Membrane electrode catalyst, catalyst layer, coating membrane, membrane electrode and fuel cell that are resistant to CO poisoning

Abstract

A membrane electrode catalyst resistant to CO poisoning, comprising an active metal and a porous carbon support for carrying the active metal, characterized in that the distribution peak area of ​​the most probable pore size of the membrane electrode catalyst is ≤ 5 nm.

Description

[0001] The present invention relates to the technical field of fuel cells, in particular to a membrane electrode catalyst, a catalyst layer, a coating membrane, a membrane electrode and a fuel cell which are resistant to CO poisoning.

[0002] The membrane electrode is the core component of the proton exchange membrane fuel cell. The performance and durability of a membrane electrode depend largely on the structure of the catalyst layer of the coating membrane (CCM) of the catalyst in the membrane electrode. Typically, CCM is divided into a three-layer structure, with the proton exchange membrane located in the center and an anodic catalyst layer and a cathodic catalyst layer on either side of the proton exchange membrane. The working principle of a fuel cell is that the anode is where the hydrogen oxidation reaction (HOR) is completed, and the cathode is where the oxygen reduction reaction (ORR) is completed.The electrons generated at the anode perform work through the external circuit and then flow to the cathode, and the [H+] generated at the same time flows through the electrolyte membrane to reach the cathode, where it then reacts with oxygen to produce water.

[0003] In the anodic catalyst layer of the fuel cell, traces of impurity gases (CO / H2S, etc.) in the hydrogen can easily lead to poisoning of the anode catalyst, thereby affecting the HOR process and significantly deteriorating the performance of the membrane electrode. Among them, CO poisoning of the anodic catalyst layer is particularly serious, because the bonding ability of CO to Pt in the anode catalyst is much stronger than that of H2 to Pt, and even a small amount of CO adsorbed on Pt cannot be quickly removed. At the same time, when Pt adsorbs CO, a strong lateral repulsion force is formed around the Pt-CO, preventing hydrogen from adsorbing on the adjacent Pt sites that are not poisoned by CO for the HOR reaction. Even high-purity hydrogen usually contains traces of CO.GB / T7445-1995 stipulates that the CO content in high-purity hydrogen must be ≤ 1 ppm. The national standard GB / T37244-2018 for hydrogen fuel cells for proton exchange membrane vehicles requires that the CO content in hydrogen must be ≤ 0.2 ppm for the fuel cell to function normally. Therefore, it is particularly important to address the problem of CO poisoning of the anodic catalyst layer, especially the CO tolerance of the anodic catalyst layer in the CO concentration range of 0.2 to 1.0 ppm.

[0004] Generally, the following strategies are used to solve the problem of CO poisoning of the anodic catalyst layer of fuel cells: The electrochemical oxidation capacity of CO on PGM (platinum group metal) is enhanced by bifunctional sites to remove CO; the adsorption of CO on PGM is weakened by tuning the electronic structure of the catalyst; a gas barrier layer that only allows H2 to pass through is constructed by the difference in the molecular size of H2 and CO to prevent CO from coming into contact with PGM; non-precious metal catalysts that are resistant to CO, etc. These solutions are tailored both in terms of the composition of the material (e.g., using non-precious metal alloy catalysts) and the structure of the material, which brings with it the problem of non-precious metal dissolution and the decrease of HOR activity.Although there are many research results, it is still difficult to achieve industrial applications.

[0005] In order to overcome at least one of the above-mentioned deficiencies (shortcomings) of the prior art, the present invention aims to provide a membrane electrode catalyst, a catalyst layer, a coating membrane, a membrane electrode and a fuel cell that are resistant to CO poisoning, thereby improving the tolerance of the anode catalyst to CO.

[0006] The present invention has for its object to provide a membrane electrode catalyst resistant to CO poisoning, comprising an active metal and a porous carbon support for supporting the active metal, wherein the distribution peak range of the most probable pore size of the membrane electrode catalyst is ≤ 5 nm.

[0007] The inventors found that conventional catalysts have a very small proportion of pores below 5 nm and a very large proportion of pores above 10 nm. This is one of the reasons for the insufficient resistance of the membrane electrode to CO poisoning. When the distribution peak area of ​​the most probable pore size of the catalyst is ≤ 5 nm, the resistance to trace CO poisoning of the membrane electrode is significantly improved. The reason may be that when the distribution peak area of ​​the most probable pore size of the catalyst is ≤ 5 nm, most of such active metals are distributed in the pores. Due to the smaller pores, the permeability of H2 is larger than that of CO, which blocks part of the CO. When the catalyst has a large proportion of pores > 10 nm, a large amount of active metals is distributed in these pores > 10 nm, so that CO can easily penetrate.During fuel cell operation, Pt in the large pore size is poisoned by CO, resulting in a loss of HOR capability. Therefore, when using conventional carbon-supported metal catalysts, an anodic catalyst layer is required to increase the support capacity of the active metal to improve the CO tolerance of the membrane electrode.

[0008] In this technical solution, the pores on the catalyst are distributed with a pore size of ≤ 5 nm on the porous carbon support, where the catalyst is an anode catalyst. The distribution peak range of the most probable pore size of the catalyst is limited to less than 5 nm, thereby improving the CO resistance of the catalyst without introducing metals or other new materials resistant to CO poisoning. This avoids the introduced material having a negative impact on the catalyst, and the structure is simple, which is suitable for industrial mass production. In addition, active metals are generally expensive. The catalyst of the invention can improve the CO tolerance of the catalyst without increasing the carrying capacity of the active metal on the carbon support, thus saving resources and costs.

[0009] Furthermore, it is intended that the pore volume corresponding to the pores of the membrane electrode catalyst ≤ 5 nm constitutes ≥ 35% of the total pore volume.

[0010] In this technical solution, the pore volume corresponding to the catalyst pores ≤ 5 nm is limited to ≥ 35% to ensure that sufficient active particles can be carried within ≤ 5 nm, thereby improving the catalyst's resistance to CO.

[0011] It is further provided that the active metal is platinum or a platinum-based alloy.

[0012] Furthermore, it is envisaged that the distribution peak range of the most probable pore size of the catalyst is between 2 nm and 5 nm, with the 2-5 nm pores of the catalyst accounting for 35% to 70% of the total pore volume of the catalyst.

[0013] Furthermore, it is intended that the load-bearing capacity of the active metal on the porous carbon support is 20 wt% to 60 wt%.

[0014] In this technical solution, if the carrying capacity of the active metal on the catalyst is too high, it will lead to aggregation of the catalyst particles. The catalyst particles are too large, thereby decreasing the catalytic activity. In the present invention, the distribution peak range of the most probable pore size is limited to ≤ 5 nm, and its corresponding pore volume on the catalyst accounts for greater than or equal to 35%, so that the pores with small pore sizes account for a larger amount. Due to too many active metal particles, the pores on the catalyst are easily clogged, which impairs mass transfer. If the carrying capacity is too low, the thickness of the catalyst layer of the membrane electrode will be increased, and the durability of the support will be reduced.Therefore, the appropriate supporting capacity of the active metal on the catalyst ensures that the catalyst has sufficient catalytic performance and resistance to CO poisoning, thus ensuring normal mass transfer.

[0015] Another object of the present invention is to provide an anodic catalyst layer of a membrane electrode of a fuel cell, wherein the catalyst on the anodic catalyst layer comprises an active metal and a porous carbon support for supporting the active metal, wherein the distribution peak range of the most probable pore size of the catalyst is ≤ 5 nm.

[0016] Furthermore, it is provided that the active metal is platinum or a platinum-based alloy, wherein the platinum carrying capacity on the anodic catalyst layer is ≤ 0.1 mg / c 2 amounts.

[0017] Furthermore, it is intended that the pore volume corresponding to the pores of the catalyst ≤ 5 nm constitutes ≥ 35% of the total pore volume.

[0018] Furthermore, it is intended that the load-bearing capacity of the active metal on the porous carbon support is 20 wt% to 60 wt%.

[0019] Furthermore, it is intended that the diameter of the active metal is between 1.5 nm and 5 nm.

[0020] Another object of the present invention is to provide a coating membrane for a catalyst of a fuel cell, comprising a proton exchange membrane and an anodic catalyst layer and a cathodic catalyst layer coated on both sides of the proton exchange membrane, wherein the anodic catalyst layer is one of the above-mentioned anodic catalyst layers.

[0021] Another object of the present invention is to provide a CO poisoning-resistant membrane electrode of a fuel cell, comprising a proton exchange membrane, a cathodic catalyst layer, an anodic catalyst layer, an anodic diffusion layer and a cathodic diffusion layer, wherein the cathodic catalyst layer and the anodic catalyst layer are arranged on both sides of the proton exchange membrane, wherein the anodic diffusion layer is arranged on the outside of the anodic catalyst layer, wherein the cathodic diffusion layer is arranged on the outside of the cathodic catalyst layer, wherein the anodic catalyst layer comprises one of the above-mentioned catalysts.

[0022] Furthermore, it is intended that the diameter of the active metal is between 1.5 nm and 5 nm.

[0023] Furthermore, it is intended that the load-bearing capacity of the active metal on the porous carbon support is 30 wt% to 60 wt%.

[0024] Furthermore, it is intended that the carrying capacity of the active metal on the anodic catalyst layer is 0.01 to 0.1 mg / cm 2 amounts.

[0025] Another object of the present invention is to provide a CO poisoning resistant fuel cell comprising any of the above-mentioned membrane electrodes, wherein the membrane electrodes are sequentially repeatedly arranged to form a laminated structure, wherein a first bipolar plate is arranged on both sides of the membrane electrode, wherein the same electrode plate is used between the membrane electrode structures of every two adjacent fuel cells, wherein a second bipolar plate is arranged on both sides of the laminated structure.

[0026] The pore size and pore volume according to the above technical solution are calculated by isothermal nitrogen adsorption and desorption tests on the sample and calculating the nitrogen desorption data according to the BJH model.

[0027] The advantageous effects of the present invention compared to the prior art are: (1) In the present invention, the distribution peak range of the most probable pore size of the catalyst is limited to less than 5 nm, thereby improving the CO resistance of the catalyst without introducing metals or other new materials resistant to CO poisoning. This avoids the introduced material having a negative influence on the catalyst, and the structure is simple, which is suitable for industrial mass production. (2) The pore volume corresponding to the pores of the catalyst ≤ 5 nm is limited to ≥ 35% to ensure that enough active particles can be carried within ≤ 5 nm, thereby improving the resistance of the catalyst to CO. (3) In the present invention, if the carrying capacity of the active metal on the catalyst is too high, it will lead to aggregation of the catalyst particles. The catalyst particles are too large, thereby decreasing the catalytic activity. In the present invention, the distribution peak range of the most probable pore size is limited to ≤ 5 nm, and its corresponding pore volume on the catalyst accounts for greater than or equal to 35%, so that the pores with small pore sizes account for larger pores. Due to too many active metal particles, the pores on the catalyst are easily clogged, which impairs mass transfer. If the carrying capacity is too low, the thickness of the catalyst layer of the membrane electrode will be increased, and the durability of the support will be reduced.Therefore, the appropriate load-bearing capacity of the active particles ensures that the catalyst has sufficient catalytic performance, thereby ensuring normal mass transfer.

[0028] Further advantages, features and possible applications of the present invention will become apparent from the following description in conjunction with the embodiments shown in the drawings.

[0029] In the drawing means: Fig. 1 is a schematic diagram of the structure of a catalyst in a prior art membrane electrode; Fig. 2 is a schematic diagram of the structure of a catalyst in a membrane electrode according to the present invention; Fig. 3 is a pore size distribution diagram of a catalyst according to Embodiments 1 to 6; Fig.4 is a pore size distribution diagram of a catalyst according to Comparative Examples 1 to 3; and Fig. 5 is a diagram of the performance test of a membrane electrode in CO according to Working Examples 1, 2, 4 and Comparative Examples 1 to 4.

[0030] The present utility model is described in more detail below in combination with the attached drawings.

[0031] The drawings of the present invention are merely illustrative and not limiting. To better illustrate the following embodiments, some parts of the drawings are omitted, enlarged, or reduced in size, and do not represent the dimensions of the actual product. Those skilled in the art will understand that certain well-known structures and their explanations may be omitted from the drawings.

[0032] The present invention provides a CO poisoning-resistant membrane electrode catalyst comprising an active metal 200 and a porous carbon support 100 for supporting the catalyst, wherein the pore size of the porous carbon support is 100 ≤ 5 nm, as described in Fig. 2 shown.

[0033] The inventors found that conventional catalysts have a very low proportion of pores below 5 nm and a very large proportion of pores of 10 nm. This is one of the reasons for the insufficient resistance of the membrane electrode to CO poisoning. When the distribution peak area of ​​the most likely pore size of the catalyst is ≤ 5 nm, the resistance to trace CO poisoning of the membrane electrode is significantly improved. The reason may be that when the catalyst has a large proportion of pores below 5.0 nm, most of such active metals are distributed in the pores. Through the smaller pores, the permeability of H2 is larger than that of CO, which blocks part of the CO. When the catalyst has a large proportion of pores > 10 nm, a large amount of active metals is distributed in these pores > 10 nm, so that CO can easily penetrate.Pt in the large pore size is poisoned by CO, so that the HOR capability is lost. Therefore, when using conventional carbon-supported metal catalysts, an anodic catalyst layer is required to increase the carrying capacity of the active metal to improve the CO tolerance of the membrane electrode, as described in [References]. Fig. 1 shown.

[0034] Furthermore, it is intended that the pore volume corresponding to the pores of the catalyst ≤ 5 nm constitutes ≥ 35% of the total pore volume.

[0035] It is further provided that the active metal is platinum or a platinum-based alloy.

[0036] Furthermore, it is envisaged that the distribution peak range of the most probable pore size of the catalyst is between 2 nm and 5 nm, with the 2-5 nm pores of the catalyst accounting for 35% to 70% of the total pore volume of the catalyst.

[0037] Furthermore, it is intended that the load-bearing capacity of the active metal on the porous carbon support is 20 wt% to 60 wt%.

[0038] Another object of the present invention is to provide an anodic catalyst layer of a membrane electrode of a fuel cell, wherein the catalyst on the anodic catalyst layer comprises an active metal and a porous carbon support for supporting the active metal, wherein the distribution peak range of the most probable pore size of the catalyst is ≤ 5 nm.

[0039] It is further provided that the active metal is platinum or a platinum-based alloy, wherein the platinum carrying capacity on the anodic catalyst layer is ≤ 0.1 mg / cm 2 amounts.

[0040] Furthermore, it is intended that the pore volume corresponding to the pores of the catalyst ≤ 5 nm constitutes ≥ 35% of the total pore volume.

[0041] Furthermore, it is intended that the load-bearing capacity of the active metal on the porous carbon support is 20 wt% to 60 wt%.

[0042] Furthermore, it is intended that the diameter of the active metal is between 1.5 nm and 5 nm.

[0043] Another object of the present invention is to provide a coating membrane for a catalyst of a fuel cell, comprising a proton exchange membrane and an anodic catalyst layer and a cathodic catalyst layer coated on both sides of the proton exchange membrane, wherein the anodic catalyst layer is one of the above-mentioned anodic catalyst layers.

[0044] A process for producing a coating membrane of a catalyst, comprising the following steps: S1: Add the catalyst to water, mix uniformly, continue adding the perfluorosulfonic acid resin dispersion, mix uniformly, continue adding ethanol and mix uniformly to form a predispersed slurry; S2: Dispersing the predispersed slurry obtained in step S1 by a disperser and then defoaming to prepare an anode catalyst slurry; S3: Coating the anode catalyst slurry prepared in step S2 onto the other side of the proton-conducting membrane with a cathode catalyst layer on one side to form a CCM.

[0045] Another object of the present invention is to provide a CO poisoning-resistant membrane electrode of a fuel cell, comprising a proton exchange membrane, a cathodic catalyst layer, an anodic catalyst layer, an anodic diffusion layer and a cathodic diffusion layer, wherein the cathodic catalyst layer and the anodic catalyst layer are arranged on both sides of the proton exchange membrane, wherein the anodic diffusion layer is arranged on the outside of the anodic catalyst layer, wherein the cathodic diffusion layer is arranged on the outside of the cathodic catalyst layer, wherein the anodic catalyst layer comprises one of the above-mentioned catalysts.

[0046] Furthermore, it is intended that the diameter of the active metal is between 1.5 nm and 5 nm.

[0047] Furthermore, it is intended that the load-bearing capacity of the active metal on the porous carbon support is 30 wt% to 60 wt%.

[0048] Furthermore, it is intended that the carrying capacity of the active metal on the anodic catalyst layer is 0.01 to 0.1 mg / cm 2 amounts.

[0049] Another object of the present invention is to provide a CO poisoning resistant fuel cell comprising any of the above-mentioned membrane electrodes, wherein the membrane electrodes are sequentially repeatedly arranged to form a laminated structure, wherein a first bipolar plate is arranged on both sides of the membrane electrode, wherein the same electrode plate is used between the membrane electrode structures of every two adjacent fuel cells, wherein a second bipolar plate is arranged on both sides of the laminated structure.

[0050] In the following, the present application is explained in more detail in connection with specific embodiments. Example 1

[0051] According to the present embodiment, there is provided a CO poisoning-resistant membrane electrode catalyst comprising an active metal Pt and a porous carbon support 100 for supporting the active metal Pt, wherein the catalyst is Pt / C, wherein the supporting capacity of Pt for Pt / C is 40 wt%, wherein the most likely pore size of the catalyst is 2.33 nm, wherein the main distribution peak range of the pore size of the catalyst is between 2.33 nm and 4.33 nm, wherein the pore volume of the respective pores accounts for 52.3% of the total pore volume of Pt / C. Example 2

[0052] According to the present embodiment, there is provided a CO poisoning-resistant membrane electrode catalyst comprising Pt and a porous carbon support for supporting Pt, wherein the catalyst is Pt / C, wherein the supporting capacity of Pt for Pt / C is 60 wt%, wherein the most likely pore size of the catalyst is 3.91 nm, wherein the main distribution peak range of the pore size of the catalyst is between 2.34 nm and 4.38 nm, wherein the pore volume of the respective pores accounts for 39.3% of the total pore volume of Pt / C. Example 3

[0053] According to the present embodiment, there is provided a CO poisoning-resistant membrane electrode catalyst comprising Pt and a porous carbon support for supporting Pt, wherein the catalyst is Pt / C, wherein the supporting capacity of Pt for Pt / C is 50 wt%, wherein the most likely pore size of the catalyst is 3.51 nm, wherein the main distribution peak range of the pore size of the catalyst is between 3.34 nm and 4.37 nm, wherein the pore volume of the respective pores accounts for 49.4% of the total pore volume of Pt / C. Example 4

[0054] According to the present embodiment, there is provided a CO poisoning-resistant membrane electrode catalyst comprising Pt and a porous carbon support for supporting Pt, wherein the catalyst is Pt / C, wherein the supporting capacity of Pt for Pt / C is 30 wt%, wherein the most likely pore size of the catalyst is 3.50 nm, wherein the main distribution peak range of the pore size of the catalyst is between 2.17 nm and 4.39 nm, wherein the pore volume of the respective pores accounts for 35.4% of the total pore volume of Pt / C. Example 5

[0055] According to the present embodiment, there is provided a CO poisoning-resistant membrane electrode catalyst comprising Pt and a porous carbon support for supporting Pt, wherein the catalyst is Pt / C, wherein the supporting capacity of Pt for Pt / C is 40 wt%, wherein the most likely pore size of the catalyst is 3.92 nm, wherein the main distribution peak range of the pore size of the catalyst is between 3.16 nm and 4.36 nm, wherein the pore volume of the respective pores accounts for 36.1% of the total pore volume of Pt / C. Example 6

[0056] According to the present embodiment, there is provided a CO poisoning-resistant membrane electrode catalyst comprising Pt and a porous carbon support for supporting Pt, wherein the catalyst is Pt / C, wherein the supporting capacity of Pt for Pt / C is 50 wt%, wherein the most likely pore size of the catalyst is 3.89 nm, wherein the main distribution peak range of the pore size of the catalyst is between 3.17 nm and 4.38 nm, wherein the pore volume of the respective pores accounts for 42.0% of the total pore volume of Pt / C. Comparison example 1

[0057] The present comparative example is a commercial Pt / C catalyst, model TEC10EA50e, wherein the carrying capacity of the Pt is 50 wt%, wherein the pore size distribution peak range of the catalyst is between 3.5 nm and 4.4 nm and ≥ 12 nm, wherein the pore volume corresponding to the pores from 3.5 nm to 4.4 nm accounts for 6.8% of the total pore volume of the catalyst, wherein the most probable pore size of the catalyst is 82.0 nm, wherein the main pore size distribution peak range of the catalyst is ≥ 12 nm (12 nm - out of the detection range). Comparison example 2

[0058] The present comparative example is a commercial Pt / C catalyst, model TEC10EA30e, wherein the carrying capacity of the Pt is 30 wt%, wherein the pore size distribution peak range of the catalyst is between 3.5 nm and 4.4 nm and ≥ 10 nm, wherein the pore volume corresponding to the pores from 3.5 nm to 4.4 nm accounts for 7.2% of the total pore volume of the catalyst, wherein the most probable pore size of the catalyst is 92.3 nm, wherein the main pore size distribution peak range of the catalyst is ≥ 10 nm (10 nm - out of the detection range). Comparison example 3

[0059] The present comparative example is a commercial Pt / C catalyst, model Elyst Pt20 0390, wherein the carrying capacity of the Pt is 20 wt%, wherein the distribution peak range of the pore size of the catalyst is between 2.33 nm and 4.35 nm and ≥ 10 nm, wherein the pore volume corresponding to the pores ≤ 5 nm accounts for 5.0% of the total pore volume of the catalyst, wherein the most probable pore size of the catalyst is ≥ 10 nm (10 nm - out of the detection range). Comparison example 4

[0060] According to the present comparative example, a membrane electrode of a fuel cell is provided, comprising a proton exchange membrane, a cathodic catalyst layer, an anodic catalyst layer, an anodic diffusion layer, and a cathodic diffusion layer, wherein the cathodic catalyst layer and the anodic catalyst layer are arranged on both sides of the proton exchange membrane, wherein the anodic diffusion layer is arranged on the outside of the anodic catalyst layer, wherein the cathodic diffusion layer is arranged on the outside of the cathodic catalyst layer, wherein the catalyst on the anodic catalyst layer is provided by the catalyst according to Comparative Example 1 and a platinum carrying capacity on the anodic catalyst layer of 0.1 mg / cm 2 has. Comparison example 5

[0061] According to the present comparative example, there is provided a membrane electrode catalyst of a fuel cell comprising Pt and a porous carbon support for supporting Pt, wherein the catalyst is Pt / C, wherein the distribution peak range of the pore size of the catalyst is between 3.16 nm and 4.36 nm and ≥ 10 nm, wherein the distribution peak range of the most probable pore size of the catalyst is ≥ 6 nm, wherein the pore volume corresponding to the pores on the catalyst ≤ 5 nm accounts for 35.0% of the total pore volume of Pt / C.

[0062] The pore size distribution and pore volume of the porous carbon supports of the catalysts according to the working examples 1 to 6 and the comparative examples 1 to 3 are shown in Table 1. The pore size distribution of the porous carbon supports of the catalysts according to the working examples 1 to 6 is shown in Fig.3. The pore size distribution of the porous carbon supports of the catalysts according to Comparative Examples 1 to 3 is shown in Fig. 4 shown. Table 1 BJH total pore volume of the catalyst (cc / g) Pore ​​volume of ≤ 5 nm of the catalyst (cc / g) BJH pore volume of ≤ 5 nm of the catalyst (%) Example 1 0,332 0,174 52,3 Example 2 0,789 0,310 39,3 Example 3 1,029 0,508 49,4 Example 4 1,734 0,613 35,4 Example 5 1,652 0,597 36,1 Example 6 1,024 0,431 42,0 Comparison example 1 0,718 0,052 7,2 Comparison example 2 0,966 0,066 6,8 Comparison example 3 0,666 0,033 5,0

[0063] The pore size and pore volume according to the embodiment and the comparative example are calculated by isothermal nitrogen adsorption and desorption tests on the sample and calculating the nitrogen desorption data according to the BJH model.

[0064] The membrane electrodes were prepared using the catalysts according to Working Examples 1 to 6 and Comparative Examples 1 to 3 as anode catalyst by the following methods: S1: 16.7 g of 20 wt% D2020 perfluorosulfonic acid resin dispersion, 28.6 g of ethanol, 6.2 g of catalyst, and 48.4 g of ultrapure water were weighed. The catalyst was slowly added to water with stirring, stirred for 5 min, the perfluorosulfonic acid resin dispersion was added, and stirred for 2 min. Ethanol was added and stirred for a further 2 min to form a predispersed slurry. The predispersed slurry was dispersed using a bead mill at a speed of 3,000 rpm and a dispersion time of 30 min. The dispersed catalyst slurry was collected and defoamed to prepare an anode catalyst slurry. S2: The anode catalyst slurry prepared in S1 was coated on the catalyst-free side of the proton exchange membrane coated with a cathodic catalyst layer on one side by the slot coating method to prepare a CCM, with the platinum carrying capacity on the anodic catalyst layer being 0.05 mg / cm 2 amounts. S3: The frame and the diffusion layer were further assembled to form a membrane electrode.

[0065] The membrane electrode obtained above and the membrane electrode in Comparative Example 4 were each subjected to a CO tolerance test, and the performance of the membrane electrode was tested at a CO concentration of 400 ppb. The test results according to Working Examples 1, 2, and 4 and Comparative Examples 1 to 4 are shown in Fig.5. From the graph, it can be seen that according to Comparative Examples 1 to 4, after 4 hours of CO poisoning, the performance decreases by 62, 50, 61, and 51 mV, respectively. The test results corresponding to the performance of Comparative Example 5 are similar to those of Comparative Example 2. The test results corresponding to Working Examples 3 and 6 are similar to those of Working Example 1. It can be seen that the resistance of the membrane electrode to CO poisoning is poor when the existing conventional Pt / C catalyst is used for the anodic catalyst layer of the membrane electrode. At a CO concentration of 400 ppb, the performance of the membrane electrode decreases rapidly.From the data of Comparative Example 1 and Comparative Example 4, it can be seen that when conventional Pt / C catalysts were used, the resistance of the membrane electrode to CO poisoning was not significantly improved, although the carrying capacity of Pt on the anode of the membrane electrode was increased to 0.1 mg / cm. 2was increased. In Working Examples 1 and 2, decreases of 20 and 32 mV were observed, respectively. Compared with the comparative example, the resistance of the membrane electrode to CO poisoning in the Working Examples is significantly improved. At the same time, the initial performance of the membrane electrode with small pore size catalysts (Working Examples 1 to 2) did not deteriorate with respect to the performance of the membrane electrode in which 400 ppb CO was not introduced (first 1 hour). Of course, the above Working Examples of the present invention are only examples to clearly illustrate the technical solutions of the present invention and do not limit the specific embodiments of the present invention.All changes, equivalent substitutions and improvements made within the spirit and principle of the claims of the present invention are to be included within the scope of the claims of the present invention. List of reference symbols 100 Porous carbon support 200 Active Metal

Claims

[1] A membrane electrode catalyst resistant to CO poisoning, comprising an active metal and a porous carbon support for supporting the active metal, characterized by that the distribution peak range of the most probable pore size of the membrane electrode catalyst is ≤ 5 nm. [2] A membrane electrode catalyst resistant to CO poisoning according to claim 1, characterized by that the pore volume corresponding to the pores of the membrane electrode catalyst ≤ 5 nm is ≥ 35% of the total pore volume. [3] A membrane electrode catalyst resistant to CO poisoning according to claim 1 or 2, characterized by that the active metal is platinum or a platinum-based alloy. [4] A membrane electrode catalyst resistant to CO poisoning according to any one of claims 1 to 3, characterized by that the distribution peak range of the most probable pore size of the membrane electrode catalyst is between 2 nm and 5 nm. [5] A membrane electrode catalyst resistant to CO poisoning according to any one of claims 1 to 4, characterized by that the carrying capacity of the active metal on the porous carbon support is 20 wt% to 60 wt%. [6] Anodic catalyst layer of a membrane electrode of a fuel cell, wherein the catalyst on the anodic catalyst layer comprises an active metal and a porous carbon support for supporting the active metal, characterized by that the distribution peak range of the most probable pore size of the catalyst is ≤ 5 nm. [7] Anodic catalyst layer of a membrane electrode of a fuel cell according to claim 6, characterized by that the active metal is platinum or a platinum-based alloy, the platinum carrying capacity on the anodic catalyst layer being ≤ 0.1 mg / cm 2 amounts. [8] Anodic catalyst layer of a membrane electrode of a fuel cell according to claim 6 or 7, characterized by that the pore volume corresponding to the pores of the catalyst ≤ 5 nm represents ≥ 35% of the total pore volume. [9] Coating membrane for a catalyst of a fuel cell, comprising a proton exchange membrane and an anodic catalyst layer and a cathodic catalyst layer coated on both sides of the proton exchange membrane, characterized by that the anodic catalyst layer is an anodic catalyst layer according to one of claims 6 to 8. [10] A fuel cell membrane electrode resistant to CO poisoning, comprising a proton exchange membrane, a cathodic catalyst layer, an anodic catalyst layer, an anodic diffusion layer and a cathodic diffusion layer, wherein the cathodic catalyst layer and the anodic catalyst layer are arranged on both sides of the proton exchange membrane, wherein the anodic diffusion layer is arranged on the outside of the anodic catalyst layer, wherein the cathodic diffusion layer is arranged on the outside of the cathodic catalyst layer, characterized by that the anodic catalyst layer comprises a catalyst according to one of claims 1 to 5. [11] A fuel cell membrane electrode resistant to CO poisoning according to claim 10, characterized by that the diameter of the active metal is between 1.5 nm and 5 nm. [12] A fuel cell membrane electrode resistant to CO poisoning according to claim 10 or 11, characterized by that the carrying capacity of the active metal on the porous carbon support is 30 wt% to 60 wt%. [13] A membrane electrode of a fuel cell resistant to CO poisoning according to any one of claims 10 to 12, characterized by that the carrying capacity of the active metal on the anodic catalyst layer is 0.01 to 0.1 mg / cm 2 amounts. [14] A fuel cell resistant to CO poisoning, comprising a membrane electrode of a fuel cell according to any one of claims 10 to 13, characterized bythat the membrane electrodes of the fuel cell are arranged sequentially and repeatedly to form a laminated structure, wherein a first bipolar plate is arranged on both sides of the membrane electrode, wherein the same electrode plate is used between the membrane electrode structures of every two adjacent fuel cells, wherein a second bipolar plate is arranged on both sides of the laminated structure.

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