Membrane electrode anode for electrolysis of water and method for producing same

Abstract

This application relates to the field of proton exchange membrane electrolysis for hydrogen production, and particularly to a membrane electrode anode for water electrolysis and its preparation method. The membrane electrode anode for water electrolysis includes a proton exchange membrane, an anode catalyst layer, a hydrogen elimination layer, and a hydrogen barrier layer. The anode catalyst layer is located on one side of the proton exchange membrane, the hydrogen elimination layer is located between the proton exchange membrane and the anode catalyst layer, and the hydrogen barrier layer is disposed on the side of the hydrogen elimination layer closest to the proton exchange membrane. The hydrogen elimination layer includes perfluorosulfonic acid resin, a hydrogen elimination catalyst, and a corrosion-resistant catalyst. The hydrogen barrier layer includes perfluorosulfonic acid resin and inorganic nanomaterials. The inorganic nanomaterials contained in the hydrogen barrier layer enable the hydrogen barrier layer to form dense and tortuous nanoscale channels, reducing the hydrogen permeability. The hydrogen elimination catalyst in the hydrogen elimination layer eliminates the hydrogen permeated from the hydrogen barrier layer by converting hydrogen into water, achieving efficient hydrogen barrier and long-lasting hydrogen elimination. At the same time, the addition of the corrosion-resistant catalyst further improves the durability of the membrane electrode anode.

Description

Technical Field

[0001] This application relates to the field of proton exchange membrane electrolysis for hydrogen production, and in particular to a membrane electrode anode for water electrolysis and its preparation method. Background Technology

[0002] Hydrogen energy, as a clean and efficient energy carrier, has attracted much attention in its production technology. Among them, proton exchange membrane (PEM) water electrolysis for hydrogen production has become a key development focus due to its advantages such as high efficiency, fast response, and good hydrogen purity. However, this technology still faces two major challenges in practical applications: First, the hydrogen permeation problem. During operation, hydrogen can permeate back from the high-voltage cathode side to the anode, which not only reduces hydrogen production efficiency but also mixes with oxygen at the anode, creating an explosion risk and accelerating the degradation of the membrane and catalyst. Second, the membrane electrode durability is insufficient. The anode is exposed to a high-potential, strongly acidic, and high-oxygen environment for a long time, which easily leads to problems such as catalyst corrosion and carrier degradation, resulting in performance decline.

[0003] Currently, a common approach to alleviate hydrogen permeation problems is to add a hydrogen removal layer to the membrane electrode assembly (MEA). Existing patents propose a four-layer structure: "anodic catalyst layer - insulating layer - hydrogen removal layer - proton exchange membrane." This structure utilizes the insulating layer to protect platinum and palladium-based hydrogen removal catalysts from oxidation and deactivation, while also ensuring proton conduction efficiency, thus improving the hydrogen removal stability of the MEA by more than 30%. However, this method only focuses on eliminating already permeated hydrogen and fails to strengthen the hydrogen barrier at its source, nor does it improve the durability of the anode itself.

[0004] Therefore, there is an urgent need to develop a membrane module that can simultaneously achieve efficient hydrogen blocking, long-term hydrogen removal, and significantly improve anode durability to solve the above problems. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, this application provides a membrane electrode anode for water electrolysis and its preparation method. The specific technical solution is as follows: On one hand, this application provides a membrane electrode anode for water electrolysis, comprising: Proton exchange membrane; An anode catalyst layer is located on one side of the proton exchange membrane; A hydrogen removal layer is located between the proton exchange membrane and the anode catalyst layer, and the hydrogen removal layer includes perfluorosulfonic acid resin, a hydrogen removal catalyst and a corrosion-resistant catalyst. A hydrogen barrier layer is disposed on the side of the hydrogen removal layer near the proton exchange membrane, and the hydrogen barrier layer includes perfluorosulfonic acid resin and inorganic nanomaterials.

[0006] In a possible implementation, the mass ratio between the perfluorosulfonic acid resin and the inorganic nanomaterial in the hydrogen barrier layer is (5~60):1.

[0007] In a possible implementation, the thickness of the hydrogen barrier layer ranges from 10 nm to 5 μm.

[0008] In a possible implementation, the mass ratio of the perfluorosulfonic acid resin, the hydrogen-eliminating catalyst, and the corrosion-resistant catalyst in the hydrogen-eliminating layer is (0.1~45):(0.5~3):(0.5~1.5).

[0009] In a possible implementation, the thickness of the hydrogen-removing layer ranges from 10 nm to 5 μm.

[0010] In a possible implementation, the membrane electrode anode satisfies at least one of the following characteristics: The inorganic nanomaterials include at least one of SiO2, nano TiO2, nano ZnO, nano ZrO2, nano Ta2O5, nano CeO2, nano Mo2O3, nano MgO, nano Nb2O5, and montmorillonite nanosheets; The corrosion-resistant catalyst includes at least one of platinum-based catalysts, palladium-based catalysts, noble metal-metal oxide composite catalysts, iridium-based oxide catalysts, and iridium-based conductive polymer composite catalysts. The corrosion-resistant catalyst has a particle size of 10~30nm; The hydrogen removal catalyst is a Pt-based catalyst, and the platinum content in the Pt-based catalyst is 10-100%.

[0011] On the other hand, this application provides a method for preparing a membrane electrode anode for water electrolysis as described in any of the above embodiments, the method comprising: S1: Obtain the slurry for the proton exchange membrane and anode catalyst layer; S2: Mix perfluorosulfonic acid resin, hydrogen removal catalyst, corrosion-resistant catalyst and first solvent to obtain hydrogen removal layer slurry; S3: Mix perfluorosulfonic acid resin, inorganic nanomaterials, a second solvent and a dispersant to obtain a hydrogen barrier layer slurry; S4: The hydrogen barrier layer slurry, the hydrogen elimination layer slurry, and the anode catalyst layer slurry are sequentially coated onto the proton exchange membrane and dried after coating to obtain the membrane electrode anode for water electrolysis; in the membrane electrode anode for water electrolysis, the hydrogen elimination layer is located between the proton exchange membrane and the anode catalyst layer, and the hydrogen barrier layer is disposed on the side of the hydrogen elimination layer closer to the proton exchange membrane.

[0012] In a possible implementation, the mixing of the perfluorosulfonic acid resin, inorganic nanomaterials, second solvent, and dispersant includes: S31: Inorganic nanomaterials are mixed with a second solvent and subjected to a first dispersion treatment to disperse the inorganic nanomaterials, thereby obtaining a suspension; S32: Mix the suspension, the perfluorosulfonic acid resin and the dispersant to obtain a hydrogen barrier slurry.

[0013] In a possible implementation, the method satisfies at least one of the following characteristics: In the hydrogen-removing slurry, the mass ratio of the perfluorosulfonic acid resin, the hydrogen-removing catalyst, the corrosion-resistant catalyst, and the first solvent is (0.1~45):(0.5~3):(0.5~1.5):(10~250); In the hydrogen barrier slurry, the mass ratio of the perfluorosulfonic acid resin, the inorganic nanomaterial, the second solvent, and the dispersant is (5~60):1:(1~6):(0.1~3). The dispersant is a nonionic surfactant or a silane coupling agent.

[0014] In a possible implementation, the method satisfies at least one of the following characteristics: The particle size D50 of the hydrogen barrier layer slurry, the hydrogen elimination layer slurry, and the anode catalyst layer slurry is all less than 1 μm; The solid content of the hydrogen barrier layer slurry, the hydrogen elimination layer slurry, and the anode catalyst layer slurry is all less than 50 wt%.

[0015] Based on the above technical solution, this application has the following beneficial effects: The membrane electrode anode for water electrolysis disclosed in this application comprises a proton exchange membrane, an anode catalyst layer, a hydrogen removal layer, and a hydrogen barrier layer. The anode catalyst layer is located on one side of the proton exchange membrane, the hydrogen removal layer is located between the proton exchange membrane and the anode catalyst layer, and the hydrogen barrier layer is disposed on the side of the hydrogen removal layer closest to the proton exchange membrane. The hydrogen removal layer comprises perfluorosulfonic acid resin, a hydrogen removal catalyst, and a corrosion-resistant catalyst. The hydrogen barrier layer comprises perfluorosulfonic acid resin and inorganic nanomaterials. The inorganic nanomaterials in the hydrogen barrier layer create dense and tortuous nanoscale channels, increasing the path and resistance of hydrogen passage and reducing hydrogen permeability. Simultaneously, the inorganic nanomaterials physically block hydrogen, further reducing hydrogen permeability. Furthermore, the hydrogen removal catalyst in the hydrogen removal layer eliminates hydrogen permeating from the hydrogen barrier layer by converting hydrogen into water, achieving highly efficient hydrogen barrier and long-lasting hydrogen removal. The addition of the corrosion-resistant catalyst further improves the durability of the membrane electrode anode. Detailed Implementation

[0016] The technical solutions in the embodiments of this application will be clearly and completely described below with reference to the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0017] For the terms defined below, unless a different definition is given elsewhere in the claims or this specification, these definitions shall apply. All numerical values, whether explicitly indicated or not, are defined herein as being modified by the term "about." The term "about" generally refers to a range of numerical values ​​that a person skilled in the art would consider equivalent to the stated values ​​to produce substantially the same properties, functions, results, etc. A range of numerical values ​​indicated by a low value and a high value is defined as including all numerical values ​​included within that range and all subranges included within that range.

[0018] It should be noted that the terms "first," "second," etc., in the specification and claims of this application are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be interchanged where appropriate so that the embodiments of this application described herein can be implemented in orders other than those described herein. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion.

[0019] The following describes a membrane electrode anode for water electrolysis provided in an embodiment of this application, comprising: Proton exchange membrane; The anode catalyst layer is located on one side of the proton exchange membrane; The hydrogen removal layer is located between the proton exchange membrane and the anode catalyst layer. The hydrogen removal layer includes perfluorosulfonic acid resin, hydrogen removal catalyst and corrosion-resistant catalyst. The hydrogen barrier layer is disposed on the side of the hydrogen elimination layer near the proton exchange membrane, and the hydrogen barrier layer includes perfluorosulfonic acid resin and inorganic nanomaterials.

[0020] In some embodiments, the mass ratio of perfluorosulfonic acid resin to inorganic nanomaterials in the hydrogen barrier layer is (5~60):1. A suitable mass ratio of resin to inorganic nanomaterials allows the resin to form a three-dimensional continuous network, encapsulating and connecting the inorganic materials, while the inorganic nanomaterials form a framework that is in contact with or close to each other. This balances the proton conductivity and hydrogen barrier performance of the hydrogen barrier layer, while also providing sufficient mechanical strength and thermochemical stability. Preferably, the mass ratio of perfluorosulfonic acid resin to inorganic nanomaterials in the hydrogen barrier layer is (16~60):1. More preferably, the mass ratio of perfluorosulfonic acid resin to inorganic nanomaterials in the hydrogen barrier layer is 16:1.

[0021] In some embodiments, the thickness of the hydrogen barrier layer ranges from 10 nm to 5 μm. The upper limit of the hydrogen barrier layer thickness can be, but is not limited to, 5 μm, 4 μm, 3 μm, etc., and the lower limit can be, but is not limited to, 10 nm, 11 nm, 12 nm, etc.; understandably, the thickness of the hydrogen barrier layer can also be any value within the above range, which will not be enumerated here. Increasing the thickness of the hydrogen barrier layer will further lengthen the path length and resistance of hydrogen molecule diffusion, thereby significantly reducing the cross-permeability of hydrogen. However, excessive thickness will also increase the transport distance of protons from the catalyst layer to the proton exchange membrane, thereby increasing the proton conduction ohmic resistance of the system, leading to an increase in the electrolytic cell voltage and a reduction in electrolysis efficiency. Furthermore, excessive coating thickness will result in greater internal stress in the hydrogen barrier layer, making it prone to cracking or peeling from the substrate, affecting the durability of the hydrogen barrier layer.

[0022] In some embodiments, the mass ratio of perfluorosulfonic acid resin, hydrogen elimination catalyst, and corrosion-resistant catalyst in the hydrogen elimination layer is (0.1~45):(0.5~3):(0.5~1.5). An excessively high proportion of the hydrogen elimination catalyst may lead to intensified side reactions, competing with the main reaction (oxygen evolution reaction) for electrons and protons, resulting in a decrease in the oxygen production efficiency of the membrane module. The ratio of the hydrogen elimination catalyst to the corrosion-resistant catalyst affects the pore structure of the hydrogen elimination layer. A suitable ratio of perfluorosulfonic acid resin, hydrogen elimination catalyst, and corrosion-resistant catalyst helps to form continuous gas and proton channels, thereby ensuring that hydrogen can quickly reach the hydrogen elimination catalyst sites and be oxidized. Preferably, the mass ratio of perfluorosulfonic acid resin, hydrogen elimination catalyst, and corrosion-resistant catalyst in the hydrogen elimination layer is (2~8):(1~2):(0.5~1.5). More preferably, the mass ratio of perfluorosulfonic acid resin, hydrogen elimination catalyst, and corrosion-resistant catalyst in the hydrogen elimination layer is 5.77:1.92:1.

[0023] In some embodiments, the thickness of the hydrogen removal layer ranges from 10 nm to 5 μm. The upper limit of the hydrogen removal layer thickness can be, but is not limited to, 5 μm, 4 μm, 3 μm, etc., and the lower limit can be, but is not limited to, 10 nm, 11 nm, 12 nm, etc.; understandably, the thickness of the hydrogen removal layer can also be any value within the above range, which will not be enumerated here. By limiting this thickness range, the hydrogen removal layer has more catalytically active sites, thus ensuring complete removal of hydrogen. At the same time, it avoids the problem that excessive thickness may lengthen the proton transport path from the membrane to the anode catalyst layer, leading to a decrease in the electrolysis efficiency of the membrane module. Furthermore, an excessively thick hydrogen removal layer is more prone to cracking, thus reducing the durability of the membrane module.

[0024] In some embodiments, the inorganic nanomaterials include at least one selected from SiO2, nano-TiO2, nano-ZnO, nano-ZrO2, nano-Ta2O5, nano-CeO2, nano-Mo2O3, nano-MgO, nano-Nb2O5, and montmorillonite nanosheets. These inorganic nanomaterials exhibit good electrical conductivity and can bond well with perfluorosulfonic acid resins to form continuous proton channels. Preferably, the inorganic nanomaterial is SiO2 or montmorillonite nanosheets. More preferably, the inorganic nanomaterial is montmorillonite nanosheets. Montmorillonite nanosheets have a sheet-like structure, which makes the pathway in the hydrogen barrier layer more tortuous and longer, greatly reducing hydrogen permeability. Compared with spherical particles, montmorillonite nanosheets more easily form a dense barrier layer with low porosity and no through-channels. Furthermore, the main component of montmorillonite is aluminosilicate, which has good thermal stability and chemical inertness in acidic environments, improving the stability of the hydrogen barrier layer, and its cost is low.

[0025] In some embodiments, the packing density of the inorganic nanomaterials is 1.5~2.0 g / cm³. 3 The upper limit of the packing density of inorganic nanomaterials can be, but is not limited to, 2.0 g / cm³. 3 1.9g / cm 3 1.8g / cm 3 The lower limit of the packing density of inorganic nanomaterials can be, but is not limited to, 1.5 g / cm³. 3 1.6g / cm 3 1.7g / cm 3 Etc.; understandably, the packing density of inorganic nanomaterials can also be any value within the above range, which will not be enumerated here. Preferably, the packing density of inorganic nanomaterials is 1.7~1.9 g / cm³. 3 Further preferably, the packing density of the inorganic nanomaterial is 1.8 g / cm³. 3The packing density of inorganic nanomaterials affects the porosity and tortuosity of the diffusion path of the hydrogen barrier layer. A suitable packing density of inorganic nanomaterials results in a dense arrangement of inorganic nanoparticles, low porosity, and high tortuosity in the hydrogen barrier layer, which greatly reduces the permeability of hydrogen.

[0026] In some embodiments, the particle size of the inorganic nanomaterials is 1~100 nm. If the particle size of the inorganic nanomaterials is too large, it will cause the hydrogen barrier layer to form large pores, thus reducing the hydrogen barrier effect, while if the particle size is too small, it will cause pore blockage, hindering the transport of water and oxygen.

[0027] In some embodiments, the corrosion-resistant catalyst includes at least one selected from platinum-based catalysts, palladium-based catalysts, noble metal-metal oxide composite catalysts, iridium-based oxide catalysts, and iridium-conductive polymer composite catalysts. Limiting the types of corrosion-resistant catalysts described above improves the electrochemical durability of the hydrogen removal layer while ensuring hydrogen removal efficiency. Preferably, the corrosion-resistant catalyst is a noble metal-metal oxide composite catalyst. Specifically, the corrosion-resistant catalyst is cerium dioxide. Ce is present in the crystal lattice of cerium dioxide. 3+ / Ce 4+ The reversible redox pair has excellent oxygen storage / release capabilities. Its surface oxygen vacancies can efficiently capture and eliminate free radicals, thereby providing a more stable reaction microenvironment for the hydrogen elimination catalyst and slowing down its oxidation and dissolution.

[0028] In some embodiments, the density of the corrosion-resistant catalyst is 6-8 g / cm³. 3 The upper limit of the density of corrosion-resistant catalysts can be, but is not limited to, 8.0 g / cm³. 3 7.9g / cm 3 7.8g / cm 3 The lower limit of the density of corrosion-resistant catalysts can be, but is not limited to, 6 g / cm³. 3 6.1g / cm 3 6.2g / cm 3 Etc.; understandably, the density of the corrosion-resistant catalyst can also be any value within the above range, which will not be enumerated here. Preferably, the density of the corrosion-resistant catalyst is 7.13 g / cm³. 3 Limiting the density range described above helps to form a predictable and optimized mesoporous structure for the hydrogen removal layer, facilitating oxygen removal and water transport.

[0029] In some embodiments, the specific surface area of ​​the corrosion-resistant catalyst is 85-95 m². 2 / g. The upper limit of the specific surface area of ​​the corrosion-resistant catalyst can be, but is not limited to, 95m². 2 / g, 94m 2 / g, 93m 2 / g, etc., the lower limit of the specific surface area of ​​corrosion-resistant catalysts can be, but is not limited to, 85m².2 / g, 86m 2 / g, 87m 2 / g, etc.; understandably, the specific surface area of ​​the corrosion-resistant catalyst can also be any value within the above range, which will not be enumerated here. Preferably, the specific surface area of ​​the corrosion-resistant catalyst is 90.86 g / cm³. 3 A suitable specific surface area results in a larger and tighter contact interface with the resin, which is conducive to the formation of more continuous and permeable proton transport channels. A higher specific surface area indicates a higher concentration of oxygen vacancies on the surface, thus improving the durability of the hydrogen removal layer.

[0030] In some embodiments, the particle size of the corrosion-resistant catalyst is 10-30 nm. The upper limit of the particle size of the corrosion-resistant catalyst can be, but is not limited to, 30 nm, 29 nm, 28 nm, etc., and the lower limit can be, but is not limited to, 10 nm, 11 nm, 12 nm, etc.; understandably, the particle size of the corrosion-resistant catalyst can also be any value within the above range, which will not be enumerated here. Limiting the particle size range can further increase the concentration of oxygen vacancies on its surface defects, thereby improving the oxygen storage capacity and thus enhancing the durability of the hydrogen removal catalyst.

[0031] In some embodiments, the hydrogen removal catalyst is a platinum-based catalyst. Specifically, the platinum-based catalyst is a platinum black catalyst. Platinum black catalysts exhibit high catalytic activity and good stability for the hydrogen oxidation reaction, and are resistant to high-potential corrosion.

[0032] In some embodiments, the platinum content in the platinum-based catalyst is 10-100%. The upper limit of the platinum content in the platinum-based catalyst can be, but is not limited to, 100%, 97%, 95%, etc., and the lower limit can be, but is not limited to, 10%, 11%, 12%, etc.; understandably, the platinum content in the platinum-based catalyst can also be any value within the above range, which will not be enumerated here. Preferably, the platinum content in the platinum-based catalyst is 100%. Increasing the noble metal loading in the platinum-based catalyst can reduce the electrode thickness and decrease mass transfer resistance.

[0033] Specifically, the electrochemically active surface area (ECSA) of the platinum-based catalyst is 10–30 m² / gPt. A higher ECSA value results in higher platinum utilization and better nanoparticle dispersion. Preferably, the ECSA of the platinum-based catalyst is 25–30 m² / gPt.

[0034] In some embodiments, the anode catalyst layer includes an oxygen evolution reaction catalyst and a perfluorosulfonic acid resin.

[0035] Specifically, the oxygen evolution reaction catalyst is a noble metal oxide catalyst. More specifically, the noble metal oxide catalyst is an iridium oxide catalyst. More specifically, the iridium content of the iridium oxide catalyst is 70-80 wt%. Preferably, the iridium content of the iridium oxide catalyst is 77 wt%.

[0036] In some embodiments, the mass ratio of oxygen evolution reaction catalyst to perfluorosulfonic acid resin in the anode catalyst layer is 1:3.

[0037] This invention incorporates a hydrogen removal layer and a hydrogen barrier layer in the anode of a water electrolysis membrane electrode. The hydrogen removal layer is located between the proton exchange membrane and the anode catalyst layer, while the hydrogen barrier layer is positioned on the side of the hydrogen removal layer closest to the proton exchange membrane. The hydrogen removal layer comprises perfluorosulfonic acid resin, a hydrogen removal catalyst, and a corrosion-resistant catalyst. The hydrogen barrier layer comprises perfluorosulfonic acid resin and inorganic nanomaterials. The inorganic nanomaterials in the hydrogen barrier layer create dense and tortuous nanoscale channels, increasing the path and resistance of hydrogen passage and reducing hydrogen permeability. Simultaneously, the inorganic nanomaterials physically block hydrogen, further reducing hydrogen permeability. Furthermore, the hydrogen removal catalyst in the hydrogen removal layer eliminates hydrogen permeating from the hydrogen barrier layer by converting hydrogen into water, achieving highly efficient hydrogen barrier and long-lasting hydrogen removal. The addition of the corrosion-resistant catalyst further improves the durability of the membrane electrode anode.

[0038] On the other hand, this embodiment also provides a method for preparing the membrane electrode anode for water electrolysis of any of the above embodiments, the method comprising: S1: Obtain the slurry for the proton exchange membrane and anode catalyst layer; In some embodiments, obtaining the proton exchange membrane and anode catalyst layer slurry includes: S11: Obtain the proton exchange membrane; S12: The oxygen evolution reaction catalyst, perfluorosulfonic acid resin and third solvent are mixed and ball-milled to disperse the mixture, thus obtaining the anode catalyst slurry.

[0039] Specifically, the ball milling dispersion process includes: placing the mixed slurry in a ball mill and ball milling and dispersing it at a first preset speed for a first preset time to obtain an anode catalyst layer slurry.

[0040] Specifically, the first preset speed is 200~400 rpm. Preferably, the first preset speed is 300 rpm.

[0041] Specifically, the first preset time is 2 to 8 hours. Preferably, the first preset time is 5 hours.

[0042] In some embodiments, the solid content of the perfluorosulfonic acid resin is 10-30%. Preferably, the solid content of the perfluorosulfonic acid resin is 20%.

[0043] In some embodiments, the mixture of the oxygen evolution reaction catalyst, perfluorosulfonic acid resin, and a third solvent comprises: The oxygen evolution reaction catalyst and a third solvent are mixed to wet the oxygen evolution reaction catalyst to obtain a catalyst slurry; the catalyst slurry is mixed with perfluorosulfonic acid resin and ball-milled to disperse it to obtain an anode catalyst layer slurry.

[0044] In some embodiments, prior to ball milling dispersion, the method further includes mixing the catalyst slurry with perfluorosulfonic acid resin and performing a first pre-dispersion treatment to obtain a slurry after the first pre-dispersion treatment.

[0045] Specifically, the first pre-dispersion treatment can be performed using water bath ultrasonication or shearing. This application does not specify the form of the first pre-dispersion treatment.

[0046] In some embodiments, the oxygen evolution reaction catalyst is a noble metal oxide catalyst. Specifically, the noble metal oxide catalyst is an iridium oxide catalyst.

[0047] Specifically, the iridium loading of the anode catalyst layer is 1 mg / cm³. 2 .

[0048] In some embodiments, the third solvent includes at least one selected from water, ethanol, isopropanol, and n-propanol. Preferably, the third solvent is water and n-propanol.

[0049] In some embodiments, after ball milling and dispersion, the method further includes degassing the slurry after ball milling and dispersion.

[0050] S2: Mix perfluorosulfonic acid resin, hydrogen removal catalyst, corrosion-resistant catalyst and first solvent to obtain hydrogen removal layer slurry; In some embodiments, the mass ratio of perfluorosulfonic acid resin, hydrogen-eliminating catalyst, corrosion-resistant catalyst, and first solvent in the hydrogen-eliminating layer slurry is (0.1~45):(0.5~3):(0.5~1.5):(10~250). By limiting the above mass ratio, the hydrogen-eliminating layer can form a highly efficient and interconnected proton network, while avoiding the encapsulation and coverage of catalyst active sites, thereby reducing catalyst utilization. The ratio of solid components to solvent directly determines the solid content of the wet film. A suitable ratio can form a predominantly mesoporous, interconnected pore network, preventing cracking, curling, or the formation of closed macropores due to improper ratio. Preferably, the mass ratio of perfluorosulfonic acid resin, hydrogen-eliminating catalyst, corrosion-resistant catalyst, and first solvent in the hydrogen-eliminating layer slurry is 4.5:(1.5~2):(0.78~1):25. More preferably, in the hydrogen-removing slurry, the mass ratio of perfluorosulfonic acid resin, hydrogen-removing catalyst, corrosion-resistant catalyst, and first solvent is 4.5:1.5:0.78:25.

[0051] In some embodiments, the perfluorosulfonic acid resin, the hydrogen removal catalyst, the corrosion-resistant catalyst, and the first solvent are mixed, including: The hydrogen removal catalyst, the corrosion-resistant catalyst, and the first solvent are mixed to obtain a mixed slurry; The mixed slurry is mixed with perfluorosulfonic acid resin and then ground and dispersed to obtain a hydrogen-free layer slurry.

[0052] In some embodiments, the grinding and dispersion process includes: placing the mixed slurry in a ball mill and dispersing it at a second preset rotation speed for a second preset time to obtain a hydrogen-free layer slurry.

[0053] Specifically, the second preset speed is 300 rpm.

[0054] Specifically, the second preset time is 4 hours.

[0055] In some embodiments, prior to the grinding and dispersion treatment, the method further includes: mixing the mixed slurry with a perfluorosulfonic acid resin and performing a second pre-dispersion treatment to obtain a slurry after the second pre-dispersion treatment.

[0056] Specifically, the second pre-dispersion treatment can be performed using water bath ultrasonication or shearing. This application does not specify the form of the second pre-dispersion treatment.

[0057] In some embodiments, after the grinding and dispersing process, the method further includes degassing the slurry after grinding and dispersing.

[0058] In some embodiments, the first solvent includes at least one selected from water, ethanol, isopropanol, and n-propanol. Preferably, the first solvent is water and n-propanol.

[0059] In some embodiments, the hydrogen removal catalyst is a Pt-based catalyst. Pt-based catalysts exhibit high catalytic activity and good stability for hydrogen oxidation reactions, and are resistant to high-potential corrosion.

[0060] Specifically, the hydrogen removal catalyst is a platinum black catalyst.

[0061] Specifically, the platinum content in the platinum black catalyst is 90-100%. The upper limit of the platinum content in the platinum black catalyst can be, but is not limited to, 100%, 97%, 95%, etc., and the lower limit can be, but is not limited to, 90%, 93%, 95%, etc.; understandably, the platinum content in the platinum black catalyst can also be any value within the above range, which will not be enumerated here. Preferably, the platinum content in the platinum black catalyst is 99%.

[0062] Specifically, the electrochemically active surface area (ECSA) in the platinum black catalyst is 10~30 m² / gPt.

[0063] In some embodiments, the corrosion-resistant catalyst includes at least one selected from platinum-based catalysts, palladium-based catalysts, noble metal-metal oxide composite catalysts, iridium-based oxide catalysts, and iridium-conductive polymer composite catalysts. Preferably, the corrosion-resistant catalyst is a noble metal-metal oxide composite catalyst. Specifically, the corrosion-resistant catalyst is cerium dioxide.

[0064] In some embodiments, the density of the corrosion-resistant catalyst is 6-8 g / cm³. 3 The upper limit of the density of corrosion-resistant catalysts can be, but is not limited to, 8.0 g / cm³. 3 7.9g / cm 3 7.8g / cm 3 The lower limit of the density of corrosion-resistant catalysts can be, but is not limited to, 6 g / cm³. 3 6.1g / cm 3 6.2g / cm 3 Etc.; understandably, the density of the corrosion-resistant catalyst can also be any value within the above range, which will not be enumerated here. Preferably, the density of the corrosion-resistant catalyst is 7.13 g / cm³. 3 .

[0065] In some embodiments, the specific surface area of ​​the corrosion-resistant catalyst is 85-95 m². 2 / g. The upper limit of the specific surface area of ​​the corrosion-resistant catalyst can be, but is not limited to, 95m². 2 / g, 94m 2 / g, 93m 2 / g, etc., the lower limit of the specific surface area of ​​corrosion-resistant catalysts can be, but is not limited to, 85m². 2 / g, 86m 2 / g, 87m 2 / g, etc.; understandably, the specific surface area of ​​the corrosion-resistant catalyst can also be any value within the above range, which will not be enumerated here. Preferably, the specific surface area of ​​the corrosion-resistant catalyst is 90.86 g / cm³. 3 .

[0066] In some embodiments, the particle size of the corrosion-resistant catalyst is 10~30nm. The upper limit of the particle size of the corrosion-resistant catalyst can be, but is not limited to, 30nm, 29nm, 28nm, etc., and the lower limit of the particle size of the corrosion-resistant catalyst can be, but is not limited to, 10nm, 11nm, 12nm, etc.; it is understood that the particle size of the corrosion-resistant catalyst can also be any value within the above range, which will not be enumerated here.

[0067] S3: Mix perfluorosulfonic acid resin, inorganic nanomaterials, a second solvent and a dispersant to obtain a hydrogen barrier layer slurry; In some embodiments, a mixture of perfluorosulfonic acid resin, inorganic nanomaterials, a second solvent, and a dispersant is included, comprising: S31: Inorganic nanomaterials are mixed with a second solvent and subjected to a first dispersion treatment to disperse the inorganic nanomaterials, thereby obtaining a suspension; S32: The suspension, perfluorosulfonic acid resin, and dispersant are mixed to obtain a hydrogen barrier slurry. Through dispersion treatment, the inorganic nanoparticles can be fully dispersed, forming a more uniform and tortuous barrier network in the membrane, maximizing the hydrogen barrier effect.

[0068] In some embodiments, the first dispersion process includes: ultrasonically dispersing the mixed inorganic nanomaterial solution to obtain a suspension.

[0069] Specifically, the ultrasonic dispersion time is 20-40 minutes. The upper limit of the ultrasonic dispersion time can be, but is not limited to, 40 minutes, 39 minutes, 38 minutes, etc., and the lower limit can be, but is not limited to, 20 minutes, 21 minutes, 22 minutes, etc.; understandably, the ultrasonic dispersion time can also be any value within the above range, which will not be enumerated here. Preferably, the ultrasonic dispersion time is 30 minutes.

[0070] In some embodiments, the suspension, perfluorosulfonic acid resin, and dispersant are mixed, including: The suspension is mixed with perfluorosulfonic acid resin and stirred at a preset stirring speed for a preset stirring time. Then, a dispersant is added and stirring continues to be carried out to obtain a hydrogen barrier slurry.

[0071] In some embodiments, the suspension, perfluorosulfonic acid resin, and dispersant are mixed, including: The suspension is mixed with perfluorosulfonic acid resin and stirred at a preset stirring speed for a preset stirring time. A dispersant is added during the stirring process. The resulting slurry is then ball-milled to obtain a hydrogen barrier layer slurry. This setup effectively prevents the agglomeration of sheet-like inorganic nanomaterials.

[0072] Specifically, the ball milling time in the ball milling process is 1 to 3 hours. Preferably, the ball milling time in the ball milling process is 2 hours.

[0073] Specifically, the ball milling speed during the ball milling process is 200~400 rpm. Preferably, the ball milling speed during the ball milling process is 300 rpm.

[0074] In some embodiments, the preset stirring speed is 400-600 rpm. The upper limit of the preset stirring speed can be, but is not limited to, 600 rpm, 599 rpm, 598 rpm, etc., and the lower limit of the preset stirring speed can be, but is not limited to, 400 rpm, 401 rpm, 402 rpm, etc.; understandably, the preset stirring speed can also be any value within the above range, which will not be enumerated here. Preferably, the preset stirring speed is 500 rpm.

[0075] In some embodiments, the preset stirring time is 0.5 to 1.5 hours. The upper limit of the preset stirring time can be, but is not limited to, 1.5 hours, 1.4 hours, 1.3 hours, etc., and the lower limit can be, but is not limited to, 0.5 hours, 0.6 hours, 0.7 hours, etc.; understandably, the preset stirring time can also be any value within the above range, which will not be enumerated here. Preferably, the preset stirring time is 1 hour. By limiting the above stirring speed and stirring time, the inorganic nanomaterials can be fully dispersed, avoiding agglomeration.

[0076] In some embodiments, the solid content of the perfluorosulfonic acid resin used in the hydrogen barrier layer slurry is 5%.

[0077] In some embodiments, the second solvent includes at least one selected from water, ethanol, isopropanol, and n-propanol. Preferably, the second solvent is water.

[0078] In some embodiments, the inorganic nanomaterial includes at least one selected from SiO2, nano TiO2, nano ZnO, nano ZrO2, nano Ta2O5, nano CeO2, nano Mo2O3, nano MgO, nano Nb2O5, and montmorillonite nanosheets. Preferably, the inorganic nanomaterial is SiO2 or montmorillonite nanosheets. More preferably, the inorganic nanomaterial is montmorillonite nanosheets.

[0079] In some embodiments, the packing density of the inorganic nanomaterials is 1.5~2.0 g / cm³. 3 The upper limit of the packing density of inorganic nanomaterials can be, but is not limited to, 2.0 g / cm³. 3 1.9g / cm 3 1.8g / cm 3 The lower limit of the packing density of inorganic nanomaterials can be, but is not limited to, 1.5 g / cm³. 3 1.6g / cm 3 1.7g / cm 3 Etc.; understandably, the packing density of inorganic nanomaterials can also be any value within the above range, which will not be enumerated here. Preferably, the packing density of inorganic nanomaterials is 1.7~1.9 g / cm³. 3 Further preferably, the packing density of the inorganic nanomaterial is 1.8 g / cm³. 3.

[0080] In some embodiments, the particle size of the inorganic nanomaterial is 1~100nm.

[0081] In some embodiments, the dispersant is a nonionic surfactant or a silane coupling agent. By adding a dispersant, the agglomeration between nanoparticles or nanosheets can be broken, improving slurry stability and preventing particle sedimentation. This ensures the formation of a wet film with uniform thickness and a smooth surface. Furthermore, it promotes the compatibility of inorganic nanomaterials with perfluorosulfonic acid resin, preventing phase separation. Preferably, the nonionic surfactant is polyethylene glycol octylphenyl ether, and the silane coupling agent is γ-glycidoxypropyltrimethoxysilane.

[0082] In some embodiments, the mass ratio of perfluorosulfonic acid resin, inorganic nanomaterials, a second solvent, and a dispersant in the hydrogen barrier layer slurry is (5~60):1:(1~6):(0.1~3). Appropriate amounts of perfluorosulfonic acid resin and inorganic nanomaterials promote the formation of a proton-continuous phase in the hydrogen barrier layer, encapsulating and connecting inorganic particles, achieving a balance between structural strength, proton conduction, and gas transport. An appropriate amount of the second solvent ensures the uniformity of the hydrogen barrier layer slurry, thereby forming a dense structure. Furthermore, excessive amounts of dispersant can interfere with resin film formation or decompose during subsequent drying, generating impurities and additional pores. By limiting the above mass ratio, a balance can be achieved between the proton conductivity, hydrogen permeability, and mechanical strength of the hydrogen barrier layer. Preferably, in the hydrogen barrier layer slurry, the mass ratio of perfluorosulfonic acid resin, inorganic nanomaterial, second solvent, and dispersant is (16~60):1:(2~4):(1~2). More preferably, in the hydrogen barrier layer slurry, the mass ratio of perfluorosulfonic acid resin, inorganic nanomaterial, second solvent, and dispersant is 16:1:2:1.

[0083] In some embodiments, the particle size D50 of the hydrogen barrier layer slurry, the hydrogen elimination layer slurry, and the anode catalyst layer slurry is all less than 1 μm. This configuration ensures slurry stability, achieves uniform coating, and forms a dense, uniform, defect-free coating, thereby enabling the formation of a microstructure with smaller pores and higher tortuosity.

[0084] In some embodiments, the solid content of the hydrogen barrier layer slurry, the hydrogen elimination layer slurry, and the anode catalyst layer slurry is all less than 50 wt%. By limiting the above solid content range, the rheological properties of the slurry are improved, resulting in a smooth wet film and a thinner coating. Within the lower solid content range, particles can move more freely and find more stable positions, which is beneficial for forming a dense nanostructure with high tortuosity.

[0085] S4: The hydrogen barrier layer slurry, the hydrogen elimination layer slurry, and the anode catalyst layer slurry are sequentially coated onto the proton exchange membrane and dried after coating to obtain the membrane electrode anode for water electrolysis; in the membrane electrode anode for water electrolysis, the hydrogen elimination layer is located between the proton exchange membrane and the anode catalyst layer, and the hydrogen barrier layer is disposed on the side of the hydrogen elimination layer closer to the proton exchange membrane.

[0086] In some embodiments, hydrogen barrier slurry, hydrogen elimination slurry, and anode catalyst slurry are sequentially coated onto a proton exchange membrane and dried after coating, including: S41: Coat one side of the proton exchange membrane with a hydrogen barrier slurry and dry it to obtain a proton exchange membrane with a hydrogen barrier layer. S42: Coat the hydrogen removal layer slurry onto the surface of the hydrogen barrier layer of the proton exchange membrane with the hydrogen barrier layer, and dry it to obtain a proton exchange membrane with both a hydrogen barrier layer and a hydrogen removal layer. S43: The anode catalyst layer is coated on the surface of the hydrogen removal layer of a proton exchange membrane with a hydrogen barrier layer and a hydrogen removal layer, and after drying, a membrane electrode anode for water electrolysis is obtained.

[0087] Specifically, the coating methods in this embodiment include, but are not limited to, spraying, scraping, slot coating, sputtering, screen printing, inkjet printing, etc. This application does not specifically limit the coating method. For example, the coating method can be spraying.

[0088] In some embodiments, the thickness of the hydrogen barrier layer in the anode of the membrane electrode for water electrolysis ranges from 10 nm to 5 μm. The upper limit of the hydrogen barrier layer thickness can be, but is not limited to, 5 μm, 4 μm, 3 μm, etc., and the lower limit can be, but is not limited to, 10 nm, 11 nm, 12 nm, etc.; understandably, the thickness of the hydrogen barrier layer can also be any value within the above range, which will not be enumerated here. Preferably, the thickness of the hydrogen barrier layer is 0.3 μm.

[0089] In some embodiments, the thickness of the hydrogen-removing layer in the anode of the membrane electrode for water electrolysis ranges from 10 nm to 5 μm. The upper limit of the hydrogen-removing layer thickness can be, but is not limited to, 5 μm, 4 μm, 3 μm, etc., and the lower limit can be, but is not limited to, 10 nm, 11 nm, 12 nm, etc.; understandably, the thickness of the hydrogen-removing layer can also be any value within the above range, which will not be enumerated here. Preferably, the thickness of the hydrogen-removing layer is 2 μm.

[0090] In some embodiments, the mass ratio of perfluorosulfonic acid resin, hydrogen-removing catalyst, and corrosion-resistant catalyst in the hydrogen-removing layer of the membrane electrode anode for water electrolysis is (0.1~45):(0.5~3):(0.5~1.5). Preferably, the mass ratio of perfluorosulfonic acid resin, hydrogen-removing catalyst, and corrosion-resistant catalyst is (4~6):(1~2):(0.5~1.5). More preferably, the mass ratio of perfluorosulfonic acid resin, hydrogen-removing catalyst, and corrosion-resistant catalyst is 5.77:1.92:1.

[0091] In some embodiments, the mass ratio of perfluorosulfonic acid resin to inorganic nanomaterials in the hydrogen barrier layer of the membrane electrode anode for water electrolysis is (5~60):1. Preferably, the mass ratio of perfluorosulfonic acid resin to inorganic nanomaterials in the hydrogen barrier layer is (15~20):1. More preferably, the mass ratio of perfluorosulfonic acid resin to inorganic nanomaterials in the hydrogen barrier layer is 16:1.

[0092] The membrane electrode anode for water electrolysis prepared by the above preparation method of the present invention has a hydrogen permeability as low as 0.47 Vol.%, and the anode has excellent durability, achieving the effect of efficient hydrogen blocking and long-term hydrogen elimination.

[0093] The following describes specific embodiments of this application in conjunction with the aforementioned membrane module for water electrolysis and its preparation method. The following embodiments describe the technical solutions of this application in more detail. These embodiments are for illustrative purposes only, as various modifications and variations within the scope of the disclosure of this application will be apparent to those skilled in the art. The reagents used in the embodiments are commercially available or synthesized using conventional methods and can be used directly without further processing. Similarly, the instruments and apparatus used in the embodiments are commercially available.

[0094] Example 1 This embodiment provides a method for preparing a membrane electrode anode for water electrolysis, the method comprising: S100: 2.0g of iridium oxide catalyst (iridium content 77wt%) and 12.4g of water were mixed, and then 11.6g of n-propanol was added to obtain a catalyst slurry. The catalyst slurry was mixed with 6g of perfluorosulfonic acid resin with a solid content of 20% and subjected to water bath ultrasonication. The slurry after water bath ultrasonication was then dispersed by ball milling at a preset speed of 300 rpm for a preset time of 5 hours. Finally, the dispersed slurry was degassed to obtain the anode catalyst layer slurry. The iridium oxide catalyst was manufactured by Tanaka Precious Metals. The iridium loading of the anode catalyst layer was 1 mg / cm³. 2 ; S200: 1.5g of platinum black catalyst, 0.78g of CeO2 nanoparticles, and 12.8g of water were thoroughly wetted, and then 12.2g of n-propanol was added to obtain a mixed slurry. 4.5g of perfluorosulfonic acid resin with a solid content of 20% was added to the mixed slurry, followed by water bath ultrasonication. The slurry after water bath ultrasonication was then dispersed by ball milling at a preset speed of 300 rpm for 4 hours. Finally, the dispersed slurry was degassed to obtain a hydrogen-removing layer slurry. The platinum black catalyst was manufactured by Jiping New Energy Technology Co., Ltd., and contained 97% platinum with an electrochemical active surface area (ECSA) of 25-30 m² / gPt. The density of the CeO2 nanoparticles was 7.13g / cm³. 3 The specific surface area is 90.86 g / cm³. 3 The particle size is 10~30nm; S300: Mix 5g of montmorillonite nanosheets and 10g of water and ultrasonically disperse for 30min to obtain a suspension; mix the suspension with 80g of perfluorosulfonic acid resin with a solid content of 5% and stir at 500rpm for 1h; add 5g of polyethylene glycol octylphenyl ether during stirring for 1h; then ball mill the mixture at 300rpm for 2h to obtain a hydrogen barrier layer slurry, wherein the bulk density of the montmorillonite nanosheets is 1.8g / cm³. 3 .

[0095] S400: A hydrogen barrier slurry is coated onto one side surface of a proton exchange membrane, and after drying, a proton exchange membrane with a hydrogen barrier layer is obtained; a hydrogen elimination slurry is coated onto the surface of the hydrogen barrier layer of the proton exchange membrane with the hydrogen barrier layer, and after drying, a proton exchange membrane with both a hydrogen barrier layer and a hydrogen elimination layer is obtained; an anode catalyst layer is coated onto the surface of the hydrogen elimination layer of the proton exchange membrane with both a hydrogen barrier layer and a hydrogen elimination layer, and after drying, a membrane electrode anode for water electrolysis is obtained.

[0096] In this embodiment, the thickness of the hydrogen barrier layer is 0.3 μm, and the thickness of the hydrogen elimination layer is 2 μm.

[0097] Example 2 This embodiment provides a method for preparing a membrane electrode anode for water electrolysis. The similarities to those in Embodiment 1 will not be repeated here. The differences between this embodiment and Embodiment 1 are as follows: S300: Mix 10g of SiO2 nanoparticles and 100g of water and ultrasonically disperse for 30min to obtain a suspension; mix the suspension with 70g of perfluorosulfonic acid resin with a solid content of 5% and stir at 500rpm for 1h; then add 5g of γ-glycidyl etheroxypropyltrimethoxysilane and continue stirring for 30min to obtain a hydrogen barrier slurry.

[0098] In this embodiment, the thickness of the hydrogen barrier layer is 0.3 μm, and the thickness of the hydrogen elimination layer is 2 μm.

[0099] Example 3 This embodiment provides a method for preparing a membrane electrode anode for water electrolysis. The similarities to Example 1 will not be repeated here. The difference lies in the following steps: S300: 2.5g of montmorillonite nanosheets and 10g of water are mixed and ultrasonically dispersed for 30min to obtain a suspension. The suspension is then mixed with 150g of perfluorosulfonic acid resin with a solid content of 5% and stirred at 500rpm for 1h. During the 1h stirring process, 5g of polyethylene glycol octylphenyl ether is added. The resulting slurry is then ball-milled at 300rpm for 2h to obtain a hydrogen-barrier layer slurry. In this embodiment, the thickness of the hydrogen-barrier layer is 0.3μm, and the thickness of the hydrogen-eliminating layer is 2μm.

[0100] Example 4 This embodiment provides a method for preparing a membrane electrode anode for water electrolysis. The similarities to Example 1 are not repeated here, but the difference lies in the following steps: S200: 2g of platinum black catalyst, 1g of CeO2 nanoparticles, and 12.8g of water are thoroughly wetted, and then 12.2g of n-propanol is added to obtain a mixed slurry. 4.5g of perfluorosulfonic acid resin with a solid content of 20% is added to the mixed slurry, followed by water bath ultrasonication. The slurry after water bath ultrasonication is then dispersed by ball milling at a second preset speed of 300 rpm for a second preset time of 4 hours. Finally, the dispersed slurry is degassed to obtain a hydrogen-removing layer slurry. The platinum black catalyst is manufactured by Jiping New Energy Technology Co., Ltd., and has a platinum content of 97% and an electrochemical active surface area (ECSA) of 25~30 m² / gPt. The density of the CeO2 nanoparticles is 7.13g / cm³. 3 The specific surface area is 90.86 g / cm³. 3 The particle size is 10~30nm; in this comparative example, the thickness of the hydrogen barrier layer is 0.3μm and the thickness of the hydrogen elimination layer is 2μm.

[0101] Comparative Example 1 This comparative example provides a method for preparing a membrane electrode anode for water electrolysis, the method comprising: S100: 2.0g of iridium oxide catalyst (iridium content 77wt%) and 12.4g of water were mixed, and then 11.6g of n-propanol was added to obtain a catalyst slurry. The catalyst slurry was mixed with 6g of perfluorosulfonic acid resin with a solid content of 20% and subjected to water bath ultrasonication. The slurry after water bath ultrasonication was then dispersed by ball milling at a preset speed of 300 rpm for a preset time of 5 hours. Finally, the dispersed slurry was degassed to obtain the anode catalyst layer slurry. The iridium oxide catalyst was manufactured by Tanaka Precious Metals. The iridium loading of the anode catalyst layer was 1 mg / cm³.2 ; S200: The anode catalyst layer is coated onto the surface of the proton exchange membrane, and after drying, a membrane electrode anode for water electrolysis is obtained. In this comparative example, the thickness of the hydrogen barrier layer is 0.3 μm, and the thickness of the hydrogen elimination layer is 2 μm.

[0102] Comparative Example 2 This comparative example provides a method for preparing the anode of a membrane electrode for water electrolysis. The similarities to those in Example 1 will not be repeated here. The differences between this method and Example 1 are as follows: S200: 1.5g of platinum black catalyst, 0.78g of CeO2 nanoparticles, and 12.8g of water were thoroughly wetted, and then 12.2g of n-propanol was added to obtain a mixed slurry. 4.5g of perfluorosulfonic acid resin with a solid content of 20% was added to the mixed slurry, followed by water bath ultrasonication. The slurry after water bath ultrasonication was then dispersed by ball milling at a preset speed of 300 rpm for 4 hours. Finally, the dispersed slurry was degassed to obtain a hydrogen-free layer slurry. The platinum black catalyst was manufactured by Jiping New Energy Technology Co., Ltd., and contained 97% platinum with an electrochemical active surface area (ECSA) of 25-30 m² / gPt. The density of the CeO2 nanoparticles was 1.2g / cm³. 3 The particle size is 200 nm; In this comparative example, the thickness of the hydrogen barrier layer is 0.3 μm, and the thickness of the hydrogen elimination layer is 2 μm.

[0103] Comparative Example 3 This comparative example provides a method for preparing the anode of a membrane electrode for water electrolysis. The similarities to those in Example 1 will not be repeated here. The differences between this method and Example 1 are as follows: S300: Mix 5g of nano Al2O3 and 10g of water and ultrasonically disperse for 30min to obtain a suspension; mix the suspension with 80g of perfluorosulfonic acid resin with a solid content of 5% and stir at 500rpm for 1h; add 5g of polyethylene glycol octylphenyl ether during the stirring process; then ball mill the mixed slurry at 300rpm for 2h to obtain a hydrogen barrier layer slurry.

[0104] In this comparative example, the thickness of the hydrogen barrier layer is 0.3 μm, and the thickness of the hydrogen elimination layer is 2 μm.

[0105] Comparative Example 4 This comparative example provides a method for preparing the anode of a membrane electrode for water electrolysis. The similarities to those in Example 1 will not be repeated here. The differences between this method and Example 1 are as follows: S300: 5g of montmorillonite nanosheets and 10g of water were mixed and ultrasonically dispersed for 30min to obtain a suspension. The suspension was mixed with 80g of perfluorosulfonic acid resin with a solid content of 5% and stirred at 500rpm for 1h. During the 1h stirring process, 5g of polyethylene glycol octylphenyl ether was added. The resulting slurry was then ball-milled at 300rpm for 2h to obtain a hydrogen barrier layer slurry, wherein the bulk density of the montmorillonite nanosheets was 2.6 g / cm³. 3 In this comparative example, the thickness of the hydrogen barrier layer is 0.3 μm, and the thickness of the hydrogen elimination layer is 2 μm.

[0106] Comparative Example 5 This comparative example provides a method for preparing the anode of a membrane electrode for water electrolysis. The similarities to those in Example 1 will not be repeated here. The differences between this method and Example 1 are as follows: S300: Mix 3g of montmorillonite nanosheets and 10g of water and ultrasonically disperse for 30min to obtain a suspension; mix the suspension with 12g of perfluorosulfonic acid resin with a solid content of 5% and stir at 500rpm for 1h; add 5g of polyethylene glycol octylphenyl ether during the stirring process; then ball mill the mixed slurry at 300rpm for 2h to obtain a hydrogen barrier layer slurry.

[0107] In this comparative example, the thickness of the hydrogen barrier layer is 0.3 μm, and the thickness of the hydrogen elimination layer is 2 μm.

[0108] Comparative Example 6 This comparative example provides a method for preparing a membrane electrode anode for water electrolysis. The similarities to Example 1 will not be repeated here. The difference lies in the following steps: S200: 0.5g of platinum black catalyst, 0.2g of CeO2 nanoparticles, and 12.8g of water are thoroughly wetted, and then 12.2g of n-propanol is added to obtain a mixed slurry. 4.5g of perfluorosulfonic acid resin with a solid content of 20% is added to the mixed slurry, followed by water bath ultrasonication. The slurry after water bath ultrasonication is then dispersed by ball milling at a second preset speed of 300 rpm for a second preset time of 4 hours. Finally, the dispersed slurry is degassed to obtain a hydrogen-removing layer slurry. The platinum black catalyst is manufactured by Jiping New Energy Technology Co., Ltd., and has a platinum content of 97% and an electrochemical active surface area (ECSA) of 25~30 m² / gPt. The density of the CeO2 nanoparticles is 7.13g / cm³. 3 The specific surface area is 90.86 g / cm³. 3 The particle size is 10~30nm; In this comparative example, the thickness of the hydrogen barrier layer is 0.3 μm, and the thickness of the hydrogen elimination layer is 2 μm.

[0109] The above embodiments and comparative examples adopted the following test methods: 1. Hydrogen content test in oxygen: The membrane electrode anodes of the water electrolysis cells prepared in the above examples and comparative examples were hot-pressed with a porous transport layer and a frame to form a membrane electrode. The membrane electrode was then assembled into a fixture to form a single electrolysis cell. After the membrane electrode was fully activated, it was operated under constant current with a current density of 0.2 A / cm². 2 The anode is at atmospheric pressure and the cathode pressure is 3 MPa. The hydrogen content in oxygen is measured until it reaches a stable value, which is the measured hydrogen content in oxygen.

[0110] Results Analysis: Table 1 shows that, combined with Examples 1-2, the hydrogen barrier effect of using montmorillonite nanosheets as inorganic nanomaterials is better than that of using silicon dioxide. This may be because the montmorillonite nanosheets have a sheet-like structure, which makes the path in the hydrogen barrier layer more tortuous and longer, greatly reducing the hydrogen permeability. Combined with Examples 1-2 and Comparative Example 1, compared with Comparative Example 1, the addition of a hydrogen elimination layer and a hydrogen barrier layer in Examples 1-2 greatly reduces the hydrogen permeability. Combined with Examples 1 and 3-4, a higher resin content in the hydrogen barrier layer or hydrogen elimination layer slightly increases the hydrogen permeability of the anode. Combined with Examples 1 and Comparative Example 2, a lower density and higher particle size of the corrosion-resistant catalyst increases the hydrogen permeability of the anode. Combined with Examples 1 and Comparative Example 3, changing the type of inorganic nanomaterial to Al2O3 increases the hydrogen permeability of the anode. Combined with Examples 1 and Comparative Example 4, ... Increasing the packing density of montmorillonite nanosheets leads to an increase in hydrogen permeability at the anode, possibly due to the influence on the porosity of the hydrogen barrier layer and the tortuosity of the diffusion path, thus resulting in increased hydrogen permeability at the anode. Referring to Examples 1 and 5, changing the ratio of resin to nanomaterials and reducing the resin content may result in the absence of a three-dimensional continuous network, meaning the inorganic material is not encapsulated and connected, thereby increasing hydrogen permeability at the anode. Referring to Examples 1 and 6, reducing the content of the corrosion-resistant catalyst increases hydrogen permeability at the anode, possibly due to the lack of continuous gas and proton channels, leading to the aforementioned results.

[0111] Table 1

[0112] The foregoing description has fully disclosed the specific embodiments of this application. It should be noted that any modifications made by those skilled in the art to the specific embodiments of this application do not depart from the scope of the claims. Accordingly, the scope of the claims of this application is not limited to the foregoing specific embodiments.

Claims

1. A membrane electrode anode for water electrolysis, characterized in that, include: Proton exchange membrane; An anode catalyst layer is located on one side of the proton exchange membrane; A hydrogen removal layer is located between the proton exchange membrane and the anode catalyst layer, and the hydrogen removal layer includes perfluorosulfonic acid resin, a hydrogen removal catalyst and a corrosion-resistant catalyst. A hydrogen barrier layer is disposed on the side of the hydrogen removal layer near the proton exchange membrane, and the hydrogen barrier layer includes perfluorosulfonic acid resin and inorganic nanomaterials.

2. The membrane electrode anode according to claim 1, characterized in that, In the hydrogen barrier layer, the mass ratio between the perfluorosulfonic acid resin and the inorganic nanomaterial is (5~60):

1.

3. The membrane electrode anode according to claim 1, characterized in that, The thickness of the hydrogen barrier layer ranges from 10 nm to 5 μm.

4. The membrane electrode anode according to claim 1, characterized in that, In the hydrogen removal layer, the mass ratio of the perfluorosulfonic acid resin, the hydrogen removal catalyst, and the corrosion-resistant catalyst is (0.1~45):(0.5~3):(0.5~1.5).

5. The membrane electrode anode according to claim 1, characterized in that, The thickness of the hydrogen-removing layer ranges from 10 nm to 5 μm.

6. The membrane electrode anode according to any one of claims 1-5, characterized in that, The membrane electrode anode satisfies at least one of the following characteristics: The inorganic nanomaterials include at least one of SiO2, nano TiO2, nano ZnO, nano ZrO2, nano Ta2O5, nano CeO2, nano Mo2O3, nano MgO, nano Nb2O5, and montmorillonite nanosheets; The corrosion-resistant catalyst includes at least one of platinum-based catalysts, palladium-based catalysts, noble metal-metal oxide composite catalysts, iridium-based oxide catalysts, and iridium-based conductive polymer composite catalysts. The corrosion-resistant catalyst has a particle size of 10~30nm; The hydrogen removal catalyst is a Pt-based catalyst, and the platinum content in the Pt-based catalyst is 10-100%.

7. A method for preparing a membrane electrode anode for water electrolysis as described in any one of claims 1 to 6, characterized in that, The method includes: S1: Obtain the slurry for the proton exchange membrane and anode catalyst layer; S2: Mix perfluorosulfonic acid resin, hydrogen removal catalyst, corrosion-resistant catalyst and first solvent to obtain hydrogen removal layer slurry; S3: Mix perfluorosulfonic acid resin, inorganic nanomaterials, a second solvent and a dispersant to obtain a hydrogen barrier layer slurry; S4: The hydrogen barrier layer slurry, the hydrogen elimination layer slurry, and the anode catalyst layer slurry are sequentially coated onto the proton exchange membrane and dried after coating to obtain the membrane electrode anode for water electrolysis; in the membrane electrode anode for water electrolysis, the hydrogen elimination layer is located between the proton exchange membrane and the anode catalyst layer, and the hydrogen barrier layer is disposed on the side of the hydrogen elimination layer closer to the proton exchange membrane.

8. The method according to claim 7, characterized in that, The process of mixing perfluorosulfonic acid resin, inorganic nanomaterials, a second solvent, and a dispersant includes: S31: Inorganic nanomaterials are mixed with a second solvent and subjected to a first dispersion treatment to disperse the inorganic nanomaterials, thereby obtaining a suspension; S32: Mix the suspension, the perfluorosulfonic acid resin and the dispersant to obtain a hydrogen barrier slurry.

9. The method according to claim 7, characterized in that, The method satisfies at least one of the following characteristics: In the hydrogen-removing slurry, the mass ratio of the perfluorosulfonic acid resin, the hydrogen-removing catalyst, the corrosion-resistant catalyst, and the first solvent is (0.1~45):(0.5~3):(0.5~1.5):(10~250). In the hydrogen barrier slurry, the mass ratio of the perfluorosulfonic acid resin, the inorganic nanomaterial, the second solvent, and the dispersant is (5~60):1:(1~6):(0.1~3); The dispersant is a nonionic surfactant or a silane coupling agent.

10. The method according to any one of claims 7-9, characterized in that, The method satisfies at least one of the following characteristics: The particle size D50 of the hydrogen barrier layer slurry, the hydrogen elimination layer slurry, and the anode catalyst layer slurry is all less than 1 μm; The solid content of the hydrogen barrier layer slurry, the hydrogen elimination layer slurry, and the anode catalyst layer slurry is all less than 50 wt%.

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