Dehydrogenation layer and preparation method thereof, dehydrogenation proton exchange membrane, membrane electrode and water electrolysis hydrogen production device

Abstract

The invention discloses a hydrogen elimination layer and a preparation method thereof, a hydrogen elimination proton exchange membrane, a membrane electrode and a water electrolysis hydrogen production device, and relates to the technical field of water electrolysis hydrogen production, the hydrogen elimination layer comprises the following components by weight: 10-20 parts of a metal oxide, 10-20 parts of a catalyst, and 2-10 parts of an ionomer; the catalyst comprises at least one of a platinum black catalyst, an iridium black catalyst and a palladium black catalyst. The hydrogen elimination layer can effectively reduce the hydrogen content in oxygen at the anode side of the proton exchange membrane.

Description

Technical Field

[0001] The present application relates to the technical field of water electrolysis hydrogen production, and specifically to a hydrogen removal layer and a preparation method thereof, a hydrogen removal proton exchange membrane, a membrane electrode, and a water electrolysis hydrogen production device. Background Art

[0002] Membrane Electrode Assembly (MEA), also known as membrane electrode, is an important component of PEM (polymer electrolyte membrane) water electrolysis hydrogen production device, which includes a proton exchange membrane, an anode catalyst layer on the anode side of the proton exchange membrane, and a cathode catalyst layer on the cathode side of the proton exchange membrane. The proton exchange membrane can selectively conduct protons (hydrogen ions) under the action of an electric field, while preventing electrons and gases (such as hydrogen and oxygen) from passing directly. During the electrolysis process, water molecules undergo an oxidation reaction on the anode side, losing electrons to generate oxygen and protons. Protons are conducted to the cathode side through the proton exchange membrane, where they combine with electrons to generate hydrogen.

[0003] In theory, the thinner the proton exchange membrane, the lower the voltage loss of the membrane's internal resistance, thereby reducing the electrolyzer voltage and improving electrolysis efficiency. However, thinner proton exchange membranes also bring new problems. When the proton exchange membrane becomes thinner, its gas permeability also increases. Under high-voltage working conditions, the hydrogen produced on the cathode side may penetrate through the membrane to the anode side, causing hydrogen to be mixed with the oxygen produced on the anode side (also known as "hydrogen in oxygen"). This will not only reduce the purity of the anode product, but may also cause safety issues. Summary of the invention

[0004] The technical problem solved by the present application is to reduce the hydrogen content in oxygen on the anode side of the proton exchange membrane.

[0005] In order to solve the above technical problems, this application provides the following technical solutions:

[0006] In a first aspect, the present application provides a dehydrogenation layer, comprising the following components in parts by weight: 10 to 20 parts of metal oxide, 10 to 20 parts of catalyst, and 2 to 10 parts of ionomer; the catalyst comprises at least one of a platinum black catalyst, an iridium black catalyst, and a palladium black catalyst.

[0007] In some embodiments of the first aspect, the ionomer includes at least one of sulfonated polysulfone, sulfonated polyethersulfone, perfluorosulfonic acid resin, sulfonated polyetheretherketone, sulfonated polyphenylene sulfide, perfluorocarboxylic acid resin, and perfluorophosphoric acid resin.

[0008] In some embodiments of the first aspect, the metal oxide consists of aluminum oxide, zirconium oxide and cerium oxide, and the weight ratio is (1-2):(2-3):(7-10).

[0009] In some embodiments of the first aspect, the metal oxide consists of aluminum oxide, zirconium oxide and cerium oxide, and the weight ratio is (1-2):1:(7-8).

[0010] In some embodiments of the first aspect, the metal oxide consists of zirconium oxide and cerium oxide in a weight ratio of 2:3.

[0011] In some embodiments of the first aspect, the ionomer consists of Nafion D2020 and Nafion NR50 in a weight ratio of (1-5):(1-5).

[0012] In some embodiments of the first aspect, the ionomer is Nafion D2020.

[0013] In some embodiments of the first aspect, the catalyst consists of a platinum black catalyst and an iridium black catalyst, and the weight ratio is (1-3):1.

[0014] In some embodiments of the first aspect, the catalyst consists of an iridium black catalyst and a palladium black catalyst in a weight ratio of 2:1.

[0015] In some embodiments of the first aspect, the weight ratio of the metal oxide, the catalyst, and the ionomer is (1-5):(1-10):1.

[0016] In a second aspect, the present application provides a method for preparing a hydrogen removal layer according to any one of the above items, comprising the following steps: mixing metal oxides, catalysts and ionomers, and adding solvents and stirring to prepare hydrogen removal layer slurry; coating the hydrogen removal layer slurry on the surface of a substrate and drying to form the hydrogen removal layer.

[0017] In some embodiments of the second aspect, the preparation method satisfies at least one of the following conditions: (1) the solvent includes at least one of water, ethanol, isopropanol, n-propanol, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; (2) the solid content of the dehydrogenation layer slurry is 3% to 40%; (3) the coating thickness is 1 μm to 100 μm; preferably, the coating thickness is 1 μm to 10 μm; (4) the drying temperature is 50°C to 200°C, and the drying time is 10 minutes to 4 hours; (5) the coating method is one of spraying, blade coating, and slit coating; preferably, the coating method is slit coating; (6) the substrate is a transfer substrate, a proton exchange membrane, or an anode catalyst layer.

[0018] In a third aspect, the present application provides a hydrogen-scavenging proton exchange membrane, comprising a proton exchange membrane and any one of the above-described hydrogen-scavenging layers located on a surface of the proton exchange membrane.

[0019] In some embodiments of the third aspect, the thickness of the proton exchange membrane is 50 μm to 130 μm, preferably 50 μm to 80 μm.

[0020] In a fourth aspect, the present application provides a membrane electrode, comprising an anode catalyst layer, the above-mentioned hydrogen-scavenging proton exchange membrane, and a cathode catalyst layer arranged in sequence, wherein the hydrogen-scavenging layer faces the anode catalyst layer.

[0021] In a fifth aspect, the present application provides a water electrolysis hydrogen production device, comprising the above-mentioned membrane electrode.

[0022] Compared with the prior art, this application has the following beneficial effects:

[0023] The present application uses a specific combination of metal oxides, catalysts and ionomers as the components of the hydrogen removal layer, which can reduce the hydrogen content in the oxygen on the anode side of the proton exchange membrane when a thinner proton exchange membrane is used. Furthermore, by optimizing the types and ratios of each component, not only can the oxygen purity on the anode side be improved for a long time, but also the hydrogen purity on the cathode side can be higher. Furthermore, the effect of improving the electrolysis efficiency can be achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The following drawings describe in detail the exemplary embodiments disclosed in this application. The same reference numerals represent similar structures in several views of the drawings. Those skilled in the art will understand that these embodiments are non-limiting, exemplary embodiments, and the drawings are only used for the purpose of illustration and description, and are not intended to limit the scope of this application. Other embodiments may also accomplish the inventive intent in this application. It should be understood that the drawings are not drawn to scale. Among them:

[0025] Figure 1 This is a scanning electron microscope image of a cross section of the hydrogen-removing proton exchange membrane prepared in Example 1 of the present application;

[0026] Figure 2 This is the polarization curve of the membrane electrode prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0027] The following description provides specific application scenarios and requirements of the present application, with the purpose of enabling those skilled in the art to make and use the content in the present application. It will be apparent to those skilled in the art that various local modifications to the disclosed embodiments are apparent, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the present application. Therefore, the present application is not limited to the embodiments shown, but to the widest scope consistent with the claims.

[0028] Generally speaking, the oxygen purity at the anode outlet is between 99% and 99.5% (current density is 1A / cm2 , 80°C, atmospheric pressure). If the water electrolysis hydrogen production device is operated under pressure, then as the pressure of the gas product increases, the gas permeability in the proton exchange membrane will also increase, resulting in a further decrease in the purity of the oxygen product, and the increase in the hydrogen content in the oxygen may cause safety problems. Therefore, when optimizing the performance of the proton exchange membrane, multiple factors need to be considered comprehensively. On the one hand, it is hoped that the membrane can be as thin as possible to reduce voltage loss; on the other hand, it is necessary to ensure a high purity of the oxygen product.

[0029] Based on this, the present application provides a hydrogen removal layer and a preparation method thereof, a hydrogen removal proton exchange membrane, a membrane electrode, and a water electrolysis hydrogen production device. By arranging the hydrogen removal layer on the proton exchange membrane and optimizing the composition of the hydrogen removal layer, the hydrogen content in the oxygen on the anode side of the proton exchange membrane can be reduced when a thinner proton exchange membrane is used.

[0030] The hydrogen removal layer of the present application comprises the following components in parts by weight: 10 to 20 parts of metal oxide, 10 to 20 parts of catalyst, and 2 to 10 parts of ionomer. The catalyst comprises at least one of a platinum black catalyst, an iridium black catalyst, and a palladium black catalyst.

[0031] When the hydrogen generated on the cathode side enters the hydrogen elimination layer, in the presence of at least one of the platinum black catalyst, the iridium black catalyst and the palladium black catalyst, the metal oxide can react with the hydrogen to eliminate the hydrogen. At the same time, at least one of the platinum black catalyst, the iridium black catalyst and the palladium black catalyst can convert the hydrogen into H + , and can convert the oxygen entering the hydrogen removal layer into O 2- , H + and O 2- Combined with each other, water molecules are generated, which further eliminates hydrogen. The addition of ionomers can increase the oxygen permeability, so that the oxygen generated on the anode side can enter the hydrogen elimination layer, increase the concentration of oxygen in the hydrogen elimination layer, and make hydrogen more fully consumed by oxygen, further improving the effect of eliminating hydrogen. At the same time, the specific weight ratio of metal oxides, catalysts and ionomers can make the concentration of oxygen entering the hydrogen elimination layer within a reasonable range without escaping too much to the cathode side.

[0032] In some preferred embodiments, the metal oxide is 10 to 15 parts, the catalyst is 15 to 20 parts, and the ionomer is 4 to 8 parts.

[0033] In some preferred embodiments, the weight ratio of the metal oxide, the catalyst, and the ionomer is (1-5):(1-10):1.

[0034] In some preferred embodiments, the metal oxide is composed of aluminum oxide (Al2O3), zirconium oxide (ZrO2) and cerium oxide (CeO2), and the weight ratio is (1-2): (2-3): (7-10). Preferably, the weight ratio is (1-2): 1: (7-8), and more preferably 1: 1: 8.

[0035] In some preferred embodiments, the metal oxide consists of zirconium oxide and cerium oxide in a weight ratio of 2:3.

[0036] In some embodiments, the ionomer includes at least one of sulfonated polysulfone, sulfonated polyethersulfone, perfluorosulfonic acid resin, sulfonated polyetheretherketone, sulfonated polyphenylene sulfide, perfluorocarboxylic acid resin, and perfluorophosphoric acid resin.

[0037] In some preferred embodiments, the ionomer is composed of Nafion D2020 and Nafion NR50, and the weight ratio is (1-5):(1-5). In some preferred embodiments, the weight ratio of Nafion D2020 and Nafion NR50 is 1:5.

[0038] In some preferred embodiments, the ionomer is Nafion D2020.

[0039] In some embodiments, the catalyst is composed of a platinum black catalyst and an iridium black catalyst, and the weight ratio is (1-3): 1. More preferably, the weight ratio of the platinum black catalyst to the iridium black catalyst is 1:1.

[0040] In some preferred embodiments, the catalyst consists of an iridium black catalyst and a palladium black catalyst in a weight ratio of 2:1.

[0041] The present application also provides a method for preparing the above-mentioned hydrogen removal layer, comprising the following steps:

[0042] S1: Mix metal oxides, catalysts and ionomers, add solvents and stir to prepare hydrogen removal layer slurry;

[0043] S2: coating the hydrogen removal layer slurry on the surface of the substrate and drying it to form the hydrogen removal layer.

[0044] In some preferred embodiments, in step S1, the solvent includes at least one of water, ethanol, isopropanol, n-propanol, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0045] In some preferred embodiments, in step S1, the weight proportion of the solvent in the hydrogen removal layer slurry may be 10 to 100 parts.

[0046] In some preferred embodiments, in step S1, the solid content of the hydrogen removal layer slurry is 3% to 40%.

[0047] In step S2, the position where the hydrogen removal layer slurry is applied is determined by the membrane electrode preparation process. In some embodiments, the substrate is a transfer substrate, such as a PTFE transfer substrate. In some embodiments, the substrate is a proton exchange membrane. In some embodiments, the substrate is an anode catalyst layer.

[0048] In some preferred embodiments, in step S2, the coating method is one of spray coating, blade coating, and slit coating. Further preferably, the coating method is slit coating.

[0049] In some preferred embodiments, in step S2, the coating thickness is 1 μm to 100 μm. More preferably, the coating thickness is 1 μm to 10 μm.

[0050] In some preferred embodiments, in step S2, the drying temperature is 50°C to 200°C, and the drying time is 10 minutes to 4 hours.

[0051] The present application also provides a hydrogen-removing proton exchange membrane, comprising a proton exchange membrane and a hydrogen-removing layer, wherein the hydrogen-removing layer is located on the surface of the proton exchange membrane. The presence of the hydrogen-removing layer ensures that the proton exchange membrane will not cause a decrease in the purity of the oxygen product and safety issues even when it is relatively thin. The proton exchange membrane can be any commercial proton exchange membrane used for hydrogen production by water electrolysis. For example, the proton exchange membrane can be a Nafion 212 membrane.

[0052] In some preferred embodiments, the thickness of the proton exchange membrane is 50 μm to 130 μm, more preferably 50 μm to 80 μm.

[0053] The membrane electrode of the present application comprises an anode catalyst layer, the above-mentioned hydrogen removal proton exchange membrane and a cathode catalyst layer arranged in sequence, wherein the hydrogen removal layer faces the anode catalyst layer. Under high pressure or normal pressure, the membrane electrode can have both low hydrogen content in oxygen on the anode side and high efficiency.

[0054] The present application also provides a water electrolysis hydrogen production device, comprising the aforementioned membrane electrode, wherein the presence of the hydrogen consumption layer improves the hydrogen production efficiency, lifespan and safety of the water electrolysis hydrogen production device.

[0055] The following will be combined with the embodiments of the present application to clearly and completely describe the technical solution of the present application. Unless otherwise specified, the reagents and raw materials used can be purchased through commercial channels. The experimental methods in the following examples that do not specify specific conditions are selected according to conventional methods and conditions, or according to the product specifications.

[0056] In the following examples, the aluminum oxide powder used was purchased from Sinopharm Chemical Reagent Co., Ltd. and was analytically pure; the zirconium oxide powder used was purchased from Sinopharm Chemical Reagent Co., Ltd. and was analytically pure; the cerium oxide powder used was purchased from Sinopharm Chemical Reagent Co., Ltd. and was analytically pure; the platinum black catalyst used was purchased from Anhui Masu Water New Energy Technology Co., Ltd., model SSPB-01; the iridium black catalyst used was purchased from Anhui Masu Water New Energy Technology Co., Ltd., model SS-Ir-2002; the palladium black catalyst used was purchased from Anhui Masu Water New Energy Technology Co., Ltd., model Acros-C19515; the Nafion D2020, Nafion NR50, and Nafion 212 membranes (51 μm) used were all purchased from Chemours.

[0057] Example 1

[0058] This embodiment provides a hydrogen removal layer, including: aluminum oxide, zirconium oxide, cerium oxide, a platinum black catalyst, an iridium black catalyst, Nafion D2020 and Nafion NR50.

[0059] The preparation method of the hydrogen removal layer comprises the following steps:

[0060] (1) According to the weight ratio shown in Table 1, aluminum oxide powder, zirconium oxide powder, cerium oxide powder, platinum black catalyst, iridium black catalyst, Nafion D2020, and Nafion NR50 were weighed and mixed, and water and N,N-dimethylformamide were added and stirred to prepare a dehydrogenation layer slurry;

[0061] (2) The hydrogen removal layer slurry was coated on the surface of the PTFE transfer substrate by slit coating, with a coating thickness of 5 μm, and then dried at 80° C. for 30 minutes to obtain a hydrogen removal layer.

[0062] This embodiment also provides a hydrogen-removing proton exchange membrane and a membrane electrode, and a preparation method thereof comprises the following steps:

[0063] (1) The hydrogen removal layer prepared in this example was transferred from the PTFE transfer substrate to one surface of a 51 μm Nafion 212 membrane to obtain a hydrogen removal proton exchange membrane.

[0064] (2) A cathode catalyst slurry was coated on the other surface of the Nafion 212 membrane using a coating machine, and a 5 μm cathode catalyst layer was obtained after drying. An anode catalyst slurry was coated on the surface of the hydrogen removal layer, and a 5 μm anode catalyst layer was obtained after drying.

[0065] The anode catalyst layer includes iridium black and Nafion D2020 in a weight ratio of 2:1, and the cathode catalyst layer includes platinum black and Nafion D2020 in a weight ratio of 2:1.

[0066] Example 2

[0067] Compared with Example 1, the only difference of the hydrogen removal layer in this example is that the weight ratio of aluminum oxide, zirconium oxide and cerium oxide is 2:1:7.

[0068] The preparation method of the hydrogen removal layer, hydrogen removal proton exchange membrane and membrane electrode of this embodiment is the same as that of Example 1.

[0069] Example 3

[0070] Compared with Example 1, the only difference of the hydrogen removal layer in this example is that the weight ratio of aluminum oxide, zirconium oxide and cerium oxide is 1:1:8.

[0071] The preparation method of the hydrogen removal layer, hydrogen removal proton exchange membrane and membrane electrode of this embodiment is the same as that of Example 1.

[0072] Example 4

[0073] Compared with Example 1, the only difference of the hydrogen removal layer in this example is that the weight ratio of aluminum oxide, zirconium oxide and cerium oxide is 1:3:10.

[0074] The preparation method of the hydrogen removal layer, hydrogen removal proton exchange membrane and membrane electrode of this embodiment is the same as that of Example 1.

[0075] Example 5

[0076] Compared with Example 1, the only difference of the hydrogen removal layer in this example is that no platinum black catalyst is added, and the weight ratio of the iridium black catalyst to the palladium black catalyst is 10:5.

[0077] The preparation method of the hydrogen removal layer, hydrogen removal proton exchange membrane and membrane electrode of this embodiment is the same as that of Example 1.

[0078] Example 6

[0079] Compared with Example 1, the only difference of the hydrogen removal layer in this example is that the weight ratio of the platinum black catalyst to the iridium black catalyst is 7.5:7.5.

[0080] The preparation method of the hydrogen removal layer, hydrogen removal proton exchange membrane and membrane electrode of this embodiment is the same as that of Example 1.

[0081] Example 7

[0082] Compared with Example 1, the only difference of the hydrogen removal layer in this example is that the weight ratio of the platinum black catalyst to the iridium black catalyst is 11.25:3.75.

[0083] The preparation method of the hydrogen removal layer, hydrogen removal proton exchange membrane and membrane electrode of this embodiment is the same as that of Example 1.

[0084] Example 8

[0085] Compared with Example 1, the only difference of the hydrogen removal layer in this example is that the weight ratio of Nafion D2020 to Nafion NR50 is 1:5.

[0086] The preparation method of the hydrogen removal layer, hydrogen removal proton exchange membrane and membrane electrode of this embodiment is the same as that of Example 1.

[0087] Example 9

[0088] Compared with Example 1, the only difference of the hydrogen removal layer in this example is that no aluminum oxide is added, and the weight ratio of zirconium oxide to cerium oxide is 4:6.

[0089] The preparation method of the hydrogen removal layer, hydrogen removal proton exchange membrane and membrane electrode of this embodiment is the same as that of Example 1.

[0090] Example 10

[0091] Compared with Example 1, the only difference of the hydrogen removal layer in this example is that Nafion NR50 is not added, and the balance of the ionomer is supplemented by Nafion D2020.

[0092] The preparation method of the hydrogen removal layer, hydrogen removal proton exchange membrane and membrane electrode of this embodiment is the same as that of Example 1.

[0093] Table 1 Composition of hydrogen removal layer slurry

[0094]

[0095] Comparative Example 1

[0096] This comparative example provides a membrane electrode, which is different from Example 1 only in that no hydrogen removal layer is provided.

[0097] Comparative Example 2

[0098] This comparative example provides a hydrogen removal layer and a preparation method thereof, a hydrogen removal proton exchange membrane and a membrane electrode and a preparation method thereof, which is different from Example 1 only in that no metal oxide is added when preparing the hydrogen removal layer slurry.

[0099] Comparative Example 3

[0100] This comparative example provides a hydrogen removal layer and a preparation method thereof, a hydrogen removal proton exchange membrane and a membrane electrode and a preparation method thereof, which is different from Example 1 only in that no catalyst is added when preparing the hydrogen removal layer slurry.

[0101] Scanning electron microscope test

[0102] The hydrogen removal proton exchange membrane prepared in Example 1 was tested using a scanning electron microscope of the FE-SEM SU500 model. The test conditions were: using liquid nitrogen brittle fracture method to prepare the CCM cross section, and the electron beam voltage was 5 kV. For the test results, please refer to Figure 1 . Figure 1 The red box in the middle is the hydrogen-scavenging layer in the hydrogen-scavenging proton exchange membrane, and its thickness is close to 5μm.

[0103] Hydrogen removal layer performance test

[0104] The membrane electrode was installed in a single cell test device for online testing. After collecting hydrogen on the cathode side and oxygen on the anode side, gas chromatography was used to perform component analysis to obtain the results of hydrogen in oxygen and oxygen in hydrogen.

[0105] Referring to Table 2, when the membrane electrode of all embodiments produces hydrogen by electrolysis of water, the hydrogen content in the oxygen on the anode side is maintained at 0% from 0 hours to 200 hours. Therefore, by setting a hydrogen removal layer, the embodiment of the present application can achieve the effect of improving the oxygen purity for a long time by using a thinner proton exchange membrane (51 μm).

[0106] Further, the oxygen content in hydrogen is analyzed. The oxygen content in hydrogen data of Examples 1 to 3, Example 9, Comparative Example 1, and Comparative Example 2 are compared, and the oxygen content in hydrogen is ranked from small to large as follows: Example 2, Example 9, Example 3, Comparative Example 1 (no hydrogen removal layer is provided), Comparative Example 2, and Example 1. It can be seen that compared with Comparative Example 1 in which no hydrogen removal layer is provided, when the metal oxide is composed of aluminum oxide, zirconium oxide, and cerium oxide, and the weight ratio range is preferably (1 to 2): 1: (7 to 8), or the metal oxide is composed of zirconium oxide and cerium oxide, and the weight ratio is preferably 2: 3, not only can the oxygen purity on the anode side be improved for a long time, but also the hydrogen purity on the cathode side can be higher. Although the oxygen content in hydrogen of Example 4 is higher than that of Comparative Example 1, it still remains at a relatively low level in the industry.

[0107] Comparing the oxygen in hydrogen data of Example 1, Examples 5 to 7, Comparative Example 1 and Comparative Example 3, the oxygen content in hydrogen is from small to large as follows: Example 5, Comparative Example 3, Example 6, Comparative Example 1, Example 7, Example 1. It can be seen that the catalyst is preferably composed of an iridium black catalyst and a palladium black catalyst, and the weight ratio is 2:1, or the catalyst is preferably composed of a platinum black catalyst and an iridium black catalyst, and the weight ratio is 1:1.

[0108] The oxygen in hydrogen data of Example 1, Example 8, Example 10 and Comparative Example 1 are compared, and the oxygen content in hydrogen is from small to large as follows: Example 10, Example 8, Comparative Example 1, Example 1. It is further obtained that the ionomer is preferably composed of Nafion D2020 and Nafion NR50, and the weight ratio is 1:5, or the ionomer preferably includes Nafion D2020.

[0109] Table 2 Test results of hydrogen in oxygen and oxygen in hydrogen

[0110]

[0111] Membrane electrode performance test

[0112] The membrane electrode prepared above was tested using an electrolytic water test bench. The specific test method is as follows:

[0113] 1) Prepare the test environment (water resistivity is greater than 3MΩ / cm), ensure that the water and gas pipelines are correctly constructed, and that the temperature control system can work normally;

[0114] 2) Assemble the electrolytic water fixture. Place the electrolytic water fixture on the table and assemble from bottom to top: cathode end plate → cathode gold-plated plate → graphite plate → cathode gasket → carbon paper → membrane electrode → anode gasket → sintered titanium plate → anode flow channel plate → anode end plate. After all parts are placed, tighten the screws with a torque wrench in a fixed order with a torque of 2 → 3 → 4 → 5 Nm per turn. Then install the electrolytic water fixture on the test bench.

[0115] 3) Install the DC power supply load line and SENSE line, turn on the flow meter so that the upper end of the float is close to the 100mL / min scale line. Press the heating button. Wait for the fixture temperature to rise to the set temperature of 80℃ and start the test.

[0116] 4) Enter the test program (increase 0.2A / cm per stage 2 , each stage stays for four minutes) to carry out polarization curve test.

[0117] Figure 2 Table 3 shows the polarization curves of the membrane electrode prepared in Example 1 under normal pressure and high pressure (3Mpa) test pressure. Table 3 shows the polarization curves of the membrane electrode prepared in Examples 1 to 10 and Comparative Example 1 under high pressure (3Mpa) test conditions at 2A / cm 2 The voltage value at that time.

[0118] Table 3 Membrane electrode performance test results

[0119] project Voltage value Example 1 1.65 Example 2 1.66 Example 3 1.64 Example 4 1.63 Example 5 1.64 Example 6 1.63 Example 7 1.66 Example 8 1.63 Example 9 1.62 Example 10 1.64 Comparative Example 1 1.65

[0120] The results show that compared with the comparative example 1 without the hydrogen removal layer, after the hydrogen removal layer of the present application is provided, at the same current density, the voltage values ​​of the embodiments 1, 2 and 7 are equivalent to or only slightly increased with the comparative example 1, while the voltage values ​​of the embodiments 3 to 6 and 8 to 10 are slightly reduced. Therefore, the hydrogen removal layer of the present application will not have a significant impact on the electrolysis efficiency of the membrane electrode.

[0121] In particular, when the metal oxide is composed of aluminum oxide, zirconium oxide and cerium oxide in a weight ratio of 1:1:8, or when the metal oxide is composed of zirconium oxide and cerium oxide in a weight ratio of 2:3, it can not only reduce the hydrogen content in oxygen and the oxygen content in hydrogen, but also improve the electrolysis efficiency.

[0122] When the catalyst is composed of an iridium black catalyst and a palladium black catalyst in a weight ratio of 2:1, or when the catalyst is composed of a platinum black catalyst and an iridium black catalyst in a weight ratio of 1:1, the effect of reducing the hydrogen content in oxygen and the oxygen content in hydrogen and improving the electrolysis efficiency can also be achieved.

[0123] When the ionomer is composed of Nafion D2020 and Nafion NR50 with a weight ratio of 1:5, or when the ionomer is composed of Nafion D2020 alone, the electrolysis efficiency can also be improved while reducing the hydrogen content in oxygen and the oxygen content in hydrogen.

[0124] The above description of the embodiments is to facilitate those of ordinary skill in the art to understand and apply the present application. It is obvious that those familiar with the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without having to pay creative labor. Therefore, the present application is not limited to the embodiments herein, and improvements and modifications made by those skilled in the art based on the contents disclosed in the present application without departing from the scope and spirit of the present application are within the scope of the present application.

Claims

1. A hydrogen removal layer, characterized in that: The invention comprises the following components in parts by weight: 10 to 20 parts of metal oxide, 10 to 20 parts of catalyst and 2 to 10 parts of ionomer; the catalyst comprises at least one of platinum black catalyst, iridium black catalyst and palladium black catalyst.

2. The hydrogen removal layer according to claim 1, characterized in that: The ionomer comprises at least one of sulfonated polysulfone, sulfonated polyethersulfone, perfluorosulfonic acid resin, sulfonated polyetheretherketone, sulfonated polyphenylene sulfide, perfluorocarboxylic acid resin, and perfluorophosphoric acid resin; The metal oxide is composed of aluminum oxide, zirconium oxide and cerium oxide, and the weight ratio is (1-2):(2-3):(7-10), preferably (1-2):1:(7-8); or, the metal oxide is composed of zirconium oxide and cerium oxide, and the weight ratio is 2:

3.

3. The hydrogen removal layer according to claim 2, characterized in that: The ionomer is composed of Nafion D2020 and Nafion NR50, and the weight ratio is (1-5): (1-5); or the ionomer is Nafion D2020.

4. The hydrogen removal layer according to claim 1, characterized in that: The catalyst is composed of a platinum black catalyst and an iridium black catalyst, and the weight ratio is (1-3):1; or, the catalyst is composed of an iridium black catalyst and a palladium black catalyst, and the weight ratio is 2:

1.

5. The hydrogen removal layer according to any one of claims 1 to 4, characterized in that: The weight ratio of the metal oxide, the catalyst and the ionomer is (1-5):(1-10):

1.

6. A method for preparing a hydrogen removal layer according to any one of claims 1 to 5, characterized in that: The following steps are involved: Mixing metal oxides, catalysts and ionomers, adding solvents and stirring to prepare hydrogen removal layer slurry; The hydrogen removal layer slurry is coated on the surface of a substrate and dried to form the hydrogen removal layer.

7. The preparation method according to claim 6, characterized in that: The preparation method satisfies at least one of the following conditions: (1) The solvent includes at least one of water, ethanol, isopropanol, n-propanol, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; (2) The solid content of the hydrogen removal layer slurry is 3% to 40%; (3) The coating thickness is 1 μm to 100 μm; preferably, the coating thickness is 1 μm to 10 μm; (4) The drying temperature is 50°C to 200°C and the drying time is 10 minutes to 4 hours; (5) The coating method is one of spray coating, blade coating, and slit coating; preferably, the coating method is slit coating; (6) The substrate is a transfer substrate, a proton exchange membrane or an anode catalyst layer.

8. A proton exchange membrane for removing hydrogen, characterized in that: A method of manufacturing a proton exchange membrane comprising a proton exchange membrane and a hydrogen removal layer according to any one of claims 1 to 5 located on the surface of the proton exchange membrane.

9. The hydrogen-removing proton exchange membrane according to claim 8, characterized in that: The thickness of the proton exchange membrane is 50 μm to 130 μm, preferably 50 μm to 80 μm.

10. A membrane electrode, characterized in that: It comprises an anode catalyst layer, the hydrogen-scavenging proton exchange membrane according to claim 8 or 9, and a cathode catalyst layer which are arranged in sequence, wherein the hydrogen-scavenging layer faces the anode catalyst layer.

11. A hydrogen production device by electrolysis of water, characterized in that: Comprising the membrane electrode according to claim 10.

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