Anode catalyst slurry, membrane electrode and application for proton exchange membrane water electrolysis to produce hydrogen

Abstract

The present invention provides an anode catalyst slurry, a membrane electrode and an application for hydrogen production by proton exchange membrane water electrolysis. The anode catalyst slurry includes a core-shell catalyst of iridium-loaded metal oxide, a dispersant, a binder and a solvent. The core-shell catalyst has a metal oxide surface modified with ‑NH2 and / or ‑SH as a core and metal iridium nanoparticles as an outer shell. The present invention uses a low-iridium catalyst of iridium-loaded metal oxide as a main body, which can improve the utilization rate of precious metal iridium and reduce economic costs. The catalyst slurry is prepared by combining a binder, a solvent and a dispersant in a specific proportion, and the catalyst slurry is evenly distributed on the proton exchange membrane by ultrasonic spraying, which can expose more electrochemically active surfaces, thereby better contacting with the gas diffusion layer, effectively transferring water, electrons and heat, so that the final water electrolysis device has good catalytic activity.

Description

Technical Field

[0001] The present invention relates to the field of electrocatalysis technology, and in particular to an anode catalyst slurry, a membrane electrode and applications thereof for producing hydrogen through proton exchange membrane water electrolysis. Background Art

[0002] Proton exchange membrane water electrolysis (PEMWE) has become a core technology for the future hydrogen-based economy with its high power density and excellent load capacity, providing a new strategy for sustainable hydrogen production in large-scale energy storage environments. The most important element in PEMWE is the membrane electrode assembly (MEA), which mainly consists of a proton exchange membrane located in the middle, a cathode catalyst layer located on both sides of the proton exchange membrane in close contact with the proton exchange membrane, an anode catalyst layer, electrode plates, and a gas diffusion layer located outside the two catalyst layers. When the water electrolysis device is working, water produces and releases oxygen under the catalysis of the anode catalyst, and produces and releases hydrogen under the catalysis of the cathode catalyst. For the anode catalyst layer of the water electrolysis device, the selected catalyst material and the state of the catalyst slurry have an important influence on the microstructure of the formed catalyst layer.

[0003] The anode catalyst layer is prepared by combining the anode catalyst with some additives to form a catalyst slurry, which is then coated and transferred onto the proton exchange membrane. The main methods include doctor blade coating, ultrasonic spray coating, screen printing, sputtering, or electrochemical deposition. Ultrasonic spray coating is widely used for preparing catalyst layers due to its advantages of saving catalyst dosage, high catalyst dispersion, and uniform catalyst distribution. It is also simple to operate, highly automated, and suitable for mass production of MEAs. However, the state of the catalyst slurry used in ultrasonic spray coating directly affects the dispersion of the catalyst layer, thereby affecting the performance of the water electrolysis device. Summary of the Invention

[0004] In view of this, the present invention aims to provide an anode catalyst slurry, membrane electrode, and application for hydrogen production via proton exchange membrane water electrolysis. The anode catalyst slurry utilizes a specific low-iridium catalyst as the main component, along with a binder, solvent, and dispersant in specific proportions. Ultrasonic spraying allows the catalyst to be evenly distributed across the proton exchange membrane, resulting in a water electrolysis device with excellent catalytic activity.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides an anode catalyst slurry for proton exchange membrane water electrolysis to produce hydrogen, comprising an iridium-loaded metal oxide core-shell catalyst, a dispersant, a binder, and a solvent.

[0007] Preferably, the core-shell catalyst comprises a metal oxide as the core and metal iridium nanoparticles as the shell. Preferably, the metal oxide comprises any one or more of titanium dioxide, niobium pentoxide, tantalum oxide, tungsten oxide or tin oxide.

[0008] Preferably, the surface of the metal oxide is modified with functional groups, and the functional groups include -NH2 and / or -SH.

[0009] Preferably, the mass ratio of the solvent, the core-shell catalyst, the dispersant and the binder is 1:(0.01-0.05):(0.01-1:0.05):0.01.

[0010] Preferably, the dispersant is selected from polyethylene glycol octylphenyl ether.

[0011] Preferably, the binder is selected from any one or more of perfluorosulfonic acid resin, polytetrafluoroethylene, or polyvinylidene fluoride-hexafluoropropylene copolymer.

[0012] Preferably, the solvent is selected from any one or more of isopropyl alcohol, ethanol, nitrogen-methylpyrrolidone, nitrogen, nitrogen-dimethylformamide, dimethyl sulfoxide or glycerol.

[0013] In a second aspect, the present invention provides a membrane electrode for hydrogen production by proton exchange membrane water electrolysis, comprising an anode catalyst layer, a cathode catalyst layer, and a proton exchange membrane positioned between the anode catalyst layer and the cathode catalyst layer. The anode catalyst layer is prepared by ultrasonic spraying the anode catalyst slurry described in the above technical solution.

[0014] Preferably, the proton exchange membrane is selected from Nafion membrane or Gore membrane.

[0015] In a third aspect, the present invention provides a method for preparing a membrane electrode, comprising the following steps:

[0016] The anode catalyst slurry and the cathode catalyst slurry are sprayed on both sides of the proton exchange membrane respectively by adopting the ultrasonic spraying method to obtain the membrane electrode.

[0017] Preferably, the anode catalyst slurry comprises an iridium-loaded metal oxide core-shell catalyst, a dispersant, a binder, and a solvent. The core-shell catalyst comprises a metal oxide core and iridium nanoparticles as an outer shell, wherein the metal oxide comprises one or more of titanium dioxide, niobium pentoxide, tantalum oxide, tungsten oxide, or tin oxide.

[0018] Preferably, the cathode catalyst slurry comprises a Pt / C catalyst, a dispersant, a binder and a solvent.

[0019] Preferably, the discharge flow rate of the ultrasonic spraying is 0.5 to 1.0 mL / min.

[0020] Preferably, the spraying amount of the anode catalyst slurry is 0.3-0.8 mg / cm 2 ;

[0021] Preferably, the spraying amount of the cathode catalyst slurry is 0.2-0.4 mg / cm 2 .

[0022] In a fourth aspect, the present invention provides a device for producing hydrogen by electrolyzing water using a proton exchange membrane, comprising the membrane electrode involved in the above technical solution.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The present invention provides an anode catalyst slurry for hydrogen production by proton exchange membrane water electrolysis. The anode catalyst slurry is mainly composed of a low-iridium catalyst in which iridium is loaded with metal oxide, which can improve the utilization rate of the precious metal iridium and reduce economic costs. The low-iridium catalyst is prepared into a catalyst slurry by combining a binder, a solvent, and a dispersant in a specific ratio. The catalyst slurry is evenly distributed on the proton exchange membrane by ultrasonic spraying, which can expose more electrochemically active surfaces, thereby better contacting with the gas diffusion layer, effectively transferring water, electrons, and heat, and making the final water electrolysis device have good catalytic activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 TEM image of the low-iridium catalyst obtained in Preparation Example 1;

[0026] Figure 2 This is a comparison chart of the water electrolysis curves of the membrane electrodes obtained in Examples 1-2 and Comparative Example 1. DETAILED DESCRIPTION

[0027] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0028] In order to improve the catalytic performance of the proton exchange membrane water electrolysis hydrogen production device in the prior art and further improve its hydrogen production efficiency, the present invention provides an anode catalyst slurry for proton exchange membrane water electrolysis hydrogen production, including an iridium-loaded metal oxide core-shell catalyst, a dispersant, a binder and a solvent.

[0029] The core-shell catalyst comprises a metal oxide as a core and metallic iridium nanoparticles as an outer shell. The metal oxide comprises any one or more of titanium dioxide, niobium pentoxide, tantalum oxide, tungsten oxide, or tin oxide. The metal oxide is surface-modified with functional groups comprising -NH2 and / or -SH. The present invention utilizes -NH2 and / or -SH to coordinate the metal oxide with metallic iridium, thereby obtaining a catalyst having a core-shell structure. The mass ratio of the metal oxide to the iridium nanoparticles is 1:(0.6-1.5). The particle size of the iridium nanoparticles is 4-8 nm, preferably 5-6 nm.

[0030] In some embodiments of the present invention, the core-shell catalyst can be prepared according to the following method:

[0031] A metal oxide with a surface modified with a functional group, an iridium source, a solvent and a surfactant are mixed and subjected to a solvent thermal reaction in an inert atmosphere at 80 to 120° C., and then the obtained product is heat-treated in an inert atmosphere at 200 to 500° C. to obtain the core-shell catalyst.

[0032] The metal oxide surface modified with functional groups is prepared by reacting a metal oxide with a molecule containing functional groups at 60-130°C for 8-36 hours. The metal oxide is as described in the above technical solution and will not be described in detail here. The molecule containing functional groups mainly refers to a molecule containing -NH2 and / or -SH, and can be selected from any one or more of urea, thioglycolic acid, thiourea, or 3-mercaptobenzoic acid. In the present invention, the ratio of the metal oxide to the molecule containing functional groups is 1:(10-20). In some embodiments of the present invention, after the above reaction is completed, the product obtained by the reaction is preferably washed, centrifuged, and dried. The washing reagents include anhydrous ethanol and water, and the water can be any one or more of deionized water, distilled water, or ultrapure water. The centrifugation can be carried out according to conventional methods, and the present invention has no particular limitation on the centrifugal speed. The drying can be any conventional drying method. In the present invention, the centrifuged product is preferably dried at 40-80°C for 4-12 hours.

[0033] After introducing functional groups onto the surface of the metal oxide, according to the present invention, the metal oxide modified with the functional groups, an iridium source, a solvent, and a surfactant are mixed and subjected to a solvothermal reaction in an inert atmosphere at 80-120°C. The resulting product is then heat-treated in an inert atmosphere at 200-500°C to obtain the core-shell catalyst. The iridium source is selected from any one or more of chloroiridic acid, iridium acetylacetonate, iridium chloride, potassium chloroiridate, sodium chloroiridate, or iridium acetate; the solvent is selected from any one or more of ethanol, ethylene glycol, or isopropanol; and the surfactant is used to disperse the metal oxide to prevent it from agglomerating into large particles, and can be selected from any one or more of cetyltrimethylammonium bromide, ethylenediaminetetraacetic acid, or polyvinylpyrrolidone. In some embodiments of the present invention, the metal oxide with a surface modified with a functional group, the iridium source, the solvent, and the surfactant are mixed in an inert atmosphere at 80 to 120° C. in a mass ratio of 10:(0 to 1) to the surfactant and 0.1:(1 to 2) to the solvent, and then the solvent thermal reaction is carried out for 4 to 8 hours in an inert atmosphere. The obtained product is then reacted in a tube furnace at 200 to 500° C. in an inert atmosphere for 2 to 4 hours to obtain a core-shell catalyst having a mass ratio of metal oxide to iridium of 1:(0.6 to 1.5). The inert atmosphere is an atmosphere well known to those skilled in the art, and in the present invention, nitrogen is preferably used.

[0034] In some embodiments of the present invention, after the solvent thermal reaction is completed, the obtained product is preferably washed, centrifuged and dried before continuing to be subjected to high-temperature treatment in a tube furnace under an inert atmosphere. The washing reagents include anhydrous ethanol and water, and the water can be any one or more of deionized water, distilled water or ultrapure water. The centrifugation can be carried out according to conventional methods, and the present invention has no particular limitation on the centrifugal speed. The drying can be any conventional drying method. The present invention preferably dries the centrifuged product at 40-80°C for 4-12 hours.

[0035] The preparation method of the core-shell catalyst is simple and easy, does not require expensive equipment, and is easy to achieve industrial or industrial production.

[0036] In the present invention, the dispersant is a nonionic surfactant, specifically polyethylene glycol octylphenyl ether. The binder is selected from any one or more of perfluorosulfonic acid resin, polytetrafluoroethylene, or polyvinylidene fluoride-hexafluoropropylene copolymer. The solvent is selected from any one or more of isopropyl alcohol, ethanol, nitrogen-methyl pyrrolidone, nitrogen, nitrogen-dimethylformamide, dimethyl sulfoxide, or glycerol.

[0037] The dispersion of the anode catalyst layer prepared from the anode catalyst slurry is mainly affected by the ratio of each component. According to research, if the amount of solvent added is too high, the slurry will be thinner and the sedimentation phenomenon will be obvious in the later stage. It is easy to clog the nozzle in the subsequent process of preparing the catalyst layer by ultrasonic spraying. If the amount added is too small, the slurry will be too viscous, resulting in uneven spraying. Therefore, in some embodiments of the present invention, the mass ratio of the solvent to the core-shell catalyst is 1: (0.01 to 0.08), preferably 1: (0.01 to 0.05). If the amount of dispersant added is too small, the slurry will be unevenly dispersed, and if it is too much, the catalytic performance will be adversely affected. Therefore, in some embodiments of the present invention, the mass ratio of the solvent to the dispersant is 1: (0.01 to 0.08), preferably 1: (0.01 to 0.05). If the amount of the binder added is too much, it may cause a coating effect on the catalyst, resulting in a reduction in the effective catalytic area of ​​the catalyst, while if the amount added is too little, it may result in poor adhesion between the catalyst and the proton exchange membrane, affecting the proton transport between the catalyst layer and the proton exchange membrane. Therefore, in some embodiments of the present invention, the mass ratio of the core-shell catalyst to the binder component is determined to be (1-8):1, preferably (1-5):1. The present invention mixes the solvent, core-shell catalyst, dispersant and binder in a mass ratio of 1:(0.01-0.05):(0.01-1:0.05):0.01, so that the solid content of the obtained slurry is 1-10%, which can ensure that the core-shell catalyst can be uniformly dispersed in the mixed solution of solvent, binder and dispersant, and is not easy to settle. Subsequently, uniform ultrasonic spraying can be performed on the surface of the proton exchange membrane.

[0038] The anode catalyst slurry for proton exchange membrane water electrolysis to produce hydrogen provided by the present invention is mainly composed of a low-iridium catalyst of iridium-loaded titanium dioxide, and is combined with the above-mentioned specific proportions of binder, solvent and dispersant. The obtained slurry is evenly dispersed and has moderate viscosity, and is convenient for being evenly distributed on the proton exchange membrane by ultrasonic spraying to obtain a membrane electrode, which can expose more electrochemically active surface, thereby better contacting with the gas diffusion layer, effectively transferring water, electrons and heat, and making the final water electrolysis device have good catalytic activity.

[0039] The present invention also provides a cathode catalyst slurry, comprising a Pt / C catalyst, a dispersant, a binder and a solvent. Wherein, the Pt / C catalyst is commercial Pt / C, which can be a general commercial product. The specific selection of the dispersant, binder and solvent is as described in the relevant content of the above technical solution, and will not be repeated here. As described in the above technical solution, the amount of dispersant, binder and solvent will affect the dispersion state of the cathode catalyst layer prepared by the final slurry. After continuous experimental exploration, the present invention determines the mass ratio of solvent to Pt / C catalyst to be 1: (0.01 to 0.08), preferably 1: (0.01 to 0.05), the mass ratio of solvent to dispersant to be 1: (0.01 to 0.08), preferably 1: (0.01 to 0.05), and the mass ratio of binder to Pt / C catalyst to be 1: (0.1 to 0.7), preferably 1: (0.1 to 0.5). The present invention mixes a solvent, a Pt / C catalyst, a dispersant and a binder in a mass ratio of 1:(0.01-0.05):(0.01-0.05):0.1, so that the solid content of the obtained slurry is 1-10%. This ensures that the Pt / C catalyst can be uniformly dispersed in the mixed solution of the solvent, the binder and the dispersant and is not prone to sedimentation. Subsequently, uniform ultrasonic spraying can be performed on the surface of the proton exchange membrane.

[0040] The anode catalyst slurry and cathode catalyst slurry can be obtained by uniformly mixing a low-iridium catalyst (or Pt / C catalyst), a binder, a solvent, and a dispersant. In some embodiments of the present invention, the anode catalyst slurry is prepared as follows:

[0041] The low-iridium catalyst (or Pt / C catalyst), binder, solvent and dispersant are ball-milled and mixed, and then ultrasonically mixed and dispersed uniformly.

[0042] According to the present invention, a low-iridium catalyst (or Pt / C catalyst), a binder, a solvent and a dispersant are ball-milled and mixed, then ultrasonically mixed and dispersed uniformly, and finally deaerated to obtain the anode catalyst slurry. Wherein, the specific selection and proportional relationship of the low-iridium catalyst (or Pt / C catalyst), binder, solvent and dispersant are as described in the relevant contents of the above technical solution, and will not be repeated here. In some embodiments of the present invention, after the low-iridium catalyst (or Pt / C catalyst), binder, solvent and dispersant are placed in a ball mill in proportion, the resulting slurry is ultrasonically dispersed in a temperature-controlled ultrasonic disperser for 0.5 to 2 hours, and the ultrasonic temperature is 0 to 5°C and the frequency is 30Hz.

[0043] The preparation method of the catalyst slurry provided by the present invention is simple, does not require expensive instruments and equipment, and can be obtained after uniform ultrasonic dispersion. It is easy to operate and is conducive to industrialization or industrial production.

[0044] After the above-mentioned anode catalyst slurry and cathode catalyst slurry are prepared, they can be used to make membrane electrodes. The membrane electrode includes a proton exchange membrane located in the middle and an anode catalyst layer and a cathode catalyst layer located on both sides of the proton exchange membrane and in close contact with the proton exchange membrane. Among them, the proton exchange membrane can be a commercial Nafion membrane or Gore membrane, which is a general commercial product. The preparation method of the membrane electrode is simple. By using an ultrasonic spraying method, the anode catalyst slurry and the cathode catalyst slurry are sprayed on the surface of the solid proton exchange membrane respectively to obtain a membrane electrode. In some embodiments of the present invention, the proton exchange membrane is placed on an electric heating plate and fixed by the negative pressure of an air compressor. Among them, the temperature of the electric heating plate is 100-120°C. Then, using ultrasonic spraying equipment, the cathode catalyst slurry and the anode catalyst slurry are evenly sprayed on both sides of the proton exchange membrane at a discharge flow rate of 0.5-1.0 mL / min to obtain the membrane electrode. In some embodiments of the present invention, the spraying amount of the anode catalyst slurry is 0.3-0.8 mg / cm 2 , preferably 0.5 mg / cm 2 The spraying amount of the cathode catalyst slurry is 0.2-0.4 mg / cm 2 , preferably 0.2 mg / cm 2 .

[0045] The present invention also provides a proton exchange membrane water electrolysis hydrogen production device, including the membrane electrode obtained above. The water electrolysis performance test was carried out at 60 ° C, and it was found that at a current density of 2A / cm 2 The electrolysis voltage under the condition does not exceed 2V, indicating that it has good water electrolysis performance and low energy consumption.

[0046] To further illustrate the present invention, the following examples are provided for detailed description. The experimental raw materials used in the following examples of the present invention can be purchased from the market or prepared according to conventional preparation methods well known to those skilled in the art.

[0047] Preparation Example 1

[0048] This preparation example provides a low-iridium catalyst, and the preparation method is as follows:

[0049] 500 mg of titanium dioxide was added to 1M 100 mL of urea aqueous solution, ultrasonically dispersed evenly, heated and stirred at 70°C in a water bath for 36 hours, and then the obtained product was washed with deionized water and anhydrous ethanol, centrifuged, and then dried in a vacuum oven at 50°C for 6 hours to obtain a titanium dioxide carrier with surface modified with amino groups. 50 mg of surface-modified titanium dioxide carrier material was added to a mixed solution of chloroiridic acid, ethanol and polyvinylpyrrolidone (PVP) (the mass ratio of PVP to chloroiridic acid was 0.4:10, and the mass ratio of ethanol to chloroiridic acid was 10:1), and ultrasonically dispersed uniformly, and the mass ratio of metal iridium to titanium dioxide was controlled to be m(Ir):m(TiO2)=2:3. Under a nitrogen atmosphere, the solvent thermal reaction was carried out in an oil bath at 80°C for 8 hours, and then washed with deionized water and anhydrous ethanol, centrifuged, and dried in a vacuum oven at 50°C for 6 hours. The low-iridium catalyst was obtained by high-temperature heat treatment at 300°C for 2 hours in an inert atmosphere.

[0050] The TEM image of the low iridium catalyst is as follows Figure 1 As shown, it can be seen that the low iridium catalyst is small in size, with a diameter of about 5 to 6 nm, and is evenly dispersed.

[0051] Example 1

[0052] This embodiment provides a membrane electrode for PEM water electrolysis to produce hydrogen, and the preparation method is as follows:

[0053] (1) Take 50 mL of a mixed solution of polyethylene glycol octylphenyl ether and an isopropanol aqueous solution (the mass ratio of isopropanol solvent to polyethylene glycol octylphenyl ether is 1:0.02; the volume ratio of deionized water to isopropanol is 1:1), then weigh 1.5 g of the low iridium catalyst obtained in Preparation Example 1 and 0.5 g of a 5 wt% Nafion solution, add the mixture to the above mixed solution, place in a ball mill, and then ultrasonicate for 1 h to disperse uniformly to obtain an anode catalyst slurry;

[0054] (2) Take 50 mL of a mixed solution of polyethylene glycol octylphenyl ether and isopropanol aqueous solution (the mass ratio of isopropanol solvent to polyethylene glycol octylphenyl ether is 1:0.02; the volume ratio of deionized water to isopropanol is 1:3), then weigh 0.5 g of a 40 wt% commercial Pt / C catalyst and 1 g of a 5 wt% Nafion solution, add them to the above mixed solution, place it in a ball mill, and then ultrasonically disperse it for 1 hour to obtain a cathode catalyst slurry;

[0055] (3) An N115 proton exchange membrane with an area of ​​5 cm × 5 cm was placed on an electric heating plate at 100°C and fixed using the negative pressure of an air compressor. Then, an ultrasonic spraying device was used to spray the cathode catalyst slurry at a flow rate of 0.5 mL / min at a concentration of 0.2 mg / cm 2, anode catalyst slurry 0.5mg / cm 2 The cathode and anode catalyst slurries are evenly sprayed on both sides of the proton exchange membrane in a ratio of , to obtain the membrane electrode.

[0056] Example 2

[0057] This embodiment provides a membrane electrode for PEM water electrolysis to produce hydrogen, and the preparation method is as follows:

[0058] (1) Take 50 mL of a mixed solution of polyethylene glycol octylphenyl ether and an isopropanol aqueous solution (the mass ratio of isopropanol solvent to polyethylene glycol octylphenyl ether is 1:0.02; the volume ratio of deionized water to isopropanol is 1:3), then weigh 1.5 g of the low iridium catalyst obtained in Preparation Example 1 and 0.5 g of a 5 wt% Nafion solution, add the mixture to the above-mentioned mixed solution, place it in a ball mill, and then ultrasonically disperse it for 1 h to obtain an anode catalyst slurry;

[0059] (2) Take 50 mL of a mixed solution of polyethylene glycol octylphenyl ether and isopropanol aqueous solution (the mass ratio of isopropanol solvent to polyethylene glycol octylphenyl ether is 1:0.02; the volume ratio of deionized water to isopropanol is 1:3), then weigh 0.5 g of a 20 wt% commercial Pt / C catalyst and 1 g of a 5 wt% Nafion solution, add them to the above mixed solution, place it in a ball mill, and then ultrasonically disperse it for 1 hour to obtain a cathode catalyst slurry;

[0060] (3) An N115 proton exchange membrane with an area of ​​5 cm × 5 cm was placed on an electric heating plate at 100°C and fixed using the negative pressure of an air compressor. Then, an ultrasonic spraying device was used to spray the cathode catalyst slurry at a flow rate of 0.5 mL / min at a concentration of 0.2 mg / cm 2 , anode catalyst slurry 0.5mg / cm 2 The cathode and anode catalyst slurries are evenly sprayed on both sides of the proton exchange membrane in a ratio of , to obtain the membrane electrode.

[0061] Comparative Example 1

[0062] This comparative example provides a membrane electrode for PEM water electrolysis to produce hydrogen. The only difference from Example 1 is that the low-iridium catalyst obtained in Preparation Example 1 is replaced by an equal amount of 75wt% commercial IrO2 solid catalyst, and the remaining parameters and steps are consistent with Example 1.

[0063] The membrane electrode assemblies obtained in Examples 1-2 and Comparative Example 1 were tested for water electrolysis performance. The test results are shown in Tables 1 and Figure 1 As shown:

[0064] Table 1

[0065] Group <![CDATA[2A / cm 2 Electrolysis voltage (V)]]> Example 1 1.982 Example 2 1.995 Comparative Example 1 2.228

[0066] Figure 2 The electrolysis curves of the membrane electrodes obtained in Examples 1 to 2 and Comparative Example 1 are shown in Table 1 and Figure 1 It can be seen that the electrolysis voltage of the membrane electrode provided by the present invention in a single water electrolysis cell is lower than the electrolysis voltage of the membrane electrode assembly obtained in the comparative example in a single water electrolysis cell, indicating that the energy consumption required for the membrane electrode provided by the present invention is lower when producing the same volume of hydrogen.

[0067] The above description of the disclosed embodiments will enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is to be construed in the widest manner consistent with the principles and novel features disclosed herein.

Claims

1. An anode catalyst slurry for proton exchange membrane water electrolysis to produce hydrogen, characterized in that: The invention comprises a core-shell catalyst of an iridium-supported metal oxide, a dispersant, a binder and a solvent; The core-shell catalyst has a metal oxide as the core and metal iridium nanoparticles as the shell; The metal oxide includes any one or more of titanium dioxide, niobium pentoxide, tantalum oxide, tungsten oxide or tin oxide; The metal oxide surface is modified with functional groups, and the functional groups include -NH2 and / or -SH; The mass ratio of the solvent, the core-shell catalyst, the dispersant and the binder is 1:(0.01-0.05):(0.01-0.05):0.

01.

2. The anode catalyst slurry according to claim 1, characterized in that The dispersant is selected from polyethylene glycol octylphenyl ether; The binder is selected from any one or more of perfluorosulfonic acid resin, polytetrafluoroethylene or polyvinylidene fluoride-hexafluoropropylene copolymer; The solvent is selected from any one or more of isopropyl alcohol, ethanol, nitrogen-methyl pyrrolidone, nitrogen, nitrogen-dimethylformamide, dimethyl sulfoxide or glycerol.

3. A membrane electrode for producing hydrogen by electrolysis of water using a proton exchange membrane, characterized in that: It includes an anode catalyst layer, a cathode catalyst layer and a proton exchange membrane located between the anode catalyst layer and the cathode catalyst layer; The anode catalyst layer is prepared from the anode catalyst slurry according to claim 1 or 2 by an ultrasonic spraying method.

4. The membrane electrode according to claim 3, characterized in that The proton exchange membrane is selected from Nafion membrane or Gore membrane.

5. A method for preparing a membrane electrode, characterized in that: The following steps are involved: The anode catalyst slurry and cathode catalyst slurry according to claim 1 or 2 are sprayed on both sides of the proton exchange membrane respectively by an ultrasonic spraying method to obtain the membrane electrode.

6. The preparation method according to claim 5, characterized in that The cathode catalyst slurry includes a Pt / C catalyst, a dispersant, a binder and a solvent.

7. The preparation method according to claim 5, characterized in that The discharge flow rate of the ultrasonic spraying is 0.5-1.0 mL / min.

8. The preparation method according to claim 5, characterized in that The spraying amount of the anode catalyst slurry is 0.3~0.8 mg / cm 2 ; The spraying amount of the cathode catalyst slurry is 0.2~0.4 mg / cm 2 .

9. A device for producing hydrogen by electrolysis of water using a proton exchange membrane, characterized in that: The invention comprises the membrane electrode according to claim 3 or 4 or the membrane electrode prepared by the preparation method according to any one of claims 5 to 8.

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