Functionalized CCM and preparation method thereof

Abstract

The invention belongs to the field of fuel cells, and provides a functionalized CCM and a preparation method thereof, and the functionalized CCM comprises a free radical quenching functionalized proton exchange membrane, a conventional anode platinum-carbon catalyst layer, an anti-reverse anode catalyst layer and a cathode platinum-carbon catalyst layer. According to the method disclosed by the invention, only the finished proton exchange membrane needs to be modified, and the dispersion and performance of the traditional catalyst layer slurry are not influenced. The CCM prepared by the method has excellent performance and durability.

Description

Technical Field

[0001] The present invention belongs to the field of fuel cells, and particularly relates to a functionalized CCM and a preparation method thereof. Background Art

[0002] Disclosing the information of this background art section is only intended to enhance the understanding of the overall background of the present invention, and is not necessarily regarded as an admission or an implication in any form that this information constitutes the prior art already known to those of ordinary skill in the art.

[0003] Proton exchange membrane fuel cells are one of the most promising power sources for electric vehicles. The basic unit constituting a proton exchange membrane fuel cell is a single fuel cell.

[0004] Among them, the proton exchange membrane (PEM) is the core component of a proton exchange membrane fuel cell (PEMFC) and plays a crucial role in the performance of the battery. It not only has a barrier function but also has the function of conducting protons.

[0005] In view of the attractive application potential of the proton exchange membrane, extensive research has been carried out at home and abroad. For example, Patent CN114361545A discloses a cross-temperature zone membrane electrode and its proton exchange membrane fuel cell, in which the catalyst slurry is coated on a substrate, or a proton exchange membrane, or the microporous layer of a gas diffusion layer by one of spraying, impregnation, etc. and dried to obtain a cathode catalytic layer and an anode catalytic layer. There is also research on setting a reinforcing layer containing a radical quencher on the anode side of the proton exchange membrane. However, the catalytic performance and durability of the CCM prepared by the above methods still need to be improved. Summary of the Invention

[0006] To solve the above problems, the present invention provides a functionalized CCM and a preparation method thereof. The anti-reversal catalyst and the radical quencher of the present invention are respectively coated on the outside of the traditional anode catalytic layer and the proton exchange membrane, without changing the formulation of the traditional Pt-based catalytic layer slurry, and it is more conducive to the functioning of the functionalized catalyst.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] In the first aspect of the present invention, a functionalized CCM is provided, including: a radical quenching functionalized proton exchange membrane; an anode catalytic layer and a cathode catalytic layer are respectively arranged on both sides of the radical quenching functionalized proton exchange membrane;

[0009] The radical quenching functionalized proton exchange membrane includes: a proton exchange membrane and functionalized reinforcing layers on both sides thereof; the functionalized reinforcing layers contain both a radical quencher and a fluorine-containing ion exchange resin.

[0010] In some embodiments, the functionalized reinforcing layer is made of raw materials with the following mass percentages: 0.001-60 wt% of a fluorine-containing ion exchange resin, 0.1-99 wt% of a radical quencher, and the sum of the percentages of the raw materials is 100%. Among them, the fluorine-containing ion exchange resin is used to transfer protons, and the radical quencher is used to eliminate radicals and protect the proton exchange membrane.

[0011] In some embodiments, the total thickness of the radical quenching functionalized proton exchange membrane is 1-400 μm. The proton exchange membrane includes one of a perfluorinated proton exchange membrane, a partially fluorinated polymeric proton exchange membrane (PFSA), a non-fluorinated polymeric proton exchange membrane, and a composite proton exchange membrane. The thickness of the proton exchange membrane is 1-300 μm, preferably 5-15 μm, and the thickness of the functionalized reinforcing layers on both sides thereof is 0.1-100 μm each, preferably 0.5-5 μm.

[0012] In some embodiments, the radical quencher is selected from at least one of cerium oxide, molybdenum sulfide, and composites formed therefrom.

[0013] In some embodiments, the loading of the active component of the radical quencher is 0.001-30 mg / cm 2 or 0.01-0.1 mg / cm 2 .

[0014] In some embodiments, a conventional anode platinum-carbon catalytic layer and a cathode platinum-carbon catalytic layer are used. Both contain a fluorine-containing ion exchange resin, a carrier, and a catalyst active component supported on the carrier. The mass percentages of the components in the anode catalytic layer and the cathode catalytic layer are as follows: the mass percentage of the fluorine-containing ion exchange resin is 0.5-90 wt%, the mass percentage of the carrier is 5-99 wt%, and the mass percentage of the catalyst active component supported on the carrier is 0.1-80 wt%; the thickness of the cathode catalytic layer is 0.05-200 μm, preferably 1-30 μm, and the loading of the catalyst active component therein is 0.001-20 mg / cm 2 , preferably 0.1-1.2 mg / cm 2 ; the thickness of the anode catalytic layer is 0.05-200 μm, preferably 0.5-20 μm, and the loading of the catalyst active component therein is 0.001-20 mg / cm 2 , preferably 0.005-0.5 mg / cm 2 . The carrier in the anode catalytic layer and the cathode catalytic layer is a conductive carbon material, and the conductive carbon material is selected from, but not limited to, one or more combinations of carbon black, graphite carbon, mesoporous carbon, and carbon nanotubes. The catalyst active component includes, but is not limited to, one or more of a Pt-based catalyst and a non-platinum catalyst.

[0015] In some embodiments, an anti-reversal functionalized anode catalyst layer is further provided on the anode catalyst layer. The anti-reversal functionalized anode catalyst layer includes an anti-reversal functional catalyst and a fluorine-containing ion exchange resin. Among them, the fluorine-containing ion exchange resin is used to transfer protons, and the anti-reversal catalyst is used to supply protons for electrolyzed water to protect the catalyst layer.

[0016] In some embodiments, the anti-reversal functionalized anode catalyst layer is made of raw materials with the following mass percentages: 0.001-60 wt% of fluorine-containing ion exchange resin, 0.1-99 wt% of anti-reversal catalyst, and the sum of the percentages of each raw material is 100%.

[0017] In some embodiments, the anti-reversal functional catalyst is selected from at least one of IrRuO x / C, iridium dioxide, ruthenium dioxide, and composites formed therefrom.

[0018] In some embodiments, the loading of the active component of the anti-reversal catalyst is 0.001-30 mg / cm 2 or 0.001-0.1 mg / cm 2 .

[0019] In some embodiments, the fluorine-containing ion exchange resin includes, but is not limited to, all sulfonic acid ion exchange resins, partial fluorosulfonic acid ion exchange resins, and one or more of cyclic structure backbone matrix ionomers, with an EW value of 100 g / mol - 5000 g / mol, preferably 500 g / mol - 2000 g / mol.

[0020] The second aspect of the present invention provides a method for preparing a functionalized CCM, including:

[0021] Mixing and uniformly dispersing a fluorine-containing ion exchange resin solution, a radical quencher, water, and an organic solvent to obtain a radical quenching catalyst slurry;

[0022] Separately preparing an anode catalyst slurry and a cathode catalyst slurry;

[0023] Coating the radical quenching catalyst slurry on both sides of the proton exchange membrane and drying to obtain a radical quenching functionalized proton exchange membrane;

[0024] Coating the anode catalyst slurry and the cathode catalyst slurry on both sides of the radical quenching functionalized proton exchange membrane respectively and drying to form an anode catalyst layer and a cathode catalyst layer respectively, thus obtaining the product.

[0025] Preferably, it further includes:

[0026] Mixing and uniformly dispersing a fluorine-containing ion exchange resin solution, an anti-reversal catalyst, water, and an organic solvent to obtain an anti-reversal catalyst slurry;

[0027] In some embodiments, the specific method for uniform dispersion is selected from at least one of magnetic stirring, ultrasonication, primix shearing, and ball milling;

[0028] In some embodiments, the coating method is selected from one of ultrasonic spraying, bar coating, knife coating, and slot coating.

[0029] More specifically, it includes:

[0030] 1) Preparation of catalyst slurry: A is a free radical quenching catalyst slurry, B is an anti-reversal catalyst slurry, and C is a conventional platinum-based or non-platinum-based catalyst slurry;

[0031] The catalyst and the functionalized catalyst are respectively added to a fluoride ion exchange resin solution, deionized water, and an organic solution, and after being treated by one or more processes of magnetic stirring, ultrasonication, primix shearing, and ball milling, a uniformly dispersed catalyst slurry is obtained. Then, a catalytic layer is prepared by one of ultrasonic spraying, bar coating, knife coating, and slot coating; the material ratios in this preparation method are as follows: the solid content of the catalyst slurry is 0.1-50 wt%, preferably 0.5-10 wt%; the mass ratio of the perfluorinated ion resin to the carrier is 0.3-5, preferably 0.3-3; the mass ratio of the organic matter to water is 1:1-30:1, preferably 1:1-20:1; the mass of the functionalized catalyst material is 0-10 wt%, preferably 0-1 wt%;

[0032] 2) Preparation of the free radical quenching functionalized proton exchange membrane: The uniformly dispersed free radical quenching catalyst slurry in step 1) is coated on both sides of the proton exchange membrane by one of spraying, bar coating, knife coating, and slot coating, and after being dried at 60°C to 100°C, a free radical quenching functionalized proton exchange membrane is obtained. Among them, in the anode catalytic layer and the cathode catalytic layer: the mass ratio of the ion resin to the carrier is 0.3-3, the mass ratio of the organic solvent to water is 1:1 to 20:1, and the solid content is 0.5% to 10%; the loading of the anode catalyst particles is 0.001-20 mg / cm 2 ; the loading of the cathode catalyst particles is 0.001-20 mg / cm 2 ;

[0033] 3) Preparation of the catalytic layer: The uniformly dispersed conventional platinum-based or non-platinum-based catalyst slurry in step 1) is coated on the proton exchange membrane in step 2) by one of spraying, bar coating, knife coating, and slot coating, and after being dried at 60°C to 90°C, a cathode catalytic layer and an anode catalytic layer are obtained; among them, in the anode catalytic layer and the cathode catalytic layer, the mass ratio of the ion exchange resin to the carrier is 0.3-3, the mass ratio of the organic solvent to water is 1:1 to 20:1, and the solid content is 0.5% to 10%; the loading of the anode catalyst particles is 0.001-1 mg / cm 2, the loading of the cathode catalyst particles is 0.001 - 5 mg / cm 2 ;

[0034] 4) Preparation of the anti-reversal functionalized anode catalyst layer: The uniformly dispersed anti-reversal catalyst slurry is coated on the anode catalyst layer prepared in step 3) by one of spraying, bar coating, knife coating, and slot coating, and dried at 80°C to 200°C to obtain the anti-reversal functionalized anode catalyst layer; wherein, the mass ratio of the organic solvent to water in the anti-reversal functionalized catalyst layer is 1:1 to 20:1, the solid content is 0.1% to 5%, the mass of the ion resin accounts for about 0 to 10 wt%, and the loading of the anti-reversal catalyst particles is 0.001 - 1 mg / cm 2 .

[0035] In the third aspect of the present invention, there is provided an application of the above functionalized CCM in the preparation of a proton exchange membrane fuel cell.

[0036] Advantages of the present invention

[0037] The present invention does not need to change the traditional Pt / C catalyst slurry formula, and reduces the adverse effects of the functionalized catalyst on the dispersion of the Pt / C catalyst slurry and the preparation of the catalyst layer. And placing the anti-reversal catalyst in the gas diffusion layer is beneficial for the anti-reversal catalyst to electrolyze water in time to provide protons to the catalyst layer when reverse polarization occurs; placing the radical quenching catalyst on the surface of the proton exchange membrane is beneficial for timely eliminating the generated radicals, thereby protecting the proton membrane. This method can give full play to the role of the functionalized catalyst without affecting the catalytic efficiency of the Pt / C catalyst, and thus improve the durability of the membrane electrode. The specific advantages are as follows:

[0038] 1) Functionalization of the proton exchange membrane. Placing the radical quenching catalyst on the surface of the proton exchange membrane is beneficial for timely eliminating the generated radicals, thereby protecting the proton membrane.

[0039] 2) Adding the anti-reversal catalyst layer outside the traditional catalyst layer to improve the utilization rate of the anti-reversal catalyst.

[0040] 3) Functionalized CCM structure, which does not affect the catalytic efficiency of the traditional catalyst layer and improves the durability of the membrane electrode.

[0041] 4) All catalyst slurries are prepared separately without affecting each other's dispersion and stability. Description of the drawings

[0042] The specification drawings forming a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention.

[0043] Figure 1Schematic diagram of the preparation process and structure of a functionalized membrane electrode according to the present invention; wherein, Slurry A: radical quenching catalyst slurry; Slurry B: anti-reversal polarization functionalized slurry; Slurry C: conventional platinum-based or non-platinum-based catalyst slurry. P1: radical quenching catalytic layer on the anode side; P: proton exchange membrane; P2: radical quenching catalytic layer on the cathode side; L1: conventional anode catalytic layer; L2: conventional cathode catalytic layer; G01: conventional anode gas diffusion layer; G1: anti-reversal polarization functionalized anode catalytic layer; G02: cathode gas diffusion layer;

[0044] Figure 2 Voltage-time graph of the reversal polarization test of the membrane electrode prepared in the examples and comparative examples of the present invention;

[0045] Figure 3 I-V graph of the membrane electrode prepared in the examples and comparative examples of the present invention before and after the Fenton experiment; wherein, the treatment is to use Fenton reagent for high-temperature treatment at 120 °C for 24 h. Detailed implementation manners

[0046] It should be noted that the following detailed description is exemplary and is intended to provide further illustration of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.

[0047] The present invention will be further described in detail below with reference to specific examples. It should be noted that the specific examples are interpretations rather than limitations of the present invention.

[0048] In the following examples and comparative examples, the organic solvent is ethanol.

[0049] Example 1

[0050] Taking the radical quencher CeO2, the anti-reversal polarization catalyst IrO2, and the conventional catalyst as 60% platinum-carbon catalyst as an example, the method for preparing the membrane electrode is as follows:

[0051] Step 1: Prepare CeO2 catalyst slurry, IrO2 catalyst slurry, and conventional Pt / C catalyst slurry respectively. First, according to the mass ratio of organic solvent to water of 19:1, the solid content (CeO2 and resin) of 0.2%, and the mass of fluorine-containing ion exchange resin of 2 wt%, after cell disruption for 45 min and ultrasonic dispersion for 30 min, a uniformly dispersed CeO2 catalyst slurry is obtained for standby; then, according to the mass ratio of organic solvent to water of 15:1, the solid content (IrO2 and resin) of 0.5%, and the mass of fluorine-containing ion exchange resin (all sulfonic acid ion exchange resin, purchased from Sichuan Dongcai New Materials) of 2 wt%, after cell disruption for 45 min and ultrasonic dispersion for 30 min, a uniformly dispersed IrO2 catalyst slurry is prepared for standby; finally, according to the mass ratio of fluorine-containing ion exchange resin to carrier of 0.6, the mass ratio of organic solvent to water of 12:1, and the solid content (Pt / C catalyst and resin) of 5%, after cell disruption for 45 min and ultrasonic dispersion for 30 min, a uniformly dispersed conventional Pt / C catalyst slurry is prepared for standby.

[0052] Step 2: Coat the uniformly dispersed CeO2 catalyst slurry in Step 1 on both sides of the proton exchange membrane by spraying, and obtain a free radical quenching functionalized proton exchange membrane after drying at 90 °C, with a Ce loading of 0.015 mg / cm 2 , and a thickness of 0.8 μm;

[0053] Step 3: Coat the uniformly dispersed Pt / C catalyst slurry in Step 1 on the proton exchange membrane in Step 2 by spraying, and obtain a conventional cathode catalyst layer and anode catalyst layer after drying at 80 °C, with a Pt loading of 0.1 mg / cm 2 for the anode catalyst layer, and a thickness of 2 μm, and a Pt loading of 0.4 mg / cm 2 for the cathode catalyst layer, and a thickness of 9.5 μm;

[0054] Step 4: Coat the uniformly dispersed IrO2 catalyst slurry in Step 1 on the traditional anode catalyst layer in Step 3 by spraying, and obtain an anti-reversal functionalized microporous layer after drying at 120 °C, with an Ir loading of 0.01 mg / cm 2 , and a thickness of 0.5 μm, and a functionalized CCM is prepared.

[0055] Step 5: Thermocompress the conventional gas diffusion layer (H14CX653 of Freudenberg) at 150 °C under a pressure of 0.5 Mpa for 3 min, and place it on the surface of the anode / cathode catalyst layer respectively to prepare a membrane electrode.

[0056] Example 2

[0057] The difference from Example 1 is that a free radical quencher MoS2 (loading of 0.001 mg / cm2 ), the anti-reverse electrode catalyst IrRuO x / C (loading is 0.001 mg / cm 2 ), the conventional catalyst is 5% palladium on carbon catalyst, the carrier is graphite carbon, the fluorine-containing ion exchange resin is a partial fluorosulfonic acid ion exchange resin, and the EW value is 100 g / mol;

[0058] The proton exchange membrane is a partially fluorinated proton exchange membrane with a thickness of 1 μm.

[0059] The thickness of the bilateral free radical quenching functionalized strengthening layer is 0.1 μm each.

[0060] The thickness of the anode catalyst layer is 0.05 μm, and the loading of the catalyst active component is 0.001 mg / cm 2 ;

[0061] The thickness of the cathode catalyst layer is 0.05 μm, and the loading of the catalyst active component is 0.001 mg / cm 2 .

[0062] Example 3

[0063] The difference from Example 1 is that the free radical quencher MoS2 and CeO2 (the molar ratio of the two is 1:1, and the loading is 30 mg / cm 2 ), the anti-reverse electrode catalyst RuO2 (loading is 30 mg / cm 2 ), the conventional catalyst is 20% platinum on carbon catalyst, the carrier is mesoporous carbon, the fluorine-containing ion exchange resin is a cyclic structure framework matrix ionomer, and the EW value is 5000 g / mol;

[0064] The proton exchange membrane is a non-fluorinated polymer proton exchange membrane with a thickness of 300 μm.

[0065] The thickness of the bilateral free radical quenching functionalized strengthening layer is 100 μm each.

[0066] The thickness of the anode catalyst layer is 200 μm, and the loading of the catalyst active component is 20 mg / cm 2 ;

[0067] The thickness of the cathode catalyst layer is 200 μm, and the loading of the catalyst active component is 20 mg / cm 2 .

[0068] Example 4

[0069] The difference from Example 1 is that the free radical quencher MoS2 (loading is 0.01 mg / cm 2 ), the anti-reverse electrode catalyst IrO2 and RuO2 (the molar ratio of the two is 1:1, and the loading is 0.001 mg / cm2 ) The conventional catalyst is a 40% platinum-carbon catalyst, the carrier is carbon nanotubes, the fluorine-containing ion exchange resin is all sulfonic acid ion exchange resin, and the EW value is 500 g / mol;

[0070] The proton exchange membrane is a composite proton exchange membrane with a thickness of 5 μm.

[0071] The thickness of each of the bilateral radical quenching functionalized reinforcement layers is 0.5 μm.

[0072] The thickness of the anode catalyst layer is 0.5 μm, and the loading of the catalyst active component is 0.005 mg / cm 2 ;

[0073] The thickness of the cathode catalyst layer is 1 μm, and the loading of the catalyst active component therein is 0.1 mg / cm 2 .

[0074] Example 5

[0075] The difference from Example 1 is that a radical quencher MoS2 (loading of 0.1 mg / cm 2 ), an anti-reversal catalyst IrO2 (loading of 0.1 mg / cm 2 ) are used, the conventional catalyst is a 60% platinum-carbon catalyst; the carrier is graphite carbon and carbon nanotubes, and the mass ratio of the two is 1:1; the fluorine-containing ion exchange resin is all sulfonic acid ion exchange resin, and the EW value is 2000 g / mol;

[0076] The proton exchange membrane is a partially fluorinated proton exchange membrane with a thickness of 15 μm.

[0077] The thickness of each of the bilateral radical quenching functionalized reinforcement layers is 5 μm.

[0078] The thickness of the anode catalyst layer is 20 μm, and the loading of the catalyst active component is 0.5 mg / cm 2 ;

[0079] The thickness of the cathode catalyst layer is 30 μm, and the loading of the catalyst active component therein is 1.2 mg / cm 2 .

[0080] Comparative Example 1: A traditional membrane electrode prepared with a conventional Pt / C catalyst

[0081] The preparation method is as follows:

[0082] Step 1: Prepare a uniformly dispersed conventional Pt / C catalyst for standby according to a mass ratio of fluorine-containing ion exchange resin to carrier of 0.6, a mass ratio of organic solvent to water of 10:1, a solid content of 5%, after cell disruption for 45 min and ultrasonic dispersion for 30 min.

[0083] Step 2: The evenly dispersed Pt / C catalyst slurry in Step 1 is coated on the proton exchange membrane in Step 2 by spraying, and then dried at 80 °C to obtain a conventional cathode catalyst layer and an anode catalyst layer, with the Pt loading and thickness being the same as those in Example 1;

[0084] Step 3: The conventional gas diffusion layer (H14CX653 from Freudenberg) is hot-pressed at 150 °C under a pressure of 0.5 Mpa for 3 min and placed on the surfaces of the anode / cathode catalyst layers respectively to prepare a conventional membrane electrode.

[0085] Comparative Example 2: Preparation of a membrane electrode with a functional enhancement layer only on the anode side of the proton exchange membrane

[0086] The difference from Example 1 is that in Step 2, only the CeO2 catalyst slurry is sprayed on the anode side of the proton exchange membrane.

[0087] Comparative Example 3: No anti-polarization functional microporous layer is provided.

[0088] The difference from Example 1 is that Step 4 is omitted.

[0089] It can be seen from Figure 2 that Comparative Example 1 fails within 0.5 h under the anti-polarization state; Example 1 can maintain for more than 6 h under the anti-polarization state.

[0090] It can be seen from Figure 3 that after being treated with Fenton's reagent, the performance of Comparative Example 1 decreases significantly, and the voltage drops by more than 100 mV at a current density of 1 A / cm 2 ; while the performance of Example 1 basically remains unchanged after being treated with Fenton's reagent.

[0091] In summary, the present invention can give full play to the role of the functionalized catalyst on the premise of not affecting the catalytic efficiency of the Pt / C catalyst, thereby improving the durability of the membrane electrode.

[0092] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A functionalized CCM, characterized in that: include: Free radical quenching functionalized proton exchange membrane; The free radical quenching functionalized proton exchange membrane is provided with an anode catalyst layer and a cathode catalyst layer on both sides thereof; The free radical quenching functionalized proton exchange membrane comprises: a proton exchange membrane and functionalized reinforcing layers located on both sides thereof; the functionalized reinforcing layers contain both free radical quenchers and fluorine-containing ion exchange resins.

2. The functionalized CCM of claim 1, wherein: The functionalized reinforcement layer is made of the following raw materials in percentage by weight: 0.001-60 wt % of fluorine-containing ion exchange resin, 0.1-99 wt % of free radical quencher, and the sum of the percentages of the raw materials is 100%.

3. The functionalized CCM of claim 2, wherein: The total thickness of the free radical quenching functionalized proton exchange membrane is 1-400 μm; Or, the thickness of the proton exchange membrane is 1-300um or 5-15um; Alternatively, the thickness of each of the functionalized reinforcement layers is 0.1-100 μm or 0.5-5 μm.

4. The functionalized CCM of claim 2, wherein: The free radical quencher is selected from at least one of cerium oxide, molybdenum sulfide and composite materials formed therefrom; Or, the loading amount of the free radical quencher active component is 0.001-30 mg / cm 2 or 0.01-0.1mg / cm 2 .

5. The functionalized CCM of claim 1, wherein: An anti-reverse polarity functionalized anode catalyst layer is also arranged on the anode catalyst layer, and the anti-reverse polarity functionalized anode catalyst layer comprises an anti-reverse polarity functional catalyst and a fluorine-containing ion exchange resin.

6. The functionalized CCM of claim 5, wherein: The anti-reverse polarity functionalized anode catalyst layer is made of the following raw materials in percentage by weight: 0.001-60 wt % of fluorine-containing ion exchange resin and 0.1-99 wt % of anti-reverse polarity catalyst, and the sum of the percentages of the raw materials is 100%.

7. The functionalized CCM of claim 1, wherein: The anti-reversal functionalized catalyst is selected from IrRuO x / C, at least one of tantalum dioxide, ruthenium dioxide and a composite material formed thereof; Or, the loading amount of the active component of the anti-reversal catalyst is 0.001-30 mg / cm 2 ,or, 0.001-0.1mg / cm 2 。 8. A method for preparing a functionalized CCM, characterized in that: include: The fluorine-containing ion exchange resin solution, the free radical quencher, water and the organic solvent are mixed and dispersed uniformly to obtain a free radical quenching catalyst slurry; preparing an anode catalyst slurry and a cathode catalyst slurry respectively; The free radical quenching catalyst slurry is coated on both sides of the proton exchange membrane and dried to obtain a free radical quenching functionalized proton exchange membrane; The anode catalyst slurry and the cathode catalyst slurry are respectively coated on both sides of the proton exchange membrane functionalized by radical quenching, and dried to form an anode catalyst layer and a cathode catalyst layer respectively.

9. The method for preparing the functionalized CCM according to claim 8, characterized in that: Also includes: The fluorine-containing ion exchange resin solution, the anti-reversal catalyst, water and the organic solvent are mixed and dispersed uniformly to obtain an anti-reversal catalyst slurry; The anti-reverse polarity catalyst slurry is coated on the anode catalyst layer and dried to obtain an anti-reverse polarity functionalized anode catalyst layer.

10. Use of the functionalized CCM according to any one of claims 1 to 7 in the preparation of a proton exchange membrane fuel cell.

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