Membrane electrode for anion exchange membrane water electrolysis hydrogen production and preparation method thereof

Abstract

The invention discloses a membrane electrode for anion exchange membrane water electrolysis hydrogen production and a preparation method thereof. The membrane electrode comprises an anion exchange membrane, and a cathode catalyst layer and an anode catalyst layer are arranged on the two sides of the anion exchange membrane respectively; the catalyst loading capacity in the cathode catalyst layer is 0.2-1.0 mg / cm < 2 >, and the cathode catalyst layer comprises a platinum-carbon catalyst, a platinum-ruthenium-carbon catalyst and / or a platinum-ruthenium-carbon catalyst; the catalyst loading capacity in the anode catalyst layer is 1.0-10mg / cm < 2 >, and the anode catalyst layer comprises a nickel-iron oxide catalyst, an iridium oxide catalyst, a cobaltosic oxide catalyst, a cobalt-iron alloy catalyst and a cobalt-nickel catalyst, and / or the catalyst loading capacity in the anode catalyst layer is 1.0-10mg / cm < 2 >; by accurately controlling the thickness and particle distribution of the catalyst layer, the interface contact between the catalyst and the membrane material is optimized, the resistance loss in the electrolysis process is reduced, and meanwhile, the catalytic activity is improved.

Description

Technical Field

[0001] The invention relates to the technical field of membrane electrodes, and in particular to a membrane electrode used for anion exchange membrane water electrolysis to produce hydrogen and a preparation method thereof. Background Art

[0002] As the global demand for clean energy grows, hydrogen energy, as a green and renewable energy carrier, has received more and more attention. Hydrogen has broad application prospects in fuel cells, industrial chemical synthesis and energy storage. Especially in the field of transportation, the rapid development of hydrogen fuel cell vehicles has made efficient and economical hydrogen production methods a research hotspot. Although traditional hydrogen production methods, such as natural gas reforming and coal gasification, can meet market demand in the short term, they cannot achieve sustainable development due to their high carbon emissions and resource consumption. Therefore, water electrolysis to produce hydrogen as a zero-carbon emission, renewable hydrogen production method has gradually become a mainstream choice.

[0003] Water electrolysis hydrogen production technology is based on the electrolysis of water to decompose water into hydrogen and oxygen. With the continuous advancement of membrane electrode technology, anion exchange membrane water electrolysis has become one of the water electrolysis hydrogen production methods that has attracted much attention in recent years. Compared with traditional proton exchange membrane water electrolysis, anion exchange membrane water electrolysis systems have multiple advantages, such as lower cost, wider operating temperature range, and better adaptability to non-precious metal catalysts. Therefore, the development of efficient and stable anion exchange membrane water electrolysis systems has become the key to improving hydrogen production efficiency and reducing costs.

[0004] In anion exchange membrane water electrolysis, the preparation of membrane electrode assembly is one of the core technologies to achieve the technology. The performance of membrane electrode directly determines the efficiency and stability of water electrolysis system, and the preparation process of membrane electrode has a profound impact on its structure, conductivity, catalytic activity and other performance indicators. Therefore, the development of an efficient and low-cost membrane electrode preparation method is of great significance to promote the application of anion exchange membrane water electrolysis hydrogen production technology. Summary of the invention

[0005] The purpose of the present invention is to provide a membrane electrode for anion exchange membrane water electrolysis to produce hydrogen and a preparation method thereof, so as to solve the following technical problems:

[0006] How to improve the efficiency of membrane electrodes used for anion exchange membrane water electrolysis to produce hydrogen.

[0007] The purpose of the present invention can be achieved through the following technical solutions:

[0008] In the first aspect, the present invention discloses a membrane electrode for anion exchange membrane water electrolysis to produce hydrogen, comprising an anion exchange membrane, wherein a cathode catalyst layer and an anode catalyst layer are respectively arranged on both sides of the anion exchange membrane; the catalyst loading in the cathode catalyst layer is 0.2-1.0 mg / cm 2 , including platinum carbon catalyst, platinum ruthenium carbon catalyst, and / or; the catalyst loading in the anode catalyst layer is 1.0-10 mg / cm 2 , including nickel-iron oxide catalysts, iridium oxide catalysts, cobalt tetroxide catalysts, cobalt-iron alloy catalysts, cobalt-nickel catalysts, and / or.

[0009] Preferably, the catalyst loading in the cathode catalyst layer is 0.5 mg / cm 2 .

[0010] Preferably, the catalyst loading in the anode catalyst layer is 1.5-2.5 mg / cm 2 , more preferably 2 mg / cm 2 .

[0011] Preferably, the anion exchange membrane is any one of PiperION-A20-HCO3, PiperION-A40-HCO3, PiperION-A60-HCO3, PiperION-A80-HCO3, PiperION-A10R-HCO3, PiperION-A15R-HCO3, Fumapem-FAA-3-PE-30 / 50, Fumasep-FAAM-15 / 20 / 40, Sustainion XC37-FA, SustainionXC37-50Grade RT, and Sustainion XC37-50 Grade 60.

[0012] In the present invention, the anion exchange membrane is more preferably Sustainion XC37-50 Grade RT.

[0013] In a second aspect, the present invention also discloses a method for preparing a membrane electrode for anion exchange membrane water electrolysis to produce hydrogen as described above, comprising the following preparation steps: laying the anion exchange membrane flat on a vacuum adsorption table, coating the cathode catalyst slurry and the anode catalyst slurry on both sides of the proton exchange membrane respectively, and attaching corresponding cathode diffusion layers and anode diffusion layers on both sides after drying, thereby forming a membrane electrode.

[0014] Preferably, the cathode diffusion layer is carbon cloth, and the anode diffusion layer is nickel foam.

[0015] Preferably, the cathode catalyst slurry comprises the following raw materials in parts by weight: 20 parts of cathode catalyst, 60-120 parts of anion exchange membrane resin solution, and 600-1400 g of solvent.

[0016] Preferably, the anode catalyst slurry comprises the following raw materials in parts by weight: 10 parts of anode catalyst, 40-80 parts of anion exchange membrane resin solution, and 400-800 g of solvent.

[0017] Preferably, the preparation method of the cathode catalyst slurry / anode catalyst slurry is: mix the cathode catalyst / anode catalyst, anion exchange membrane resin solution, and solvent evenly, then first ultrasonically disperse under 5°C cooling circulating water conditions, and then high-speed shear disperse to obtain the cathode catalyst slurry / anode catalyst slurry.

[0018] Preferably, the anion exchange membrane resin solution is PiperION-A5-HCO3-EtOH, Fumion FAA-3-SOLUT-10, Sustainion XA-9, Sustainion XB-7, Sustainion XC-1 / 2, and / or.

[0019] Preferably, the solvent is a mixture of low-fat alcohol and deionized water, and the mass ratio of the two is 1:(0.1-1).

[0020] Preferably, the low-fat alcohol is ethanol, isopropanol, n-propanol, ethylene glycol, and / or.

[0021] Beneficial effects of the present invention:

[0022] The present invention optimizes the preparation method of the membrane electrode for hydrogen production by anion exchange membrane water electrolysis, adopts commercial catalysts and advanced membrane electrode preparation and assembly processes, and significantly improves the electrolysis efficiency and stability of the membrane electrode. By precisely controlling the thickness and particle distribution of the catalyst layer, the interface contact between the catalyst and the membrane material is optimized, the resistance loss during the electrolysis process is reduced, and the catalytic activity is improved. The experimental results show that with the increase of current density, the voltage growth rate of the electrolyzer is significantly lower than that of the traditional membrane electrode system, indicating that the membrane electrode system can maintain a lower voltage at a higher current density, thereby improving the hydrogen generation efficiency and reducing the energy loss of the overall system. This method has a fast and stable electrolysis efficiency, and can effectively reduce the cost of hydrogen production, improve the economy and sustainability of hydrogen energy preparation, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The present invention will be further described below in conjunction with the accompanying drawings.

[0024] Figure 1 is an electron microscope morphology image of the membrane electrode prepared in Example 1 of the present invention;

[0025] Figure 2 is an electron microscope morphology image of the membrane electrode prepared in Example 2 of the present invention;

[0026] Figure 3 is an electron microscope morphology image of the membrane electrode prepared in Example 3 of the present invention;

[0027] Figure 4 It is a comparison diagram of the relationship between voltage and current at different currents after the membrane electrodes prepared in Examples 1-3 of the present invention are assembled into an electrolytic cell. DETAILED DESCRIPTION

[0028] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] The experimental methods in the following examples, unless otherwise specified, are all conventional methods, and are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials, reagents, etc. used in the following examples, unless otherwise specified, can all be obtained from commercial channels.

[0030] Example 1

[0031] Preparation of membrane electrode for anion exchange membrane water electrolysis to produce hydrogen:

[0032] (1) Preparation of catalyst slurry:

[0033] A. 100 mg of platinum-carbon catalyst (Jiping New Energy Company, Pt content is 50 wt%), 400 mg of PiperION-A5-HCO3-EtOH (solid content 5 wt%), 1070 mg of deionized water, and 10730 mg of isopropanol were mixed evenly, and then ultrasonically dispersed for 5 min under 5 ° C cooling circulating water conditions, and then dispersed at 18000 rpm high-speed shear for 60 min to obtain a cathode catalyst slurry with a solid content of 1 wt%;

[0034] B. 100 mg of nickel-iron oxide (Shanghai Aladdin Biochemical Technology Co., Ltd.), 500 mg of PiperION-A5-HCO3-EtOH (solid content 5 wt%), 1240 mg of deionized water, and 12100 mg of isopropanol were mixed evenly, and then ultrasonically dispersed for 10 min under cooling circulating water at 5°C, and then dispersed at 18000 rpm for 60 min to obtain an anode catalyst slurry with a solid content of 1 wt%.

[0035] (2) Preparation of membrane electrode:

[0036] The cathode catalyst slurry and the anode catalyst slurry prepared in step (1) were respectively injected into the liquid supply injector of the ultrasonic sprayer, and the anti-precipitation system of the liquid supply injector was turned on at the same time. The cathode catalyst slurry was sprayed to 25 cm by ultrasonic spraying. 2 The anode catalyst slurry was sprayed on one side of the anion exchange membrane (Sustainion XC37-50 Grade RT) and the cathode catalyst and anode catalyst slurry were sprayed on the other side; the cathode catalyst and anode catalyst were 0.5 mg / cm 2 and 2.0mg / cm 2 , maintain the vacuum adsorption heating stage temperature at 80℃, dry for 5 minutes, and attach 25cm 2 A membrane electrode can be obtained by adding a diffusion layer with a thickness of 250um (the anode is nickel foam and the cathode is carbon cloth).

[0037] The nozzle height of the ultrasonic sprayer is 60 mm, the liquid feeding rate is 0.5 mL / min, and the spraying area is 25 cm 2 , spray width 5mm, vacuum adsorption table temperature of ultrasonic spray machine 80℃, vacuum adsorption pressure 0.01MPa.

[0038] Example 2

[0039] Preparation of membrane electrode for anion exchange membrane water electrolysis to produce hydrogen:

[0040] (1) Preparation of catalyst slurry: The preparation steps and conditions are exactly the same as those in step (1) of Example 1.

[0041] (2) Preparation of membrane electrode: Compared with step (2) in Example 1, the only difference is that the loading amount of the anode catalyst is 1.5 mg / cm 2 , the other steps and conditions are exactly the same, and finally the membrane electrode is produced.

[0042] Example 3

[0043] Preparation of membrane electrode for anion exchange membrane water electrolysis to produce hydrogen:

[0044] (3) Preparation of catalyst slurry: The preparation steps and conditions are exactly the same as those of step (1) in Example 1.

[0045] (4) Preparation of membrane electrode: Compared with step (2) in Example 1, the only difference is that the loading amount of the anode catalyst is 2.5 mg / cm 2 , the other steps and conditions are exactly the same, and finally the membrane electrode is produced.

[0046] The membrane electrodes for anion exchange membrane water electrolysis hydrogen production prepared in Examples 1-3 were photographed using a microscope to obtain the following images: Figure 1-3 Electron microscope morphology of Figure 1-3 It can be seen from observation that the particles on the surface of the membrane electrode prepared in Examples 1-3 are evenly distributed.

[0047] The membrane electrodes for anion exchange membrane water electrolysis and hydrogen production prepared in Examples 1-3 were tested for performance respectively. The testing method was as follows: the membrane electrodes were packaged with Teflon frames and then stacked with nickel plates to form an electrolytic cell. The cell air tightness was tested with 100 kPa of high-purity nitrogen, and a KOH solution with a concentration of 1 mol / L was passed into the anode of the electrolytic cell. The cell temperature was 70°C. The input current of the electrolytic cell was adjusted to 2.5 A, 5 A, 12.5 A, 15 A, 17.5 A, 20 A, 22.5 A, 25 A, and 27.5 A in sequence. Each current was maintained for 2 minutes. The relationship between the voltage and current of the electrolytic cell was tested, and the following was obtained: Figure 4 The curve comparison diagram shown in Figure 4 Analysis shows that the membrane electrode prepared in Examples 1-3 improves the performance of the electrolyzer. When the current density increases, the rate of voltage increase slows down, indicating that the optimization of the catalyst layer effectively reduces the resistance loss during the electrolysis process and improves the hydrogen generation efficiency. By analyzing the current-voltage curve, it is possible to clearly see the performance of the electrolyzer under high current conditions, further proving the superiority of this method in increasing hydrogen production and reducing energy loss.

[0048] In summary, it can be inferred that the membrane electrode for anion exchange membrane water electrolysis to produce hydrogen produced by the present invention has a significant gain effect in improving hydrogen production efficiency, extending electrode life and reducing costs.

[0049] The above is a detailed description of an embodiment of the present invention, but the content is only a preferred embodiment of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A membrane electrode for anion exchange membrane water electrolysis to produce hydrogen, comprising an anion exchange membrane, wherein a cathode catalyst layer and an anode catalyst layer are respectively arranged on both sides of the anion exchange membrane; characterized in that: The catalyst loading in the cathode catalyst layer is 0.2-1.0 mg / cm 2 , including platinum carbon catalyst, platinum ruthenium carbon catalyst, and / or; the catalyst loading in the anode catalyst layer is 1.0-10 mg / cm 2 , including nickel-iron oxide catalysts, iridium oxide catalysts, cobalt tetroxide catalysts, cobalt-iron alloy catalysts, cobalt-nickel catalysts, and / or.

2. The membrane electrode for anion exchange membrane water electrolysis to produce hydrogen according to claim 1, characterized in that: The anion exchange membrane is any one of PiperION-A20-HCO3, PiperION-A40-HCO3, PiperION-A60-HCO3, PiperION-A80-HCO3, PiperION-A10R-HCO3, PiperION-A15R-HCO3, Fumapem-FAA-3-PE-30 / 50, Fumasep-FAAM-15 / 20 / 40, Sustainion XC37-FA, Sustainion XC37-50 Grade RT, and Sustainion XC37-50Grade 60.

3. A method for preparing a membrane electrode for anion exchange membrane water electrolysis to produce hydrogen as claimed in any one of claims 1 to 2, characterized in that: The preparation process includes the following steps: laying an anion exchange membrane flat on a vacuum adsorption table, coating cathode catalyst slurry and anode catalyst slurry on both sides of the proton exchange membrane respectively, and attaching corresponding cathode diffusion layers and anode diffusion layers on both sides after drying to form a membrane electrode.

4. The method for preparing a membrane electrode for anion exchange membrane water electrolysis to produce hydrogen according to claim 3, characterized in that: The cathode catalyst slurry comprises the following raw materials in parts by weight: 20 parts of cathode catalyst, 60-120 parts of anion exchange membrane resin solution, and 600-1400 g of solvent.

5. The method for preparing a membrane electrode for anion exchange membrane water electrolysis to produce hydrogen according to claim 3, characterized in that: The anode catalyst slurry comprises the following raw materials in parts by weight: 10 parts of anode catalyst, 40-80 parts of anion exchange membrane resin solution, and 400-800 g of solvent.

6. The method for preparing a membrane electrode for anion exchange membrane water electrolysis to produce hydrogen according to any one of claims 4 or 5, characterized in that: The preparation method of the cathode catalyst slurry / anode catalyst slurry is: the cathode catalyst / anode catalyst, anion exchange membrane resin solution and solvent are uniformly mixed, and then ultrasonically dispersed under 5° C. cooling circulating water conditions, and then high-speed shear dispersed to obtain the cathode catalyst slurry / anode catalyst slurry.

7. The method for preparing a membrane electrode for anion exchange membrane water electrolysis to produce hydrogen according to any one of claims 4 or 5, characterized in that: The anion exchange membrane resin solution is PiperION-A5-HCO3-EtOH, Fumion FAA-3-SOLUT-10, Sustaini on XA-9, Sustainion XB-7, Sustaini on XC-1 / 2, and / or.

8. The method for preparing a membrane electrode for anion exchange membrane water electrolysis to produce hydrogen according to any one of claims 4 or 5, characterized in that: The solvent is a mixture of low-fat alcohol and deionized water, and the mass ratio of the two is 1:(0.1-1).

9. The method for preparing a membrane electrode for anion exchange membrane water electrolysis to produce hydrogen according to claim 7, characterized in that: The low-fat alcohol is ethanol, isopropanol, n-propanol, ethylene glycol, and / or.

10. The method for preparing a membrane electrode for anion exchange membrane water electrolysis to produce hydrogen according to claim 3, characterized in that: The cathode diffusion layer is carbon cloth, and the anode diffusion layer is nickel foam.

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