium with the thickness of 1 mu m, drying, and continuing ultrasonic spraying anode catalytic layer slurry B to enable the catalyst loading capacity to be 4mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Continuing to spray protonsExchanging layer slurry D to make Nafion layer thickness reach 100 μm, drying for later use
(4) And (5) hot pressing crystallization: and (3) attaching the catalytic layers of the anode and cathode porous diffusion layers after spraying the slurry, placing the catalytic layers in the middle of two flat polyimide sheets, placing the polyimide sheets on a workbench of a hot press, and hot-pressing the polyimide sheets at the temperature of 5MPa and 180 ℃ for 300 seconds, so that the binding force of each layer is enhanced, and meanwhile, the Nafion membrane layer is partially crystallized, thus obtaining the PEM water electrolysis five-in-one membrane electrode assembly.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
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 (7)
1. A method for preparing a PEM water electrolysis membrane electrode comprising the steps of:
a) Mixing a platinum-based catalyst, water, a Nafion solution, a nanocellulose solution and a solvent to obtain cathode catalytic layer slurry;
mixing an iridium-based catalyst, water, nafion solution, nano cellulose solution and a solvent to obtain anode catalytic layer slurry;
mixing Nafion solution and nano cellulose solution to obtain surface coating slurry;
mixing Nafion solution and nano cellulose solution to obtain proton exchange layer slurry;
b) Precoating surface coating slurry on the cathode diffusion layer, drying, spraying cathode catalytic layer slurry, and drying to obtain a cathode catalytic layer;
precoating surface coating slurry on the anode diffusion layer, drying, spraying anode catalytic layer slurry, and spraying proton exchange layer slurry to obtain an anode catalytic layer;
c) Carrying out hot pressing on the cathode catalytic layer and the anode catalytic layer to obtain a PEM water electrolysis membrane electrode;
in the process of preparing the cathode catalytic layer slurry, the platinum-based catalyst is selected from Pt/C catalyst, the concentration of Nafion solution is 5-10wt%, and the concentration of nano cellulose solution is 1-5wt%; the Pt/C catalyst comprises 50-70wt% of Pt, the mass ratio of Pt in the Pt/C catalyst to Nafion in the Nafion solution is 1 (0.5-10), and the nanocellulose in the nanocellulose solution is 0.05-1wt% of the solid content of the cathode catalytic layer slurry;
in the process of preparing anode catalytic layer slurry, the iridium-based catalyst is Ir black or IrO 2 The concentration of the Nafion solution is 5-10wt% and the concentration of the nanocellulose solution is 1-5wt%; 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 is 0.05-1 wt% of the solid content of the anode catalytic layer slurry;
in the preparation process of the surface coating slurry, the concentration of the Nafion solution is 5-10wt%, the concentration of the nano cellulose solution is 1-5wt%, and the nano cellulose in the nano cellulose solution is 1-10wt% 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 nanocellulose solution is 1-5 wt%, and the nanocellulose in the nanocellulose solution is 1-10 wt% of the solid content of the proton exchange layer slurry.
2. The method according to claim 1, wherein in the step of obtaining the cathode catalyst layer, the thickness of the surface coating slurry is 1 to 10 μm, and the catalyst loading isIs 0.3-2.0 mg/cm 2 。
3. The method according to claim 1, wherein in the step of obtaining the anode catalytic layer, the thickness of the surface coating slurry is 1 to 10 μm, and the catalyst loading is 1 to 8mg/cm 2 The thickness of the proton exchange layer slurry is 100-200 mu m.
4. The method according to claim 1, wherein the hot pressing is performed at a pressure of 1 to 10MPa, a temperature of 100 to 200 ℃ and a time of 60 to 300s.
5. The method according to any one of claims 1 to 4, wherein the nanocellulose in the cathode catalytic layer slurry, the nanocellulose in the anode catalytic layer slurry, the nanocellulose in the surface coating slurry, and the nanocellulose in the proton exchange layer slurry have diameters of 10 to 100nm and lengths of 100 to 500nm independently.
6. The PEM water electrolysis membrane electrode prepared by the preparation method of any one of claims 1 to 5, comprising an anode catalytic layer and a cathode catalytic layer which are sequentially arranged, wherein the surfaces of the anode catalytic layer and the cathode catalytic layer both contain nanocellulose.
7. Use of a PEM water electrolysis membrane electrode prepared by the method of any one of claims 1 to 5 or of a PEM water electrolysis membrane electrode according to claim 6 in an electrolysis cell.
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