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

Abstract

The present application belongs to the technical field of water electrolysis hydrogen production, and provides a water electrolysis hydrogen production diaphragm, a preparation method thereof, and a water electrolysis hydrogen production device. The water electrolysis hydrogen production diaphragm includes a substrate and a catalytic layer disposed on at least one side of the substrate. The catalytic layer is used to catalyze the reaction of hydrogen and oxygen. The surface of the diaphragm of the present application has a catalytic layer. When hydrogen enters the anode side or oxygen enters the cathode side, the hydrogen and oxygen can undergo a catalytic reaction at the catalytic layer, thereby reducing the mixing of hydrogen and oxygen during the water electrolysis hydrogen production process and improving the safety of the hydrogen production process.

Description

Technical Field

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

[0002] During the alkaline electrolysis of water to produce hydrogen, a small amount of hydrogen can diffuse from the cathode side through the diaphragm to the anode side. Alternatively, if the gas-liquid separation during the electrolyte circulation process is incomplete, some hydrogen in the electrolyte can enter the anode side, resulting in a certain concentration of hydrogen on the anode side, affecting the safety of the electrolysis device. Furthermore, oxygen on the anode side can also penetrate the diaphragm and enter the cathode side, which still poses a safety issue and reduces the purity of the discharged hydrogen, requiring further purification. Therefore, improving the safety of the hydrogen production process by electrolysis of water 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 membrane, 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 arranged on at least one side of the substrate, and 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 thickness of the substrate is 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 substrate has a porosity of 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 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 surface 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 to 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 to 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, polysulfone resin, porogen and 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 base. The base 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 of the porogen to the resin is 1:(0.01-0.1).

[0037] Optionally, the solidification temperature is 5°C~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 hydrolysis hydrogen production diaphragm as described in the first aspect or the hydrolysis hydrogen production diaphragm prepared by the preparation method of the hydrolysis hydrogen production diaphragm as described in the second aspect.

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

[0041] This application relates to a diaphragm design for use in water electrolysis hydrogen production, wherein the diaphragm has a catalytic layer on its surface. When hydrogen is generated on the anode side or oxygen is generated on the cathode side, these gases 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, and thus significantly improving the safety of the water electrolysis hydrogen production process. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is a schematic structural diagram 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 embodiment and example, the application is further described in detail These embodiment and example are only used to illustrate the application and are not used to limit the scope of the application, and the purpose of providing these embodiment and example is to make the understanding of the disclosure of the application more thorough and comprehensive. It should also be understood that the application can be implemented in many different forms and is not limited to the embodiment and example described herein. Those skilled in the art can make various changes or modifications without violating the connotation of the application, and the equivalent form obtained also falls within the protection scope of the application. In addition, in the description below, a large amount of specific details are given in order to provide a more complete understanding of the application, and it should be understood that the 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 pertains. The terms used herein in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application.

[0047] In this application, the terms "optionally," "optional," and "optional" mean optional or dispensable, i.e., they refer to either option being selected from two parallel options: "with" or "without." If a technical solution contains multiple "optional" clauses, each "optional" clause is independent unless otherwise specified and there are no contradictions or constraints.

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

[0049] In this 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 this application, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​within the numerical interval is deemed to be continuous and includes the two numerical endpoints of the numerical interval (i.e., the minimum and maximum values), as well as each numerical value between the two numerical endpoints. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, it includes the two endpoint integers of the numerical range, as well as each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe a feature or characteristic, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. "Numerical interval" is broadly allowed to include 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 in their entirety and for all purposes. When 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 cited documents are involved in this application, the examples and preferred embodiments of the cited relevant technical features may also be incorporated into this application as references, but are limited to the ability to implement 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 adaptively amended according to the description in this application.

[0052] Conventional technologies reduce the gas permeability of the diaphragm to prevent mixing of hydrogen and oxygen. For example, conventional technologies increase the diaphragm's bubble point to improve its gas barrier properties, preventing hydrogen from crossing the membrane and reducing the concentration of hydrogen in the oxygen. Specifically, conventional technologies create composite diaphragms with a certain degree of crosslinking (3% to 10%), increasing the bubble point to improve gas barrier properties. Alternatively, conventional technologies create multilayered hydrogen-producing diaphragms, enhancing their gas barrier properties through a multilayered structure to reduce the concentration of hydrogen in the oxygen. While increasing the diaphragm's gas permeability can reduce the rate of mixing between hydrogen and oxygen, the gases still mix through the diaphragm. After the electrolysis process has run for a while, the gas mixture reaches a certain concentration, posing safety concerns.

[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 catalytic layer 120 disposed on at least one side of the substrate 110 , and the catalytic layer 120 is used to catalyze the reaction of hydrogen and oxygen.

[0054] The surface of the diaphragm in this 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 1.0 mg / cm 2 The present application selects the catalyst content in the catalytic layer as described 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.

[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. By introducing inorganic particles into the substrate, the present invention can improve the hydrophilicity and stability of the diaphragm, 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, as 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] A second aspect of the present application provides a method for preparing a hydrolysis hydrogen production membrane, the method 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 membrane 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 understood that the formation method can be appropriately selected based on the type of catalyst layer. For example, it can be chemical deposition or physical deposition. Optionally, the catalyst layer can be formed by 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 surface of the substrate.

[0079] In some embodiments, a pH adjuster is further added to the first solution. Optionally, the pH adjuster comprises 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, 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 catalytic 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 to 1 mol / L, for example, 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, polysulfone resin, porogen and 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 base. The base 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 of the porogen to 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, 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] Adding polysulfone resin and porogen into the first dispersion and dispersing them uniformly to form the slurry.

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

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

[0104] In some embodiments, the solidification method includes: soaking the support layer having 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 at a mass ratio of inorganic particles to solvent of 1:(0.8-1.5), stirring at 500 rpm-2500 rpm for 1 h-5 h to form a first dispersion;

[0107] S2. Add polysulfone resin and porogen to the first dispersion, wherein the mass ratio of polysulfone resin to inorganic particles is 1:(1-8), and the mass ratio of porogen to resin is 1:(0.01-0.1), and disperse at 500 rpm to 3000 rpm for 4 h to 24 h to form the slurry;

[0108] S3, coating the slurry on the surface of the support layer to form a slurry layer, and immersing the support layer in a coagulation bath at 5°C to 60°C to coagulate, so that the slurry layer is converted 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] 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.

[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 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 with reference to the examples. It should be understood that these examples are intended to illustrate the present application only 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 manuals or conventional conditions in this area, or according to the conditions recommended by the manufacturer, or with reference to experimental methods known in the art.

[0116] Example 1

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

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

[0119] S3. The slurry was applied to both sides of the polyphenylene sulfide mesh, allowed to stand in air for pre-evaporation, and then immersed in 25°C water for phase inversion. After curing, a substrate was obtained. The porosity of the substrate was 58%, and the median pore diameter of the pore structure was 500 nm.

[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] A hydrolysis hydrogen production membrane was prepared according to the method of Example 1, except that steps S4 to S6 were 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 catalytic layer is palladium, and the palladium content in the catalytic 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 rpm for 5 h to form a first dispersion;

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

[0133] S3. The slurry was applied to both sides of the polyphenylene sulfide mesh, allowed to stand in air for pre-evaporation, and then immersed in 25°C water for phase inversion. After solidification, a substrate was obtained. The porosity of the substrate was 52%, and the median pore diameter of the pore structure was 250 nm.

[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] A hydrolysis hydrogen production membrane was prepared according to the method of Example 3, except that steps S4 to S6 were 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 catalytic layer is palladium, and the palladium content in the catalytic layer is 0.13 mg / cm 2 .

[0144] Example 5

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

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

[0147] S3. The slurry was applied to both sides of the polyphenylene sulfide mesh, allowed to stand in air for pre-evaporation, and then immersed in 25°C water for phase inversion. After curing, a substrate was obtained. The porosity of the substrate was 62%, and the median pore diameter of the pore structure was 280 nm.

[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] A hydrolysis hydrogen production membrane was prepared according to the method of Example 5, except that steps S4 to S6 were 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 catalytic layer is palladium, and the palladium content in the catalytic layer is 0.15 mg / cm 2 .

[0158] Example 7

[0159] S1, dispersing 100g of 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 25 g of polysulfone resin to the first dispersion, fully dissolve it at 2500 rpm at room temperature for 4 h, add 1 g of polyvinyl pyrrolidone and continue stirring for 1 h to form a slurry;

[0161] S3, coating the slurry on both sides of the polyphenylene sulfide mesh, allowing it to stand in air for pre-evaporation, and then immersing it in water at 25°C for phase inversion. After curing, a substrate is obtained. The porosity of the substrate is 56%, and the median pore diameter of the pore structure is 230 nm;

[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] A hydrolysis hydrogen production membrane was prepared according to the method of Example 7, except that steps S4 to S6 were 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, aqueous ammonia, 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 aqueous ammonia 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, repeat step S6 three times to obtain a hydrolysis hydrogen production membrane, wherein the material of the catalytic layer is palladium, and the palladium content in the catalytic layer is 0.4 mg / cm 2 .

[0172] Example 9

[0173] A hydrolysis hydrogen production membrane was prepared according to the method of Example 1, except that steps S4 to S6 were 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, repeat step S6 five times to obtain a hydrolysis hydrogen production membrane, wherein the material of the catalytic layer is palladium, and the palladium content in the catalytic layer is 0.3 mg / cm 2 .

[0178] Example 10

[0179] A hydrolysis hydrogen production membrane was prepared according to the method of Example 1, except that steps S4 to S6 were 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, repeat step S6 five times to obtain a hydrolysis hydrogen production membrane, wherein the material of the catalytic layer is palladium, and the palladium content in the catalytic layer is 0.35 mg / cm 2 .

[0184] Example 11

[0185] The hydrolysis hydrogen production membrane was prepared according to the method of Example 1, with the only difference being that in step S7, the catalyst layer was formed repeatedly to obtain 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, with the only difference being that in step S7, the catalyst layer was formed repeatedly 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 hydrolysis hydrogen production membranes prepared in the above examples and comparative examples were assembled to form a water electrolysis hydrogen production device, wherein the electrolyte used was 30% KOH solution, the cathode used was Raney nickel, and the anode used was nickel mesh.

[0197] The performance test of the above-mentioned water electrolysis hydrogen production device is carried out, and the test method includes:

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

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

[0200] Hydrogen concentration in oxygen test: Reference standard GB / T 19774-2005.

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

[0202] Table 1

[0203]

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

[0205] (1) Comparing Example 1 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 hydrolysis hydrogen production process and improving the safety of the hydrogen production process.

[0207] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned 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 merely represent several implementation methods of the present application. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present application. It should be noted that a person of ordinary skill in the art may make various modifications and improvements without departing from the spirit of the present application, and such modifications and improvements fall within the scope of protection of the present application. Therefore, the scope of protection of the present application shall be determined by the appended claims.

Claims

1. A hydrolysis hydrogen production membrane, characterized in that The hydrolysis hydrogen production membrane includes a substrate and a catalytic layer provided on at least one side of the substrate, wherein the catalytic layer is used to catalyze the reaction of hydrogen and oxygen; the substrate contains a porous structure and inorganic particles, wherein the material of the inorganic particles includes at least one of silicon dioxide, titanium dioxide and zirconium dioxide, and the mass proportion of the inorganic particles in the substrate is 50% to 90%; The preparation method of the hydrolysis hydrogen production membrane comprises: preparing a first solution containing a catalytic raw material; preparing a second solution containing a reducing agent and a complexing agent; 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 surface of the substrate.

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 porosity of the substrate is 40% to 60%, and the median pore diameter of the pore structure is 200nm to 1000nm.

4. The hydrolysis hydrogen production membrane according to claim 1, characterized in that The volume average particle size Dv50 of the inorganic particles is 10 nm to 500 nm.

5. The hydrolysis hydrogen production membrane according to any one of claims 1 to 4, characterized in that: The substrate comprises a supporting layer and base material layers arranged on both side surfaces of the supporting layer.

6. The hydrolysis hydrogen production membrane according to claim 5, characterized in that The material of the support layer includes at least one of polyphenylene sulfide, polyetheretherketone and polytetrafluoroethylene.

7. The hydrolysis hydrogen production membrane according to claim 5, characterized in that The material of the base material layer includes polysulfone resin.

8. The hydrolysis hydrogen production membrane according to claim 5, characterized in that The material of the substrate layer includes at least one of sulfonated polysulfone, polyethersulfone, poly(arylene ethersulfone), tertiary aminated polysulfone and chloromethyl polysulfone.

9. A method for preparing a membrane for producing hydrogen by hydrolysis, characterized in that: The preparation method of the hydrolysis hydrogen production membrane comprises: preparing a first solution containing a catalytic raw material; preparing a second solution containing a reducing agent and a complexing agent; Immersing a substrate in the first solution, then transferring the substrate to the second solution, and depositing a catalytic layer on at least one side of the substrate, wherein the catalytic layer is used to catalyze the reaction of hydrogen and oxygen; The substrate contains a porous structure and inorganic particles, the material of the inorganic particles includes at least one of silicon dioxide, titanium dioxide and zirconium dioxide, and the mass proportion of the inorganic particles in the substrate is 50% to 90%.

10. The method for preparing a membrane for producing hydrogen by hydrolysis according to claim 9, wherein: The catalytic raw material includes at least one of platinum salt, palladium salt, rhodium salt, iridium salt and ruthenium salt.

11. The method for preparing a membrane for producing hydrogen by hydrolysis according to claim 9, wherein: The catalytic raw material includes at least one of platinum chloride, palladium chloride, potassium chloroplatinate, rhodium chloride, iridium chloride and ruthenium chloride.

12. The method for preparing a membrane for producing hydrogen by hydrolysis according to claim 9, wherein: The molar concentration of the catalytic raw material in the first solution is 10 μmol / L to 2000 μmol / L.

13. The method for preparing a membrane for producing hydrogen by hydrolysis according to claim 9, wherein: 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 to 30 minutes; (2) The deposition temperature is 25°C to 120°C, and the deposition time is 5 minutes to 120 minutes.

14. The method for preparing a membrane for producing hydrogen by hydrolysis according to claim 9, wherein: The preparation method of the hydrolysis hydrogen production membrane also meets 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 comprises 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 to 1 mol / L.

15. The method for preparing a membrane for producing hydrogen by hydrolysis according to any one of claims 9 to 14, characterized in that: The preparation method of the substrate comprises: preparing a slurry containing inorganic particles, polysulfone resin, porogen and solvent; 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 base. The base includes a support layer and substrate layers arranged on both sides of the support layer.

16. The method for preparing a membrane for producing hydrogen by hydrolysis according to claim 15, wherein: The mass ratio between the inorganic particles and the solvent is 1:(0.8-1.5).

17. The method for preparing a membrane for producing hydrogen by hydrolysis according to claim 15, wherein: The mass ratio of the polysulfone resin to the inorganic particles is 1:(1-8).

18. The method for preparing a membrane for producing hydrogen by hydrolysis according to claim 15, wherein: The mass ratio between the porogen and the resin is 1:(0.01-0.1).

19. The method for preparing a membrane for producing hydrogen by hydrolysis according to claim 15, wherein: The solidification temperature is 5°C to 60°C.

20. The method for preparing a membrane for producing hydrogen by hydrolysis according to claim 15, wherein: The solvent includes at least one of N,N dimethylformamide, N,N dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, ethanol and water.

21. A water electrolysis hydrogen production device, characterized in that: The water electrolysis hydrogen production device includes the hydrolysis hydrogen production membrane according to any one of claims 1 to 8 or the hydrolysis hydrogen production membrane prepared by the preparation method of the hydrolysis hydrogen production membrane according to any one of claims 9 to 20.

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