Membrane electrode for producing hydrogen by electrolyzing water and electrolytic bath

Abstract

The invention provides a water electrolysis hydrogen production membrane electrode and an electrolytic bath, and belongs to the technical field of water electrolysis hydrogen production, the water electrolysis hydrogen production membrane electrode comprises an anion exchange membrane, a cathode catalyst layer and an anode catalyst layer, the cathode catalyst layer is arranged on one side of the anion exchange membrane, and the cathode catalyst layer comprises a first cathode catalyst and a second cathode catalyst; the anode catalyst layer is arranged on the side, away from the cathode catalyst layer, of the anion exchange membrane, and the anode catalyst layer comprises a first anode catalyst and a second anode catalyst. Wherein the first cathode catalyst, the second cathode catalyst, the first anode catalyst and the second anode catalyst are all non-noble metal catalysts, the first cathode catalyst is different from the second cathode catalyst, and the first anode catalyst is different from the second anode catalyst. The water electrolysis hydrogen production membrane electrode provided by the embodiment of the invention can ensure good catalytic activity and stability while reducing the cost.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of hydrogen production by water electrolysis, and particularly relates to a hydrogen production by water electrolysis membrane electrode and electrolytic cell. BACKGROUND

[0002] Hydrogen production by water electrolysis is efficient and pollution-free, and is an economical and effective way to prepare green hydrogen. Anion exchange membrane water electrolysis (AEMWE) has the advantages of small volume, no risk of high-concentration alkali leakage, and higher hydrogen purity of the prepared hydrogen, and the like, of both alkaline water electrolysis (AWE) and proton exchange membrane water electrolysis (PEMWE) systems.

[0003] The hydrogen evolution reaction (HER) activity of a platinum (Pt) based catalyst is relatively high, and the water electrolysis catalyst in the AEMWE has good performance. However, the noble metal in the conventional noble metal catalyst (for example, Pt / C, iridium oxide) has low reserves on earth, high cost, and is easily poisoned and deactivated by impurities, which affects the application of the noble metal catalyst in the AEMWE. SUMMARY

[0004] Embodiments of the application provide a hydrogen production by water electrolysis membrane electrode and electrolytic cell, which can reduce the cost of the membrane electrode and ensure the catalytic activity and stability of the membrane electrode.

[0005] In a first aspect, embodiments of the application provide a hydrogen production by water electrolysis membrane electrode, comprising:

[0006] an anion exchange membrane;

[0007] a cathode catalytic layer, the cathode catalytic layer being arranged on one side of the anion exchange membrane, and the cathode catalytic layer comprising a first cathode catalyst and a second cathode catalyst;

[0008] an anode catalytic layer, the anode catalytic layer being arranged on the side of the anion exchange membrane away from the cathode catalytic layer, and the anode catalytic layer comprising a first anode catalyst and a second anode catalyst;

[0009] wherein the first cathode catalyst and the second cathode catalyst are both non-noble metal cathode catalysts, and the first cathode catalyst and the second cathode catalyst are different; and the first anode catalyst and the second anode catalyst are both non-noble metal anode catalysts, and the first anode catalyst and the second anode catalyst are different.

[0010] In some embodiments, the first cathode catalyst comprises at least one of molybdenum diboride, molybdenum disulfide, nickel-molybdenum alloy, and molybdenum carbide;

[0011] and / or, the second cathode catalyst comprises at least one of trinickel disulfide, dinickel phosphide, iron phosphide, and carbon-supported cobalt nitride.

[0012] In some embodiments, the first cathode catalyst is molybdenum disulfide, and the second cathode catalyst is iron phosphide.

[0013] In some embodiments, the mass ratio of the first cathode catalyst and the second cathode catalyst is (0.1-2):1.

[0014] In some embodiments, the cathode catalyst layer comprises a first cathode catalyst sublayer and a second cathode catalyst sublayer, the first cathode catalyst sublayer is arranged close to the anion exchange membrane, and the second cathode catalyst sublayer is arranged on the side of the first cathode catalyst sublayer away from the anion exchange membrane.

[0015] In some embodiments, the anion exchange membrane ionomer is included in both the first cathode catalyst sublayer and the second cathode catalyst sublayer.

[0016] In some embodiments, the mass percentage of the anion exchange membrane ionomer in the first cathode catalyst sublayer is m1, the mass percentage of the anion exchange membrane ionomer in the second cathode catalyst sublayer is m2, and m1>m2.

[0017] In some embodiments, 5%≤m1≤50%.

[0018] And / or, 5%≤m2≤40%.

[0019] In some embodiments, the water electrolysis hydrogen production membrane electrode further comprises a cathode gas diffusion layer, the cathode gas diffusion layer is arranged on the side of the cathode catalyst layer away from the anion exchange membrane, and the cathode catalyst layer is coated on the cathode gas diffusion layer.

[0020] In some embodiments, the cathode gas diffusion layer comprises at least one of nickel felt, titanium felt, stainless steel felt, copper felt, and graphite felt.

[0021] In some embodiments, in the cathode catalyst layer, the total amount of the first cathode catalyst and the second cathode catalyst is 1 mg / cm 2 -20 mg / cm 2 .

[0022] In some embodiments, the first anode catalyst comprises at least one of nickel-molybdenum alloy, nickel-cobalt alloy, nickel-cobalt-iron alloy, nickel-iron alloy, nickel powder, iron powder, and cobalt powder.

[0023] And / or, the second anode catalyst comprises at least one of nickel-iron layered double hydroxide, cobalt trioxide, nickel-iron oxide, nickel-cobalt oxide, iron-cobalt oxide, and iron-manganese oxide.

[0024] In some embodiments, the first anode catalyst is nickel-cobalt alloy, and the second anode catalyst is nickel-iron layered double hydroxide.

[0025] In some embodiments, the mass ratio of the first anode catalyst and the second anode catalyst is (0.1-1):1.

[0026] In some embodiments, the anode catalytic layer comprises a first anode catalytic sub-layer and a second anode catalytic sub-layer, the first anode catalytic sub-layer is arranged close to the anion exchange membrane, and the second anode catalytic sub-layer is arranged on the side of the first anode catalytic sub-layer away from the anion exchange membrane.

[0027] In some embodiments, the anion exchange membrane ionomer is included in both the first anode catalytic sub-layer and the second anode catalytic sub-layer.

[0028] In some embodiments, the mass percentage of the anion exchange membrane ionomer in the first anode catalytic sub-layer is m3, the mass percentage of the anion exchange membrane ionomer in the second anode catalytic sub-layer is m4, and m3 > m4.

[0029] In some embodiments, 5% ≤ m3 ≤ 50%.

[0030] And / or, 5% ≤ m4 ≤ 40%.

[0031] In some embodiments, in the anode catalytic layer, the total amount of the first anode catalyst and the second anode catalyst is 1 mg / cm 2 - 20 mg / cm 2 .

[0032] In some embodiments, the electrolytic water hydrogen production membrane electrode further comprises an anode gas diffusion layer, the anode gas diffusion layer is arranged on the side of the anode catalytic layer away from the anion exchange membrane, and the anode catalytic layer is coated on the anode gas diffusion layer.

[0033] In some embodiments, the anode gas diffusion layer comprises at least one of nickel felt, titanium felt, stainless steel felt, copper felt and graphite felt.

[0034] In a second aspect, the embodiments of the present application provide an electrolytic cell comprising the electrolytic water hydrogen production membrane electrode as above.

[0035] The beneficial effects of the embodiments of the present application are as follows:

[0036] In the embodiments of the present application, the water electrolysis hydrogen production membrane electrode comprises an anion exchange membrane, a cathode catalyst layer and an anode catalyst layer. The cathode catalyst layer is arranged on one side of the anion exchange membrane, and the cathode catalyst layer comprises a first cathode catalyst and a second cathode catalyst. The anode catalyst layer is arranged on the side of the anion exchange membrane away from the cathode catalyst layer, and the anode catalyst layer comprises a first anode catalyst and a second anode catalyst. The first cathode catalyst, the second cathode catalyst, the first anode catalyst and the second anode catalyst are all non-noble metal catalysts, and the first cathode catalyst and the second cathode catalyst are different, and the first anode catalyst and the second anode catalyst are different. By replacing the noble metal catalyst in the prior art with a non-noble metal cathode catalyst, the cost of the membrane electrode can be reduced. By the synergistic effect of the different first cathode catalyst and second cathode catalyst, and the synergistic effect of the first anode catalyst and the second anode catalyst, the catalytic activity can be effectively improved, which helps to reduce the overpotential of water electrolysis reaction and improve the hydrogen production efficiency. And the non-noble metal catalyst can exhibit better chemical stability and mechanical stability under some conditions, which can ensure the stability and service life of the membrane electrode. That is, the water electrolysis hydrogen production membrane electrode provided by the embodiments of the present application can reduce the cost while ensuring good catalytic activity and stability. BRIEF DESCRIPTION OF DRAWINGS

[0037] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. 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.

[0038] Figure 1 is a schematic cross-sectional structure of the water electrolysis hydrogen production membrane electrode provided by the embodiments of the present application Figure 1 ;

[0039] Figure 2 is a schematic cross-sectional structure of the water electrolysis hydrogen production membrane electrode provided by the embodiments of the present application Figure 2 ;

[0040] Figure 3 is a polarization performance curve of the electrolytic cell.

[0041] BRIEF DESCRIPTION OF DRAWINGS

[0042] 10, anion exchange membrane; 20, cathode catalyst layer; 21, first cathode catalyst sublayer; 22, second cathode catalyst sublayer; 30, cathode gas diffusion layer; 40, anode catalyst layer; 41, first anode catalyst sublayer; 42, second anode catalyst sublayer; 50, anode gas diffusion layer. DETAILED DESCRIPTION

[0043] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application. In addition, it should be understood that the specific implementation described herein is only used to illustrate and explain the present application, and is not used to limit the present application.

[0044] In a first aspect, as shown in the specification, Figure 1 The embodiments of the present application provide an electrolytic water hydrogen production membrane electrode, including an anion exchange membrane 10, a cathode catalyst layer 20 and an anode catalyst layer. The cathode catalyst layer 20 is arranged on one side of the anion exchange membrane 10, and the cathode catalyst layer 20 includes a first cathode catalyst and a second cathode catalyst. The anode catalyst layer is arranged on the side of the anion exchange membrane away from the cathode catalyst layer, and the anode catalyst layer includes a first anode catalyst and a second anode catalyst. The first cathode catalyst, the second cathode catalyst, the first anode catalyst and the second anode catalyst are all non-noble metal catalysts, and the first cathode catalyst and the second cathode catalyst are different, and the first anode catalyst and the second anode catalyst are different. By replacing the noble metal catalyst in the prior art with a non-noble metal cathode catalyst, the cost of the membrane electrode can be reduced. Through the synergistic effect of the different first cathode catalyst and second cathode catalyst, and the synergistic effect of the first anode catalyst and the second anode catalyst, the catalytic activity can be effectively improved, which helps to reduce the overpotential of the electrolytic water reaction and improve the hydrogen production efficiency. And the non-noble metal catalyst can exhibit better chemical stability and mechanical stability under some conditions, which can ensure the stability and service life of the membrane electrode. That is, the electrolytic water hydrogen production membrane electrode provided by the embodiments of the present application can reduce the cost while ensuring good catalytic activity and stability.

[0045] In some embodiments, the first cathode catalyst includes at least one of molybdenum diboride (MoB2), molybdenum disulfide, nickel-molybdenum alloy, and molybdenum carbide. Among the molybdenum (Mo)-based materials, due to the similar outer electron structure of Mo to platinum (Pt) and the corrosion resistance of Mo itself, the Mo-based materials have excellent HER catalytic activity and stability. Among them, molybdenum diboride (MoB2) and molybdenum carbide (MoC) have metal-level conductivity, and the high electronegativity of C and B regulates the electronic structure of Mo, optimizes the adsorption energy of the reaction intermediates, and provides high catalytic activity; molybdenum disulfide (MoS2) has a layered structure, which exposes a large number of active sites, which is conducive to the full contact of reactants with active sites and fast mass transfer; in nickel-molybdenum alloy (NiMo), nickel (Ni) also helps to optimize the hydrogen adsorption energy by locally regulating the electronic structure of Mo, thereby realizing fast adsorption of reaction intermediates and desorption of products, and showing excellent catalytic activity, while having good electrical conductivity and stability. These materials have low cost and good catalytic activity.

[0046] In some embodiments, the second cathode catalyst includes at least one of triniickel disulfide, nickel phosphide, iron phosphide, molybdenum diboride, and carbon-supported cobalt nitride. Both transition metal phosphides and transition metal-nitrogen co-doped carbon materials have excellent HER activity, among which the negatively charged phosphorus (P) atoms and the positively charged metal atoms act as proton acceptors and anion acceptors, respectively, which affect the overall effect of synergistically promoting HER; and the transition metal-nitrogen co-doped carbon material is inspired by natural enzymes or homogeneous metal complexes, and has excellent HER catalytic activity. Nickel phosphide (Ni2P), iron phosphide (FeP), and carbon-supported cobalt nitride (CoN / C) all have good electrocatalytic activity and stability, which can reduce costs while ensuring good catalytic activity.

[0047] In some embodiments, the first cathode catalyst is molybdenum disulfide, and the second cathode catalyst is iron phosphide.

[0048] Molybdenum disulfide and iron phosphide have different electronic structures, among which molybdenum disulfide and iron phosphide themselves have high HER activity, Ni and iron (Fe) synergistically act on the interface, the electronic structure is locally modulated, and the adsorption / desorption energy of the reaction intermediates is optimized; and the dynamic extraction and embedding of sulfur (S) and P ions also regulate the local electronic structure of the active sites, providing high catalytic activity; at the same time, the catalyst realizes high stability. In addition, molybdenum disulfide and iron phosphide can maintain a low cost.

[0049] In some embodiments, the cathode catalyst layer 20 includes a first cathode catalyst sublayer 21 and a second cathode catalyst sublayer 22. The first cathode catalyst sublayer 21 is disposed close to the anion exchange membrane 10, and the second cathode catalyst sublayer 22 is disposed on the side of the first cathode catalyst sublayer 21 facing away from the anion exchange membrane 10. The mass ratio of the first cathode catalyst to the second cathode catalyst is (0.1-2):1. By setting the mass ratio of the first cathode catalyst to the second cathode catalyst within the above range, the metal ion ratio in the catalyst can be adjusted, the local electronic structure near the active sites is modulated, and the adsorption and desorption energies of reaction intermediates in water electrolysis for hydrogen production can be balanced, thereby improving intrinsic activity, promoting the reaction, and achieving highly efficient catalytic HER.

[0050] For example, the mass ratio of the first cathode catalyst to the second cathode catalyst can be 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1.

[0051] In some embodiments, such as Figure 2 As shown, the cathode catalyst layer 20 includes a first cathode catalyst sublayer 21 and a second cathode catalyst sublayer 22. The first cathode catalyst sublayer 21 is disposed close to the anion exchange membrane 10, and the second cathode catalyst sublayer 22 is disposed on the side of the first cathode catalyst sublayer 21 facing away from the anion exchange membrane 10. Both the first cathode catalyst sublayer 21 and the second cathode catalyst sublayer 22 contain anion exchange membrane ionomers. The mass percentage of the anion exchange membrane ionomers in the first cathode catalyst sublayer 21 is m1, and the mass percentage of the anion exchange membrane ionomers in the second cathode catalyst sublayer 22 is m2, where m1 > m2.

[0052] Among them, the anion exchange membrane ionomer mainly plays the roles of binding the catalyst, providing mechanical stability of the catalyst layer, forming a porous network in the catalyst layer, and effectively transporting the ion support from the membrane to the active site of the catalyst.

[0053] By setting different mass percentages of anion exchange membrane ionomers in the first cathode catalyst layer 21 and the second cathode catalyst layer 22, it helps to reduce the contact resistance between the cathode catalyst layer 20 and the anion exchange membrane 10, generate different hydrophilic properties and porosities in each catalyst layer, optimize the gas and liquid transport efficiency in the cathode catalyst layer 20, and improve the catalytic efficiency of hydrogen production by water electrolysis.

[0054] The first cathode catalytic sub-layer 21 is arranged close to the anion exchange membrane 10, and the mass percentage of the anion exchange membrane ionomer in the first cathode catalytic sub-layer 21 is high, which can reduce the contact resistance between the first cathode catalytic sub-layer 21 and the anion exchange membrane 10, improve the electrical conductivity, effectively transfer the charge carriers from the membrane to the catalytic layer, and improve the reaction efficiency. By making m1>m2, the porosity in the second cathode catalytic sub-layer 22 can be greater than that in the first cathode catalytic sub-layer 21, which helps to discharge the generated hydrogen gas from the catalytic layer to the gas diffusion layer side, improves the gas transmission efficiency, optimizes the water management, avoids the accumulation of gas bubbles in the catalytic layer, blocks the active sites, and the electrolyte is not fully contacted, thereby improving the catalytic efficiency.

[0055] In some embodiments, the mass percentage of the anion exchange membrane ionomer in the first cathode catalytic sub-layer 21 is m1, which satisfies: 5%≤m1≤50%.

[0056] By making the mass percentage of the anion exchange membrane ionomer in the first cathode catalytic sub-layer 21 be 5%-50%, the charge carriers in the first cathode catalytic sub-layer 21 can be effectively transferred to the active sites, but the electronic transmission will not be hindered due to too much anion exchange membrane ionomer, resulting in poor electrical conductivity, and a mechanically reliable catalytic layer is formed to ensure the stability of the membrane electrode. In addition, the mass percentage of the anion exchange membrane ionomer in the above range can also reduce the contact resistance between the first cathode catalytic sub-layer 21 and the anion exchange membrane 10, and ensure the electrochemical performance of the entire membrane electrode.

[0057] For example, the mass percentage of the anion exchange membrane ionomer in the first cathode catalytic sub-layer 21 can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%.

[0058] In some embodiments, the mass percentage of the anion exchange membrane ionomer in the first cathode catalytic sub-layer 21 is 30%.

[0059] In some embodiments, the mass percentage of the anion exchange membrane ionomer in the second cathode catalytic sub-layer 22 is m2, which satisfies: 5%≤m2≤40%.

[0060] Similar to the first cathode catalytic sub-layer 21, by setting the mass ratio of the anion exchange membrane ionomer in the second cathode catalytic sub-layer 22 to 5%-40%, the ion carrier in the second cathode catalytic sub-layer 22 can be effectively transported to the active site, but the excessive anion exchange membrane ionomer does not hinder the electron transport to cause poor electrical conductivity, and a mechanically reliable catalytic layer is formed, which is firmly combined with the first cathode catalytic sub-layer 21 to form a stable interface, thereby ensuring the stability of the membrane electrode. In addition, the different pore structures formed by different ionomer contents in the two catalytic sub-layers are beneficial to the diffusion of hydrogen gas to the gas diffusion layer, avoiding the accumulation of bubbles in the catalytic layer to block the active site, and improving the catalytic efficiency.

[0061] Exemplarily, the mass percentage m2 of the anion exchange membrane ionomer in the second cathode catalytic sub-layer 22 can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%.

[0062] In some embodiments, the mass percentage m2 of the anion exchange membrane ionomer in the second cathode catalytic sub-layer 22 is 15%.

[0063] In some embodiments, the water electrolysis hydrogen production membrane electrode further comprises a cathode gas diffusion layer 30, which is arranged on the side of the cathode catalytic layer 20 away from the anion exchange membrane 10, and the cathode catalytic layer 20 is coated on the cathode gas diffusion layer 30.

[0064] The cathode gas diffusion layer 30 is arranged on the side of the cathode catalytic layer 20 away from the cathode exchange membrane, which functions to timely discharge the product hydrogen gas, avoiding the accumulation of hydrogen gas in the cathode catalytic layer 20 to block the active site and improve the reaction efficiency. The cathode gas diffusion layer 30 can also quickly and uniformly transport the electrolyte reactant to the catalytic layer through its porous structure, thereby improving the reaction rate. The cathode catalytic layer 20 is coated on the cathode gas diffusion layer 30, which provides physical support for the cathode catalytic layer 20, maintains the exposure of the active site, prevents the aggregation and shedding of the catalyst particles, and stabilizes the electrode structure, thereby prolonging the service life of the entire membrane electrode. In addition, the cathode gas diffusion layer 30 with high electrical conductivity also has the function of providing an electron channel for the cathode electrode reaction.

[0065] In some embodiments, the cathode gas diffusion layer 30 comprises at least one of nickel felt, titanium felt, stainless steel felt, copper felt, and graphite felt. These materials have good electrical conductivity, mechanical stability, chemical stability, and thermal stability, and the felt structure is beneficial to reducing the contact resistance between the catalytic layer and the electrode, and the cost is relatively low.

[0066] In some embodiments, the metal felt such as nickel felt, titanium felt, stainless steel felt, and copper felt comprises at least one of fiber felt, powder felt, foam structure felt, and composite structure felt.

[0067] In some embodiments, the total loading of the first cathode catalyst and the second cathode catalyst in the cathode catalytic layer 20 is 1 mg / cm 2 - 20 mg / cm 2 .

[0068] The catalyst loading refers to the loading of the catalyst per unit area. By setting the total loading of the first cathode catalyst and the second cathode catalyst to 1 mg / cm 2 - 20 mg / cm 2 , sufficient catalytic active sites can be provided to ensure good catalytic performance, and the utilization of the catalyst can be improved.

[0069] For example, the total loading of the first cathode catalyst and the second cathode catalyst in the cathode catalytic layer 20 can be 1 mg / cm 2 , 2 mg / cm 2 , 3 mg / cm 2 , 4 mg / cm 2 , 5 mg / cm 2 , 6 mg / cm 2 , 7 mg / cm 2 , 8 mg / cm 2 , 9 mg / cm 2 , 10 mg / cm 2 , 11 mg / cm 2 , 12 mg / cm 2 , 13 mg / cm 2 , 14 mg / cm 2 , 15 mg / cm 2 , 16 mg / cm 2 , 17 mg / cm 2 , 18 mg / cm 2 , 19 mg / cm 2 , or 20 mg / cm 2 .

[0070] In some embodiments, the total loading of the first cathode catalyst and the second cathode catalyst in the cathode catalytic layer 20 is 5 mg / cm 2 .

[0071] In some embodiments, the first anode catalyst includes at least one of a nickel-molybdenum alloy, a nickel-cobalt alloy, a nickel-cobalt-iron alloy, a nickel-iron alloy, nickel powder, iron powder, and cobalt powder.

[0072] Materials such as nickel-molybdenum alloy (NiMo), nickel-cobalt alloy (NiCo), nickel-iron alloy (NiFe), and nickel-cobalt-iron alloy (NiCoFe) can break the inherent adsorption energy scale of a single metal due to alloying, so that the adsorption energy of each intermediate is closer to the theoretical optimal value, thereby significantly reducing the oxygen evolution overpotential and having good catalytic activity. At the same time, the corrosion resistance brought by alloying ensures the working life of the catalyst. The large specific surface area of metal nanopowders such as nickel powder, iron powder, and cobalt powder exposes a large number of active sites, and the high electrical conductivity is the basis for being an efficient electrochemical catalyst. At the same time, the transition metal powder has a mature industrial method, a large amount of earth reserves, and a huge cost advantage in large-scale industrial application.

[0073] In some embodiments, the second anode catalyst includes at least one of nickel-iron layered double hydroxide (NiFe-LDH), cobalt trioxide (Co3O4), nickel-iron oxide, nickel-cobalt oxide, iron-cobalt oxide, and iron-manganese oxide. The oxides or hydroxides mentioned above are all oxygen evolution catalysts with high intrinsic activity. In an alkaline and highly oxidizing environment, the oxide or hydroxide itself is a stable intermediate state or final product in thermodynamics, and it is not easy to collapse the structure during continuous oxidation; the layered double hydroxide tolerates the volume change of OH- insertion and extraction, and the spinel oxide rigid skeleton resists structural collapse; it has both chemical stability and mechanical stability, and the cost is lower than that of the noble metal anode catalyst.

[0074] In some embodiments, the first anode catalyst is a nickel-cobalt alloy (NiCo), and the second anode catalyst is a nickel-iron layered double hydroxide (NiFe-LDH).

[0075] Among the nickel-cobalt alloy and the nickel-iron layered double hydroxide, the nickel-cobalt alloy can provide high electrical conductivity in the high-efficiency catalytic layer, providing an electron channel for the reaction; while the nickel-iron layered double hydroxide has excellent catalytic oxygen evolution activity, the two work together to promote anode oxygen evolution and accelerate water electrolysis. In addition, in an alkaline and highly oxidizing environment, the catalyst surface is reconstructed into a high-activity species of oxygen / hydroxide, and the three metal ions regulate the local electronic structure through the reconstructed heterojunction interface to obtain the optimal adsorption energy of the reaction intermediates, thereby improving the oxygen evolution efficiency. At the same time, the high stability of the two materials also provides a guarantee for the service life of the membrane electrode.

[0076] In some embodiments, the mass ratio of the first anode catalyst to the second anode catalyst is (0.1-1):1. By setting the mass ratio of the first anode catalyst to the second anode catalyst in the above range, the metal ion ratio in the catalyst can be adjusted, and the local electronic structure near the active site is modulated, which can balance the adsorption / desorption energy of the reaction intermediates in the hydrogen production by water electrolysis, thereby accelerating the reaction process and improving the overall catalytic activity.

[0077] For example, the mass ratio of the first anode catalyst to the second anode catalyst can be 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1 or 1:1.

[0078] In some embodiments, such as Figure 2 As shown, the anode catalyst layer 40 includes a first anode catalyst sublayer 41 and a second anode catalyst sublayer 42. The first anode catalyst sublayer 41 is disposed close to the anion exchange membrane 10, and the second anode catalyst sublayer 42 is disposed on the side of the first anode catalyst sublayer 41 facing away from the anion exchange membrane 10. Both the first anode catalyst sublayer 41 and the second anode catalyst sublayer 42 contain anion exchange membrane ionomers. The mass percentage of anion exchange membrane ionomers in the first anode catalyst sublayer 41 is m3, and the mass percentage of anion exchange membrane ionomers in the second anode catalyst sublayer 42 is m4, where m3 > m4.

[0079] By setting different mass percentages of anion exchange membrane ionomers in the first anode catalyst sublayer 41 and the second anode catalyst sublayer 42, it helps to reduce the contact resistance between the anode catalyst layer 40 and the anion exchange membrane 10, generate different hydrophilic properties and porosities in each catalyst layer, optimize the gas and electrolyte transport in the anode catalyst layer 40, and improve the catalytic efficiency of hydrogen production by water electrolysis.

[0080] The first anode catalyst sublayer 41 is disposed close to the anion exchange membrane 10, and its anion exchange membrane ionomer has a high mass percentage, which can improve the contact resistance between the first anode catalyst sublayer and the anion exchange membrane 10, improve ion transport efficiency, and increase the reaction rate. By making m3 > m4, the porosity in the second anode catalyst sublayer 42 can also be greater than that in the first anode catalyst sublayer 41, which helps the generated oxygen to be discharged from the catalyst layer to the gas diffusion layer side, improves gas transport efficiency, optimizes water management, and avoids bubble accumulation, blockage of active sites, and insufficient electrolyte contact in the catalyst layer, thereby improving catalytic efficiency. In some embodiments, the mass percentage of anion exchange membrane ionomer in the first anode catalyst sublayer 41, m3, satisfies: 5% ≤ m3 ≤ 50%.

[0081] By setting the mass ratio of the anion exchange membrane ionomer in the first anode catalytic sub-layer 41 to be 5%-50%, the charge carriers in the first anode catalytic sub-layer 41 can be effectively transported to the active sites, but not too much anion exchange membrane ionomer to hinder electron transport and lead to poor electrical conductivity, while forming a mechanically reliable catalytic layer, avoiding catalyst shedding, and ensuring the stability of the membrane electrode. In addition, the mass ratio of the anion exchange membrane ionomer in the above range can also reduce the contact resistance between the first anode catalytic sub-layer 41 and the anion exchange membrane 10, and ensure the electrochemical performance of the entire membrane electrode. For example, the mass percentage m1 of the anion exchange membrane ionomer in the first anode catalytic sub-layer 41 can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%.

[0082] In some embodiments, the mass percentage m4 of the anion exchange membrane ionomer in the second anode catalytic sub-layer 42 satisfies 5%≤m4≤40%.

[0083] Similar to the first anode catalytic sub-layer 41, by setting the mass ratio of the anion exchange membrane ionomer in the second anode catalytic sub-layer 42 to be 5%-40%, the charge carriers in the second anode catalytic sub-layer 42 can be effectively transported to the active sites, but not too much anion exchange membrane ionomer to hinder electron transport and lead to poor electrical conductivity, while forming a mechanically reliable catalytic layer, firmly combining with the first anode catalytic sub-layer 41 to form a stable interface, and ensuring the stability of the membrane electrode. In addition, the different ionomer contents in the two catalytic sub-layers form different pore structures, which are conducive to the diffusion of hydrogen gas to the gas diffusion layer, avoiding the accumulation of bubbles in the catalytic layer and blocking the active sites, and improving the catalytic efficiency.

[0084] For example, the mass percentage m2 of the anion exchange membrane ionomer in the second anode catalytic sub-layer 42 can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%.

[0085] In some embodiments, the water electrolysis hydrogen production membrane electrode further comprises an anode gas diffusion layer 50, which is arranged on the side of the anode catalytic layer 40 away from the anion exchange membrane 10, and the anode catalytic layer 40 is coated on the anode gas diffusion layer 50.

[0086] The anode gas diffusion layer 50 is disposed on the side of the anode catalyst layer 40 facing away from the cathode exchange film, and functions to timely discharge the product oxygen, avoid accumulation of oxygen in the anode catalyst layer 40, block the active sites, and improve the reaction efficiency. The anode gas diffusion layer 50 can also quickly and uniformly transport the reactant electrolyte to the catalyst layer through its porous structure, thereby improving the reaction rate. The anode catalyst layer 40 is coated on the anode gas diffusion layer 50, which provides physical support for the anode catalyst layer 40, maintains the exposure of the active sites, prevents the aggregation and shedding of the catalyst particles, stabilizes the electrode structure, and prolongs the service life of the entire membrane electrode. In addition, the anode gas diffusion layer 50 with high electrical conductivity also functions to provide an electron channel for the anode electrode reaction.

[0087] In some embodiments, the anode gas diffusion layer 50 includes at least one of nickel felt, titanium felt, stainless steel felt, copper felt, and graphite felt. These materials have good electrical conductivity, mechanical stability, chemical stability, thermal stability, and corrosion resistance, and the felt structure is conducive to reducing the contact resistance between the catalyst layer and the catalyst layer, and the cost is relatively low.

[0088] In some embodiments, in the anode catalyst layer 40, the total amount of the first anode catalyst and the second anode catalyst is 1 mg / cm 2 -20 mg / cm 2 .

[0089] By making the total amount of the first anode catalyst and the second anode catalyst 1 mg / cm 2 -20 mg / cm 2 , sufficient catalytic active sites can be provided to ensure good catalytic performance, and the utilization rate of the catalyst can be improved.

[0090] Exemplarily, in the anode catalyst layer 40, the total amount of the first anode catalyst and the second anode catalyst can be 1 mg / cm 2 , 2 mg / cm 2 , 3 mg / cm 2 , 4 mg / cm 2 , 5 mg / cm 2 , 6 mg / cm 2 , 7 mg / cm 2 , 8 mg / cm 2 , 9 mg / cm 2 , 10 mg / cm 2 , 11 mg / cm 2 , 12 mg / cm 2 , 13 mg / cm 2 , 14 mg / cm 2 , 15 mg / cm 2 , 16 mg / cm 217 mg / cm 2 18 mg / cm 2 19 mg / cm 2 or 20 mg / cm 2 .

[0091] In some embodiments, in the anode catalytic layer 40, the total amount of the first anode catalyst and the second anode catalyst is 5 mg / cm 2 .

[0092] In some embodiments, the anion exchange membrane ionomer includes at least one of Sustainion, Nafion, Aquivion, Aemion, PiperIon, Alkymer I-250, Pention, Fumion, and Tokuyama.

[0093] In a second aspect, the embodiments of the present application also provide an electrolytic cell, including the water electrolysis hydrogen production membrane electrode as described above.

[0094] The electrolytic cell provided by the embodiments of the present application has all the beneficial effects of the water electrolysis hydrogen production membrane electrode as described above, which will not be repeated here.

[0095] Exemplarily, the preparation method of the water electrolysis hydrogen production membrane electrode provided by the embodiments of the present application includes:

[0096] dispersing the first cathode catalyst, the second cathode catalyst, and the anion exchange membrane ionomer into a solvent to obtain a first slurry;

[0097] dispersing the first cathode catalyst, the second cathode catalyst, and the anion exchange membrane ionomer into a solvent to obtain a second slurry;

[0098] dispersing the first anode catalyst, the second anode catalyst, and the anion exchange membrane ionomer into a solvent to obtain a third slurry;

[0099] dispersing the first anode catalyst, the second anode catalyst, and the anion exchange membrane ionomer into a solvent to obtain a fourth slurry;

[0100] coating the second slurry on the cathode gas diffusion layer 30 to form a second cathode catalyst sublayer 22, coating the first slurry on a side of the second cathode catalyst sublayer 22 away from the cathode gas diffusion layer 30 to form a first cathode catalyst sublayer 21, to obtain a cathode with the cathode gas diffusion layer 30 and the cathode catalyst layer 20;

[0101] The fourth slurry is coated on the anode gas diffusion layer 50 to form a second anode catalyst sublayer 42, the third slurry is coated on the side of the second anode catalyst sublayer 42 away from the anode gas diffusion layer 50 to form a first anode catalyst sublayer 41, and an anode with the anode gas diffusion layer 50 and the anode catalyst layer 40 is obtained.

[0102] The cathode, the anion exchange membrane 10 and the anode are sequentially stacked to obtain a hydrogen production membrane electrode.

[0103] The solvent can be at least one of methanol, ethanol, n-propanol, isopropanol, DMSO, DMF, ethylene glycol, glycerol and water.

[0104] During preparation of the first slurry, the second slurry, the third slurry and the fourth slurry, shearing or ultrasonic dispersion treatment can be performed. The dispersion time can be 20-60 min, and the temperature is kept within a range of less than 5℃.

[0105] The membrane electrode is assembled with a cathode plate (with a flow field), an anode plate (with a flow field), an end plate and an insulating plate to form an electrolytic cell.

[0106] The embodiments of the present application are further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and not to limit the scope of the present application. The experimental methods in the following examples, if not specified, are generally performed according to the conditions recommended by the manufacturer.

[0107] Unless otherwise specified, the preparation method of the membrane electrode in the following examples and comparative examples is as follows:

[0108] The first cathode catalyst, the second cathode catalyst and the anion exchange membrane ionomer are dispersed into a solvent, and shearing dispersion is performed for 20 min to obtain a first slurry;

[0109] The first cathode catalyst, the second cathode catalyst and the anion exchange membrane ionomer are dispersed into a solvent, and shearing dispersion is performed for 20 min to obtain a second slurry;

[0110] The first anode catalyst, the second anode catalyst and the anion exchange membrane ionomer are dispersed into a solvent, and shearing dispersion is performed for 20 min to obtain a third slurry;

[0111] The first anode catalyst, the second anode catalyst and the anion exchange membrane ionomer are dispersed into a solvent, and shearing dispersion is performed for 20 min to obtain a fourth slurry;

[0112] The second slurry is coated on the cathode gas diffusion layer 30 to form a second cathode catalyst sublayer 22, and the first slurry is coated on the side of the second cathode catalyst sublayer 22 away from the cathode gas diffusion layer 30 to form a first cathode catalyst sublayer 21, and a cathode with the cathode gas diffusion layer 30 and the cathode catalyst layer 20 is obtained.

[0113] The fourth slurry is coated on the anode gas diffusion layer 50 to form the second anode catalyst sublayer 42, and the third slurry is coated on the side of the second anode catalyst sublayer 42 away from the anode gas diffusion layer 50 to form the first anode catalyst sublayer 41, thereby obtaining an anode gas with the anode gas diffusion layer 50 and the anode catalyst layer 40;

[0114] The cathode, the anion exchange membrane 10 and the anode are sequentially stacked to obtain a hydrogen production membrane electrode for electrolysis of water.

[0115] The solvent is a solution of ethanol and water in a volume ratio of 1:1.

[0116] Example 1

[0117] In this embodiment, the first cathode catalyst is molybdenum disulfide, the second cathode catalyst is iron phosphide, and the mass ratio of molybdenum disulfide to iron phosphide in the membrane electrode is 0.1, and the total loading of molybdenum disulfide and iron phosphide is 5 mg / cm 2 ; the mass percentage of anion exchange membrane ionomer in the first cathode catalyst sublayer 21 is 30%, and the mass percentage of anion exchange membrane ionomer in the second cathode catalyst sublayer 22 is 15%;

[0118] The first anode catalyst is a nickel-cobalt alloy, the second anode catalyst is a nickel-iron layered double hydroxide, and the mass ratio of the nickel-cobalt alloy to the nickel-iron layered double hydroxide in the membrane electrode is 0.1, and the total loading of the nickel-cobalt alloy and the nickel-iron layered double hydroxide is 5 mg / cm 2 ; the mass percentage of anion exchange membrane ionomer in the first anode catalyst sublayer 41 is 30%, and the mass percentage of anion exchange membrane ionomer in the second anode catalyst sublayer 42 is 15%;

[0119] The anion exchange membrane ionomer is Alkymer I-250, the anion exchange membrane 10 is Alkymer W75 anion exchange membrane 10, and the cathode gas diffusion layer 30 and the anode gas diffusion layer 50 are both nickel felt.

[0120] Example 2

[0121] In this embodiment, the first cathode catalyst is molybdenum disulfide, the second cathode catalyst is iron phosphide, and the mass ratio of molybdenum disulfide to iron phosphide in the membrane electrode is 2, and the total loading of molybdenum disulfide and iron phosphide is 5 mg / cm 2 ; the mass percentage of anion exchange membrane ionomer in the first cathode catalyst sublayer 21 is 30%, and the mass percentage of anion exchange membrane ionomer in the second cathode catalyst sublayer 22 is 15%;

[0122] The first anode catalyst is a nickel-cobalt alloy, the second anode catalyst is a nickel-iron layered double hydroxide, and the mass ratio of the nickel-cobalt alloy and the nickel-iron layered double hydroxide in the membrane electrode is 1, and the total amount of the nickel-cobalt alloy and the nickel-iron layered double hydroxide is 5 mg / cm 2 ; the mass percentage of the anion exchange membrane ionomer in the first anode catalyst sub-layer 41 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second anode catalyst sub-layer 42 is 15%;

[0123] The anion exchange membrane ionomer is Alkymer I-250, the anion exchange membrane 10 is Alkymer W75 anion exchange membrane 10, and the cathode gas diffusion layer 30 and the anode gas diffusion layer 50 are both nickel felt.

[0124] Example 3

[0125] In this embodiment, the first cathode catalyst is molybdenum disulfide, the second cathode catalyst is iron phosphide, and the mass ratio of the molybdenum disulfide and the iron phosphide in the membrane electrode is 0.5, and the total amount of the molybdenum disulfide and the iron phosphide is 5 mg / cm 2 ; the mass percentage of the anion exchange membrane ionomer in the first cathode catalyst sub-layer 21 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second cathode catalyst sub-layer 22 is 15%;

[0126] The first anode catalyst is a nickel-cobalt alloy, the second anode catalyst is a nickel-iron layered double hydroxide, and the mass ratio of the nickel-cobalt alloy and the nickel-iron layered double hydroxide in the membrane electrode is 0.25, and the total amount of the nickel-cobalt alloy and the nickel-iron layered double hydroxide is 5 mg / cm 2 ; the mass percentage of the anion exchange membrane ionomer in the first anode catalyst sub-layer 41 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second anode catalyst sub-layer 42 is 15%;

[0127] The anion exchange membrane ionomer is Alkymer I-250, the anion exchange membrane 10 is Alkymer W75 anion exchange membrane 10, and the cathode gas diffusion layer 30 and the anode gas diffusion layer 50 are both nickel felt.

[0128] Example 4

[0129] In this embodiment, the first cathode catalyst is molybdenum disulfide, the second cathode catalyst is iron phosphide, and the mass ratio of the molybdenum disulfide and the iron phosphide in the membrane electrode is 0.5, and the total amount of the molybdenum disulfide and the iron phosphide is 5 mg / cm 2 ; the mass percentage of the anion exchange membrane ionomer in the first cathode catalyst sub-layer 21 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second cathode catalyst sub-layer 22 is 15%;

[0130] The first anode catalyst is a nickel-cobalt alloy, the second anode catalyst is a nickel-iron layered double hydroxide, and the mass ratio of the nickel-cobalt alloy to the nickel-iron layered double hydroxide in the membrane electrode is 0.25, and the total amount of the nickel-cobalt alloy and the nickel-iron layered double hydroxide is 5 mg / cm 2 The mass percentage of the anion exchange membrane ionomer in the first anode catalyst sub-layer 41 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second anode catalyst sub-layer 42 is 15%;

[0131] The anion exchange membrane ionomer is Alkymer I-250, the anion exchange membrane 10 is Alkymer W75 anion exchange membrane 10, and the cathode gas diffusion layer 30 and the anode gas diffusion layer 50 are both nickel felt.

[0132] Example 5

[0133] In this embodiment, the first cathode catalyst is molybdenum disulfide, the second cathode catalyst is iron phosphide, and the mass ratio of the molybdenum disulfide to the iron phosphide in the membrane electrode is 0.5, and the total amount of the molybdenum disulfide and the iron phosphide is 5 mg / cm 2 The mass percentage of the anion exchange membrane ionomer in the first cathode catalyst sub-layer 21 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second cathode catalyst sub-layer 22 is 15%;

[0134] The first anode catalyst is a nickel-cobalt alloy, the second anode catalyst is a nickel-iron layered double hydroxide, and the mass ratio of the nickel-cobalt alloy to the nickel-iron layered double hydroxide in the membrane electrode is 0.25, and the total amount of the nickel-cobalt alloy and the nickel-iron layered double hydroxide is 5 mg / cm 2 The mass percentage of the anion exchange membrane ionomer in the first anode catalyst sub-layer 41 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second anode catalyst sub-layer 42 is 15%;

[0135] The anion exchange membrane ionomer is Alkymer I-250, the anion exchange membrane 10 is Alkymer W75 anion exchange membrane 10, and the cathode gas diffusion layer 30 and the anode gas diffusion layer 50 are both nickel felt.

[0136] Example 6

[0137] In this embodiment, the first cathode catalyst is molybdenum disulfide, the second cathode catalyst is iron phosphide, and the mass ratio of the molybdenum disulfide to the iron phosphide in the membrane electrode is 0.5, and the total amount of the molybdenum disulfide and the iron phosphide is 5 mg / cm 2 The mass percentage of the anion exchange membrane ionomer in the first cathode catalyst sub-layer 21 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second cathode catalyst sub-layer 22 is 15%;

[0138] The first anode catalyst is a nickel-cobalt alloy, the second anode catalyst is a nickel-iron layered double hydroxide, and the mass ratio of the nickel-cobalt alloy and the nickel-iron layered double hydroxide in the membrane electrode is 0.25, and the total amount of the nickel-cobalt alloy and the nickel-iron layered double hydroxide is 5 mg / cm 2 The mass percentage of the anion exchange membrane ionomer in the first anode catalyst sub-layer 41 is 50%, and the mass percentage of the anion exchange membrane ionomer in the second anode catalyst sub-layer 42 is 40%;

[0139] The anion exchange membrane ionomer is Alkymer I-250, the anion exchange membrane 10 is Alkymer W75 anion exchange membrane 10, and the cathode gas diffusion layer 30 and the anode gas diffusion layer 50 are both nickel felt.

[0140] Example 7

[0141] In this embodiment, the first cathode catalyst is molybdenum disulfide, the second cathode catalyst is iron phosphide, and the mass ratio of the molybdenum disulfide and the iron phosphide in the membrane electrode is 0.5, and the total amount of the molybdenum disulfide and the iron phosphide is 5 mg / cm 2 The mass percentage of the anion exchange membrane ionomer in the first cathode catalyst sub-layer 21 is 10%, and the mass percentage of the anion exchange membrane ionomer in the second cathode catalyst sub-layer 22 is 5%;

[0142] The first anode catalyst is a nickel-cobalt alloy, the second anode catalyst is a nickel-iron layered double hydroxide, and the mass ratio of the nickel-cobalt alloy and the nickel-iron layered double hydroxide in the membrane electrode is 0.25, and the total amount of the nickel-cobalt alloy and the nickel-iron layered double hydroxide is 5 mg / cm 2 The mass percentage of the anion exchange membrane ionomer in the first anode catalyst sub-layer 41 is 10%, and the mass percentage of the anion exchange membrane ionomer in the second anode catalyst sub-layer 42 is 5%;

[0143] The anion exchange membrane ionomer is Alkymer I-250, the anion exchange membrane 10 is Alkymer W75 anion exchange membrane 10, and the cathode gas diffusion layer 30 and the anode gas diffusion layer 50 are both nickel felt.

[0144] Example 8

[0145] In this embodiment, the first cathode catalyst is molybdenum disulfide, the second cathode catalyst is iron phosphide, and the mass ratio of the molybdenum disulfide and the iron phosphide in the membrane electrode is 0.5, and the total amount of the molybdenum disulfide and the iron phosphide is 5 mg / cm 2 The mass percentage of the anion exchange membrane ionomer in the cathode catalyst layer 20 is 30%;

[0146] The first anode catalyst is a nickel-cobalt alloy, the second anode catalyst is a nickel-iron layered double hydroxide, and the mass ratio of the nickel-cobalt alloy and the nickel-iron layered double hydroxide in the membrane electrode is 0.25, and the total amount of the nickel-cobalt alloy and the nickel-iron layered double hydroxide is 5 mg / cm 2 ; the mass percentage of the anion exchange membrane ionomer in the anode catalytic layer 40 is 30%;

[0147] The anion exchange membrane ionomer is Alkymer I-250, the anion exchange membrane 10 is Alkymer W75 anion exchange membrane 10, and the cathode gas diffusion layer 30 and the anode gas diffusion layer 50 are both nickel felt.

[0148] Comparative Example 1

[0149] In this comparative example, the cathode catalyst is Pt / C, and the total amount of Pt / C in the membrane electrode is 1 mg / cm 2 ; the mass percentage of the anion exchange membrane ionomer in the first cathode sub-catalytic layer 21 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second cathode sub-catalytic layer 22 is 15%;

[0150] The first anode catalyst is a nickel-cobalt alloy, the second anode catalyst is a nickel-iron layered double hydroxide, and the mass ratio of the nickel-cobalt alloy and the nickel-iron layered double hydroxide in the membrane electrode is 0.25, and the total amount of the nickel-cobalt alloy and the nickel-iron layered double hydroxide is 5 mg / cm 2 ; the mass percentage of the anion exchange membrane ionomer in the first anode sub-catalytic layer 41 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second anode sub-catalytic layer 42 is 15%;

[0151] The anion exchange membrane ionomer is Alkymer I-250, the anion exchange membrane 10 is Alkymer W75 anion exchange membrane 10, and the cathode gas diffusion layer 30 and the anode gas diffusion layer 50 are both nickel felt.

[0152] Comparative Example 2

[0153] In this comparative example, the first cathode catalyst is molybdenum disulfide, the second cathode catalyst is iron phosphide, and the mass ratio of the molybdenum disulfide and the iron phosphide in the membrane electrode is 0.5, and the total amount of the molybdenum disulfide and the iron phosphide is 5 mg / cm 2 ; the mass percentage of the anion exchange membrane ionomer in the first cathode sub-catalytic layer 21 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second cathode sub-catalytic layer 22 is 15%;

[0154] The anode catalyst is RuO2, and the total amount of RuO2 in the membrane electrode is 1 mg / cm 2; the mass percentage of the anion exchange membrane ionomer in the first anode catalytic sub-layer 41 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second anode catalytic sub-layer 42 is 15%;

[0155] The anion exchange membrane ionomer is Alkymer I-250, the anion exchange membrane 10 is Alkymer W75 anion exchange membrane 10, and the cathode gas diffusion layer 30 and the anode gas diffusion layer 50 are both nickel felt.

[0156] Comparative Example 3

[0157] In the present comparative example, the cathode catalyst is Pt / C, and the total loading of Pt / C in the membrane electrode is 1 mg / cm 2 ; the mass percentage of the anion exchange membrane ionomer in the first cathode catalytic sub-layer 21 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second cathode catalytic sub-layer 22 is 15%;

[0158] The anode catalyst is RuO2, and the total loading of RuO2 in the membrane electrode is 1 mg / cm 2 ; the mass percentage of the anion exchange membrane ionomer in the first anode catalytic sub-layer 41 is 30%, and the mass percentage of the anion exchange membrane ionomer in the second anode catalytic sub-layer 42 is 15%;

[0159] The anion exchange membrane ionomer is Alkymer I-250, the anion exchange membrane 10 is Alkymer W75 anion exchange membrane 10, and the cathode gas diffusion layer 30 and the anode gas diffusion layer 50 are both nickel felt.

[0160] The membrane electrodes in Examples 1-8 and Comparative Examples 1-3 are assembled with a cathode plate (with flow field), an anode plate (with flow field), an end plate, and an insulating plate to form different electrolytic cells, respectively, and the polarization curves and stability curves of the different electrolytic cells are tested.

[0161] The tests are all conducted at an electrolytic cell temperature of 80℃ and an electrolyte of 1M potassium hydroxide solution. The polarization curve test method is as follows: an electrochemical workstation is used, a step current method is adopted, the system current density is increased from 0 A / cm 2 to 1 A / cm 2 , and a polarization curve graph is obtained through data processing. The stability curve test method is as follows: an electrochemical workstation is used, a chronopotentiometry method is adopted, the system current density is 1 A / cm 2 , and a stability curve graph is obtained through data processing. The ohmic resistance: an electrochemical workstation is used to test the constant voltage alternating current impedance of the tested object at the open circuit potential, the high frequency is set to 10000 Hz, the low frequency is 1 Hz, and the amplitude is 10 mV. After fitting the test results, the ohmic resistance (HFR) value is recorded. The test results are shown in the following table and Figure 3 .

[0162]

[0163]

[0164] From the comparison of Example 1 and Comparative Example 1 in the above table, it can be seen that the noble metal catalyst Pt / C is used in Comparative Example 1 instead of the non-noble metal first cathode catalyst and the second cathode catalyst in Example 1, the ohmic resistance of Example 1 is lower, and the voltage required under the same current density is lower. From the comparison of Example 1 and Comparative Example 2 in the above table, it can be seen that the noble metal catalyst RuO2 is used in Comparative Example 2 instead of the non-noble metal first cathode catalyst and the second cathode catalyst in Example 1, the ohmic resistance of Example 1 is lower, and the voltage required under the same current density is lower. From the comparison of Examples 1-8 and Comparative Example 3 in the above table, it can be seen that the noble metal catalyst is used in the cathode and the anode of Comparative Example 3, while the non-noble metal first cathode catalyst, the second cathode catalyst, the first anode catalyst and the second anode catalyst are used in Examples 1-8, the ohmic resistance of Examples 1-8 is lower, and the voltage required under the same current density is lower.

[0165] The above describes the embodiments of the present application in detail, and the principles and implementation manners of the present application are described by applying specific examples; the above description of the embodiments is only used to help understand the method of the present application and its core idea; meanwhile, for those skilled in the art, according to the idea of the present application, the specific implementation manner and application range will be changed, and the above description of the present application should not be understood as a limitation.

Claims

1. A hydrogen producing membrane electrode for electrolysis of water, characterized by, Comprise: an anion exchange membrane; a cathode catalytic layer disposed on one side of the anion exchange membrane, the cathode catalytic layer comprising a first cathode catalyst and a second cathode catalyst; an anode catalytic layer disposed on the side of the anion exchange membrane away from the cathode catalytic layer, the anode catalytic layer comprising a first anode catalyst and a second anode catalyst; wherein the first cathode catalyst and the second cathode catalyst are both non-precious metal cathode catalysts, and the first cathode catalyst and the second cathode catalyst are different; the first anode catalyst and the second anode catalyst are both non-precious metal anode catalysts, and the first anode catalyst and the second anode catalyst are different.

2. The water electrolysis hydrogen production membrane electrode according to claim 1, characterized in that, The first cathode catalyst comprises at least one of molybdenum diboride, molybdenum disulfide, nickel-molybdenum alloy, and molybdenum carbide; and / or, the second cathode catalyst comprises at least one of trinickel disulfide, dinickel phosphide, iron phosphide, and carbon-supported cobalt nitride.

3. The water electrolysis hydrogen production membrane electrode according to claim 2, characterized in that, The first cathode catalyst is molybdenum disulfide, and the second cathode catalyst is iron phosphide.

4. The water electrolysis hydrogen production membrane electrode according to claim 1, wherein The mass ratio of the first cathode catalyst to the second cathode catalyst is (0.1-2):

1.

5. The water electrolysis hydrogen production membrane electrode according to claim 1, wherein The cathode catalytic layer comprises a first cathode catalytic sublayer and a second cathode catalytic sublayer, the first cathode catalytic sublayer being disposed close to the anion exchange membrane, and the second cathode catalytic sublayer being disposed on the side of the first cathode catalytic sublayer away from the anion exchange membrane.

6. The water electrolysis hydrogen producing membrane electrode of claim 5, wherein, The first cathode catalytic sublayer and the second cathode catalytic sublayer both comprise anion exchange membrane ionomer; wherein the mass percentage of the anion exchange membrane ionomer in the first cathode catalytic sublayer is m1, and the mass percentage of the anion exchange membrane ionomer in the second cathode catalytic sublayer is m2, m1>m2.

7. The water electrolysis hydrogen producing membrane electrode according to claim 6, wherein, 5％≤m1≤50％； and / or, 5%≤m2≤40%.

8. The water electrolysis hydrogen production membrane electrode of claim 1, wherein, The water electrolysis hydrogen production membrane electrode further comprises a cathode gas diffusion layer disposed on the side of the cathode catalytic layer away from the anion exchange membrane, and the cathode catalytic layer is coated on the cathode gas diffusion layer.

9. The water electrolysis hydrogen production membrane electrode according to claim 8, wherein, The cathode gas diffusion layer comprises at least one of nickel felt, titanium felt, stainless steel felt, copper felt, and graphite felt.

10. The water electrolysis hydrogen production membrane electrode according to claim 1, wherein, The total amount of the first cathode catalyst and the second cathode catalyst in the cathode catalytic layer is 1 mg / cm 2 - 20 mg / cm 2 .

11. The water electrolysis hydrogen production membrane electrode according to claim 1, wherein The first anode catalyst comprises at least one of nickel-molybdenum alloy, nickel-cobalt alloy, nickel-cobalt-iron alloy, nickel-iron alloy, nickel powder, iron powder, and cobalt powder; and / or, the second anode catalyst comprises at least one of nickel-iron layered double hydroxide, tricobalt tetroxide, nickel-iron oxide, nickel-cobalt oxide, iron-cobalt oxide, and iron-manganese oxide.

12. The water electrolysis hydrogen production membrane electrode according to claim 11, wherein, The first anode catalyst is nickel-cobalt alloy, and the second anode catalyst is nickel-iron layered double hydroxide.

13. The water electrolysis hydrogen production membrane electrode of claim 1, wherein, The mass ratio of the first anode catalyst to the second anode catalyst is (0.1-1):

1.

14. The water electrolysis hydrogen production membrane electrode of claim 1, wherein, The anode catalytic layer comprises a first anode catalytic sublayer and a second anode catalytic sublayer, the first anode catalytic sublayer being disposed close to the anion exchange membrane, and the second anode catalytic sublayer being disposed on the side of the first anode catalytic sublayer away from the anion exchange membrane.

15. The water electrolysis hydrogen production membrane electrode of claim 14, wherein, The first anode catalytic sublayer and the second anode catalytic sublayer both comprise anion exchange membrane ionomer; The mass percentage of the anion exchange membrane ionomer in the first anode catalytic sub-layer is m3, the mass percentage of the anion exchange membrane ionomer in the second anode catalytic sub-layer is m4, and m3>m4.

16. The water electrolysis hydrogen production membrane electrode of claim 15, wherein, 5％≤m3≤50％； And / or, 5%≤m4≤40%.

17. The water electrolysis hydrogen production membrane electrode of claim 1, wherein, The total amount of the first anode catalyst and the second anode catalyst in the anode catalytic layer is 1 mg / cm 2 - 20 mg / cm 2 .

18. The water electrolysis hydrogen producing membrane electrode according to any one of claims 1-17, wherein, The electrolytic water hydrogen production membrane electrode further comprises an anode gas diffusion layer, the anode gas diffusion layer is arranged on the side of the anode catalytic layer away from the anion exchange membrane, and the anode catalytic layer is coated on the anode gas diffusion layer.

19. The water electrolysis hydrogen production membrane electrode of claim 18, wherein, The anode gas diffusion layer comprises at least one of nickel felt, titanium felt, stainless steel felt, copper felt and graphite felt.

20. An electrolytic cell characterized by, The electrolytic water hydrogen production membrane electrode comprises the electrolytic water hydrogen production membrane electrode according to any one of claims 1-19.

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