Electrode plate and hydrogen production electrolytic cell

Abstract

The utility model provides an electrode plate and a hydrogen production electrolytic tank. The electrode plate comprises a diffusion layer, a first electrode and a second electrode, an electrode catalyst layer formed on the diffusion layer; wherein the coverage rate of the electrode catalyst layer on the surface of one side of the diffusion layer is greater than or equal to 70%. According to the electrode plate and the hydrogen production electrolytic cell provided by the utility model, the catalyst performance of the electrode can be improved.

Description

[0001] The present application is a divisional application of the Chinese Utility Model Patent Application No. 202422277910.6, with the title of "A Membrane Electrode and a Hydrogen Production Electrolytic Cell", filed on September 18, 2024. TECHNICAL FIELD

[0002] The utility model relates to electrode preparation technical field, especially to an electrode sheet and a hydrogen production electrolytic cell. BACKGROUND

[0003] As the core component of water electrolysis hydrogen production technology, the membrane electrode is composed of an electrode catalyst layer, an electrode catalyst layer and a membrane layer, which plays a role in proton conduction, catalytic reaction and gas separation, and determines the performance, efficiency, service life and cost of water electrolysis hydrogen production.

[0004] However, in the membrane electrode, the electrode catalyst layer and the membrane layer are prone to peeling off, and the stability of the membrane electrode is poor. At the same time, during the electrolysis process, hydrogen can penetrate from the cathode to the anode through the membrane layer, and the mixing of hydrogen and oxygen will reduce the performance of the membrane electrode, and in severe cases, it will cause explosion, and the safety problem is prominent. SUMMARY

[0005] The utility model provides a hydrogen production electrolytic cell electrode sheet, comprising:

[0006] diffusion layer;

[0007] electrode catalyst layer, formed on the diffusion layer;

[0008] Among them, the coverage of the electrode catalyst layer on the one side surface of the diffusion layer is greater than or equal to 70%.

[0009] In an embodiment of the utility model, the coverage of the electrode catalyst layer on the one side surface of the diffusion layer is 75%-99%.

[0010] In an embodiment of the utility model, the electrode catalyst layer is formed on one side or opposite two sides of the diffusion layer.

[0011] In an embodiment of the utility model, the electrode catalyst layer comprises nanoparticles, nanowires or nanochains.

[0012] The utility model also provides a hydrogen production electrolytic cell, comprising:

[0013] membrane layer;

[0014] diffusion layer;

[0015] electrode catalyst layer, formed on one side of the membrane layer and the diffusion layer;

[0016] The coverage of the electrode catalyst layer on the surface of the diffusion layer is greater than or equal to 70%.

[0017] In an embodiment of the present application, the electrode catalyst layer on the membrane layer is an anode catalyst layer, which comprises a hydrogen consumption layer and an anode catalyst base layer.

[0018] In an embodiment of the present application, part of the hydrogen consumption layer of the anode catalyst layer is embedded or fused into the membrane layer.

[0019] In an embodiment of the present application, the thickness ratio of the membrane layer, the anode catalyst layer and the cathode catalyst layer is 1:0.1:0.1-1:10:10.

[0020] In an embodiment of the present application, the electrode catalyst layer is formed on one side or opposite two sides of the diffusion layer.

[0021] In summary, the electrode sheet and the hydrogen production electrolytic cell provided by the present application can improve the catalyst performance of the electrode.

[0022] Of course, implementing any mode of the present application does not necessarily need to achieve all the advantages mentioned above at the same time. BRIEF DESCRIPTION OF DRAWINGS

[0023] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced below, and obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0024] Figure 1 It is a flowchart of the preparation method of the membrane electrode in an embodiment of the present application.

[0025] Figure 2 It is a physical diagram of the membrane electrode in an embodiment of the present application.

[0026] Figure 3 It is Figure 2 It is a micro-morphology cross-sectional view of the membrane electrode.

[0027] Figure 4 It is Figure 3 It is an enlarged view of the membrane layer and the electrode catalyst layer.

[0028] Figure 5 It is Figure 2 It is a stability curve diagram of the membrane electrode.

[0029] Figure 6It is a schematic view of the film layer and the electrode catalyst layer in one embodiment of the present application.

[0030] Figure 7 It is a micro-morphology view of the film layer and the electrode catalyst layer in one embodiment of the present application.

[0031] Figure 8 It is a structural schematic view of the film electrode in one embodiment of the present application.

[0032] Figure 9 It is a distribution schematic view of the hydrogen consumption layer on the film layer in one embodiment of the present application.

[0033] Figure 10 It is a schematic view of the flow channel in the cathode catalyst layer in one embodiment of the present application.

[0034] Figure 11 It is a distribution schematic view of the hydrogen consumption layer on the film layer in another embodiment of the present application.

[0035] Figure 12 It is a structural schematic view of the film electrode in one embodiment of the present application when being transferred.

[0036] Figure 13 It is a scanning electron microscope view of the electrode catalyst layer obtained by the transfer method of the present application in one embodiment.

[0037] Figure 14 It is a scanning electron microscope view of the electrode catalyst layer obtained by the traditional method.

[0038] Figure 15 It is a schematic view of the adhesive force test between the film electrode obtained by the present application and the film electrode obtained by the traditional method.

[0039] Figure 16 It is a schematic view of the electrode sheet of the present application. DETAILED DESCRIPTION

[0040] The embodiments of the present application will be described in detail with specific examples. Other advantages and effects of the present application can be easily understood by those skilled in the art from the content disclosed in the specification. The present application can also be implemented or applied in different specific embodiments, and the details in the specification can be modified or changed based on different views and applications without departing from the spirit of the present application. It should be noted that the following embodiments and features in the embodiments can be combined with each other without conflict.

[0041] It should be understood that the present application can be implemented in different forms, and should not be interpreted as being limited to the embodiments presented herein. On the contrary, the embodiments are provided to make the disclosure complete and complete, and to fully convey the scope of the present application to those skilled in the art.

[0042] The technical solutions of the utility model will be further described in detail in connection with the embodiments and drawings. Obviously, the described embodiments are only part of the embodiments of the utility model, rather than all the embodiments. Based on the embodiments in the utility model, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the utility model.

[0043] Please refer to Figure 1 The utility model provides a kind of preparation method of membrane electrode, at least including steps S11-S15.

[0044] S11, provide a film layer, film layer includes oppositely arranged first surface and second surface.

[0045] S12, precursor solution is coated on the first surface.

[0046] S13, bonding force enhancer is coated on precursor solution.

[0047] S14, film layer is placed in alkaline solution, growth is carried out, to grow into electrode catalyst layer on the first surface in situ.

[0048] S15, precursor solution, bonding force enhancer and alkaline solution are used to repeat the above steps to the second surface, to grow into another electrode catalyst layer on the second surface in situ, obtain membrane electrode.

[0049] Please refer to Figure 1 As shown in the utility model an embodiment, in step S11, film layer 100 is for example diaphragm, cation exchange membrane, anion exchange membrane, proton exchange membrane, porous membrane or other membrane layer that can be used for hydrogen production electrolysis, film layer 100 is for example including oppositely arranged first surface and second surface. Further, use before pretreatment is carried out to film layer 100, remove the impurity on the first surface and second surface, so that film layer 100 and the electrode catalyst layer 200 and electrode catalyst layer 300 formed subsequently can be closely attached. In the utility model an embodiment, pretreatment is for example including film layer 100 is placed in solvent at preset temperature and is soaked for preset time, then film layer 100 is taken out and is washed with deionized water, and is placed in drying oven again. Wherein, solvent is for example at least one in hydrogen peroxide and sulfuric acid etc., preset temperature is for example 50-90 DEG C, and preset time is for example 0.5h-5h.

[0050] Please refer to Figure 1As shown in the embodiment of the present application, after the film layer 100 is provided, the precursor solution is subjected to homogenization treatment before being coated in step S12, so as to obtain a uniform precursor solution. The homogenization treatment method may, for example, include ultrasonic stirring treatment of the precursor solution, and the ultrasonic stirring time may be, for example, 1 min to 2 h. In the embodiment, the precursor solution may, for example, include a metal compound and a solvent. The metal compound may, for example, be selected from at least two of a transition metal compound, a rare earth metal compound and a noble metal compound, the transition metal compound may, for example, include a metal compound of manganese, chromium, iron, cobalt, nickel, copper, zinc, molybdenum or tungsten, the rare earth metal compound may, for example, include a lanthanide rare earth metal compound, and the noble metal compound may, for example, include a platinum group noble metal compound. In the embodiment, the metal compound may, for example, be a metal salt or a metal halide, the metal salt may, for example, be a metal sulfate, a metal nitrate or a metal chromate, and the solvent may, for example, include at least one of an alcohol solvent such as ethanol, ethylene glycol, propanol or isopropanol.

[0051] Referring to Figure 1 As shown in the embodiment of the present application, after the film layer 100 is provided, the precursor solution is subjected to homogenization treatment before being coated in step S12, so as to obtain a uniform precursor solution. The homogenization treatment method may, for example, include ultrasonic stirring treatment of the precursor solution, and the ultrasonic stirring time may be, for example, 1 min to 2 h. In the embodiment, the precursor solution may, for example, include a metal compound and a solvent. The metal compound may, for example, be selected from at least two of a transition metal compound, a rare earth metal compound and a noble metal compound, the transition metal compound may, for example, include a metal compound of manganese, chromium, iron, cobalt, nickel, copper, zinc, molybdenum or tungsten, the rare earth metal compound may, for example, include a lanthanide rare earth metal compound, and the noble metal compound may, for example, include a platinum group noble metal compound. In the embodiment, the metal compound may, for example, be a metal salt or a metal halide, the metal salt may, for example, be a metal sulfate, a metal nitrate or a metal chromate, and the solvent may, for example, include at least one of an alcohol solvent such as ethanol, ethylene glycol, propanol or isopropanol.

[0052] Referring to Figure 1 As shown in the embodiment of the present application, after the film layer 100 is provided, the precursor solution is subjected to homogenization treatment before being coated in step S12, so as to obtain a uniform precursor solution. The homogenization treatment method may, for example, include ultrasonic stirring treatment of the precursor solution, and the ultrasonic stirring time may be, for example, 1 min to 2 h. In the embodiment, the precursor solution may, for example, include a metal compound and a solvent. The metal compound may, for example, be selected from at least two of a transition metal compound, a rare earth metal compound and a noble metal compound, the transition metal compound may, for example, include a metal compound of manganese, chromium, iron, cobalt, nickel, copper, zinc, molybdenum or tungsten, the rare earth metal compound may, for example, include a lanthanide rare earth metal compound, and the noble metal compound may, for example, include a platinum group noble metal compound. In the embodiment, the metal compound may, for example, be a metal salt or a metal halide, the metal salt may, for example, be a metal sulfate, a metal nitrate or a metal chromate, and the solvent may, for example, include at least one of an alcohol solvent such as ethanol, ethylene glycol, propanol or isopropanol.

[0053] Referring to Figure 1In the embodiment of the present application, after the binding force enhancer is coated on the precursor solution, the film layer 100 with the binding force enhancer and the precursor solution is soaked in the alkaline solution in step S14 for growth. The pH of the alkaline solution is, for example, 8-14. The alkaline solution is, for example, at least one selected from the group consisting of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate and potassium bicarbonate. The temperature of the alkaline solution is, for example, 30-90°C. The soaking time of the film layer 100 in the alkaline solution is, for example, 5-1200 minutes.

[0054] Referring to Figure 1 In the embodiment of the present application, during the soaking of the film layer 100 in the alkaline solution in step S14, the precursor solution coated on the film layer 100 grows in situ on the first surface to form the electrode catalyst layer 200. Moreover, during the in-situ growth, the binding force enhancer coated on the precursor solution can enhance the binding force between the electrode catalyst layer 200 and the film layer 100, so that the electrode catalyst layer 200 and the film layer 100 can be closely attached to each other, thereby improving the stability of the membrane electrode.

[0055] Referring to Figure 1 In the embodiment of the present application, after step S14, i.e., after the soaking of the film layer 100 in the alkaline solution is completed, the film layer 100 is taken out of the alkaline solution and rinsed to remove the alkaline solution adhered to the first surface. The solvent for rinsing the film layer 100 includes, for example, at least one selected from the group consisting of deionized water and alcohol reagents. Further, when the precursor solution and the binding force enhancer are coated on the first surface by the soaking method in step S12 and step S13, the protective layer on the second surface also needs to be removed before the film layer 100 is rinsed.

[0056] Referring to Figure 1 In the embodiment of the present application, after the film layer 100 is rinsed, the precursor solution, the binding force enhancer and the alkaline solution are used to repeat steps S12-S14 on the second surface in step S15 to grow the electrode catalyst layer 300 on the second surface in situ. Specifically, the precursor solution is coated on the second surface, then the binding force enhancer is coated on the precursor solution, and the film layer 100 is placed in the alkaline solution for growth. After the growth is completed, the film layer 100 is taken out of the alkaline solution and rinsed. Compared with the formation process of the electrode catalyst layer 200, the difference between the formation process of the electrode catalyst layer 300 lies in that the transition metal compound in the precursor solution includes, for example, metal compounds such as manganese, chromium, iron, cobalt, nickel, copper or zinc, and the rest is the same, which will not be described here.

[0057] Referring to Figure 1As shown, in one embodiment of this invention, after forming an electrode catalyst layer 300 on the second surface and rinsing the membrane layer 100, the membrane layer 100 is dried to obtain a membrane electrode. The membrane layer 100 is dried, for example, by vacuum drying, at a temperature of 50°C-150°C. In the preparation method provided by this invention, a precursor solution and a precursor solution are grown in situ on the first and second surfaces of the membrane layer 100 in an alkaline solution to form an electrode catalyst layer 200 on the first surface and an electrode catalyst layer 300 on the second surface of the membrane layer 100. Furthermore, during the in-situ growth process, the binding force enhancer on the precursor solution and the precursor solution can enhance the binding force between the electrode catalyst layer 200 and the first surface, as well as the binding force between the electrode catalyst layer 300 and the second surface, thereby improving the quality and stability of the membrane electrode. Moreover, the preparation method provided by this invention simplifies the membrane electrode preparation process, reduces the preparation cycle and cost, and is suitable for large-scale production of membrane electrodes.

[0058] Please see Figure 1 As shown, this invention also provides a membrane electrode obtained by the above-described membrane electrode preparation method. The membrane electrode includes, for example, a membrane layer 100, an electrode catalyst layer 200, and an electrode catalyst layer 300. The membrane layer 100 includes a first surface and a second surface disposed opposite to each other. The electrode catalyst layer 200 is disposed, for example, on the first surface, and the electrode catalyst layer 300 is disposed, for example, on the second surface. In the membrane electrode provided by this invention, a precursor solution is grown in situ on the first surface or the second surface in an alkaline solution to form the electrode catalyst layer 200 or the electrode catalyst layer 300. Furthermore, during the in-situ growth process, a binding force enhancer can strengthen the bonding force between the electrode catalyst layer 200 and the first surface, as well as the bonding force between the electrode catalyst layer 300 and the second surface, resulting in a tight bond between the membrane layer 100 and the electrode catalyst layer. This prevents the electrode catalyst layer and the membrane layer 100 from peeling off, thereby improving the stability of the membrane electrode and the utilization rate of the catalyst in the electrode catalyst layer, and increasing the efficiency of hydrogen production by water electrolysis.

[0059] Please see Figure 1 As shown, in one embodiment of this utility model, a membrane electrode is obtained according to the preparation method of the membrane electrode, and a physical image of the membrane electrode is shown below. Figure 1 to Figure 2 As shown.

[0060] Please see Figure 2 As shown, in one embodiment of this utility model, for Figure 3 to Figure 4 The membrane electrode in the membrane is characterized, for example, by scanning electron microscopy to characterize the cross-section of the membrane electrode and to magnify the region between the electrode catalyst layer 200 and the membrane layer 100. Figure 2 The magnification factor is, for example, 100x. Figure 3The magnification is, for example, 400 times. In combination Figure 4 and Figure 3 It can be seen that in the membrane electrode, the electrode catalyst layer 300 and the electrode catalyst layer 200 are respectively located on the two sides of the membrane layer 100, and there is a fusion area 201 between the electrode catalyst layer 200 and the membrane layer 100. In the fusion area 201, the electrode catalyst layer 200 grows on the membrane layer 100 and diffuses in the direction of the membrane layer 100, at this time, part of the electrode catalyst layer 200 can be embedded or fused into the membrane layer 100, the membrane layer 100 and the electrode catalyst layer 200 are tightly combined and have better combination stability. In some embodiments, the depth of the electrode catalyst layer 200 embedded in the membrane layer 100 is, for example, 10 nm to 7 μm.

[0061] It is worth noting that by the method of the present application, the electrode catalyst layer 200 can be directly grown on the opposite sides of the membrane layer 100 respectively to form the membrane electrode of the electrolytic cell. However, it is not limited thereto, and in some embodiments, by the method of the present application, only the electrode catalyst layer 200 can be grown on one side of the membrane layer 100, and on the other side of the membrane layer 100, the electrode catalyst can be formed on the diffusion layer. That is, in the membrane electrode of the present application, the electrode catalyst layer 200 can be formed on one side or opposite sides of the membrane layer 100. For example, in the AEM membrane electrode, the electrode catalyst layer 200 can be formed on one side of the membrane layer 100, and the other electrode catalyst layer 200 can be formed on the diffusion layer.

[0062] Referring to Figure 4 , in an embodiment of the present application, the stability of the membrane electrode in Figure 5 is characterized. Specifically, the membrane electrode is loaded to a predetermined current density, and the change of the voltage of the membrane electrode within 100 h is measured. The predetermined current density is, for example, 2 A / cm 2 . It can be seen from Figure 2 that within 0-70 h, the voltage of the membrane electrode stably fluctuates around 1.94 V and tends to 1.94 V, so the stability of the membrane electrode is good.

[0063] Referring to Figure 5 and Figure 6As shown in the utility model one embodiment, on the anode side of the membrane layer 100, the electrode catalyst layer 300 can include a first metal catalyst layer 301 and a second metal catalyst layer 302, the first metal catalyst layer 301 is formed on the membrane layer 100 and can partially penetrate or embed into the membrane layer 100, the second metal catalyst layer 302 is formed on the first metal catalyst layer 301, the first metal catalyst layer 301 and the second metal catalyst layer 302 can have different metal catalysts. For example, the first metal catalyst layer 301 can include platinum metal catalyst, and the second metal catalyst layer 302 can include iridium or iridium oxide metal catalyst. By using different metal catalysts, the use load of noble metal (such as iridium) catalyst can be reduced, thereby reducing the cost.

[0064] In an embodiment, the thickness of the first metal catalyst layer 301 is, for example, 5nm-200nm, and the thickness of the second metal catalyst layer 302 is, for example, 50nm-5μm.

[0065] In an embodiment, the nanoparticle size of the metal catalyst of the first metal catalyst layer 301 is, for example, 1nm-15nm, and the nanoparticle size of the metal catalyst of the second metal catalyst layer 302 is, for example, 10nm-200nm.

[0066] Please refer to Figure 7 As shown in another embodiment of the utility model, the membrane electrode provided by the utility model includes a membrane layer 100, an anode catalyst layer 11 and a cathode catalyst layer 12, etc., the anode catalyst layer 11 and the cathode catalyst layer 12 are respectively formed on both sides of the membrane layer 100, the anode catalyst layer 11 includes a hydrogen consumption layer 111 and an anode catalyst base layer 112, and the hydrogen consumption layer 11 is formed between the membrane layer 100 and the anode catalyst base layer 113. By arranging the hydrogen consumption layer 11, hydrogen permeated from the cathode side to the anode can be eliminated in time, the purity of the gas is improved, and the safety of the water electrolysis hydrogen production device is improved.

[0067] Please refer to Figure 8 As shown in an embodiment of the utility model, the membrane layer 100 is, for example, N115 proton membrane, etc., and the thickness of the membrane layer 100 is, for example, 110μm-130μm, etc., and the thickness of the N115 proton membrane is, for example, 127μm, to meet the requirements of conduction, isolation and thermal stability, etc.

[0068] Please refer to Figure 8As shown, in one embodiment of this invention, the hydrogen-removing catalyst in the hydrogen-consuming layer 111 is selected from highly active, acid-resistant, and highly stable materials such as Pt, Ir, or Pd. The anode catalyst in the anode catalyst substrate 112 is selected from catalysts used for catalyzing oxygen reactions, such as at least one of Ir, IrO2, Pt, Pd, or Ru. Through the hydrogen-removing catalyst in the hydrogen-consuming layer 11, hydrogen diffused from the cathode is converted into hydrogen ions. A portion of the oxygen generated on the anode side diffuses into the hydrogen-consuming layer 111. The hydrogen-removing catalyst in the hydrogen-consuming layer 111 can also convert the oxygen diffused into oxygen ions, causing hydrogen ions and oxygen ions to react and generate water. This allows for the reaction of hydrogen and oxygen to produce water, thereby eliminating hydrogen on the anode side, improving the purity of oxygen on the anode side, and preventing oxygen from diffusing to the cathode. This simultaneously improves the purity of both hydrogen and oxygen produced by water electrolysis, enhancing the safety of the water electrolysis device.

[0069] Please see Figure 8 As shown, in one embodiment of the present invention, the cathode catalyst in the cathode catalyst layer 12 is, for example, a catalyst for catalyzing hydrogen reaction, or at least one of Ir, IrO2, Pt / C, Pt, Pd or Ru.

[0070] Please see Figure 8 As shown, in one embodiment of this invention, the thickness ratio of the membrane layer 100, the anode catalyst layer 11, and the cathode catalyst layer 12 is, for example, 1:0.1:0.1 to 1:10:10, or, for example, 1:1.5:1.5, and the thickness ratio of the hydrogen consumption layer 111 and the anode catalyst layer 112 is, for example, 1:1 to 1:10, or 1:5, etc. In a specific embodiment of this invention, the total thickness of the membrane electrode is, for example, 154 μm. Within this thickness range, and with the thicknesses of different layers coordinated, the efficiency of water electrolysis by the membrane electrode can be improved.

[0071] Please see Figure 8 As shown, in one embodiment of this invention, the porosity of the hydrogen consumption layer 111 is, for example, 1 μm. 2 / g, the porosity of the anode catalyst substrate 112 is, for example, 100–330 μm. 2 / g, the porosity of the cathode catalyst layer 12 is, for example, 100–330 μm. 2 / g. In a specific embodiment of this invention, the porosity of the hydrogen-consuming layer 111 is, for example, 130 μm. 2 / g, the porosity of the anode catalyst substrate 112 is, for example, 160m. 2 / g, the porosity of the cathode catalyst layer 12 is, for example, 180m. 2g. Wherein, the porosity of the anode catalytic layer 11 and the cathode catalytic layer 12 on both sides of the membrane layer 100 is large, which can increase the number of membrane electrode channels, provide abundant channels for mass transfer, and thus improve the electrolysis rate.

[0072] Referring to Figure 8 As shown in the distribution diagram of the hydrogen consumption layer 111 on the membrane layer 100 in an embodiment of the present application, during the electrolysis process, the hydrogen gas permeating through the membrane layer 100 gradually accumulates from the inlet to the outlet of the anode layer flow field. In some embodiments, the loading amount of the hydrogen consumption layer can be increased along the water flow direction of the anode catalytic layer. Therefore, on the anode side of the membrane layer 100, the hydrogen consumption layer 111 increases from the end of the membrane electrode away from the water flow direction to the end close to the water flow direction, such as increasing the width, loading amount, and density of the hydrogen consumption catalyst of the hydrogen consumption layer 111, etc. In Figure 9 In part a of the above, the hydrogen consumption layer 111 includes a plurality of arranged strip structures, and the width of the strip structure of the hydrogen consumption layer 111 increases successively from the end away from the water flow direction to the end close to the water flow direction. In Figure 9 In part b of the above, the loading amount of the hydrogen consumption layer 111 increases successively from the end away from the water flow direction to the end close to the water flow direction, such as increasing the thickness of the hydrogen consumption layer 111. In Figure 9 In part c of the above, the density of the hydrogen consumption catalyst in the hydrogen consumption layer 111 increases successively from the end away from the water flow direction to the end close to the water flow direction. By arranging different amounts of the hydrogen consumption layer 111 in different regions of the membrane layer 100, the removal efficiency of the hydrogen gas on the anode side can be improved, while the amount of the hydrogen consumption catalyst used is reduced, and the cost is reduced.

[0073] Referring to Figure 9 and Figure 10 As shown in the distribution diagram of the hydrogen consumption layer 111 on the membrane layer 100 in another embodiment of the present application, the electrolytic cell includes the membrane electrode 10 and the bipolar plate 20, and the bipolar plate 20 is located outside the anode catalytic layer and the cathode catalytic layer of the membrane electrode. During the electrolysis process, the position of the cathode flow field ridge 201 of the cathode catalytic layer side of the bipolar plate 20 contacts the compressed membrane layer 100 at the contact position of the membrane layer 100, which is not conducive to hydrogen permeation, and the hydrogen content is small. The membrane layer 100 at the position of the flow channel 202 swells and has more micropore channels, which is conducive to hydrogen permeation. In some embodiments, the hydrogen consumption layer 111 can be provided with a bending structure (as shown in Figure 11 The bending structure of the hydrogen consumption layer 111 can be consistent with the flow field distribution of the bipolar plate outside the cathode catalytic layer. The hydrogen diffused from the flow channel 202 can be consumed, the removal efficiency of the hydrogen gas on the anode side can be improved, and the safety of the electrolysis can be improved.

[0074] In an embodiment of the present application, the present application further provides a preparation method of a membrane electrode, including steps S11-S12.

[0075] Step S11, forming an anode catalytic layer on one side of the film layer, the anode catalytic layer comprising a hydrogen consumption layer and an anode catalytic base layer, the hydrogen consumption layer being formed between the film layer and the anode catalytic base layer.

[0076] Step S12, forming a cathode catalytic layer on the other side of the film layer.

[0077] In an embodiment of the present application, the electrode catalytic layer (anode catalytic layer and / or cathode catalytic layer) can be formed by transfer printing, for example. When transfer printing is performed, the anode catalytic layer and the cathode catalytic layer can be simultaneously transferred or transferred in steps. The hydrogen consumption layer and the anode catalytic base layer in the anode catalytic layer can be simultaneously transferred or transferred in steps. When simultaneously transferred, the anode catalytic base layer is formed on the transfer film, and the hydrogen consumption layer is formed on the anode catalytic base layer, and then transferred to the film layer. When transferred in steps, the hydrogen consumption layer is first transferred to the film layer, and then the anode catalytic base layer is transferred to the hydrogen consumption layer. In this embodiment, the transfer printing is performed by a non-vacuum hot-press transfer printing method, for example.

[0078] Referring to Figure 11 In an embodiment of the present application, the anode catalytic slurry layer and the hydrogen consumption slurry layer are formed on the transfer film to form a first transfer film 15. The anode catalytic slurry layer comprises an anode catalyst and a resin, etc. The anode catalyst comprises a carrier and a component comprising an active metal element substance supported on the carrier. The mass ratio of the anode catalyst to the resin is 1:0.1 to 1:3, for example. The anode catalytic slurry layer is formed by a method such as blade coating, roller coating, or spraying, etc.

[0079] Referring to Figure 12 In an embodiment of the present application, the cathode catalytic slurry layer is formed on the transfer film to form a second transfer film 16. The cathode catalytic slurry layer comprises a cathode catalyst and a resin, etc. The cathode catalyst comprises a carrier and a component comprising an active metal element substance supported on the carrier. The mass ratio of the cathode catalyst to the resin is 1:0.7 to 1:2, for example. The cathode catalytic slurry layer is formed by a method such as blade coating, roller coating, or spraying, etc.

[0080] In an embodiment of the present application, the resins in the anode catalytic slurry layer, the hydrogen consumption slurry layer, and the cathode catalytic slurry layer can be the same or different. The resin is selected from at least one of a perfluoro resin solution (D2020), etc., for example.

[0081] Referring to Figure 12In an embodiment of the present application, when the film electrode is formed by the transfer printing assembly, the film layer 100 is placed in the middle position to ensure that the film layer 100 is flat and has no folding. The transfer printing plates are arranged on both sides of the film layer 100, for example, including a first transfer printing plate 131 and a second transfer printing plate 132, the first transfer printing plate 131 and the second transfer printing plate 132 are of the same size, and openings of the same size are arranged at the centers of the first transfer printing plate 131 and the second transfer printing plate 132 to determine the transfer printing area, so that the sizes of the catalytic layer areas on both sides of the film layer 100 after transfer printing are the same, and the catalytic layer areas are aligned. The air in the transfer printing process or the water vapor generated by heating can be discharged from the edges of the openings. In the present application, the size of the opening is not limited, and can be set according to the size of the film electrode to meet the preparation requirements of forming a larger film electrode.

[0082] Please refer to Figure 12 In an embodiment of the present application, positioning holes 141 are arranged at the diagonal positions of the first transfer printing plate 131 and the second transfer printing plate 132, and the positions of the positioning holes 141 on the first transfer printing plate 131 and the second transfer printing plate 132 are the same. When transfer printing is performed, the film layer 100 is placed in the middle of the first transfer printing plate 131 and the second transfer printing plate 132, and the positioning member 14 is placed in the diagonal positioning hole 141, for example, fluorine-containing rubber, etc., to fix and position the film layer of the film electrode for subsequent transfer printing process.

[0083] Please refer to Figure 12 In an embodiment of the present application, the first transfer printing film 15 is arranged on the side of the first transfer printing plate 131 away from the film layer 100, and the slurry layer on the first transfer printing film 15 faces the film layer 100. The second transfer printing film 16 is arranged on the side of the second transfer printing plate 132 away from the film layer 100, and the slurry layer on the second transfer printing film 16 faces the film layer 100. The positioning member 14 defines the positions of the first transfer printing film 15 and the second transfer printing film 16. Under the conditions of a temperature of 130-180 DEG C, a pressure of 0.5-4 MPa, and a hot pressing time of 10-600 s, pressure is applied to the side of the first transfer printing film 15 away from the film layer 100 and the side of the second transfer printing film 16 away from the film layer 100 at the same time, so that the slurry layer on the transfer printing film is transferred to the film layer, the transfer printing film is removed, and the anode catalyst layer and the cathode catalyst layer are formed. By arranging the transfer printing plate and the positioning member, the air in the gap in the middle of the sheet during the molding process or the water vapor generated by heating can be removed, and large-area bubble defects in the catalytic layer area after transfer printing can be avoided, thereby improving the quality of the film electrode. At the same time, the anode catalytic layer and the cathode catalyst layer are placed in alignment on both sides of the film layer, so that the uniformity and stability of the catalysis are ensured, and the service life of the water electrolysis device is prolonged.

[0084] As Figure 12As shown, the membrane electrode fabrication method of this application, compared with traditional electrode catalyst layers (such as...), Figure 13 to Figure 15 This can yield an electrode catalyst layer with good surface uniformity (such as...) Figure 14 In some embodiments, the surface roughness Ra of the electrode catalyst layer (anode catalyst layer and / or cathode catalyst layer) of this application may be less than or equal to 0.15 μm, for example, 0.08 μm to 0.15. Furthermore, as... Figure 13 As shown, the membrane electrode is manufactured using the method described in this application (e.g. Figure 15 a) in the text, compared to traditional electrode catalyst layers (such as...) Figure 15 (b and c in the text) are subjected to different adhesive forces (e.g., 1 N / cm). 2 and 4N / cm 2 ) test, the membrane electrode of this application (such as Figure 15 The catalyst layer in (a) will not peel off, exhibiting good stability. The adhesion between the electrode catalyst layer and the film layer can be greater than 0.8 N / cm. 2 For example, 1 to 10 N / cm 2 .

[0085] It is worth noting that, in this application, the electrode catalyst layer of the membrane electrode can be formed on the membrane layer by in-situ growth or transfer methods, and the hydrogen consumption layer of the anode catalyst layer can also be formed on the membrane layer by in-situ growth or transfer methods. In one embodiment, a portion of the hydrogen consumption layer of the anode catalyst layer can be embedded or fused into the membrane layer.

[0086] Please see Figure 15 and Figure 8 In one embodiment of this invention, after the transfer is completed, the anode catalyst layer 11 and / or the cathode catalyst layer 12 can be subjected to catalyst pore-forming treatment, for example, using a hot-cold cycle pore-forming method. Specifically, the membrane electrode is immersed in water under negative pressure. After the membrane electrode is fully swollen, it is slowly cooled, for example, to -50°C, held at that temperature for 12 hours, and then slowly heated to 70°C. This cycle is repeated to increase the pore distribution of the catalyst. In this embodiment, the pressure of the negative pressure environment is, for example, 80 kPa, the cooling rate is, for example, 0.5°C / min to 3°C / min, and the heating rate is, for example, 0.5°C / min to 3°C / min. The pore-forming treatment method improved by this application is simple and convenient to operate. After pore-forming treatment, the pore distribution of the catalyst can be increased, the porosity of the catalyst can be increased, the electrolysis rate can be increased, and the electrolysis efficiency can be improved. In one embodiment, the pore size of the catalyst pores is, for example, 1 μm to 200 μm.

[0087] The utility model discloses still provide a kind of electrolytic water device, electrolytic water device is for example proton exchange membrane electrolytic water hydrogen production device, including membrane electrode as above mentioned.The membrane electrode is applied to hydrogen production device, hydrogen and oxygen on anode side can be reacted to obtain water, so as to reach the purpose of hydrogen consumption on anode side, to improve the purity of oxygen on anode side, improve the security of electrolytic water device.Meanwhile, improve the quality of membrane electrode, ensure the uniformity and stability of catalysis, prolong the service life of electrolytic water device.Can increase electrolytic rate, improve electrolytic efficiency, be conducive to promoting the development of electrolytic water hydrogen production technology.

[0088] In some embodiments, the electrode catalyst layer can include nanoparticles, nanowires, nanochains, or other nanostructures.

[0089] In some embodiments, when the electrode catalyst layer 200 or 300 is formed on the diffusion layer, an electrode sheet can be formed. At this time, the coverage of the electrode catalyst layer on one side surface of the diffusion layer can be, for example, greater than or equal to 70%, for example, 75% to 99%. Figure 12 Figure 16 In this way, by the high coverage of the electrode catalyst layer on the diffusion layer, the catalyst performance of the electrode can be improved. In an embodiment, the coverage of the electrode catalyst layer on one side surface of the diffusion layer can be, for example, 75% to 99%. In an embodiment, the electrode catalyst layer can be formed on opposite two side surfaces of the diffusion layer, and the coverage of the electrode catalyst layer on one side surface of the diffusion layer can be, for example, greater than or equal to 70%, for example, 75% to 99%.

[0090] It is worth noting that the membrane electrode of the present application can be applied in an electrolytic cell, such as a proton exchange membrane (PEM) electrolytic cell, an anion exchange membrane (AEM), an alkaline electrolytic cell, a solid oxide (SOEC), or other electrolytic cells.

[0091] In summary, the utility model provides a kind of membrane electrode and hydrogen production electrolytic cell, electrode catalyst layer and electrode catalyst layer are respectively arranged on the first surface and the second surface of membrane layer, can enhance the binding force of electrode catalyst layer and first surface, and the binding force of electrode catalyst layer and second surface, make membrane layer and electrode catalyst layer tightly combine, electrode catalyst layer and membrane layer are not easy to peel, to improve the stability of membrane electrode, improve the utilization of catalyst in electrode catalyst layer, improve the efficiency of water electrolysis hydrogen production. Hydrogen and oxygen produced by electrolytic water can be improved simultaneously, and the security of electrolytic water device is improved. The number of membrane electrode micropores can be increased, mass transfer is provided through abundant pores, the porosity of catalyst is increased, the electrolytic rate is increased, and the electrolytic efficiency is improved. The quality of membrane electrode can be improved, and the anode catalyst layer and the cathode catalyst layer are placed in alignment on both sides of the membrane layer, ensuring the uniformity and stability of catalysis, prolonging the service life of the electrolytic water device.

[0092] The above embodiments only exemplarily illustrate the principles and effects of the present application, and are not used to limit the present application. Any person skilled in the art can modify or change the above embodiments without departing from the spirit and scope of the present application. Therefore, all equivalent modifications or changes completed by those skilled in the art without departing from the spirit and technical thought disclosed by the present application should be covered by the claims of the present application.

Claims

1. An electrode sheet for a hydrogen production electrolyzer, characterized by, The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer.

2. The electrode pad of claim 1, wherein The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%.

3. The electrode pad of claim 1, wherein The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer.

4. A hydrogen-producing electrolyzer characterized by, The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%.

5. The hydrogen-producing electrolyzer of claim 4, wherein, The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer.

6. The hydrogen-producing electrolyzer of claim 5, wherein, The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%.

7. The hydrogen-producing electrolyzer of claim 5, wherein, The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer.

8. The hydrogen-producing electrolyzer of claim 4, wherein, The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%.

9. A hydrogen-producing electrolyzer, characterized by, The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75% to 99%. The electrode catalyst layer is formed on one side or both opposite sides of the diffusion layer. The electrode catalyst layer has a coverage on the one side surface of the diffusion layer of 75%

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