CN115411277A - Ordered structure membrane electrode containing catalyst array and preparation method and application thereof - Google Patents

Ordered structure membrane electrode containing catalyst array and preparation method and application thereof Download PDF

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CN115411277A
CN115411277A CN202211165770.2A CN202211165770A CN115411277A CN 115411277 A CN115411277 A CN 115411277A CN 202211165770 A CN202211165770 A CN 202211165770A CN 115411277 A CN115411277 A CN 115411277A
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membrane
ordered structure
membrane electrode
catalyst
metal substrate
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王保国
万磊
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Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a membrane electrode containing a catalyst ordered structure, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Coating a polymer solution containing ion exchange groups on a metal substrate of a catalyst array with an ordered structure on the surface so as to completely cover the catalyst array; (2) Heating the metal substrate obtained in the step (1) and removing a solvent to obtain a compound of an ion exchange membrane and the metal substrate; (3) And (3) soaking the compound obtained in the step (2) in deionized water, and heating to separate the ion exchange membrane from the metal substrate, thereby obtaining the ordered structure membrane electrode containing the catalyst array. The preparation process of the invention does not involve high temperature and high pressure, completely and nondestructively maintains the appearance of the original ordered catalytic array, realizes 100 percent of transfer rate of the catalyst from the metal substrate to the membrane surface, and improves the membrane electrode performance.

Description

Ordered structure membrane electrode containing catalyst array and preparation method and application thereof
Technical Field
The invention belongs to the technical field of membrane electrode preparation, and relates to a membrane electrode containing a catalyst ordered structure, and a preparation method and application thereof.
Background
A Membrane Electrode Assembly (MEA) is a high-efficiency electrochemical reaction functional device, and generally comprises a Gas Diffusion Layer (GDL), a Catalyst Layer (CL) and an ion exchange Membrane, wherein the catalyst layer is disposed on two sides of the ion exchange Membrane, and different electrocatalysts are loaded according to application scenarios. The device is used for a fuel cell and a water electrolysis hydrogen production process, integrates electrochemical reaction, energy conversion and substance transmission functions into one component, not only reduces the number of components in an electrochemical device and improves the integration level and reliability of the device, but also realizes zero-spacing combination of an ionic membrane and a catalytic electrode, greatly reduces internal resistance and improves the electrochemical energy conversion efficiency. For example, when a fuel cell is in operation, the membrane electrode needs to meet the requirements of continuous hydrogen delivery and timely discharge of generated water molecules, and meet the requirements of efficient transmission of hydrogen ions and electrons. Among other things, the interface between a Proton Exchange Membrane (PEM) or an Anion Exchange Membrane (AEM) and a Catalytic Layer (CL) in a membrane electrode has a significant impact on the transport and charge transfer. In order to achieve strengthening of the Membrane Electrode (MEA) interface process, researchers have developed three generations of membrane electrode structures. The first generation membrane electrode was prepared by loading an electrocatalyst on a Gas Diffusion Layer (GDL) in various ways and then hot-pressing the membrane with a proton-conducting membrane. Although such a Gas Diffusion Electrode (GDL) is simple in preparation process, the proton conductive membrane and the electrocatalytic layer are easily delaminated and detached from each other, resulting in an increase in interface resistance. The second generation Membrane electrode, which has electrocatalyst sprayed on both sides of the PEM, has CL tightly bonded to the PEM and significantly extended Membrane electrode operating life compared to the first generation MEA, and is called CCM (Catalyst Coated Membrane) structure. The third generation membrane electrode develops an ordered membrane electrode with a specific structure through different templating approaches, designs a gas-liquid-solid three-phase mass transfer channel, optimizes the electrocatalytic reaction and the mass transfer process in the membrane electrode, and obtains the effect of improving the performance of the membrane electrode.
CN108075158A discloses a method for preparing a CCM membrane electrode of a fuel cell, which can reduce the adhesive force between a catalyst layer and a transfer film and improve the transfer efficiency of the catalyst layer by using a transition layer.
CN111224137A discloses a method for preparing an ordered structure membrane electrode of a fuel cell, firstly growing a carbon nanotube array with specific length and density on a substrate by a vapor phase chemical deposition method, then adopting a magnetron sputtering method to load a noble metal catalyst layer on the carbon nanotube array, and spraying a Nafion electrolyte coating layer. Finally, the membrane is transferred to a proton exchange membrane to be a membrane electrode by a thermal transfer printing method.
CN111326741A discloses an ordered membrane electrode using metal nitride/carbide as a carrier, the preparation process comprises the steps of constructing an ordered structure, forming the metal nitride/carbide and assembling the ordered electrode, and then annealing, transferring, acid washing and the like are carried out to form a nanotube array structure of a metal nitride/carbide layer @ catalyst, which can be used for assembling a membrane electrode used for a fuel cell.
CN105742652A discloses a membrane electrode preparation method with a double-metal-layer anode for water electrolysis, wherein an anode catalyst layer of the membrane electrode preparation method is formed by a platinum metal thin layer and an iridium metal thin layer, and metal ions are sequentially reduced and deposited on a proton exchange membrane by utilizing an ion exchange reaction and reduction deposition method to prepare a membrane electrode.
CN102260877A discloses a preparation method of a membrane electrode for pure water electrolysis hydrogen production, which comprises the steps of respectively preparing a cathode catalyst solution and an anode catalyst solution with Nafion solution, isopropanol, glycerol and distilled water; respectively coating on the transfer printing templates and drying in vacuum; fixing the two dried transfer printing templates on two sides of the ionic membrane, pressurizing and heating, then removing the transfer printing templates, and placing the ionic membrane in an oven for vacuum treatment to obtain the membrane electrode.
CN108950587A discloses a preparation method of a membrane electrode, firstly coating a catalyst on the surface of a proton exchange membrane, and incompletely covering the membrane surface; and then, etching the membrane surface by adopting an anisotropic etching method to form a pore or comb-finger-shaped structure, and then coating the catalyst again to ensure that catalyst particles are attached to the membrane surface in the pore or the comb-finger-shaped structure, so that the electrochemical active area of the membrane electrode anode catalyst is favorably improved, a water channel, an electronic channel, a proton channel and a gas channel are formed, and the mass transfer in the membrane electrode is promoted.
In the prior art, the technical performance of the membrane electrode can be obviously improved by improving the ordering degree of the membrane electrode and reducing the using amount of noble metals. However, there are several common problems with existing methods. 1) In the membrane electrode preparation process, the membrane is softened after the temperature is raised, the catalyst array with an ordered structure is transferred to the surface of the membrane in a pressurizing way, and the ordered structure of the catalyst is damaged in the pressurizing process; 2) Catalyst particles and a binder are mixed into slurry, and the slurry is combined with an ion exchange membrane by adopting a spraying or transfer printing way, so that the problems of catalyst particle aggregation, separation and the like exist in the using process, and the long-term stability of the membrane electrode is difficult to maintain; 3) A plurality of preparation steps are needed, so that the actual production process is complicated, and the quality uniformity of the membrane electrode is difficult to ensure; 4) For the ion exchange membrane with higher glass transition temperature, the temperature for softening the membrane is very high, and the ordered membrane electrode is difficult to prepare by a transfer printing method. In addition, since the manufacturing process requires sufficient mechanical strength, it is necessary to maintain a sufficient film thickness, resulting in high ion transfer resistance. In order to construct good ion conductors, electron conductors and gas-liquid mass transfer channels and arrange the mass transfer channels along the vertical direction of the surface of an ion exchange membrane so as to improve the performance of the membrane electrode, a novel membrane electrode preparation technology is urgently needed to be provided, and the defects of the prior art are overcome.
The invention utilizes the advantages that the polymer solution can be fully spread on the solid surface, and the shape of the interface between the solution and the solid catalyst is completely determined by the shape of the catalyst array. The polymer solution is dripped on the surface of the substrate containing the catalyst array, and the ion exchange membrane and the catalyst array combination is formed after the solvent is removed and dried. When the assembly is heated in water, the catalyst array is peeled from the substrate by the mechanical peel force generated by the swelling of the ion exchange membrane. The process is very slow, can completely reserve the ordered interface structure between the ion exchange membrane and the catalyst array, and meets the technical requirement of the membrane electrode on the ordered structure of the catalytic interface.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an ordered structure membrane electrode containing a catalyst array, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a method for preparing an ordered structure membrane electrode containing a catalyst array, comprising the following steps:
(1) Coating a polymer solution containing ion exchange groups on a metal substrate of a catalyst array with an ordered structure on the surface so as to completely cover the catalyst array;
(2) Heating the metal substrate obtained in the step (1) and removing the solvent to obtain a compound of the ion exchange membrane and the metal substrate;
(3) And (3) soaking the compound obtained in the step (2) in deionized water, and heating to separate the ion exchange membrane from the metal substrate, so as to obtain the ordered structure membrane electrode containing the catalyst array.
According to the invention, the catalyst array is peeled off from the substrate by covering the ion exchange membrane on the catalyst array with the ordered structure and through the mechanical peeling force generated by swelling of the ion exchange membrane, so that the ordered interface structure between the ion exchange membrane and the catalyst array can be completely reserved, ion, electron and gas-liquid mass transfer paths are arranged along the vertical direction of the ion exchange membrane, the technical requirements of the membrane electrode on the ordered structure of the catalytic interface are met, the electron transfer process in the electrochemical reaction process can be obviously improved, the gas-liquid mass transfer process is strengthened, and the ion transfer rate of the catalyst layer is enhanced.
Preferably, the metal substrate having the catalyst array with the ordered structure on the surface in the step (1) is obtained by the following method:
sequentially immersing the metal substrate into a hydrochloric acid aqueous solution and deionized water for cleaning, and removing metal oxides on the surface; and then growing a catalyst array with an ordered structure on the surface of the metal substrate.
Preferably, the method for growing the catalyst array with the ordered structure on the surface of the metal substrate is electrodeposition, solvothermal growth or vapor phase chemical deposition.
Preferably, the solution used in growing the catalyst array of ordered structure comprises the following components: niCl 2 .6H 2 0、CoCl 2 .6H 2 O and NH 4 Cl。
Preferably, the metal substrate is a nickel sheet, an aluminum sheet, a copper sheet, an iron sheet or an alloy substrate of at least two of the elements.
Preferably, the polymer containing ion exchange groups in step (1) is cation exchange resin, anion exchange resin or polybenzimidazole polymer.
Preferably, the cation exchange resin is a perfluorosulfonic acid resin.
Preferably, the solvent in the solution of the polymer containing ion exchange groups in step (1) is any one or a combination of at least two of ethanol, dimethyl sulfoxide or water.
Preferably, the heating in step (2) is at a temperature of 80-100 deg.C, such as 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C or 100 deg.C.
Preferably, the temperature increase in step (3) is to 50-80 deg.C, such as 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C or 80 deg.C.
Because the organic polymer solution in the preparation method can flow on the surface of the porous solid catalytic electrode, the interface bonding degree between the ion exchange membrane and the catalytic layer is obviously improved after the organic polymer solution is solidified, a three-dimensional interface with concave-convex fluctuation is presented, and the effective contact area is obviously increased. More electrocatalyst active sites can be exposed at the outer side of the solution, and a water channel, an electron channel, a proton channel and a gas channel are taken into consideration. By controlling the thickness of the solution on the catalytic substrate electrode, the solidified membrane casting solution is tightly attached along the uneven surface of the electrode, so that the contact area between the membrane and the electrode is increased, and the bonding firmness is enhanced. In addition, the preparation process does not involve high temperature and high pressure, the appearance of the original ordered catalytic array is completely and nondestructively maintained, and 100 percent of transfer rate of the catalyst from the metal substrate to the surface of the membrane is realized.
In another aspect, the invention provides the membrane electrode with the ordered structure and the catalyst array, which is prepared by the preparation method.
In the invention, the ordered structure catalyst array is arranged on one side of the ion exchange membrane in the ordered structure membrane electrode containing the catalyst array, and the metal ion conductor, the electronic conductor and the gas-liquid mass transfer pore channel are arranged along the vertical direction of the ion exchange membrane.
In another aspect, the present invention provides a fuel cell comprising an ordered structure membrane electrode comprising a catalyst array as described above.
In another aspect, the present disclosure provides a flow battery comprising an ordered structure membrane electrode comprising a catalyst array as described above.
In another aspect, the present invention provides the use of an ordered structure membrane electrode comprising a catalyst array as described above in the electrolysis of water.
The membrane electrode with the ordered structure and the catalyst array is used for the hydrogen production process by electrolyzing water or the oxygen production process by electrolyzing water. The membrane electrode is used for the hydrogen production process by electrolyzing water, and the current density in the hydrogen production reaction process is improved to 2000 mA-cm -2 Under the condition, the stable operation is kept for more than 700 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst array is peeled off from the substrate by using the mechanical peeling force generated by swelling of the ion exchange membrane, the ordered interface structure between the ion exchange membrane and the catalyst array can be completely reserved, ion, electron and gas-liquid mass transfer paths are arranged along the vertical direction of the ion exchange membrane, the technical requirements of a membrane electrode on the ordered structure of a catalytic interface are met, the electron transfer process in the electrochemical reaction process can be obviously improved, the gas-liquid mass transfer process is strengthened, and the ion transfer rate of the catalytic layer is enhanced.
(2) The membrane electrode is formed by casting membrane liquid on the surface of the catalytic electrode, so that the bonding force between the organic ion exchange membrane and the inorganic catalytic layer is enhanced, and the complete transfer of the inorganic porous ordered catalytic layer under the room temperature condition is realized; compared with the traditional hot-pressing transfer process of the solid ion exchange membrane and the catalytic electrode, the method improves the finished product rate and the structural integrity of the membrane electrode. Meanwhile, the membrane electrode has the characteristics of large and stable interface area of a catalyst layer/an ion exchange membrane, can effectively improve the performance and the service life of an electrochemical process, provides a universal method for developing novel membrane electrode preparation, and lays a foundation for further industrialization.
(3) Because the membrane casting solution of the ion exchange membrane can flow on the surface of the solid catalytic electrode, the thickness of the membrane is obviously reduced by regulating and controlling the thickness of the solution coating on the porous solid catalytic electrode, and the membrane casting solution forms an ultrathin membrane with a curved surface after being cured, and the thickness can be reduced to below 10 microns. The method can reduce the thickness of the cured film, can enable the ion exchange membrane to be tightly attached to the uneven surface of the electrode, obviously improves the interface bonding degree between the ion exchange membrane and the catalytic layer, enlarges the contact area between the membrane and the electrode, and enhances the bonding firmness. As the interface between the rugged electrode and the membrane formed after the solution is solidified is lengthened, the intersection point of gas phase, liquid phase and solid phase is increased, more electrocatalyst active sites can be exposed at the outer side of the solution after solidification, and the water channel, the electronic channel, the ion channel and the gas channel are taken into consideration, so that the electrochemical reaction and the mass transfer process are effectively promoted to be strengthened.
(4) The membrane electrode preparation method is simple, is easy for industrial amplification, and obviously improves the process environment condition. Compared with the traditional planar membrane, the membrane electrode prepared by casting the membrane casting solution on the surface of the catalytic electrode has a three-dimensional ion exchange membrane/catalytic layer interface structure, can effectively avoid the falling of a catalyst, provides a larger interface area, improves the ion transfer flux and improves the performance of the membrane electrode.
Drawings
FIG. 1 is a flow chart of membrane electrode preparation;
FIG. 2 is an electron microscope image of the interface between the polymer thin layer and the catalytic electrode in the membrane electrode prepared in example 1;
FIG. 3 is an electron microscope image of the interface between the polymer thin layer and the catalytic electrode in the membrane electrode prepared in example 2;
FIG. 4 is an electron microscope image of the interface between the polymer thin layer and the catalytic electrode in the membrane electrode prepared in example 3;
FIG. 5 is an electron microscope image of a cross-sectional structure of an ordered membrane electrode prepared by hot-pressing transfer printing;
FIG. 6 is a diagram of a structurally ordered membrane electrode assembly prepared in example 1;
FIG. 7 is a diagram of an ordered membrane electrode assembly prepared by hot-pressing transfer printing;
FIG. 8 is a comparison graph of polarization curves of a membrane electrode in a process of hydrogen production by water electrolysis;
FIG. 9 is a graph of the performance stability test result of the membrane electrode in the process of hydrogen production by water electrolysis.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
In this embodiment, a method for preparing an ordered structure membrane electrode containing a catalyst array is provided, which is prepared according to the flowchart shown in fig. 1, and the preparation method includes the following steps:
(1) Sequentially immersing the nickel sheet into hydrochloric acid aqueous solution and deionized water for cleaning, and removing metal oxides on the surface;
(2) Growing a porous catalyst array with an ordered structure on the surface of the nickel sheet by using an electrodeposition method, wherein the electrodeposition solution comprises the following components: niCl 2 .6H 2 0(0.1M)、CoCl 2 .6H 2 O (0.1M) and NH 4 Cl (2.0M). Performing electrodeposition by using a two-electrode system, wherein a graphite electrode is used as an anode, a nickel sheet is used as a cathode, and the concentration of the anode and the cathode are 2000mA cm -2 Carrying out electrodeposition for 90s at the current density to obtain an ordered porous foam catalytic array loaded on the surface of the nickel sheet;
(3) Preparing a perfluorinated sulfonic acid resin (Nafion D520, duPont) solution with the weight percentage concentration of 5% by taking ethanol as a solvent, coating the perfluorinated sulfonic acid resin solution on the surface of a nickel sheet, and completely covering a catalytic array;
(4) Heating the metal substrate and removing the solvent to obtain a compound of the perfluorosulfonic acid membrane and the nickel sheet;
(5) And (3) soaking the compound in deionized water, and then heating to 50 ℃ to separate the perfluorinated sulfonic acid resin film from the nickel sheet substrate to obtain the membrane electrode containing the catalyst array on the surface of the membrane.
As is apparent from the electron microscope image of fig. 2, the interface between the membrane in the dried and cured membrane electrode and the catalytic electrode is tightly attached, a part of the polymer is adhered to the surface of the solid electrode, the surface of the membrane is rough and uneven, and the membrane is in a shape of undulation along with the micropores of the catalytic substrate. And the catalytic layer structure on one side of the membrane is a porous ordered complete catalytic array.
Example 2
1) Sequentially immersing the stainless steel sheet into hydrochloric acid aqueous solution and deionized water for cleaning, and removing metal oxides on the surface;
2) Growing a porous catalyst array with an ordered structure on the surface of the stainless steel sheet by using an electrodeposition method, wherein the electrodeposition solution comprises the following components: niCl 2 .6H 2 0(0.1M)、CoCl 2 .6H 2 O (0.1M) and NH 4 Cl (2.0M). Performing electrodeposition with a two-electrode system, wherein graphite electrode is anode, stainless steel sheet is cathode, and the current density is 2000mA cm -2 Carrying out electrodeposition for 90s at the current density to obtain an ordered porous foam catalytic array loaded on the surface of the stainless steel sheet;
3) Preparing a perfluorinated sulfonic acid resin (Nafion D520, duPont) solution with the weight percentage concentration of 5% by taking ethanol as a solvent, coating the perfluorinated sulfonic acid resin solution on the surface of a stainless steel sheet, and completely covering a catalytic array;
4) And heating the metal substrate and removing the solvent to obtain the compound of the perfluorinated sulfonic acid resin film and the stainless steel sheet.
5) And (3) soaking the compound in deionized water, and then heating to 50 ℃ to separate the perfluorinated sulfonic acid resin film from the stainless steel sheet substrate to obtain the membrane electrode containing the catalyst array on the surface of the membrane.
It is obvious from the electron microscope image of fig. 3 that the interface between the membrane in the dried and cured membrane electrode and the catalytic electrode is tightly attached, part of the polymer is adhered to the surface of the solid electrode, the surface of the membrane is rough and uneven, and the membrane presents a high-low undulation shape along with the micropores of the catalytic substrate. And the catalytic layer structure on one side of the membrane is a porous ordered complete catalytic array.
Example 3
1) Sequentially immersing the nickel sheet into hydrochloric acid aqueous solution and deionized water for cleaning, and removing metal oxides on the surface;
2) Growing a porous catalyst array with an ordered structure on the surface of the nickel sheet by using a hydrothermal method, wherein the hydrothermal method is performed beforeThe composition of the body-driving solution is as follows: niCl 2 .6H 2 0(0.05M)、CoCl 2 .6H 2 O (0.1M) and urea (0.15M). Placing the treated nickel sheet and the precursor solution in a hydrothermal kettle, carrying out hydrothermal reaction for 6 hours at 120 ℃, taking out the nickel sheet after the reaction, and cleaning the nickel sheet by using deionized water to obtain the ordered porous nanowire catalytic array loaded on the surface of the nickel sheet;
3) Preparing a perfluorinated sulfonic acid resin (Nafion D520, duPont) solution with the weight percentage concentration of 5% by taking ethanol as a solvent, coating the perfluorinated sulfonic acid resin solution on the surface of a nickel sheet, and completely covering a catalytic array;
4) And heating the metal substrate and removing the solvent to obtain the compound of the perfluorinated sulfonic acid resin film and the nickel sheet.
5) And (3) soaking the compound in deionized water, and then heating to 80 ℃ to separate the perfluorinated sulfonic acid resin membrane from the nickel sheet substrate to obtain the membrane electrode containing the catalyst array on the membrane surface.
As is apparent from the electron microscope image of fig. 3, the interface between the membrane in the dried and cured membrane electrode and the catalytic electrode is tightly attached, a part of the polymer is adhered to the surface of the solid electrode, the surface of the membrane is rough and uneven, and the membrane is in a shape of undulation along with the micropores of the catalytic substrate. And the catalytic layer structure on one side of the membrane is a porous ordered complete catalytic array.
Example 4
1) Sequentially immersing the nickel sheet into hydrochloric acid aqueous solution and deionized water for cleaning, and removing metal oxides on the surface;
2) Growing a porous catalyst array with an ordered structure on the surface of the nickel sheet by using an electrodeposition method, wherein the electrodeposition solution comprises the following components: niCl 2 .6H 2 0(0.1M)、CoCl 2 .6H 2 O (0.1M) and NH 4 Cl (2.0M). Performing electrodeposition by using a two-electrode system, wherein a graphite electrode is used as an anode, a nickel sheet is used as a cathode, and the concentration of the anode and the cathode are 2000mA cm -2 Carrying out electrodeposition for 90s at the current density to obtain an ordered porous foam catalytic array loaded on the surface of the nickel sheet;
3) Polybenzimidazole with a weight percentage concentration of 5% is prepared by using ethanol as a solvent (model number of Shanghai Shengjun plastic science and technology Co., ltd.: OPBI) solution, which is coated on the surface of the nickel sheet and completely covers the catalytic array;
4) And heating the metal substrate and removing the solvent to obtain the compound of the polybenzimidazole membrane and the nickel sheet.
5) And (3) soaking the compound in deionized water, and then heating to 60 ℃ to separate the polybenzimidazole membrane from the nickel sheet substrate, thereby obtaining the membrane electrode containing the catalyst array on the membrane surface.
Example 5
1) Sequentially immersing the nickel sheet into hydrochloric acid aqueous solution and deionized water for cleaning, and removing metal oxides on the surface;
2) Growing a porous catalyst array with an ordered structure on the surface of the nickel sheet by using an electrodeposition method, wherein the electrodeposition solution comprises the following components: niCl 2 .6H 2 0(0.1M)、CoCl 2 .6H 2 O (0.1M) and NH 4 Cl (2.0M). Performing electrodeposition by using a two-electrode system, wherein a graphite electrode is used as an anode, a nickel sheet is used as a cathode, and the concentration of the anode and the cathode are 2000mA cm -2 Carrying out electrodeposition for 90s at the current density to obtain an ordered porous foam catalytic array loaded on the surface of the nickel sheet;
3) Using ethanol as a solvent to prepare an anionic dispersion liquid with a weight percentage concentration of 5%, (
Figure BDA0003861285200000111
FAA-3-SOLUT-10) solution is coated on the surface of the nickel sheet to completely cover the catalytic array;
4) And heating the metal substrate and removing the solvent to obtain the compound of the anion exchange membrane (FAA-3) and the nickel sheet.
5) And (3) soaking the compound in deionized water, and then heating to 60 ℃ to separate the anion exchange membrane from the nickel sheet substrate, thereby obtaining the membrane electrode containing the catalyst array on the membrane surface.
Comparative example 1
In this comparative example, the first-generation membrane electrode was prepared by the conventional CCS method, and the specific preparation process was as follows:
(1) The preparation method of the catalyst layer slurry comprises the following steps: 50mg of IrO was weighed 2 (or Pt/C) catalyst was placed in a 20mL glass sample bottle and slowlyDropwise adding 10mL of ethanol solution, carrying out ultrasonic dispersion in ice bath for 1h, slowly dropwise adding 200 mu L of 5 wt% perfluorosulfonic acid resin (Nafion D520, duPont) solution in the ultrasonic process, and continuing carrying out ultrasonic treatment in ice bath for 10 min to finish the preparation of catalyst slurry;
(2) Preparing a perfluorosulfonic acid resin solution with the weight percentage concentration of 5% by taking ethanol as a solvent, coating the solution on the surface of a glass plate, heating and removing the solvent to obtain a solid perfluorosulfonic acid membrane;
(3) Spraying the prepared catalyst slurry on the surface of the porous foamed nickel by using ultrasonic spraying equipment to obtain a catalyst-coated electrode;
(4) And (3) carrying out hot pressing on the solid perfluorosulfonic acid membrane and the electrode coated with the catalyst for 5 minutes at the temperature of 120 ℃ and under the pressure of 0.1MPa to obtain the traditional first-generation membrane electrode.
Comparative example 2
In this comparative example, a first-generation membrane electrode was prepared by a conventional CCM method, specifically by the following steps:
(1) The preparation method of the catalyst layer slurry comprises the following steps: weighing 50mg of IrO 2 (or Pt/C) catalyst is placed in a 20mL glass sample bottle, 10mL ethanol solution is slowly dripped, ice bath ultrasonic dispersion is carried out for 1h, 200 mu L perfluorosulfonic acid resin (Nafion D520, duPont company) solution with the weight percentage concentration of 5 percent is slowly dripped in the ultrasonic process, ice bath ultrasonic treatment is continuously carried out for 10 min, and the preparation of catalyst slurry is completed;
(2) Preparing a perfluorosulfonic acid resin solution with the weight percentage concentration of 5% by taking ethanol as a solvent, coating the perfluorosulfonic acid resin solution on the surface of a glass plate, heating and removing the solvent to obtain a solid perfluorosulfonic acid membrane;
(3) And spraying the prepared catalyst slurry on two sides of the solid perfluorosulfonic acid membrane by using ultrasonic spraying equipment to obtain the traditional second-generation membrane electrode.
Comparative example 3
In this comparative example, the ordered membrane electrode was prepared by hot-pressing transfer, and the specific preparation process was as follows:
(1) Sequentially immersing the nickel sheet into hydrochloric acid aqueous solution and deionized water for cleaning, and removing metal oxides on the surface;
(2) By usingThe electrodeposition method grows a porous catalyst array with an ordered structure on the surface of the nickel sheet, and the electrodeposition solution comprises the following components: niCl 2 .6H 2 0(0.1M)、CoCl 2 .6H 2 O (0.1M) and NH 4 Cl (2.0M). Performing electrodeposition with a two-electrode system, wherein a graphite electrode is used as an anode, a nickel sheet is used as a cathode, and the concentration of the anode is 2000mA cm -2 The current density electrodeposition is carried out for 90s, and the ordered porous foam catalytic array loaded on the surface of the nickel sheet can be obtained;
(3) Preparing a perfluorosulfonic acid resin solution with the weight percentage concentration of 5% by taking ethanol as a solvent, coating the perfluorosulfonic acid resin solution on the surface of a glass plate, heating and removing the solvent to obtain a solid perfluorosulfonic acid membrane;
(4) And carrying out hot pressing on the perfluorosulfonic acid membrane and a nickel sheet on which a porous foam catalytic array grows for 5 minutes at 120 ℃ under 2MPa to obtain the ordered membrane electrode prepared under the transfer printing condition.
Comparing the graph in FIG. 6 of the ordered membrane electrode prepared in example 1 with the graph in FIG. 7 of the ordered membrane electrode prepared in comparative example 1 by hot-pressing transfer, it can be seen that the ordered membrane electrode prepared in example 1 can maintain the morphology structure of the porous foam. However, the membrane electrode prepared by the conventional hot-press transfer method of comparative example 1 exhibited that the porous catalytic layer was seriously damaged and a dense and disordered catalytic layer morphology structure was formed.
The membrane electrode prepared by the method is used for producing hydrogen by electrolyzing water with the traditional first generation, second generation and third generation membrane electrodes, the voltage of the electrolyzed water changes as shown in figure 8 under different current densities, and the voltage of the electrolyzed water is reduced by more than 30 percent under the same current density; under the same electrolytic voltage, the current of the electrolyzed water is improved by more than 60 percent.
The stability of the membrane electrode during use was further examined and the results are shown in fig. 9. The membrane casting solution can flow on the surface of the porous solid catalytic electrode, the thickness of the membrane is obviously reduced by regulating and controlling the thickness of the coating of the solution, and the thickness of the membrane is reduced to be less than 20 microns after drying and curing; in addition, because the membrane casting solution is tightly attached along the uneven electrode surface, the contact area between the membrane and the electrode is enlarged, and the membrane and the porous solid catalyst are improvedThe bonding firmness of the electrode is improved. Therefore, the current density reached 2000mA cm at 60 ℃ and a voltage of 1.7V using pure water as an electrolyte -2 And the continuous operation lasts for more than 700 hours and keeps stable.
The same tests as described above show that the membrane electrodes of the embodiments 4 and 5 have porous foam morphology, and when hydrogen is produced by water electrolysis, the voltage of the water electrolysis is reduced by more than 30% under the same current density; under the same electrolytic voltage, the current of the electrolyzed water is improved by more than 60 percent, the stability of the electrode in the use process is good, and the electrode can keep stable after continuously running for more than 700 hours.
The applicant states that the present invention is illustrated by the above examples of the membrane electrode comprising a catalyst ordered structure, the preparation method and the application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (10)

1. A preparation method of an ordered structure membrane electrode containing a catalyst array is characterized by comprising the following steps:
(1) Coating a polymer solution containing ion exchange groups on a metal substrate of a catalyst array with an ordered structure on the surface so as to completely cover the catalyst array;
(2) Heating the metal substrate obtained in the step (1) and removing a solvent to obtain a compound of an ion exchange membrane and the metal substrate;
(3) And (3) soaking the compound obtained in the step (2) in deionized water, and heating to separate the ion exchange membrane from the metal substrate, thereby obtaining the ordered structure membrane electrode containing the catalyst array.
2. The production method according to claim 1, wherein the metal substrate having the catalyst array of the ordered structure on the surface thereof in the step (1) is obtained by:
sequentially immersing the metal substrate into a hydrochloric acid aqueous solution and deionized water for cleaning, and removing metal oxides on the surface; and then growing a catalyst array with an ordered structure on the surface of the metal substrate.
3. The preparation method according to claim 1 or 2, wherein the method for growing the catalyst array with the ordered structure on the surface of the metal substrate is electrodeposition, solvothermal growth or vapor phase chemical deposition;
preferably, the solution used in growing the catalyst array of ordered structure comprises the following components: niCl 2 .6H 2 0、CoCl 2 .6H 2 O and NH 4 Cl。
4. The production method according to any one of claims 1 to 3, wherein the metal substrate is a nickel sheet, an aluminum sheet, a copper sheet, an iron sheet, or an alloy substrate of at least two of the elements;
preferably, the polymer containing ion exchange groups in the step (1) is cation exchange resin, anion exchange resin or polybenzimidazole polymer;
preferably, the cation exchange resin is a perfluorosulfonic acid resin;
preferably, the solvent in the solution of the polymer containing ion exchange groups in step (1) is any one or a combination of at least two of ethanol, dimethyl sulfoxide or water.
5. The production method according to any one of claims 1 to 4, wherein the temperature of the heating in step (2) is 80 to 100 ℃.
6. The production method according to any one of claims 1 to 5, wherein the temperature rise in the step (3) is a temperature rise to 50 to 80 ℃.
7. The ordered structure membrane electrode containing the catalyst array prepared by the preparation method according to any one of claims 1 to 6.
8. A fuel cell comprising the ordered structure membrane electrode comprising a catalyst array according to claim 7.
9. A flow battery comprising the ordered structure membrane electrode comprising a catalyst array of claim 7.
10. The use of the ordered structure membrane electrode comprising a catalyst array according to claim 7 in the electrolysis of water.
CN202211165770.2A 2022-09-23 2022-09-23 Ordered structure membrane electrode containing catalyst array and preparation method and application thereof Pending CN115411277A (en)

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