Platinum alloy catalytic material, method for preparing the same, membrane electrode assembly and fuel cell

Abstract

The application relates to a platinum alloy catalytic material, a preparation method thereof, a membrane electrode assembly and a fuel cell. The platinum alloy catalytic material comprises a carrier and nitrogen-doped platinum alloy nanowires loaded on the surface of the carrier. The platinum alloy catalytic material has high mass activity, good stability, can effectively reduce the use of Pt elements, and thus reduces the cost of a proton exchange membrane fuel cell.

Description

Technical Field

[0001] This application relates to the field of fuel cells, and in particular to a platinum alloy catalytic material and its preparation method, a membrane electrode assembly, and a fuel cell. Background Technology

[0002] A proton exchange membrane fuel cell is a novel type of driving power source, mainly composed of an anode, a cathode, and a membrane electrode assembly. The membrane electrode assembly mainly consists of a proton exchange membrane, a catalyst layer, and a diffusion layer. Its working mechanism is that, with the assistance of the catalyst in the catalyst layer of the membrane electrode assembly, hydrogen oxidation and oxygen reduction reactions occur at the anode and cathode, respectively, converting the chemical energy of the reducing agent (hydrogen) and the oxidizing agent (oxygen) into electrical energy.

[0003] Compared to current lithium-ion battery electric vehicles, which require a long charging time and have a range of over 300km, proton exchange membrane fuel cells (PEMFCs) only require hydrogen refueling and can achieve a range of over 650km in just a few minutes. Furthermore, PEMFCs also feature zero emissions, high energy efficiency, and adjustable power, making them a promising candidate for future electric vehicles.

[0004] However, traditional proton exchange membrane fuel cells have poor stability and mainly use the precious metal Pt as a catalyst, which is expensive and limits their large-scale application. Summary of the Invention

[0005] Based on this, this application provides a platinum alloy catalyst material with good stability and that can effectively reduce the cost of proton exchange membrane fuel cells. It also provides a method for preparing the platinum alloy catalyst material, a membrane electrode assembly containing the platinum alloy catalyst material, and a fuel cell.

[0006] The technical solution to the above-mentioned technical problems in this application is as follows.

[0007] This application provides a platinum alloy catalytic material, including a support and nitrogen-doped platinum alloy nanowires loaded on the surface of the support.

[0008] In some embodiments, the platinum alloy catalytic material includes at least one of platinum-copper alloy, platinum-iron alloy, and platinum-nickel alloy.

[0009] In some embodiments, in the platinum alloy catalytic material, the non-platinum metal elements account for 25%-80% of the total molar amount of each metal element in the nitrogen-doped platinum alloy nanowires.

[0010] In some embodiments, in the platinum alloy catalytic material, the platinum alloy in the nitrogen-doped platinum alloy nanowires is selected from Pt3Cu, PtCu1, and PtCu. 1.5At least one of PtCu2, PtCu3, PtCu4, PtFe and PtNi.

[0011] In some embodiments, in the platinum alloy catalytic material, the nitrogen element in the nitrogen-doped platinum alloy nanowire accounts for 2% to 4% of the molar percentage of the nitrogen-doped platinum alloy nanowire.

[0012] In some embodiments, the nitrogen-doped platinum alloy nanowires in the platinum alloy catalytic material have a length of 30 nm to 60 nm and a diameter of 2 nm to 4 nm.

[0013] In some embodiments, the support in the platinum alloy catalytic material is a carbon support.

[0014] In some embodiments, the platinum alloy catalyst is N-PtCu3NWs / C.

[0015] This application also provides a method for preparing a platinum alloy catalytic material, comprising the following steps:

[0016] After loading platinum alloy nanowires onto the surface of a support, ammonia gas is introduced under a protective atmosphere and the nanowires are annealed at 200°C to 300°C to form nitrogen-doped platinum alloy nanowires, thus obtaining the platinum alloy catalytic material.

[0017] In some embodiments, the preparation method of the platinum alloy catalytic material includes the following steps:

[0018] A first liquid-phase synthesis reaction was carried out by mixing a first platinum salt precursor, a surfactant, a reducing agent and a first solvent to obtain a first mixed solution containing platinum nanowires.

[0019] The second platinum salt precursor, the non-platinum salt metal precursor, and the second solvent are mixed evenly to obtain the second mixture.

[0020] The first mixture and the second mixture are mixed to carry out a second liquid-phase synthesis reaction to obtain platinum alloy nanowires.

[0021] In some embodiments, in the preparation method of the platinum alloy catalytic material, the first platinum salt precursor and the second platinum salt precursor are each independently selected from at least one of diacetylacetonate platinum, chloroplatinic acid and potassium chloroplatinate.

[0022] In some embodiments, in the preparation method of the platinum alloy catalytic material, the metal element in the non-platinum salt metal precursor is selected from at least one of Cu, Fe and Ni.

[0023] In some embodiments, in the preparation method of the platinum alloy catalytic material, the surfactant is selected from at least one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and didodecyldimethylammonium bromide.

[0024] In some embodiments, in the preparation method of the platinum alloy catalytic material, the reducing agent is selected from at least one of glucose, tungsten hexacarbonyl and molybdenum hexacarbonyl.

[0025] In some embodiments, in the preparation method of the platinum alloy catalytic material, the first solvent and the second solvent are each independently selected from at least one of oleylamine and octadecene.

[0026] In some embodiments, in the preparation method of the platinum alloy catalytic material, the total molar amount of platinum in the first platinum salt precursor and the second platinum salt precursor is in a molar ratio of the metal element in the non-platinum salt metal precursor to 1:(0.3-4.5).

[0027] In some embodiments, in the preparation method of the platinum alloy catalytic material, the temperatures of the first liquid-phase synthesis reaction and the second liquid-phase synthesis reaction are independently selected from 150°C to 170°C.

[0028] Accordingly, this application also provides a membrane electrode assembly, including a proton exchange membrane, an anode catalyst layer and a cathode catalyst layer, wherein the anode catalyst layer and the cathode catalyst layer are disposed on both sides of the proton exchange membrane, and the cathode catalyst layer comprises the above-mentioned platinum alloy catalyst material or the platinum alloy catalyst material prepared by the above-mentioned preparation method.

[0029] This application also provides a fuel cell, including an anode plate, a cathode plate, and the above-mentioned membrane electrode assembly, wherein the anode plate is disposed on the side of the anode catalyst layer away from the proton exchange membrane, and the cathode plate is disposed on the side of the cathode catalyst layer away from the proton exchange membrane.

[0030] Compared with existing technologies, the platinum alloy catalytic material of this application has the following beneficial effects:

[0031] The aforementioned platinum alloy catalytic material includes a support and nitrogen-doped platinum alloy nanowires loaded on the surface of the support. By introducing a specific p-block nonmetallic element, nitrogen (N), into the platinum alloy nanowires, the adsorption capacity for oxygen atoms can be improved and the adsorption energy for oxygen intermediates can be reduced, thereby effectively enhancing the oxygen reduction activity of the platinum alloy catalytic material. Furthermore, the incorporation of N forms a strong covalent bond-like characteristic (NM / N-Pt) with Pt and the non-platinum metal element M in the alloy, effectively increasing the vacancy formation energy of Pt and M, and slowing down the dissolution of Pt and M, thus effectively improving the stability of the platinum alloy catalytic material. Simultaneously, the nanowire structure increases the surface area in contact with the support, strengthening the interaction between the nitrogen-doped platinum alloy and the support, thereby further enhancing the stability of the platinum alloy catalytic material. Moreover, the nanowire structure can increase the ratio of surface Pt atoms to total Pt atoms, thereby improving the mass activity of the platinum alloy catalytic material. The platinum alloy catalytic material of this application introduces a specific p-region non-metallic element N into platinum alloy nanowires. When the content of the non-platinum metallic element M is as high as 80%, its catalytic performance is still good, which can effectively reduce the use of Pt element and thus effectively reduce the cost of fuel cells.

[0032] Oxygen reduction catalysis tests showed that the above-mentioned platinum alloy catalytic material exhibits a mass activity 15.8 times that of commercial platinum-carbon nanocatalysts and a site activity increase of 13.5 times. Compared to currently available commercial carbon-supported platinum nanocatalysts, which experience a 73.7% loss in mass activity after 10,000 cycles in an oxygen atmosphere, the platinum alloy catalytic material provided in this application shows almost no loss in mass activity after 260,000 cycles in an oxygen atmosphere. Further assembly of the membrane electrode showed that the cathode Pt loading was 0.12 mg / cm³. 2 At 0.9V, the mass activity can reach 0.53A / mg, and after long-term cycling tests of 100,000 cycles, the mass activity did not decay, and the cycle stability is good, making it suitable for commercial applications. Attached Figure Description

[0033] To more clearly illustrate the technical solutions in the specific embodiments of this application or the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0034] Figure 1 Transmission electron microscopy image of N-PtCu3 NWs / C in Example 1;

[0035] Figure 2 This is a diameter distribution diagram of N-PtCu3 NWs in Example 1;

[0036] Figure 3 This is a high-resolution image of N-PtCu3 NWs from Example 1;

[0037] Figure 4 This is a distribution diagram of Pt, Cu, and N elements in N-PtCu3 NWs in Example 1;

[0038] Figure 5 The X-ray diffraction pattern of N-PtCu3 NWs in Example 1;

[0039] Figure 6 Part A of the diagram contains polarization curves for Example 1 N-PtCu3 NWs / C, Example 2 N-PtCu NWs / C, Example 3 N-Pt3CuNWs / C, Example 4 N-PtNi NWs / C, Comparative Example 1 Pt NWs / C, and commercial Pt / C. Figure 6 Part B in the graph is the corresponding Tafel curve.

[0040] Figure 7 The mass activity and specific activity graphs are for Example 1 N-PtCu3 NWs / C, Example 2 N-PtCu NWs / C, Example 3 N-Pt3Cu NWs / C, Example 4 N-PtNi NWs / C, Comparative Example 1 Pt NWs / C, and commercial Pt / C.

[0041] Figure 8 This is a mass activity graph of N-PtCu3 NWs / C after 260K cycles in Example 1;

[0042] Figure 9 Transmission electron microscope (TEM) images of N-PtCu3 NWs / C after different numbers of cycles in Example 1;

[0043] Figure 10 This is a comparison graph of the power density of Example 1 N-PtCu3 NWs / C after different numbers of cycles and the initial power density of commercial Pt / C;

[0044] Figure 11 The graph shows the changes in mass activity and battery voltage after different numbers of cycles of N-PtCu3 NWs / C in Example 1. Detailed Implementation

[0045] Reference will now be made to detailed embodiments of the present invention, one or more of which are described below. Each example is provided for explanation and not for limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made to the invention without departing from its scope or spirit. For example, features described or illustrated as part of one embodiment may be used in another embodiment to produce further embodiments.

[0046] Therefore, this invention is intended to cover such modifications and variations falling within the scope of the appended claims and their equivalents. Other objects, features, and aspects of the invention are disclosed in or will be apparent from the following detailed description. It will be understood by those skilled in the art that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the invention.

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0048] The terms “comprising,” “including,” or any other variations thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element preceded by the phrase “comprising one…” does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element. The indefinite articles “a” and “an” preceding an element or component of the invention are not restrictive in terms of the number of elements or components (i.e., the number of times they appear). Therefore, “an” or “an” should be interpreted as including one or at least one, and singular elements or components also include plural forms, unless the quantity clearly refers only to the singular. “A plurality” means at least two, such as two, three, etc., unless otherwise expressly specified.

[0049] The weights of the relevant components mentioned in the embodiments of this invention can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this invention is within the scope disclosed in the embodiments of this invention. Specifically, the weights mentioned in the embodiments of this invention can be well-known units of mass in the chemical industry, such as μg, mg, g, and kg.

[0050] Unless otherwise shown or indicated in the operational embodiments, all figures used to represent the amounts, physicochemical properties, etc., of ingredients in the specification and claims are to be understood to be adjusted by the term "about" in all cases. For example, therefore, unless stated to the contrary, the numerical parameters listed in the foregoing specification and appended claims are approximations, and those skilled in the art can appropriately modify these approximations to obtain the desired characteristics by utilizing the teachings disclosed herein. The use of numerical ranges indicated by endpoints includes all numbers within that range and any range within that range; for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, etc.

[0051] One embodiment of this application provides a platinum alloy catalytic material, including a support and nitrogen-doped platinum alloy nanowires loaded on the surface of the support.

[0052] By introducing a specific p-block nonmetallic element, nitrogen (N), into platinum alloy nanowires, the adsorption capacity for oxygen atoms can be improved and the adsorption energy for oxygen intermediates can be reduced, thereby effectively enhancing the oxygen reduction activity of the platinum alloy catalytic material. Furthermore, the incorporation of N forms a strong covalent bond (NM / N-Pt) with Pt and the non-platinum metal element M in the alloy, effectively increasing the vacancy formation energy of Pt and M, slowing down their dissolution, and thus effectively improving the stability of the platinum alloy catalytic material. Simultaneously, the nanowire structure increases the surface area in contact with the support, strengthening the interaction between the nitrogen-doped platinum alloy and the support, further enhancing the stability of the platinum alloy catalytic material. Moreover, the nanowire structure can increase the ratio of surface Pt atoms to total Pt atoms, thereby improving the mass activity of the platinum alloy catalytic material. The platinum alloy catalytic material of this application, by introducing the specific p-block nonmetallic element N into platinum alloy nanowires, maintains good catalytic performance even when the content of the non-platinum metal element M is as high as 80%, effectively reducing the use of Pt and thus effectively reducing the cost of fuel cells.

[0053] It is understandable that, in some of these examples, the nitrogen-doped platinum alloy nanowires in the platinum alloy catalytic material are one-dimensional structures.

[0054] It can also be understood that the platinum alloy in nitrogen-doped platinum alloy nanowires contains other metallic elements M (non-platinum metal elements M) in addition to Pt; further, it can be understood that non-platinum metal elements M include, but are not limited to, Cu, Fe, Ni, V, Cr, Ti, Pd, Ru, etc.

[0055] In some of these examples, in the platinum alloy catalytic materials, the platinum alloy in the nitrogen-doped platinum alloy nanowires is selected from at least one of platinum-copper alloy, platinum-iron alloy, and platinum-nickel alloy.

[0056] In some of these examples, the platinum alloy in the nitrogen-doped platinum alloy nanowires is selected from Pt3Cu, PtCu1, and PtCu. 1.5 At least one of PtCu2, PtCu3, PtCu4, PtFe and PtNi.

[0057] It is understandable that Pt3Cu, PtCu1, and PtCu... 1.5 PtCu2, PtCu3, and PtCu4 refer to the molar ratios of Pt to Cu elements of 3:1, 1:1, 1:1.5, 1:2, 1:3, and 1:4, respectively.

[0058] Furthermore, it can be understood that in the preparation of Pt3Cu, PtCu1, and PtCu... 1.5 When PtCu2, PtCu3, and PtCu4 are used, the amount of Pt metal precursor salt and Cu precursor salt added can be controlled by adjusting the molar amounts of the two salts.

[0059] Optionally, the nitrogen-doped platinum alloy nanowires are nitrogen-doped PtCu3 nanowires (N-PtCu3 NWs).

[0060] In some of these examples, in the platinum alloy catalytic materials, the non-platinum metal elements account for 25%-80% of the total molar amount of each metal element in the nitrogen-doped platinum alloy nanowires.

[0061] The percentage of non-platinum metal elements in the total molar amount of all metal elements refers to: the amount of non-platinum metal element M in the nitrogen-doped platinum alloy nanowires / (amount of platinum element + amount of non-platinum metal element M) × 100%.

[0062] It is understood that in the nitrogen-doped platinum alloy nanowires provided in this application, the amount of platinum can be as low as 20% to achieve good catalytic activity, which can greatly reduce the use of Pt and effectively reduce the cost of fuel cells.

[0063] It can also be understood that the percentage of non-platinum metal elements in the total molar amount of all metal elements includes, but is not limited to, 25%, 30%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, and 80%. In some examples, it can be any two of these point values ​​as the end values, and the same applies below.

[0064] Optionally, in nitrogen-doped platinum alloy nanowires, non-platinum metal elements account for 25%-75% of the total molar amount of each metal element.

[0065] In some of these examples, the nitrogen element in the nitrogen-doped platinum alloy nanowires accounts for 2% to 4% of the molar percentage of the nitrogen in the nitrogen-doped platinum alloy nanowires.

[0066] It is understood that the molar percentage of nitrogen in nitrogen-doped platinum alloy nanowires includes, but is not limited to, 2%, 3%, and 4%.

[0067] In some of these examples, the nitrogen-doped platinum alloy nanowires in the platinum alloy catalytic materials have a length of 30 nm to 60 nm and a diameter of 2 nm to 4 nm.

[0068] It is understood that the lengths of nitrogen-doped platinum alloy nanowires include, but are not limited to, 30nm, 32nm, 35nm, 40nm, 45nm, 50nm, 55nm, and 60nm, and the diameters include, but are not limited to, 2nm, 3nm, and 4nm.

[0069] In some of these examples, the support in the platinum alloy catalyst is a carbon support.

[0070] It is understood that carbon supports include, but are not limited to, carbon powder, carbon black, carbon nanotubes, graphene, carbon aerogel, carbon nanofibers, hollow carbon, mesoporous carbon, and carbon nanomolecular sieves.

[0071] In some of these examples, the support in the platinum alloy catalyst is carbon black.

[0072] In some of these examples, the platinum alloy catalyst is N-PtCu3 NWs / C.

[0073] It can be understood that N-PtCu3 NWs / C refers to a carbon support and nitrogen-doped PtCu3 nanowires loaded on the surface of the carbon support.

[0074] In some of these examples, the platinum alloy catalyst is N-PtCu NWs / C.

[0075] In some of these examples, the platinum alloy catalyst is N-Pt3Cu NWs / C.

[0076] In some of these examples, the platinum alloy catalyst is N-PtNi NWs / C.

[0077] One embodiment of this application provides a method for preparing a platinum alloy catalytic material, including step S10:

[0078] Platinum alloy nanowires are loaded onto the surface of a support, and then annealed at 200℃~300℃ under a protective atmosphere to form nitrogen-doped platinum alloy nanowires, thus obtaining a platinum alloy catalytic material.

[0079] It is understood that the preparation method of the platinum alloy catalytic material provided in this application can prepare the above-mentioned platinum alloy catalytic material.

[0080] Loading platinum alloy nanowires onto the surface of a support before annealing can prevent the nanowires from agglomerating during annealing, thus avoiding their impact on catalytic performance. After loading platinum alloy nanowires onto the surface of a support, annealing them under specific atmospheric conditions and temperatures allows nitrogen to act uniformly on the surface and interior of the platinum alloy, resulting in nitrogen-doped platinum alloy nanowires loaded on the support surface.

[0081] It is understood that the protective atmosphere includes, but is not limited to, nitrogen and inert gases; furthermore, the inert gases include, but are not limited to, argon and helium; the annealing temperature includes, but is not limited to, 200℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, and 300℃.

[0082] Optionally, the annealing temperature is 230℃~280℃; further, the annealing temperature is 250℃~270℃.

[0083] In some of these examples, the annealing time in step S10 is 6 to 10 hours.

[0084] It is understandable that annealing time includes, but is not limited to, 6h, 7h, 8h, 9h, and 10h.

[0085] It can be further understood that in step S10, the load can be applied in a manner commonly used in the art.

[0086] In some of these examples, step S10, which involves loading platinum alloy nanowires onto the support surface, includes step S11:

[0087] The platinum alloy nanowires, the carrier, and the third solvent were mixed and then subjected to ultrasonic dispersion, centrifugation, and drying in sequence.

[0088] It is understood that the third solvent includes, but is not limited to, chloroform, ethanol, isopropanol, tetrahydrofuran, n-butanol, dimethyl sulfoxide, toluene, or N,N-dimethylformamide.

[0089] It is understandable that controlling the specific type of the third solvent can improve the dispersion of platinum alloy nanowires and carbon supports.

[0090] In some of these examples, in step S10, the platinum alloy nanowires loaded on the surface of the carrier are placed in a quartz boat and annealed in a tube furnace under a mixture of argon and ammonia.

[0091] In some of these examples, step S10, the preparation of the platinum alloy nanowires includes steps S100 to S300:

[0092] Step S100: The first platinum salt precursor, surfactant, reducing agent and first solvent are mixed to carry out the first liquid phase synthesis reaction to obtain the first mixed solution containing platinum nanowires.

[0093] It is understood that surfactants include, but are not limited to, cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants. It is further understood that surfactants include, but are not limited to, hexadecyltrimethylammonium bromide (C... 19 H 42 (BrN), hexadecyltrimethylammonium chloride, sodium dodecylbenzenesulfonate, tetradecyltrimethylammonium bromide.

[0094] In some of these examples, in step S100, the surfactant is selected from at least one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and didodecyldimethylammonium bromide.

[0095] It is understandable that reducing agents include, but are not limited to, glucose (C6H4O). 12 O6), hexacarbonyl tungsten (W(CO)6), hexacarbonyl molybdenum, oxalic acid, sodium citrate, L-ascorbic acid.

[0096] In some of these examples, in step S100, the reducing agent is selected from at least one of glucose, tungsten hexacarbonyl, and molybdenum hexacarbonyl.

[0097] In some of these examples, in step S100, the temperature of the first liquid-phase synthesis reaction is 150°C to 170°C.

[0098] It is understood that the temperature of the first liquid-phase synthesis reaction includes, but is not limited to, 150℃, 155℃, 160℃, 165℃, 168℃, and 170℃.

[0099] In some of these examples, in step S100, the first solvent is selected from at least one of oleylamine and octadecene.

[0100] Step S200: Mix the second platinum salt precursor, the non-platinum salt metal precursor, and the second solvent evenly to obtain a second mixture.

[0101] It can be understood that non-platinum salt metal precursors refer to precursors of metal elements other than platinum. Metal elements other than platinum, M, include but are not limited to Cu, Fe, Ni, V, Cr, Ti, Pd, Ru, etc.

[0102] In some of these examples, in step S200, the metal element M in the non-platinum salt metal precursor is selected from at least one of Cu, Fe, and Ni.

[0103] It can be understood that non-platinum salt metal precursors are salts of the aforementioned metal element M, including but not limited to chlorides, nitrates, and acetates.

[0104] In some of these examples, in step S200, the non-platinum salt metal precursor is selected from copper chloride dihydrate and nickel chloride hexahydrate.

[0105] It is understood that the first platinum salt precursor and the second platinum salt precursor can be independently selected from, but not limited to, chlorides, sulfates, nitrates, and acetates of platinum metal. Further, the first platinum salt precursor and the second platinum salt precursor can be independently selected from, but not limited to, chloroplatinic acid hexahydrate, ammonium chloroplatinate, sodium chloroplatinate, platinum diacetylacetonate (Pt(acac)2), or potassium chloroplatinate.

[0106] It is understandable that the first platinum salt precursor and the second platinum salt precursor can be the same or different.

[0107] In some of these examples, the first and second platinum salt precursors in the preparation steps of the platinum alloy nanowires are both platinum diacetylacetonate.

[0108] In some of these examples, in step S200, the second solvent is at least one of oleylamine and octadecene.

[0109] In some of these examples, the mass ratio of the total mass of the first platinum salt precursor and the second platinum salt precursor to the mass of the surfactant and the reducing agent in the preparation steps of the platinum alloy nanowires is 1:(0.11~0.25):(0.33~1).

[0110] It is understood that when the total mass of the first platinum salt precursor and the second platinum salt precursor is defined as 1, the mass fraction of the surfactant includes, but is not limited to, 0.11, 0.15, 0.2, 0.22, and 0.25; and the mass fraction of the reducing agent includes, but is not limited to, 0.33, 0.5, 0.6, 0.8, and 1.

[0111] In some of these examples, the total molar amount of platinum in the first platinum salt precursor and the second platinum salt precursor is 1:(0.3 to 4.5) in the preparation steps of the platinum alloy nanowires.

[0112] It is understood that the total molar amount of platinum in the first platinum salt precursor and the second platinum salt precursor, and the molar ratio of the metal element in the non-platinum salt metal precursor, are including but not limited to 1:0.3, 1:0.5, 1:0.7, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, and 1:4.5.

[0113] Optionally, the total molar amount of platinum in the first platinum salt precursor and the second platinum salt precursor is in a molar ratio of 1:(1 to 4.5) to the molar amount of metal in the non-platinum salt metal precursor.

[0114] Furthermore, the total molar amount of platinum in the first platinum salt precursor and the second platinum salt precursor is in a molar ratio of 1:3 to that of the metal element in the non-platinum salt metal precursor.

[0115] Step S300: The first mixture and the second mixture are mixed to carry out a second liquid phase synthesis reaction to obtain platinum alloy nanowires.

[0116] It is understandable that the first and second liquid-phase synthesis reactions include processes such as reduction, nucleation, diffusion, and growth.

[0117] In some of these examples, in step S300, the temperature of the second liquid-phase synthesis reaction is 150°C to 170°C.

[0118] It is understood that the temperature of the second liquid-phase synthesis reaction includes, but is not limited to, 150℃, 155℃, 160℃, 165℃, 168℃, and 170℃.

[0119] A first liquid-phase synthesis reaction is carried out by first mixing a first platinum salt precursor, a surfactant, a reducing agent, and a first solvent to obtain a first mixed solution containing platinum nanowires; a second mixed solution is obtained by uniformly mixing a second platinum salt precursor, a non-platinum salt metal precursor, and a second solvent; and the first and second mixed solutions are then mixed to carry out a second liquid-phase synthesis reaction, which is conducive to the full reaction to form platinum alloy nanowires and avoids the formation of a mixture of nanowires and particles.

[0120] It is understandable that in some examples, surfactants and reducing agents may also be added in step S300.

[0121] The aforementioned method for preparing platinum alloy catalysts combines liquid-phase reduction and thermal annealing to obtain platinum alloy catalysts containing one-dimensional nitrogen-doped platinum alloy nanowires with controllable morphology and composition. These catalysts exhibit high catalytic activity, good stability, and the content of non-platinum elements can be effectively controlled, reaching up to 80%, thereby reducing the use of Pt and effectively lowering the cost of fuel cells. The entire reaction process is conducted under relatively mild conditions and is simple to operate.

[0122] One embodiment of this application provides the application of the above-mentioned platinum alloy catalyst in the preparation of fuel cells.

[0123] One embodiment of this application provides a membrane electrode assembly, including a proton exchange membrane and a catalyst layer, wherein the catalyst layer is disposed on both sides of the proton exchange membrane, and at least one catalyst layer comprises the above-mentioned platinum alloy catalyst material or the platinum alloy catalyst material prepared by the above-mentioned preparation method.

[0124] Furthermore, it includes an anode catalyst layer and a cathode catalyst layer, wherein the cathode catalyst layer comprises the aforementioned platinum alloy catalyst material or the platinum alloy catalyst material prepared by the aforementioned preparation method.

[0125] Furthermore, the membrane electrode assembly also includes a gas diffusion layer, which is located on the side of the catalyst layer away from the proton exchange membrane.

[0126] It can be understood that the gas diffusion layer includes a cathode gas diffusion layer and an anode gas diffusion layer. The anode gas diffusion layer is located on the side of the anode catalyst layer away from the proton exchange membrane, and the cathode gas diffusion layer is located on the side of the cathode catalyst layer away from the proton exchange membrane.

[0127] It is understood that in some examples, the membrane electrode assembly consists of a cathode diffusion layer, a cathode catalyst layer, a proton exchange membrane, an anode catalyst layer, and an anode gas diffusion layer stacked sequentially, and the cathode catalyst layer contains the aforementioned platinum alloy catalyst material or the platinum alloy catalyst material prepared by the aforementioned preparation method.

[0128] Another embodiment of this application provides a fuel cell including an anode plate, a cathode plate, and the above-mentioned membrane electrode assembly. The anode plate is disposed on the side of the anode catalyst layer away from the proton exchange membrane, and the cathode plate is disposed on the side of the cathode catalyst layer away from the proton exchange membrane.

[0129] Applying the aforementioned platinum alloy catalyst to fuel cells not only provides excellent catalytic performance but also effectively improves the stability of fuel cells and reduces their cost.

[0130] The following examples of the platinum alloy catalytic material, its preparation method, membrane electrode assembly, and fuel cell of this application are for illustrative purposes only. It should be understood that the platinum alloy catalytic material, its preparation method, membrane electrode assembly, and fuel cell of this application are not limited to the following embodiments.

[0131] Example 1

[0132] (1) Weigh 10mg Pt(acac)2 and 48mg C 19 H 42 BrN, 60mg C6H 12 O6, 5mg W(CO)6, 5mL C 18 H 37 N was added to a 30 mL reaction flask and sonicated for 3 hours to form a homogeneous system. The mixture was then placed in an oil bath preheated to 160°C and reacted for 30 minutes. After natural cooling to 80°C, the first mixture was obtained. In another 30 mL reaction flask, 10 mg Pt(acac)₂, 15 mg CuCl₂·2H₂O, and 3 mL C were added. 18 H 37N, sonicated for 1 h, to obtain a second mixture; the second mixture was injected into a first mixture and heated to 160℃ for 5 h to obtain PtCu3 nanowires;

[0133] (2) Disperse 4 mg of PtCu3 nanowires and 16 mg of carbon black obtained in step (1) in chloroform and sonicate them evenly. Then, add the chloroform mixture containing PtCu3 nanowires dropwise to the carbon black mixture, sonicate for 30 minutes, add a stir bar, stir for 10 hours, and finally centrifuge and dry in a vacuum drying oven to obtain PtCu3 nanowire catalyst (PtCu3 NWs / C), that is, PtCu3 nanowires loaded on carbon powder.

[0134] (3) Place the PtCu3 NWs / C obtained in step (2) into a quartz boat, and anneal it in a tube furnace at 250°C for 8 hours under a mixed atmosphere of argon and ammonia to obtain nitrogen-doped PtCu3 nanowires (N-PtCu3 NWs / C) loaded on carbon powder.

[0135] Inductively coupled plasma mass spectrometry (ICP-MS) determined that Cu in N-PtCu3 NWs / C accounts for 75% of the total molar percentage of Pt and Cu.

[0136] Transmission electron microscopy image of N-PtCu3 NWs / C as shown below Figure 1 As shown, the diameters of 100 nitrogen-doped PtCu3 nanowires (N-PtCu3NWs) were statistically analyzed, and the diameter distribution is as follows: Figure 2 As shown, atomic-resolution spherical aberration electron microscopy was used to characterize single N-PtCu3 NWs at the atomic level. The high-resolution images of the N-PtCu3 NWs are shown below. Figure 3 As shown in the figure, the elemental distribution of Pt, Cu, and N in N-PtCu3 NWs is as follows: Figure 4 As shown, the X-ray diffraction pattern of N-PtCu3NWs is as follows: Figure 5 As shown.

[0137] from Figure 1 It can be seen that one-dimensional nanowires with uniform size distribution were successfully synthesized with a yield close to 100%, and the nanowire structure remained almost unchanged after annealing. Figure 2 It can be seen that the average diameter of 100 N-PtCu3NWs is approximately 2.8 nm ± 0.5 nm; from Figure 3 It can be seen that the outer atoms of N-PtCu3 NWs have defects (marked by dashed circles), and these defect sites help to improve the oxygen reduction activity of the catalyst; from Figure 4 It can be seen that Pt, Cu, and N elements are uniformly distributed throughout the nanowire; from Figure 5It can be seen that, compared with the standard card of pure Pt, the diffraction characteristic peaks in the powder XRD of N-PtCu3 NWs are significantly shifted to higher diffraction angles, which is consistent with the trend of reduced lattice spacing caused by the introduction of Cu.

[0138] Example 2

[0139] The process is basically the same as in Example 1, except that in Example 2, N-PtCu NWs / C is prepared, in which Cu element accounts for 50% of the total molar percentage of Pt and Cu elements. Step (1) of Example 2 is as follows:

[0140] Weigh out 10mg Pt(acac)2 and 48mg C 19 H 42 BrN, 60mg C6H 12 O6, 5mg W(CO)6, 5mL C 18 H 37 N was added to a 30 mL reaction flask and sonicated for 3 hours to form a homogeneous system. The mixture was then placed in an oil bath preheated to 160°C and reacted for 30 minutes. After natural cooling to 80°C, the first mixture was obtained. In another 30 mL reaction flask, 10 mg Pt(acac)₂ and 12 mg CuCl₂·2H₂O were added, along with 3 mL of C. 18 H 37 N, sonicated for 1 hour, to obtain a second mixture; the second mixture was injected into a first mixture and heated to 160℃ for 5 hours to obtain PtCu nanowires.

[0141] Example 3

[0142] The results are basically the same as in Example 1, except that N-Pt3Cu NWs / C are obtained, in which Cu element accounts for 25% of the total molar percentage of Pt and Cu elements. Step (1) of Example 3 is as follows:

[0143] Weigh out 10mg Pt(acac)2 and 48mg C 19 H 42 BrN, 60mg C6H 12 O6, 5mg W(CO)6, 5mL C 18 H 37 N was added to a 30 mL reaction flask and sonicated for 3 hours to form a homogeneous system. The mixture was then placed in an oil bath preheated to 160°C and reacted for 30 minutes. After natural cooling to 80°C, the first mixture was obtained. In another 30 mL reaction flask, 10 mg Pt(acac)₂, 5 mg CuCl₂·2H₂O, and 3 mL C were added. 18 H 37N, sonicated for 1 hour, to obtain a second mixture; the second mixture was injected into a first mixture and heated to 160℃ for 5 hours to obtain Pt3Cu nanowires.

[0144] Example 4

[0145] The process is basically the same as in Example 1, except that N-PtNi NWs / C is prepared as follows:

[0146] (1) Weigh 10mg Pt(acac)2 and 48mg C 19 H 42 BrN, 60mg C6H 12 O6, 5mg W(CO)6, 5mL C 18 H 37 N was placed in a 30 mL reaction flask and sonicated for 3 hours to form a homogeneous system. Then, the mixture was placed in an oil bath preheated to 80°C and reacted for 30 minutes to obtain the first mixture. In another 30 mL reaction flask, 10 mg Pt(acac)₂ and 10 mg NiCl₂·6H₂O were added, along with 3 mL of C. 18 H 37 N, sonicated for 1 hour, to obtain a second mixture; the second mixture was injected into a first mixture and heated to 160℃ for 5 hours to obtain PtNi nanowires;

[0147] (2) Disperse 4 mg of PtNi nanowires and 16 mg of carbon black obtained in step (1) in chloroform and sonicate them evenly. Then, add the chloroform mixture containing PtNi nanowires dropwise to the carbon black mixture, sonicate for 30 minutes, add a stir bar, stir for 10 hours, and finally centrifuge and dry in a vacuum drying oven to obtain PtNi nanowire catalyst (PtNi NWs / C).

[0148] (3) Place the PtNi NWs / C obtained in step (2) into a quartz boat, and anneal it in a tube furnace at 250°C for 8 hours under a mixed atmosphere of argon and ammonia to obtain nitrogen-doped PtNi nanowires (N-PtNi NWs / C) loaded on carbon powder.

[0149] Example 5

[0150] The process is basically the same as in Example 1, except that the annealing temperature in Example 5 is different, being 270°C. Step (3) in Example 5 is as follows:

[0151] The PtCu3 NWs / C obtained in step (2) of Example 1 was placed in a quartz boat and annealed in a tube furnace at 270°C for 8 hours under a mixed atmosphere of argon and ammonia to obtain nitrogen-doped PtNi nanowires (N-PtNi NWs / C) loaded on carbon powder.

[0152] Comparative Example 1

[0153] (1) Weigh 10mg Pt(acac)2 and 90mg C 19 H 42 BrN, 5mL C 18 H 37 N was placed in a 30 mL reaction flask and sonicated for 1 h to form a homogeneous system. Then, 15 mg of W(CO)6 was quickly added, and the mixture was transferred to an oil bath heated to 160 °C and reacted for 120 min to obtain Pt NWs.

[0154] (2) Disperse 4 mg of Pt NWs and 16 mg of carbon black obtained in step (1) in chloroform and sonicate them evenly. Then, add the chloroform mixture containing Pt NWs dropwise to the carbon black mixture, sonicate for 30 minutes, add a stir bar, stir for 10 hours, and finally centrifuge and dry in a vacuum drying oven to obtain Pt NWs catalyst (Pt NWs / C).

[0155] Comparative Example 2

[0156] The PtCu3 nanowires obtained in step (1) of Example 1 were placed in a quartz boat and annealed in a tube furnace at 250°C for 8 hours under a mixed atmosphere of argon and ammonia. The PtCu3 nanowires agglomerated severely and could not be uniformly dispersed and loaded, which made it impossible to perform subsequent oxygen reduction tests.

[0157] Oxygen reduction catalytic test

[0158] The N-PtCu3 NWs / C prepared in Example 1, the N-PtCu NWs / C prepared in Example 2, the N-Pt3Cu NWs / C prepared in Example 3, the N-PtNi NWs / C prepared in Example 4, the Pt NWs / C prepared in Comparative Example 1, and commercial Pt / C (purchased from Shanghai Maclean Biochemical Technology Co., Ltd., model MFCD00011179) were tested for oxygen reduction catalysis using a three-electrode system.

[0159] A glassy carbon rotating disk electrode was selected as the working electrode, an Ag / AgCl (3.0 M KCl) electrode as the reference electrode, and a platinum wire as the counter electrode. The test was conducted in an O2-saturated 0.1 M HClO4 solution, with a potential range of 0.05 V. RHE -1.10V RHE The scan rate is 10 mV / s. -1 The electrode rotation speed is 1600 rpm; the polarization curve is as follows: Figure 6 As shown in section A, the corresponding Tafel curve is as follows: Figure 6 As shown in part B, where Figure 6The illustrations in the figure are the corresponding Tafel curves; mass activity and specific activity are as follows: Figure 7 As shown.

[0160] from Figure 6 As can be seen from Part A, compared to the Pt NWs / C catalyst of Comparative Example 1 and the commercial Pt / C catalyst, the polarization curves of the catalysts in Examples 1 to 4 show a significant positive shift; from Figure 6 Part B and Figure 7 It can be seen that the catalysts in Examples 1-4 exhibited high mass activity, among which, at 0.9V RHE At that time, the mass activity of the N-PtCu3 NWs / C catalyst in Example 1 was 2.84 A mg. -1 Pt The values ​​are commercial Pt / C (0.18 mg). -1 Pt Comparative Example 1 Pt NWs / C (0.85 mg) -1 Pt The activity was 15.8 times and 3.3 times that of the N-PtCu NWs / C in Example 2; the mass activity was 1.45A mg. -1 Pt The mass activity of N-Pt3Cu NWs / C in Example 3 was 1.10 A mg. -1 Pt The mass activity of N-PtNi NWs / C in Example 4 was 1.72 A mg. -1 Pt Consistent with the trend in mass activity, the catalysts in Examples 1-4 also exhibited high specific activity, particularly at 0.9V. RHE At that time, the specific activity of the N-PtCu3 NWs / C catalyst in Example 1 was 3.79 mA cm⁻¹. -2 The values ​​are: commercial Pt / C (0.28 mA cm⁻²), comparative example 1PtNWs / C (1.13 mA cm⁻²), and comparative example 1PtNWs / C (0.28 mA cm⁻²). -2 The specific activity of N-PtCu NWs / C in Example 2 was 13.5 times and 3.4 times that of the previous year's NWs / C, respectively; the specific activity of the N-PtCu NWs / C was 2.15 mA cm⁻¹. -2 The specific activity of N-Pt3Cu NWs / C in Example 3 was 1.63 mA cm⁻¹. -2 The specific activity of N-PtNi NWs / C in Example 4 is 2.55 mAcm. -2 .

[0161] Membrane electrode testing

[0162] 5.00 mg of each of the N-PtCu3 NWs / C prepared in Example 1, the Pt NWs / C prepared in Comparative Example 1, and commercial Pt / C were added to a mixed solution containing isopropanol (1.16 mL), ultrapure water (0.289 mL), and Nafion (0.054 mL). The mixture was sonicated for 2 hours to form a uniform catalyst ink, wherein the mass ratio of Nafion to catalyst was 0.50. The prepared ink was then sprayed onto carbon paper with a spray gun, covering an area of ​​5.0 cm². 2 After drying, the Pt content in the cathode N-PtCu3 NWs / C, Pt NWs / C, and commercial Pt / C catalysts was found to be 0.60 mg, 0.62 mg, and 0.60 mg, respectively, while the Pt content in the anode Pt / C catalyst was 0.70 mg. Humidified H2 and O2 were used in the H2-O2 fuel cell test, and the test system was a SMART2PEMDM. The fuel cell test temperature was 80℃, and the gas flow rates of H2 (1.5 bar back pressure) and O2 (1.5 bar back pressure) were 300 mL / min. -1 and 600mL min -1 N-PtCu3 NWs / C, Pt NWs / C, and commercial Pt / C catalysts were used as cathode catalysts for membrane electrode testing to evaluate their performance in practical H2-O2 PEMFCs.

[0163] Among them, the mass activity of N-PtCu3 NWs / C as the cathode catalyst in Example 1 after 260,000 (260 K) accelerated cycling cycles is as follows: Figure 8 As shown, the transmission electron microscope (TEM) images of N-PtCu3 NWs / C after the corresponding number of cycles are as follows. Figure 9 As shown; the power density after different cycles (10K, 30K, 100K) using Example 1 N-PtCu3 NWs / C as the cathode catalyst is compared with the initial power density of commercial Pt / C. Figure 10 As shown. The changes in mass activity and cell voltage after different numbers of cycles using Example 1 N-PtCu3 NWs / C as the cathode catalyst are shown below. Figure 11 As shown.

[0164] from Figures 8-9 It can be seen that the N-PtCu3 NWs / C prepared in Example 1 showed almost no loss of mass activity after 260,000 cycles in an oxygen atmosphere, and its one-dimensional morphology was well maintained; while commercially available carbon-supported platinum nanocatalysts showed a 73.7% loss of mass activity after 10,000 cycles in an oxygen atmosphere. These results indicate that N-PtCu3 NWs / C has excellent stability. Figure 10It can be seen that the N-PtCu3NWs / C catalyst exhibits a high power density (1730 mW cm⁻¹) in membrane electrode assembly. -2 This is greater than the maximum power density of 1270 mW / cm³ for commercial Pt / C catalysts. -2 Under the same test conditions, the highest power density of the N-PtCu3 NWs / C catalyst can be attributed to its optimal ORR activity, consistent with the best ORR activity observed in RDE. Notably, after 100,000 cycles, the power density of the N-PtCu3 NWs / C catalyst showed virtually no decay; from Figure 11 It can be seen that the N-PtCu3 NWs / C prepared in Example 1 has a cathode Pt loading of 0.12 mg / cm³. 2 At 0.9V, the mass activity reaches 0.53A / mg, which is higher than the initial target value (BOL) of 0.44A / mg in the U.S. Department of Energy (DOE) target. After long-term cycling tests of 100,000 cycles, the mass activity did not decay, which is far higher than the DOE target value of less than 40% decay after 30,000 cycles (EOL).

[0165] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0166] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. A method for preparing a platinum alloy catalytic material, characterized in that, Includes the following steps: A first liquid-phase synthesis reaction was carried out by mixing a first platinum salt precursor, a surfactant, a reducing agent and a first solvent to obtain a first mixed solution containing platinum nanowires. The second platinum salt precursor, the non-platinum salt metal precursor, and the second solvent are mixed evenly to obtain a second mixture; the metal element in the non-platinum salt metal precursor is Cu. The first mixture and the second mixture are mixed to carry out a second liquid-phase synthesis reaction to obtain platinum alloy nanowires; After loading the platinum alloy nanowires onto the surface of a support, ammonia gas is introduced under a protective atmosphere and the nanowires are annealed at 200°C to 300°C to form nitrogen-doped platinum alloy nanowires, thereby obtaining the platinum alloy catalytic material. In the nitrogen-doped platinum alloy nanowires, non-platinum metal elements account for 70%-80% of the total molar amount of each metal element.

2. The method for preparing the platinum alloy catalytic material as described in claim 1, characterized in that, In the nitrogen-doped platinum alloy nanowires, non-platinum metal elements account for 75%-80% of the total molar amount of all metal elements.

3. The method for preparing the platinum alloy catalytic material as described in claim 1, characterized in that, The preparation method satisfies at least one of the following conditions: (1) The first platinum salt precursor and the second platinum salt precursor are each independently selected from at least one of diacetylacetonate platinum, chloroplatinic acid and potassium chloroplatinate; (2) The surfactant is selected from at least one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and dodecyldimethylammonium bromide; (3) The reducing agent is selected from at least one of glucose, tungsten hexacarbonyl and molybdenum hexacarbonyl; (4) The first solvent and the second solvent are each independently selected from at least one of oleylamine and octadecene; (5) The total molar amount of platinum in the first platinum salt precursor and the second platinum salt precursor is 1:(1~4.5) to the molar ratio of the metal element in the non-platinum salt metal precursor.

4. The method for preparing the platinum alloy catalytic material according to any one of claims 1 to 3, characterized in that, The temperatures of the first liquid-phase synthesis reaction and the second liquid-phase synthesis reaction are independently selected from 150℃ to 170℃.

5. The method for preparing the platinum alloy catalytic material according to any one of claims 1 to 3, characterized in that, The carrier is a carbon carrier.

6. A platinum alloy catalytic material, characterized in that, The platinum alloy catalytic material was prepared using the preparation method described in any one of claims 1 to 5.

7. The platinum alloy catalytic material as described in claim 6, characterized in that, The platinum alloy catalytic material includes a support and nitrogen-doped platinum alloy nanowires loaded on the surface of the support. The platinum alloy in the nitrogen-doped platinum alloy nanowires is a platinum-copper alloy. In the platinum alloy nanowires, non-platinum metal elements account for 75%-80% of the total molar amount of each metal element.

8. The platinum alloy catalytic material as described in claim 7, characterized in that, The nitrogen-doped platinum alloy nanowires satisfy at least one of the following conditions: (1) The platinum alloy in the nitrogen-doped platinum alloy nanowire is selected from at least one of PtCu3 and PtCu4; (2) The nitrogen element in the nitrogen-doped platinum alloy nanowire accounts for 2% to 4% of the molar percentage of the nitrogen-doped platinum alloy nanowire; (3) The length of the nitrogen-doped platinum alloy nanowire is 30 nm to 60 nm and the diameter is 2 nm to 4 nm.

9. A membrane electrode assembly, characterized in that, It includes a proton exchange membrane, an anode catalyst layer, and a cathode catalyst layer, wherein the anode catalyst layer and the cathode catalyst layer are disposed on both sides of the proton exchange membrane, and the cathode catalyst layer comprises a platinum alloy catalyst material prepared by the preparation method according to any one of claims 1 to 5 or a platinum alloy catalyst material according to any one of claims 6 to 8.

10. A fuel cell, characterized in that, The device includes an anode plate, a cathode plate, and the membrane electrode assembly of claim 9, wherein the anode plate is disposed on the side of the anode catalyst layer away from the proton exchange membrane, and the cathode plate is disposed on the side of the cathode catalyst layer away from the proton exchange membrane.

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