Hydrolysis hydrogen production diaphragm, preparation method thereof and water electrolysis hydrogen production device

Abstract

The invention belongs to the technical field of water electrolysis hydrogen production, and provides a hydrolysis hydrogen production diaphragm, a preparation method thereof and a water electrolysis hydrogen production device, the hydrolysis hydrogen production diaphragm comprises a substrate and a catalyst layer arranged on at least one side surface of the substrate, and the catalyst layer is used for catalyzing the reaction of hydrogen and oxygen. The catalyst layer is arranged on the surface of the diaphragm, and when hydrogen enters the anode side or oxygen enters the cathode side, the hydrogen and the oxygen can be subjected to catalytic reaction at the catalyst layer, so that the mixing of the hydrogen and the oxygen in the hydrolysis hydrogen production process is reduced, and the safety of the hydrogen production process is improved.

Description

Technical Field

[0001] The present application relates to the technical field of hydrogen production by water electrolysis, and in particular to a hydrogen production membrane by water electrolysis, a preparation method thereof, and a hydrogen production device by water electrolysis. Background Art

[0002] In the process of producing hydrogen by alkaline water electrolysis, a small amount of hydrogen will diffuse from the cathode side through the diaphragm to the anode side, or the gas-liquid separation is not thorough during the circulation of the electrolyte, and some hydrogen in the electrolyte enters the anode side, resulting in a certain concentration of hydrogen on the anode side, affecting the safety of the electrolysis device. In addition, oxygen on the anode side may also enter the cathode side through the diaphragm, which still poses a safety problem and reduces the purity of the discharged hydrogen, requiring the hydrogen to be purified. Therefore, how to improve the safety of the process of producing hydrogen by water electrolysis has become a technical problem that urgently needs to be solved. Summary of the invention

[0003] Based on this, an embodiment of the present application provides a highly safe hydrolysis hydrogen production diaphragm and a preparation method thereof and a water electrolysis hydrogen production device.

[0004] In a first aspect, the present application provides a hydrolysis hydrogen production membrane, which includes a substrate and a catalytic layer disposed on at least one side of the substrate, wherein the catalytic layer is used to catalyze the reaction of hydrogen and oxygen.

[0005] In some embodiments, the catalyst contained in the catalytic layer includes at least one of platinum, palladium, rhodium, iridium and ruthenium.

[0006] In some embodiments, the substrate has a thickness of 50 μm to 600 μm.

[0007] In some embodiments, the catalyst content in the catalytic layer is 0.01 g / cm 2 ~1mg / cm 2 .

[0008] In some embodiments, the substrate contains a pore structure. Optionally, the porosity of the substrate is 40% to 60%, and the median pore size of the pore structure is 200 nm to 1000 nm.

[0009] In some embodiments, the substrate contains inorganic particles. Optionally, the inorganic particles account for 50% to 90% by weight of the substrate.

[0010] In some embodiments, the material of the inorganic particles includes an oxide.

[0011] In some embodiments, the material of the inorganic particles includes at least one of silicon dioxide, titanium dioxide, and zirconium dioxide.

[0012] Optionally, the volume average particle size Dv50 of the inorganic particles is 10 nm to 500 nm.

[0013] In some embodiments, the substrate includes a support layer and base material layers disposed on both side surfaces of the support layer.

[0014] Optionally, the material of the support layer includes at least one of polyphenylene sulfide, polyetheretherketone and polytetrafluoroethylene.

[0015] Optionally, the material of the substrate layer includes polysulfone resin.

[0016] Optionally, the material of the substrate layer includes at least one of sulfonated polysulfone, polyethersulfone, poly(arylene ether sulfone), tertiary aminated polysulfone and chloromethyl polysulfone.

[0017] In a second aspect, the present application provides a method for preparing a hydrolysis hydrogen production membrane, the method for preparing a hydrolysis hydrogen production membrane comprising:

[0018] A catalytic layer is formed on at least one surface of the substrate, and the catalytic layer is used for catalyzing the reaction of hydrogen and oxygen.

[0019] In some embodiments, the method for forming the catalytic layer comprises:

[0020] preparing a first solution containing a catalytic raw material;

[0021] preparing a second solution containing a reducing agent and a complexing agent;

[0022] The substrate is immersed in the first solution, and then the substrate is transferred to the second solution, and the catalytic layer is deposited on at least one side of the substrate.

[0023] Optionally, the catalytic raw material includes at least one of platinum salt, palladium salt, rhodium salt, iridium salt and ruthenium salt; optionally, the catalytic raw material includes at least one of platinum chloride, palladium chloride, potassium chloroplatinate, rhodium chloride, iridium chloride and ruthenium chloride.

[0024] Optionally, the molar concentration of the catalytic raw material in the first solution is 10 μmol / L~2000 μmol / L.

[0025] In some embodiments, the substrate is immersed in the first solution for 5 min to 30 min.

[0026] In some embodiments, the deposition temperature is 25° C. to 120° C., and the deposition time is 5 min to 120 min.

[0027] In some embodiments, the reducing agent includes at least one of hydrazine hydrochloride, hydrazine hydrate, aqueous ammonia, sodium hypophosphite, and sodium borohydride.

[0028] In some embodiments, the complexing agent includes at least one of ethylenediamine, ammonia, ethanolamine and citric acid.

[0029] In some embodiments, the mass concentration of the reducing agent in the second solution is 0.1 mol / L~1 mol / L.

[0030] In some embodiments, the mass concentration of the complexing agent in the second solution is 0.1 mol / L to 1 mol / L.

[0031] In some embodiments, the method for preparing the substrate comprises:

[0032] preparing a slurry containing inorganic particles, a polysulfone resin, a porogen and a solvent;

[0033] The slurry is used to form a slurry layer on the surface of the layer. After solidification, the slurry layer is converted into a substrate layer to form a substrate. The substrate includes a support layer and substrate layers arranged on both sides of the support layer.

[0034] Optionally, the mass ratio between the inorganic particles and the solvent is 1:(0.8~1.5).

[0035] Optionally, the mass ratio of the polysulfone resin to the inorganic particles is 1:(1-8).

[0036] Optionally, the mass ratio between the porogen and the resin is 1:(0.01-0.1).

[0037] Optionally, the solidification temperature is 5°C to 60°C.

[0038] Optionally, the solvent includes at least one of N,N dimethylformamide, N,N dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, ethanol and water.

[0039] In a third aspect, the present application provides a water electrolysis hydrogen production device, which includes the water electrolysis hydrogen production diaphragm as described in the first aspect or the water electrolysis hydrogen production diaphragm prepared by the preparation method of the water electrolysis hydrogen production diaphragm as described in the second aspect.

[0040] Compared with the traditional technology, this application has at least the following beneficial effects:

[0041] The present application relates to a diaphragm design for use in a process of producing hydrogen by water electrolysis, wherein the surface of the diaphragm has a catalytic layer. When hydrogen is generated on the anode side or oxygen is generated on the cathode side, these gases can undergo a catalytic reaction under the action of the catalytic layer, consuming the hydrogen accumulated near the diaphragm, effectively reducing the mixing of hydrogen and oxygen, thereby significantly improving the safety of the process of producing hydrogen by water electrolysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 A schematic diagram of the structure of a hydrolysis hydrogen production membrane provided in one embodiment of the present application;

[0043] Figure 2 This is a schematic structural diagram of another hydrolysis hydrogen production membrane provided in one embodiment of the present application.

[0044] Among them, 100 is a hydrolysis hydrogen production membrane; 110 is a substrate; 111 is a support layer; 112 is a substrate layer; and 120 is a catalytic layer. DETAILED DESCRIPTION

[0045] Below in conjunction with the embodiments and examples, the present application is further described in detail. These embodiments and examples are only used to illustrate the present application and are not used to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the understanding of the disclosure of the present application more thorough and comprehensive. It should also be understood that the present application can be implemented in many different forms, and is not limited to the embodiments and examples described herein. Those skilled in the art can make various changes or modifications without violating the connotation of the present application, and the equivalent form obtained also falls within the protection scope of the present application. In addition, in the description below, a large number of specific details are given in order to provide a more comprehensive understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0046] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0047] In this application, "optionally", "optional", and "optional" mean optional or dispensable, that is, any one of the two parallel schemes of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0048] In this application, the terms "first", "second", etc. in "the first aspect", "the second aspect", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0049] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0050] In the present application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to an integer in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical range disclosed in the present application should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows for a broad range of quantitative intervals such as percentage intervals, ratio intervals, and ratio intervals.

[0051] All documents mentioned in this application are cited as references in this application, just as each document is cited as reference separately. Unless they conflict with the application purpose and / or technical solution of this application, the cited documents involved in this application are cited with all contents and all purposes. When the cited documents are involved in this application, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When the cited documents are involved in this application, the examples and preferred methods of the cited relevant technical features can also be incorporated into this application as references, but are limited to the implementation of this application. It should be understood that when the cited content conflicts with the description in this application, the present application shall prevail or be modified adaptively according to the description of this application.

[0052] In traditional technology, the problem of hydrogen and oxygen mixing is avoided by reducing the gas permeability in the diaphragm. For example, in traditional technology, the gas barrier property of the diaphragm is improved by increasing the bubble point of the diaphragm to avoid hydrogen crossing the diaphragm and reduce the concentration of hydrogen in oxygen. Specifically, in traditional technology, a composite diaphragm with a certain degree of cross-linking (3%~10%) is prepared to increase the bubble point of the diaphragm to improve the gas barrier property; or, a multi-layer composite hydrogen production diaphragm is prepared to reduce the concentration of hydrogen in oxygen by improving the gas barrier property through the multi-layer structure. Although increasing the gas permeability of the diaphragm can reduce the speed at which hydrogen and oxygen mix with each other, the gas will still pass through the diaphragm to cause mixing. After the electrolysis process has been running for a period of time, the gas mixture reaches a certain concentration, and there are still safety issues.

[0053] The first aspect of the present application provides a hydrolysis hydrogen production membrane, such as Figure 1 and Figure 2 As shown, the hydrolysis hydrogen production membrane 100 includes a substrate 110 and a catalyst layer 120 disposed on at least one side of the substrate 110 , and the catalyst layer 120 is used for catalyzing the reaction of hydrogen and oxygen.

[0054] The surface of the diaphragm in the present application has a catalytic layer. When hydrogen enters the anode side or oxygen enters the cathode side, hydrogen and oxygen can undergo a catalytic reaction at the catalytic layer, thereby reducing the mixing of hydrogen and oxygen during the hydrolysis hydrogen production process and improving the safety of the hydrogen production process.

[0055] In some embodiments, the material of the catalytic layer includes at least one of platinum, palladium, rhodium, iridium, and ruthenium.

[0056] In some embodiments, the thickness of the substrate is 50 μm to 600 μm, for example, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm or 600 μm.

[0057] In some embodiments, the catalyst content in the catalytic layer is 0.01 g / cm 2 ~1mg / cm 2 , for example, it can be 0.01 mg / cm 2 , 0.05mg / cm 2 , 0.1mg / cm 2 , 0.2mg / cm 2 , 0.3mg / cm 2 , 0.4mg / cm 2 , 0.5mg / cm 2 , 0.6mg / cm 2 , 0.7mg / cm 2 , 0.8mg / cm 2 , 0.9mg / cm 2 or 1.0mg / cm 2 The present application selects the catalyst content in the catalyst layer as above, which effectively satisfies the catalytic reaction while reducing the preparation cost and energy consumption.

[0058] In some embodiments, the substrate contains a pore structure therein.

[0059] Optionally, the porosity of the substrate is 40% to 60%.

[0060] Optionally, the median pore diameter of the pore structure in the substrate layer is 200 nm to 1000 nm.

[0061] In some embodiments, the substrate contains inorganic particles. The present application can improve the hydrophilicity and stability of the diaphragm by introducing inorganic particles into the substrate, effectively reduce the energy consumption of hydrogen production by electrolysis of water, and increase the service life of the composite diaphragm.

[0062] Optionally, the mass proportion of the inorganic particles in the substrate is 50% to 90%, for example, it can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%.

[0063] In some embodiments, the material of the inorganic particles includes an oxide.

[0064] In some embodiments, the material of the inorganic particles includes at least one of silicon dioxide, titanium dioxide, and zirconium dioxide.

[0065] Optionally, the volume average particle size Dv50 of the inorganic particles is 10 nm to 500 nm, for example, 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm or 500 nm.

[0066] In some embodiments, Figure 1 and Figure 2 As shown, the substrate 110 includes a support layer 111 and base material layers 112 disposed on both side surfaces of the support layer 111 .

[0067] Optionally, the support layer has a thickness of 50 μm to 600 μm, for example, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm or 600 μm.

[0068] Optionally, the material of the support layer includes at least one of polyphenylene sulfide, polyetheretherketone and polytetrafluoroethylene.

[0069] Optionally, the material of the substrate layer includes polysulfone resin. The content of polysulfone resin in the substrate layer is 0.01 g / cm 2 ~1mg / cm 2 .

[0070] Optionally, the material of the substrate layer includes at least one of sulfonated polysulfone, polyethersulfone, poly(arylene ether sulfone), tertiary aminated polysulfone and chloromethyl polysulfone.

[0071] The second aspect of the present application provides a method for preparing a hydrolysis hydrogen production membrane, the method for preparing a hydrolysis hydrogen production membrane comprising:

[0072] A catalytic layer is formed on at least one surface of the substrate, and the catalytic layer is used for catalyzing the reaction of hydrogen and oxygen.

[0073] The present application prepares a hydrolysis hydrogen production diaphragm with a catalytic layer on the surface as described above. When hydrogen enters the anode side or oxygen enters the cathode side, hydrogen and oxygen can undergo a catalytic reaction at the catalytic layer, thereby reducing the mixing of hydrogen and oxygen during the hydrolysis hydrogen production process and improving the safety of the hydrogen production process.

[0074] It is understandable that the formation method can be reasonably selected according to the type of the catalyst layer. For example, it can be a chemical deposition method or a physical deposition method. Optionally, the formation method of the catalyst layer includes at least one of electrodeposition, magnetron sputtering and chemical vapor deposition.

[0075] In some embodiments, the method for forming the catalytic layer comprises:

[0076] preparing a first solution containing a catalytic raw material;

[0077] preparing a second solution containing a reducing agent and a complexing agent;

[0078] The substrate is immersed in the first solution, and then the substrate is transferred to the second solution, and the catalytic layer is deposited on at least one side of the substrate.

[0079] In some embodiments, a pH regulator is further added to the first solution. Optionally, the pH regulator includes at least one of HCl, KOH and NaOH. The pH of the first solution is adjusted to ensure that the catalytic raw material is completely dissolved and does not corrode the substrate.

[0080] Optionally, the catalytic raw material includes at least one of platinum salt, palladium salt, rhodium salt, iridium salt and ruthenium salt; optionally, the catalytic raw material includes at least one of platinum chloride, palladium chloride, potassium chloroplatinate, rhodium chloride, iridium chloride and ruthenium chloride.

[0081] Optionally, the molar concentration of the catalytic raw material in the first solution is 10 μmol / L~2000 μmol / L, for example, it can be 10 μmol / L, 50 μmol / L, 100 μmol / L, 200 μmol / L, 400 μmol / L, 600 μmol / L, 800 μmol / L, 1000 μmol / L, 1200 μmol / L, 1400 μmol / L, 1600 μmol / L, 1800 μmol / L or 2000 μmol / L.

[0082] In some embodiments, the substrate is immersed in the first solution for 5 min to 30 min, for example, 5 min, 6 min, 9 min, 12 min, 15 min, 18 min, 21 min, 24 min, 27 min or 30 min.

[0083] In some embodiments, the deposition temperature is 25°C to 120°C, for example, 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C or 120°C.

[0084] In some embodiments, the deposition time is 5 min to 120 min, for example, it can be 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min or 120 min.

[0085] In some embodiments, the reducing agent includes at least one of hydrazine hydrochloride, hydrazine hydrate, aqueous ammonia, sodium hypophosphite, and sodium borohydride.

[0086] In some embodiments, the steps of immersing the substrate in the first solution and depositing the catalyst layer are repeated to improve deposition efficiency.

[0087] In some embodiments, the complexing agent includes at least one of ethylenediamine, ammonia, ethanolamine, and citric acid.

[0088] In some embodiments, the mass concentration of the reducing agent in the second solution is 0.1 mol / L~1 mol / L, for example, it can be 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L or 1.0 mol / L.

[0089] In some embodiments, the mass concentration of the complexing agent in the second solution is 0.1 mol / L~1 mol / L, for example, it can be 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L or 1.0 mol / L.

[0090] In some embodiments, the method for preparing the substrate comprises:

[0091] preparing a slurry containing inorganic particles, a polysulfone resin, a porogen and a solvent;

[0092] The slurry is used to form a slurry layer on the surface of the support layer. After solidification, the slurry layer is converted into a substrate layer to form a substrate. The substrate includes a support layer and substrate layers arranged on both sides of the support layer.

[0093] Optionally, the mass ratio of the inorganic particles to the solvent is 1:(0.8-1.5), for example, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5.

[0094] Optionally, the mass ratio of the polysulfone resin to the inorganic particles is 1:(1-8), for example, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8.

[0095] Optionally, the mass ratio between the porogen and the resin is 1:(0.01-0.1).

[0096] Optionally, the porogen includes at least one of polyvinyl pyrrolidone, polyvinyl alcohol and polyethylene glycol.

[0097] Optionally, the solidification temperature is 5°C to 60°C, for example, it can be 5°C, 6°C, 12°C, 18°C, 24°C, 30°C, 36°C, 42°C, 48°C, 54°C or 60°C.

[0098] Optionally, the solvent includes at least one of N,N dimethylformamide, N,N dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, ethanol and water.

[0099] In some embodiments, the method for preparing the slurry comprises:

[0100] Dispersing inorganic particles in a solvent and stirring to form a first dispersion;

[0101] The polysulfone resin and the porogen are added to the first dispersion liquid, and the slurry is formed after being evenly dispersed.

[0102] In some embodiments, the stirring speed is 500 r / min~2500 r / min, and the time is 1 h~5 h.

[0103] In some embodiments, the dispersion speed is 500 r / min to 3000 r / min, and the time is 4 h to 24 h.

[0104] In some embodiments, the solidification method includes: soaking the support layer formed with the slurry layer in a solidification bath. Optionally, the solidification bath includes at least one of water and ethanol.

[0105] Exemplarily, a method for preparing the above-mentioned hydrolysis hydrogen production membrane is provided, comprising the following steps:

[0106] S1, dispersing inorganic particles in a solvent, with a mass ratio of inorganic particles to solvent of 1:(0.8-1.5), stirring at 500 r / min-2500 r / min for 1 h-5 h to form a first dispersion;

[0107] S2, adding polysulfone resin and porogen to the first dispersion, the mass ratio of polysulfone resin to inorganic particles is 1: (1-8), the mass ratio of porogen to resin is 1: (0.01-0.1), dispersing at 500r / min-3000r / min for 4h-24h to form the slurry;

[0108] S3, coating the slurry on the surface of the support layer to form a slurry layer, immersing the support layer in a coagulation bath at 5°C to 60°C to coagulate, and converting the slurry layer into a substrate layer to form a base;

[0109] S4, dissolving the catalytic raw material in water, and adjusting the pH with a pH adjuster and stirring until fully dissolved to obtain a first solution, wherein the molar concentration of the catalytic raw material in the first solution is 10 μmol / L to 2000 μmol / L;

[0110] S5, preparing a reducing agent, a complexing agent and water to form a second solution, wherein the molar concentration of the reducing agent in the second solution is 0.1 mol / L to 1 mol / L, and the molar concentration of the complexing agent is 0.1 mol / L to 1 mol / L;

[0111] S6, soaking the substrate in S3 in the first solution for 5 min to 30 min, and then transferring it to the second solution for deposition to form a catalytic layer, the deposition temperature is 25°C to 120°C, and the deposition time is 5 min to 120 min;

[0112] S7. Repeat step S6 to improve the deposition efficiency of the catalytic layer. Optionally, the number of cycles is 1 to 5.

[0113] A third aspect of the present application provides a water electrolysis hydrogen production device, which includes the water electrolysis hydrogen production diaphragm as described in the first aspect or the water electrolysis hydrogen production diaphragm prepared by the preparation method of the water electrolysis hydrogen production diaphragm as described in the second aspect.

[0114] In some embodiments, the water electrolysis hydrogen production device includes a cathode, an anode, the water electrolysis hydrogen production membrane and an electrolytic cell filled with an electrolyte. The water electrolysis hydrogen production membrane is arranged in the electrolytic cell to separate the electrolytic cell into a cathode side and an anode side. The cathode is arranged on the cathode side, and the anode is arranged on the anode side.

[0115] The embodiments of the present application will be described in detail below in conjunction with examples. It should be understood that these examples are only used to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods for which specific conditions are not specified in the following examples are preferably referred to the guidance provided in the present application, and can also be based on the experimental manual or normal conditions in this area, can also be based on the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

[0116] Example 1

[0117] S1, dispersing 150 g of titanium dioxide particles with a Dv50 of 100 nm in 120 mL of N,N-dimethylacetamide solvent at 2000 r / min for 5 h to form a first dispersion;

[0118] S2, add 20g polysulfone to the first dispersion, fully dissolve at 2500r / min at room temperature for 4h, add 0.5g polyvinyl pyrrolidone and continue stirring for 1h to form a slurry;

[0119] S3, coating the slurry on both sides of the polyphenylene sulfide mesh, standing in the air for pre-evaporation, and then immersing it in water at 25°C for phase inversion. After solidification, a substrate is obtained, the porosity of the substrate is 58%, and the median pore size of the pore structure is 500nm;

[0120] S4, mixing water and potassium chloroplatinate, and adding 0.1 mol / L HCl to adjust the pH of the solution until the potassium chloroplatinate is completely dissolved, to form a first solution with a potassium chloroplatinate concentration of 20 μmol / L;

[0121] S5, mixing hydrazine hydrochloride and water to form a second solution, wherein the molar concentration of hydrazine hydrochloride in the second solution is 0.2 mol / L;

[0122] S6, soaking the substrate prepared in S3 in the first solution for 10 minutes, then transferring it to the second solution, heating it to 60° C., reacting it for 30 minutes, and depositing a catalytic layer on the surface of the substrate;

[0123] S7, repeating step S6 twice to obtain a hydrolysis hydrogen production membrane, wherein the thickness of the support layer in the substrate is 500 μm; the material of the catalytic layer is platinum, and the platinum content in the catalytic layer is 0.05 mg / cm 2 .

[0124] Example 2

[0125] The hydrolysis hydrogen production membrane is prepared according to the method of Example 1, except that steps S4 to S6 are different, including:

[0126] S4, mixing water and palladium chloride, and adding 0.2 mol / L HCl to adjust the pH of the solution until the palladium chloride is completely dissolved, to form a first solution with a palladium chloride concentration of 20 μmol / L;

[0127] S5, mixing hydrazine hydrochloride and water to form a second solution, wherein the molar concentration of hydrazine hydrochloride in the second solution is 0.02 mol / L;

[0128] S6, soaking the substrate prepared in S3 in the first solution for 10 minutes, then transferring it to the second solution, heating it to 50° C., reacting it for 30 minutes, and depositing a catalytic layer on the surface of the substrate;

[0129] S7, repeating step S6 twice to obtain a hydrolysis hydrogen production membrane, wherein the material of the catalyst layer is palladium, and the palladium content in the catalyst layer is 0.15 mg / cm 2 .

[0130] Example 3

[0131] S1, dispersing 100 g of zirconium dioxide particles with a Dv50 of 120 nm in 120 mL of N-methylpyrrolidone solvent at 2000 r / min for 5 h to form a first dispersion;

[0132] S2, add 25g polysulfone to the first dispersion, fully dissolve at 2500r / min at room temperature for 4h, add 1g polyvinyl pyrrolidone and continue stirring for 1h to form a slurry;

[0133] S3, coating the slurry on both sides of the polyphenylene sulfide mesh, standing in the air for pre-evaporation, and then immersing it in water at 25°C for phase inversion. After solidification, a substrate is obtained, the porosity of the substrate is 52%, and the median pore size of the pore structure is 250nm;

[0134] S4, mixing water and potassium chloroplatinate, and adding 0.1 mol / L HCl to adjust the pH of the solution until the potassium chloroplatinate is completely dissolved, to form a first solution with a potassium chloroplatinate concentration of 20 μmol / L;

[0135] S5, mixing hydrazine hydrochloride and water to form a second solution, wherein the molar concentration of hydrazine hydrochloride in the second solution is 0.01 mol / L;

[0136] S6, soaking the substrate prepared in S3 in the first solution for 10 minutes, then transferring it to the second solution, heating it to 60° C., reacting it for 30 minutes, and depositing a catalytic layer on the surface of the substrate;

[0137] S7, repeating step S6 twice to obtain a hydrolysis hydrogen production membrane, wherein the thickness of the support layer in the substrate is 520 μm; the material of the catalytic layer is platinum, and the platinum content in the catalytic layer is 0.25 mg / cm 2 .

[0138] Example 4

[0139] The hydrolysis hydrogen production membrane is prepared according to the method of Example 3, except that steps S4 to S6 are different, including:

[0140] S4, mixing water and palladium chloride, and adding 0.2 mol / L HCl to adjust the pH of the solution until the palladium chloride is completely dissolved, to form a first solution with a palladium chloride concentration of 20 μmol / L;

[0141] S5, mixing hydrazine hydrochloride and water to form a second solution, wherein the molar concentration of hydrazine hydrochloride in the second solution is 0.02 mol / L;

[0142] S6, soaking the substrate prepared in S3 in the first solution for 10 minutes, then transferring it to the second solution, heating it to 50° C., reacting it for 30 minutes, and depositing a catalytic layer on the surface of the substrate;

[0143] S7, repeating step S6 twice to obtain a hydrolysis hydrogen production membrane, wherein the material of the catalyst layer is palladium, and the palladium content in the catalyst layer is 0.13 mg / cm 2 .

[0144] Example 5

[0145] S1, dispersing 150 g of titanium dioxide particles with a Dv50 of 200 nm in 120 mL of N,N-dimethylformamide solvent at 2000 r / min for 5 h to form a first dispersion;

[0146] S2, add 20g of polysulfone resin to the first dispersion, fully dissolve at 2500r / min at room temperature for 4h, add 0.5g of polyvinyl pyrrolidone and continue stirring for 1h to form a slurry;

[0147] S3, coating the slurry on both sides of the polyphenylene sulfide mesh, standing it in the air for pre-evaporation, and then immersing it in water at 25°C for phase inversion. After solidification, a substrate is obtained, and the porosity of the substrate is 62%, and the median pore size of the pore structure is 280nm;

[0148] S4, mixing water and potassium chloroplatinate, and adding 0.1 mol / L HCl to adjust the pH of the solution until the potassium chloroplatinate is completely dissolved, to form a first solution with a potassium chloroplatinate concentration of 20 μmol / L;

[0149] S5, mixing hydrazine hydrate and water to form a second solution, wherein the molar concentration of hydrazine hydrate in the second solution is 0.01 mol / L;

[0150] S6, soaking the substrate prepared in S3 in the first solution for 20 minutes, then transferring it to the second solution, heating it to 60° C., reacting it for 30 minutes, and depositing a catalytic layer on the surface of the substrate;

[0151] S7, repeating step S6 three times to obtain a hydrolysis hydrogen production membrane, wherein the thickness of the support layer in the substrate is 420 μm; the material of the catalytic layer is platinum, and the platinum content in the catalytic layer is 0.18 mg / cm 2 .

[0152] Example 6

[0153] The hydrolysis hydrogen production membrane is prepared according to the method of Example 5, except that steps S4 to S6 are different, including:

[0154] S4, mixing water and palladium chloride, and adding 0.2 mol / L HCl to adjust the pH of the solution until the palladium chloride is completely dissolved, to form a first solution with a palladium chloride concentration of 20 μmol / L;

[0155] S5, mixing hydrazine hydrate and water to form a second solution, wherein the molar concentration of hydrazine hydrate in the second solution is 0.02 mol / L;

[0156] S6, soaking the substrate prepared in S3 in the first solution for 20 minutes, then transferring it to the second solution, heating it to 50° C., reacting it for 30 minutes, and depositing a catalytic layer on the surface of the substrate;

[0157] S7, repeat step S6 three times to obtain a hydrolysis hydrogen production membrane, wherein the material of the catalyst layer is palladium, and the palladium content in the catalyst layer is 0.15 mg / cm 2 .

[0158] Example 7

[0159] S1, dispersing 100g zirconium dioxide particles with a Dv50 of 200nm in 120mL of N-methylpyrrolidone solvent at 2000r / min for 5h to form a first dispersion;

[0160] S2, add 25g of polysulfone resin to the first dispersion, fully dissolve at 2500r / min at room temperature for 4h, add 1g of polyvinyl pyrrolidone and continue stirring for 1h to form a slurry;

[0161] S3, coating the slurry on both sides of the polyphenylene sulfide mesh, standing in the air for pre-evaporation, and then immersing it in water at 25°C for phase inversion, and obtaining a substrate after solidification, the porosity of the substrate is 56%, and the median pore size of the pore structure is 230nm;

[0162] S4, mixing water and potassium chloroplatinate, and adding 0.1 mol / L HCl to adjust the pH of the solution until the potassium chloroplatinate is completely dissolved, to form a first solution with a potassium chloroplatinate concentration of 20 μmol / L;

[0163] S5, mixing hydrazine hydrate and water to form a second solution, wherein the molar concentration of hydrazine hydrate in the second solution is 0.01 mol / L;

[0164] S6, soaking the substrate prepared in S3 in the first solution for 20 minutes, then transferring it to the second solution, heating it to 60° C., reacting it for 30 minutes, and depositing a catalytic layer on the surface of the substrate;

[0165] S7, repeating step S6 three times to obtain a hydrolysis hydrogen production membrane, wherein the thickness of the support layer in the substrate is 520 μm; the material of the catalytic layer is platinum, and the platinum content in the catalytic layer is 0.16 mg / cm 2 .

[0166] Example 8

[0167] The hydrolysis hydrogen production membrane is prepared according to the method of Example 7, except that steps S4 to S6 are different, including:

[0168] S4, mixing water and palladium chloride, and adding 0.2 mol / L HCl to adjust the pH of the solution until the palladium chloride is completely dissolved, to form a first solution with a palladium chloride concentration of 20 μmol / L;

[0169] S5, mixing sodium hypophosphite, ammonia water and water to form a second solution, wherein the molar concentration of sodium hypophosphite in the second solution is 0.02 mol / L, and the molar concentration of ammonia water is 5 mmol / L;

[0170] S6, soaking the substrate prepared in S3 in the first solution for 20 minutes, then transferring it to the second solution, heating it to 50° C., reacting it for 30 minutes, and depositing a catalytic layer on the surface of the substrate;

[0171] S7, repeating step S6 three times to obtain a hydrolysis hydrogen production membrane, wherein the material of the catalyst layer is palladium, and the palladium content in the catalyst layer is 0.4 mg / cm 2 .

[0172] Example 9

[0173] The hydrolysis hydrogen production membrane is prepared according to the method of Example 1, except that steps S4 to S6 are different, including:

[0174] S4, mixing water and palladium chloride, and adding 0.5 mol / L NaOH to adjust the pH of the solution until the palladium chloride is completely dissolved, to form a first solution with a palladium chloride concentration of 20 μmol / L;

[0175] S5, mixing hydrazine hydrate, ethylenediamine and water to form a second solution, wherein the molar concentration of hydrazine hydrate in the second solution is 0.05 mol / L, and the molar concentration of ethylenediamine is 5 mmol / L;

[0176] S6, soaking the substrate prepared in S3 in the first solution for 10 minutes, then transferring it to the second solution, heating it to 60° C., reacting it for 30 minutes, and depositing a catalytic layer on the surface of the substrate;

[0177] S7, repeating step S6 for five times to obtain a hydrolysis hydrogen production membrane, wherein the material of the catalyst layer is palladium, and the palladium content in the catalyst layer is 0.3 mg / cm 2 .

[0178] Example 10

[0179] The hydrolysis hydrogen production membrane is prepared according to the method of Example 1, except that steps S4 to S6 are different, including:

[0180] S4, mixing water and palladium chloride, and adding 0.2 mol / L NaOH to adjust the pH of the solution until the palladium chloride is completely dissolved, to form a first solution with a palladium chloride concentration of 20 μmol / L;

[0181] S5, mixing hydrazine hydrochloride and water to form a second solution, wherein the molar concentration of hydrazine hydrate in the second solution is 0.02 mol / L;

[0182] S6, soaking the substrate prepared in S3 in the first solution for 10 minutes, then transferring it to the second solution, heating it to 60° C., reacting it for 30 minutes, and depositing a catalytic layer on the surface of the substrate;

[0183] S7, repeating step S6 for five times to obtain a hydrolysis hydrogen production membrane, wherein the material of the catalyst layer is palladium, and the palladium content in the catalyst layer is 0.35 mg / cm 2 .

[0184] Embodiment 11

[0185] The hydrolysis hydrogen production membrane was prepared according to the method of Example 1, except that in step S7, the catalyst layer was repeatedly formed to obtain a catalyst layer with a platinum content of 1.2 mg / cm 2 .

[0186] Example 12

[0187] The hydrolysis hydrogen production membrane was prepared according to the method of Example 1, except that in step S7, the catalyst layer was repeatedly formed to obtain a platinum content of 0.005 mg / cm 2 .

[0188] Comparative Example 1

[0189] The substrate prepared in Example 1 is directly used as a hydrolysis hydrogen production membrane.

[0190] Comparative Example 2

[0191] The substrate prepared in Example 3 is directly used as a hydrolysis hydrogen production membrane.

[0192] Comparative Example 3

[0193] The substrate prepared in Example 5 is directly used as a hydrolysis hydrogen production membrane.

[0194] Comparative Example 4

[0195] The substrate prepared in Example 7 is directly used as a hydrolysis hydrogen production membrane.

[0196] The hydrogen production membranes prepared in the above examples and comparative examples were assembled to form a water electrolysis hydrogen production device, wherein the electrolyte was 30% KOH solution, the cathode was Raney nickel, and the anode was nickel mesh.

[0197] The above-mentioned water electrolysis hydrogen production device is subjected to performance testing, and the testing method includes:

[0198] Bubble point test: reference standard GB / T 32361-2015.

[0199] Surface resistance test: refer to patent CN 104678173 B.

[0200] Test of hydrogen concentration in oxygen: reference standard GB / T 19774-2005.

[0201] The test results are shown in Table 1.

[0202] Table 1

[0203]

[0204] From the above table we can see that:

[0205] (1) Compared with Examples 11-12, it can be seen that the present application controls the content of the catalyst in the catalytic layer. If the content of the weak catalyst is relatively low, it is difficult to achieve a catalytic reaction, thereby failing to reduce the hydrogen content in oxygen. If the content of the catalyst is relatively high, the production process will be complicated and the cost will be greatly increased.

[0206] (4) Compared with Comparative Examples 1, 2, 3 and 4, Examples 1, 3, 4 and 7 show that the surface of the diaphragm in the present application has a catalytic layer. When hydrogen enters the anode side or oxygen enters the cathode side, hydrogen and oxygen can undergo a catalytic reaction at the catalytic layer, thereby reducing the mixing of hydrogen and oxygen during the hydrogen production process by hydrolysis and improving the safety of the hydrogen production process.

[0207] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0208] The above-described embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be construed as limiting the scope of the application. It should be noted that, for a person of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the attached claims.

Claims

1. A hydrolysis hydrogen production membrane, characterized in that: The hydrolysis hydrogen production membrane comprises a substrate and a catalytic layer arranged on at least one side surface of the substrate, and the catalytic layer is used for catalyzing the reaction of hydrogen and oxygen.

2. The hydrolysis hydrogen production membrane according to claim 1, characterized in that: The hydrolysis hydrogen production membrane meets at least one of the following conditions: (1) The catalyst contained in the catalytic layer includes at least one of platinum, palladium, rhodium, iridium and ruthenium; (2) The thickness of the substrate is 50 μm to 600 μm; (3) The catalyst content in the catalytic layer is 0.01 g / cm 2 ~1mg / cm 2 .

3. The hydrolysis hydrogen production membrane according to claim 1, characterized in that: The substrate satisfies at least one of the following conditions: (1) The substrate contains a pore structure; optionally, the porosity of the substrate is 40% to 60%, and the median pore size of the pore structure is 200 nm to 1000 nm; (2) The substrate contains inorganic particles; optionally, the mass proportion of the inorganic particles in the substrate is 50% to 90%; Optionally, the material of the inorganic particles includes oxides; Optionally, the material of the inorganic particles includes at least one of silicon dioxide, titanium dioxide and zirconium dioxide; Optionally, the volume average particle size Dv50 of the inorganic particles is 10 nm to 500 nm.

4. The hydrolysis hydrogen production membrane according to any one of claims 1 to 3, characterized in that: The substrate comprises a support layer and a base material layer arranged on both side surfaces of the support layer; Optionally, the material of the support layer includes at least one of polyphenylene sulfide, polyetheretherketone and polytetrafluoroethylene; Optionally, the material of the substrate layer includes polysulfone resin; Optionally, the material of the substrate layer includes at least one of sulfonated polysulfone, polyethersulfone, poly(arylene ether sulfone), tertiary aminated polysulfone and chloromethyl polysulfone.

5. A method for preparing a hydrolysis hydrogen production membrane, characterized in that: The preparation method of the hydrolysis hydrogen production membrane comprises: A catalytic layer is formed on at least one surface of the substrate, and the catalytic layer is used for catalyzing the reaction of hydrogen and oxygen.

6. The method for preparing a membrane for producing hydrogen by hydrolysis as claimed in claim 5, characterized in that: The method for forming the catalytic layer comprises: preparing a first solution containing a catalytic raw material; preparing a second solution containing a reducing agent and a complexing agent; Immersing the substrate in the first solution, then transferring the substrate to the second solution, and depositing the catalytic layer on at least one side of the substrate; Optionally, the catalytic raw material includes at least one of a platinum salt, a palladium salt, a rhodium salt, an iridium salt and a ruthenium salt; Optionally, the catalytic raw material includes at least one of platinum chloride, palladium chloride, potassium chloroplatinate, rhodium chloride, iridium chloride and ruthenium chloride; Optionally, the molar concentration of the catalytic raw material in the first solution is 10 μmol / L~2000 μmol / L.

7. The method for preparing a membrane for producing hydrogen by hydrolysis as claimed in claim 6, characterized in that: The preparation method of the hydrolysis hydrogen production membrane meets at least one of the following conditions: (1) The substrate is immersed in the first solution for 5 min to 30 min; (2) The deposition temperature is 25°C to 120°C, and the deposition time is 5 min to 120 min.

8. The method for preparing a membrane for producing hydrogen by hydrolysis as claimed in claim 6, characterized in that: The method for preparing the hydrolysis hydrogen production membrane also satisfies at least one of the following conditions: (1) The reducing agent includes at least one of hydrazine hydrochloride, hydrazine hydrate, ammonia water, sodium hypophosphite and sodium borohydride; (2) the complexing agent includes at least one of ethylenediamine, ammonia, ethanolamine and citric acid; (3) The mass concentration of the reducing agent in the second solution is 0.1 mol / L to 1 mol / L; (4) The mass concentration of the complexing agent in the second solution is 0.1 mol / L~1 mol / L.

9. The method for preparing a membrane for producing hydrogen by hydrolysis according to any one of claims 6 to 8, characterized in that: The method for preparing the substrate comprises: preparing a slurry containing inorganic particles, a polysulfone resin, a porogen and a solvent; The slurry is used to form a slurry layer on the surface of the support layer, and after solidification, the slurry layer is converted into a substrate layer to form a substrate, wherein the substrate includes a support layer and substrate layers arranged on both sides of the support layer; Optionally, the mass ratio between the inorganic particles and the solvent is 1:(0.8-1.5); Optionally, the mass ratio between the polysulfone resin and the inorganic particles is 1:(1-8); Optionally, the mass ratio between the porogen and the resin is 1:(0.01-0.1); Optionally, the solidification temperature is 5°C to 60°C; Optionally, the solvent includes at least one of N,N dimethylformamide, N,N dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, ethanol and water.

10. A hydrogen production device by electrolysis of water, characterized in that: The water electrolysis hydrogen production device comprises the water electrolysis hydrogen production diaphragm described in any one of claims 1-4 or the water electrolysis hydrogen production diaphragm prepared by the preparation method of the water electrolysis hydrogen production diaphragm described in any one of claims 5-9.

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