Hydrogen removal layer, preparation method therefor, hydrogen removal proton exchange membrane, membrane electrode, and water electrolysis hydrogen production apparatus

Abstract

The present application relates to the technical field of water electrolysis for hydrogen production and discloses a hydrogen removal layer, a preparation method therefor, a hydrogen removal proton exchange membrane, a membrane electrode, and a water electrolysis hydrogen production apparatus. The hydrogen removal layer comprises the following components in parts 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 removal layer described in the present application can effectively reduce the hydrogen content in oxygen on the anode side of a proton exchange membrane.

Description

Hydrogen elimination layer, preparation method thereof, hydrogen elimination proton exchange membrane, membrane electrode and water electrolysis hydrogen production device TECHNICAL FIELD

[0001] The present application relates to the technical field of water electrolysis hydrogen production, in particular to a hydrogen elimination layer, a preparation method thereof, a hydrogen elimination proton exchange membrane, a membrane electrode and a water electrolysis hydrogen production device. BACKGROUND

[0002] The membrane electrode assembly (MEA), also known as membrane electrode, is an important component of the 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 the direct passage of electrons and gases (such as hydrogen and oxygen). During the electrolysis process, water molecules undergo oxidation reaction on the anode side to generate oxygen and protons. The protons are conducted to the cathode side through the proton exchange membrane and combined with electrons to generate hydrogen gas.

[0003] In theory, the thinner the proton exchange membrane, the lower the voltage loss of the membrane resistance, thereby reducing the electrolytic cell voltage and improving the electrolysis efficiency. However, thinner proton exchange membranes also bring new problems. When the proton exchange membrane becomes thinner, its gas permeability also increases. In a high-pressure working environment, hydrogen gas generated on the cathode side may penetrate through the membrane to the anode side, resulting in hydrogen mixed in the oxygen generated on the anode side (also known as "hydrogen in oxygen"). This not only reduces the purity of the anode product, but also may cause safety problems.

[0004] SUMMARY

[0005] The technical problem solved by the present application is to reduce the content of hydrogen in oxygen on the anode side of the proton exchange membrane.

[0006] To solve the above technical problems, the present application provides the following technical solutions:

[0007] In a first aspect, the present application provides a hydrogen elimination layer, which comprises the following components by weight: 10-20 parts of metal oxide, 10-20 parts of catalyst, and 2-10 parts of ionomer; the catalyst comprises at least one of platinum black catalyst, iridium black catalyst and palladium black catalyst.

[0008] In some embodiments of the first aspect, the ionomer comprises at least one of sulfonated polysulfone, sulfonated polyether sulfone, perfluorosulfonic acid resin, sulfonated polyether ether ketone, sulfonated polyphenylene sulfide, perfluorocarboxylic acid resin and perfluorophosphoric acid resin.

[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):(2-3):(7-10).

[0010] 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).

[0011] In some embodiments of the first aspect, the metal oxide consists of zirconium oxide and cerium oxide, and the weight ratio is 2:3.

[0012] In some embodiments of the first aspect, the ionomer consists of Nafion D2020 and Nafion NR50, and the weight ratio is (1-5):(1-5).

[0013] In some embodiments of the first aspect, the ionomer is Nafion D2020.

[0014] In some embodiments of the first aspect, the catalyst consists of platinum black catalyst and iridium black catalyst, and the weight ratio is (1-3):1.

[0015] In some embodiments of the first aspect, the catalyst consists of iridium black catalyst and palladium black catalyst, and the weight ratio is 2:1.

[0016] 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.

[0017] In the second aspect, the application provides a preparation method of the hydrogen elimination layer, comprising the following steps: mixing the metal oxide, the catalyst and the ionomer, and adding a solvent to stir to prepare a hydrogen elimination layer slurry; coating the hydrogen elimination layer slurry on the surface of a substrate and drying to form the hydrogen elimination layer.

[0018] In some embodiments of the second aspect, the preparation method satisfies at least one of the following conditions: (1) the solvent comprises at least one of water, ethanol, isopropanol, n-propanol, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; (2) the solid content of the hydrogen elimination layer slurry is 3%-40%; (3) the coating thickness is 1 μm-100 μm; preferably, the coating thickness is 1 μm-10 μm; (4) the drying temperature is 50°C-200°C, and the drying time is 10 minutes-4 hours; (5) the coating method is one of spraying, doctor blade coating and slot coating; preferably, the coating method is slot coating; (6) the substrate is a transfer substrate, a proton exchange membrane or an anode catalyst layer.

[0019] In a third aspect, the application provides a hydrogen-eliminating proton exchange membrane, comprising a proton exchange membrane and the hydrogen-eliminating layer according to any one of the above on the surface of the proton exchange membrane.

[0020] In some embodiments of the third aspect, the thickness of the proton exchange membrane is 50-130 μm; preferably 50-80 μm.

[0021] In a fourth aspect, the application provides a membrane electrode, comprising an anode catalyst layer, the hydrogen-eliminating proton exchange membrane according to the above and a cathode catalyst layer arranged in sequence, wherein the hydrogen-eliminating layer faces the anode catalyst layer.

[0022] In a fifth aspect, the application provides a water electrolysis hydrogen production device, comprising the membrane electrode according to the above.

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

[0024] The application uses a specific combination of metal oxides, catalysts and ionomers as the composition of the hydrogen-eliminating layer, which can reduce the hydrogen content in oxygen on the anode side of the proton exchange membrane when a thinner proton exchange membrane is used. Further, by optimizing the types and proportions of each component, not only can the purity of the anode side oxygen be improved for a long time, but also the purity of the cathode side hydrogen can be high. Furthermore, the electrolysis efficiency can also be improved. BRIEF DESCRIPTION OF DRAWINGS

[0025] The following drawings describe the exemplary embodiments disclosed in the application in detail. The same reference signs in the several views of the drawings represent similar structures. Those skilled in the art will understand that these embodiments are non-limiting, exemplary embodiments, and the drawings are only for the purpose of illustration and description, and are not intended to limit the scope of the application, and other embodiments can also achieve the same purpose. It should be understood that the drawings are not drawn to scale. Among them:

[0026] Figure 1 is a scanning electron microscope picture of the cross section of the hydrogen-eliminating proton exchange membrane prepared in Example 1 of the application;

[0027] Figure 2 is the polarization curve of the membrane electrode prepared in Example 1 of the application. DETAILED DESCRIPTION

[0028] The following description provides specific application scenarios and requirements of the application, which is to enable those skilled in the art to manufacture and use the content in the application. Various local modifications of the disclosed embodiments are obvious to those skilled in the art, and the general principles defined herein can be applied to other embodiments and applications without departing from the spirit and scope of the application. Therefore, the application is not limited to the shown embodiments, but to the widest scope consistent with the claims.

[0029] Generally, the oxygen purity at the anode outlet is between 99% and 99.5% (current density is 1 A / cm 2 , 80℃, normal pressure). If the water electrolysis hydrogen production device is operated under pressure, the gas permeability of the proton exchange membrane will increase with the increase of the gas product pressure, resulting in further decrease of the oxygen product purity and increase of the hydrogen content in the oxygen, which may cause safety problems. Therefore, when optimizing the performance of the proton exchange membrane, multiple factors need to be considered. On the one hand, the membrane should be as thin as possible to reduce the voltage loss; on the other hand, it should ensure a high oxygen product purity.

[0030] Based on this, the application provides 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. By setting the hydrogen elimination layer on the proton exchange membrane and optimizing the composition of the hydrogen elimination layer, the hydrogen content in the oxygen on the anode side of the proton exchange membrane can be reduced while using a thinner proton exchange membrane.

[0031] The hydrogen elimination layer of the application comprises the following components in weight percentage: 10-20 parts of metal oxide, 10-20 parts of catalyst, and 2-10 parts of ionomer. The catalyst comprises at least one of platinum black catalyst, iridium black catalyst, and palladium black catalyst.

[0032] When the hydrogen produced on the cathode side enters the hydrogen elimination layer, the metal oxide can react with the hydrogen in the presence of at least one of the platinum black catalyst, the iridium black catalyst, and the palladium black catalyst, thereby playing a role in eliminating 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 convert the oxygen entering the hydrogen elimination layer into O 2- , H + , and O 2- combine to form water molecules, further playing a role in eliminating hydrogen. The addition of the ionomer can improve the oxygen permeability, so that the oxygen produced on the anode side can enter the hydrogen elimination layer, increase the oxygen concentration in the hydrogen elimination layer, and make the hydrogen be consumed by the oxygen more fully, further improving the effect of eliminating hydrogen. At the same time, the specific weight percentage ratio of the metal oxide, the catalyst, and the ionomer can make the oxygen concentration in the hydrogen elimination layer within a reasonable range without too much escaping to the cathode side.

[0033] In some preferred embodiments, the metal oxide is 10-15 parts, the catalyst is 15-20 parts, and the ionomer is 4-8 parts.

[0034] In some preferred embodiments, the weight ratio of the metal oxide, the catalyst, and the ionomer is (1-5):(1-10):1.

[0035] 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 further preferably 1:1:8.

[0036] In some preferred embodiments, the metal oxide is composed of zirconium oxide and cerium oxide, and the weight ratio is 2:3.

[0037] In some embodiments, the ionomer includes at least one of sulfonated polysulfone, sulfonated polyether sulfone, perfluorosulfonic acid resin, sulfonated polyether ether ketone, sulfonated polyphenylene sulfide, perfluorocarboxylic acid resin, and perfluorophosphoric acid resin.

[0038] 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.

[0039] In some preferred embodiments, the ionomer is Nafion D2020.

[0040] In some embodiments, the catalyst is composed of platinum black catalyst and iridium black catalyst, and the weight ratio is (1-3):1. Further preferably, the weight ratio of the platinum black catalyst and the iridium black catalyst is 1:1.

[0041] In some preferred embodiments, the catalyst is composed of iridium black catalyst and palladium black catalyst, and the weight ratio is 2:1.

[0042] The application also provides a preparation method of the above hydrogen elimination layer, comprising the following steps:

[0043] S1: mixing the metal oxide, the catalyst and the ionomer, and adding a solvent to stir to prepare a hydrogen elimination layer slurry;

[0044] S2: coating the hydrogen elimination layer slurry on the surface of the substrate and drying to form the hydrogen elimination layer.

[0045] 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.

[0046] In some preferred embodiments, in step S1, the weight fraction of the solvent in the hydrogen elimination layer slurry can be 10-100 parts.

[0047] In some preferred embodiments, the solid content of the hydrogen elimination layer slurry in step S1 is 3% to 40%.

[0048] In step S2, the position of the hydrogen elimination layer slurry coating is determined by the preparation process of the membrane electrode. 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.

[0049] In some preferred embodiments, the coating method in step S2 is one of spraying, blade coating, and slot coating. Further preferably, the coating method is slot coating.

[0050] In some preferred embodiments, the coating thickness in step S2 is 1 μm to 100 μm. Further preferably, the coating thickness is 1 μm to 10 μm.

[0051] In some preferred embodiments, the drying temperature in step S2 is 50°C to 200°C, and the drying time is 10 minutes to 4 hours.

[0052] The present application also provides a hydrogen-eliminating proton exchange membrane, which comprises a proton exchange membrane and a hydrogen-eliminating layer, and the hydrogen-eliminating layer is located on the surface of the proton exchange membrane. The presence of the hydrogen-eliminating layer makes the proton exchange membrane thinner without causing the problems of oxygen product purity reduction and safety. The proton exchange membrane can be any commercialized proton exchange membrane used for water electrolysis hydrogen production. For example, the proton exchange membrane can be a Nafion 212 membrane.

[0053] In some preferred embodiments, the thickness of the proton exchange membrane is 50 μm to 130 μm. Further preferably, the thickness is 50 μm to 80 μm.

[0054] The membrane electrode of the present application comprises an anode catalyst layer, the above-mentioned hydrogen-eliminating proton exchange membrane, and a cathode catalyst layer arranged in sequence, wherein the hydrogen-eliminating layer faces the anode catalyst layer. Under high pressure or normal pressure, the membrane electrode can have both lower hydrogen content in oxygen on the anode side and higher efficiency.

[0055] The present application also provides a water electrolysis hydrogen production device comprising the above-mentioned membrane electrode. The presence of the hydrogen-eliminating layer improves the hydrogen production efficiency, service life, and safety of the water electrolysis hydrogen production device.

[0056] The technical solutions of the present application will be described clearly and completely in combination with the embodiments of the present application. Unless otherwise specified, the reagents and raw materials used can be purchased through commercial channels. The experimental methods not specified in the following examples are selected according to conventional methods and conditions, or according to the product instructions.

[0057] In the following examples, the alumina powder used is purchased from the National Pharmaceutical Group Chemical Reagent Co., Ltd., and is analytically pure; the zirconia powder used is purchased from the National Pharmaceutical Group Chemical Reagent Co., Ltd., and is analytically pure; the ceria powder used is purchased from the National Pharmaceutical Group Chemical Reagent Co., Ltd., and is analytically pure; the platinum black catalyst used is purchased from Anhui Maishui New Energy Technology Co., Ltd., and the model is SSPB-01; the iridium black catalyst used is purchased from Anhui Maishui New Energy Technology Co., Ltd., and the model is SS-Ir-2002; the palladium black catalyst used is purchased from Anhui Maishui New Energy Technology Co., Ltd., and the model is Acros-C19515; the Nafion D2020, Nafion NR50, and Nafion 212 film (51 μm) used are all purchased from the company.

[0058] Example 1

[0059] The present example provides a hydrogen elimination layer, comprising: alumina, zirconia, ceria, platinum black catalyst, iridium black catalyst, Nafion D2020, and Nafion NR50.

[0060] The preparation method of the hydrogen elimination layer comprises the following steps:

[0061] (1) The alumina powder, zirconia powder, ceria powder, platinum black catalyst, iridium black catalyst, Nafion D2020, and Nafion NR50 are weighed according to the proportions shown in Table 1 and mixed, water and N,N-dimethylformamide are added and stirred to prepare a hydrogen elimination layer slurry;

[0062] (2) The hydrogen elimination layer slurry is coated on the surface of a PTFE transfer substrate in a slit coating manner, the coating thickness is 5 μm, and then dried at 80°C for 30 minutes to obtain a hydrogen elimination layer.

[0063] The present example also provides a hydrogen elimination proton exchange membrane and a membrane electrode, and the preparation method thereof comprises the following steps:

[0064] (1) The hydrogen elimination layer prepared in the present example is transferred from the PTFE transfer substrate to one surface of a 51 μm Nafion 212 film to obtain a hydrogen elimination proton exchange membrane.

[0065] (2) A cathode catalyst slurry is coated on the other surface of the Nafion 212 film using a coating machine, and after drying, a 5 μm cathode catalyst layer is obtained, and an anode catalyst slurry is coated on the surface of the hydrogen elimination layer, and after drying, a 5 μm anode catalyst layer is obtained.

[0066] The anode catalyst layer comprises iridium black and Nafion D2020 in a weight ratio of 2:1, and the cathode catalyst layer comprises platinum black and Nafion D2020 in a weight ratio of 2:1.

[0067] Example 2

[0068] The difference of the hydrogen elimination layer of this example from that of Example 1 is only that the weight ratio of aluminum oxide, zirconium oxide and cerium oxide is 2:1:7.

[0069] The preparation method of the hydrogen elimination layer, the hydrogen elimination proton exchange membrane and the membrane electrode of this example is the same as that of Example 1.

[0070] Example 3

[0071] The difference of the hydrogen elimination layer of this example from that of Example 1 is only that the weight ratio of aluminum oxide, zirconium oxide and cerium oxide is 1:1:8.

[0072] The preparation method of the hydrogen elimination layer, the hydrogen elimination proton exchange membrane and the membrane electrode of this example is the same as that of Example 1.

[0073] Example 4

[0074] The difference of the hydrogen elimination layer of this example from that of Example 1 is only that the weight ratio of aluminum oxide, zirconium oxide and cerium oxide is 1:3:10.

[0075] The preparation method of the hydrogen elimination layer, the hydrogen elimination proton exchange membrane and the membrane electrode of this example is the same as that of Example 1.

[0076] Example 5

[0077] The difference of the hydrogen elimination layer of this example from that of Example 1 is only that no platinum black catalyst is added, and the weight ratio of iridium black catalyst and palladium black catalyst is 10:5.

[0078] The preparation method of the hydrogen elimination layer, the hydrogen elimination proton exchange membrane and the membrane electrode of this example is the same as that of Example 1.

[0079] Example 6

[0080] The difference of the hydrogen elimination layer of this example from that of Example 1 is only that the weight ratio of platinum black catalyst and iridium black catalyst is 7.5:7.5.

[0081] The preparation method of the hydrogen elimination layer, the hydrogen elimination proton exchange membrane and the membrane electrode of this example is the same as that of Example 1.

[0082] Example 7

[0083] The difference of the hydrogen elimination layer of this example from that of Example 1 is only that the weight ratio of platinum black catalyst and iridium black catalyst is 11.25:3.75.

[0084] The preparation method of the hydrogen elimination layer, the hydrogen elimination proton exchange membrane and the membrane electrode of this example is the same as that of Example 1.

[0085] Example 8

[0086] The difference of the hydrogen elimination layer of this example compared to Example 1 is only that the weight ratio of Nafion D2020 and Nafion NR50 is 1:5.

[0087] The preparation method of the hydrogen elimination layer, the hydrogen elimination proton exchange membrane and the membrane electrode of this example is the same as that of Example 1.

[0088] Example 9

[0089] The difference of the hydrogen elimination layer of this example compared to Example 1 is only that no aluminum oxide is added, and the weight ratio of zirconium oxide and cerium oxide is 4:6.

[0090] The preparation method of the hydrogen elimination layer, the hydrogen elimination proton exchange membrane and the membrane electrode of this example is the same as that of Example 1.

[0091] Example 10

[0092] The difference of the hydrogen elimination layer of this example compared to Example 1 is only that no Nafion NR50 is added, and the rest of the ionomer is made up with Nafion D2020.

[0093] The preparation method of the hydrogen elimination layer, the hydrogen elimination proton exchange membrane and the membrane electrode of this example is the same as that of Example 1.

[0094] Table 1 Hydrogen elimination layer slurry composition

[0095] Comparative Example 1

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

[0097] Comparative Example 2

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

[0099] Comparative Example 3

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

[0101] Scanning electron microscope test

[0102] The hydrogen elimination proton exchange membrane prepared in Example 1 was tested by using a FE-SEM SU500 type scanning electron microscope, the test conditions were: using liquid nitrogen brittle fracture method to prepare CCM cross section, electron beam voltage was 5 kV, and the test results were shown in FIG. 1. The red box in FIG. 1 was the hydrogen elimination layer in the hydrogen elimination proton exchange membrane, and the thickness thereof was close to 5 μm.

[0103] Performance test of hydrogen elimination layer

[0104] After the membrane electrode was loaded into a single cell test device, online testing was performed, and after hydrogen on the cathode side and oxygen on the anode side were collected, gas chromatography was used for component analysis to obtain the hydrogen in oxygen and oxygen in hydrogen results.

[0105] Referring to Table 2, the hydrogen content in oxygen on the anode side of the membrane electrode of all examples remained at 0% from 0 hour to 200 hours when water was electrolyzed to produce hydrogen. Therefore, by setting the hydrogen elimination layer, the thinner proton exchange membrane (51 μm) can achieve the effect of improving the oxygen purity for a long time.

[0106] Further, the hydrogen in oxygen content was analyzed. The hydrogen in oxygen data of Examples 1-3, Example 9, and Comparative Examples 1 and 2 were compared, and the hydrogen in oxygen content from small to large was in turn: Example 2, Example 9, Example 3, Comparative Example 1 (without setting a hydrogen elimination layer), Comparative Example 2, and Example 1. It can be known that, compared with Comparative Example 1 without setting a hydrogen elimination layer, when the metal oxide is composed of aluminum oxide, zirconium oxide and cerium oxide, and the weight ratio range is preferably (1-2):1:(7-8), or the metal oxide is composed of zirconium oxide and cerium oxide, and the weight ratio is preferably 2:3, not only the oxygen purity on the anode side can be improved for a long time, but also the hydrogen purity on the cathode side can be higher. Although the hydrogen in oxygen content of Example 4 is higher than that of Comparative Example 1, it is still at a relatively low level in the industry.

[0107] The hydrogen in oxygen data of Examples 1, 5-7, Comparative Example 1 and Comparative Example 3 were compared, and the hydrogen in oxygen content from small to large was in turn: Example 5, Comparative Example 3, Example 6, Comparative Example 1, Example 7, and Example 1. It can be known that the catalyst is preferably composed of iridium black catalyst and palladium black catalyst, and the weight ratio is 2:1, or the catalyst is preferably composed of platinum black catalyst and iridium black catalyst, and the weight ratio is 1:1.

[0108] The hydrogen in oxygen data of Examples 1, 8, 10 and Comparative Example 1 were compared, and the hydrogen in oxygen content from small to large was in turn: Example 10, Example 8, Comparative Example 1, and Example 1. It was 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 comprises Nafion D2020.

[0109] Table 2. Results of oxygen concentration and hydrogen in oxygen test within the hydrogen elimination layer.

[0110] Membrane electrode performance testing

[0111] The membrane electrode prepared above was tested using an electrolysis water test bench. The specific test method is as follows:

[0112] 1) Prepare the test environment (water resistivity greater than 3MΩ / cm), ensure that the water and gas pipelines are set up correctly, and that the temperature control system can work normally;

[0113] 2) Assemble the water electrolysis fixture. Place the fixture on the table and assemble it from bottom to top in the following order: cathode end plate → gold-plated cathode plate → graphite plate → cathode gasket → carbon paper → membrane electrode → anode gasket → sintered titanium plate → anode flow channel plate → anode end plate. After all components are in place, tighten the screws with a torque wrench in a fixed sequence of 2→3→4→5 Nm per turn. Then install the water electrolysis fixture onto the test bench.

[0114] 3) Install the DC power supply load line and SENSE line, and turn on the flow meter so that the upper end of the float is close to the 100 mL / min mark. Press the heating button. Wait for the fixture temperature to rise to the set temperature of 80℃ before starting the test.

[0115] 4) Load the test program (increase by 0.2A / cm per stage) 2 Polarization curve tests were conducted by pausing for four minutes at each stage.

[0116] Figure 2 shows the polarization curves of the membrane electrode prepared in Example 1 under atmospheric pressure and high pressure (3 MPa) test pressure. Table 3 shows the polarization curves of the membrane electrodes prepared in Examples 1-10 and Comparative Example 1 under high pressure (3 MPa) test conditions at 2 A / cm 2 The voltage value at that time.

[0117] Table 3. Test results of membrane electrode performance

[0118] The results showed that, compared with Comparative Example 1 without a hydrogen removal layer, after adding the hydrogen removal layer of this application, the voltage values ​​of Examples 1, 2, and 7 were comparable to or only slightly higher than those of Comparative Example 1 at the same current density, while the voltage values ​​of Examples 3-6 and Examples 8-10 showed a slight decrease. Therefore, the hydrogen removal layer of this application does not have a significant impact on the electrolysis efficiency of the membrane electrode.

[0119] 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.

[0120] When the catalyst is composed of iridium black catalyst and palladium black catalyst, and the weight ratio is 2:1, or the catalyst is composed of platinum black catalyst and iridium black catalyst, and the weight ratio is 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.

[0121] When the ionomer is composed of Nafion D2020 and Nafion NR50, and the weight ratio is 1:5, or the ionomer is composed of only Nafion D2020, the electrolysis efficiency can also be improved while reducing the hydrogen content in oxygen and the oxygen content in hydrogen.

[0122] The above description of the embodiments is to facilitate the understanding and application of the present application by those of ordinary skill in the art. Those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described herein to other embodiments without having to exert creative labor. Therefore, the present application is not limited to the embodiments herein, and the improvements and modifications made by those skilled in the art based on the disclosure of 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-consuming layer, characterized in that, The components include the following components by weight: 10-20 parts of metal oxide, 10-20 parts of catalyst, 2-10 parts of ionomer; the catalyst includes at least one of platinum black catalyst, iridium black catalyst, and palladium black catalyst.

2. The hydrogen elimination layer according to claim 1, characterized in that The ionomer includes at least one of sulfonated polysulfone, sulfonated polyether sulfone, perfluorosulfonic acid resin, sulfonated polyether ether ketone, 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 elimination 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 elimination layer of claim 1, wherein The catalyst is composed of platinum black catalyst and iridium black catalyst, and the weight ratio is (1-3):1; or the catalyst is composed of iridium black catalyst and palladium black catalyst, and the weight ratio is 2:

1.

5. The hydrogen desorption 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 producing the hydrogen-absorbing layer as claimed in any one of claims 1 to 5, characterized by, The method includes the following steps: Mixing the metal oxide, the catalyst, and the ionomer, and adding a solvent to stir to prepare a hydrogen elimination layer slurry; Coating the hydrogen elimination layer slurry on the surface of a substrate and drying to form the hydrogen elimination layer.

7. The production method according to claim 6, characterized by, The preparation method meets 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 elimination layer slurry is 3%-40%; (3) The coating thickness is 1 μm-100 μm; preferably, the coating thickness is 1 μm-10 μm; (4) The drying temperature is 50°C-200°C, and the drying time is 10 minutes-4 hours; (5) The coating method is one of spraying, doctor blade coating, and slot coating; preferably, the coating method is slot coating; (6) The substrate is a transfer substrate, a proton exchange membrane, or an anode catalyst layer.

8. A hydrogen-eliminating proton exchange membrane, characterized by, The proton exchange membrane includes the hydrogen elimination layer of any one of claims 1-5 on the surface of the proton exchange membrane.

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

10. A membrane electrode characterized by, The membrane electrode includes the hydrogen elimination proton exchange membrane of claim 8 or 9 and a cathode catalyst layer arranged in sequence, wherein the hydrogen elimination layer faces the anode catalyst layer.

11. An apparatus for producing hydrogen by electrolysis of water, characterized by The membrane electrode includes the membrane of claim 10.

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