CN113839048B - Catalyst slurry for proton exchange membrane and preparation method thereof - Google Patents

Catalyst slurry for proton exchange membrane and preparation method thereof Download PDF

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CN113839048B
CN113839048B CN202110962987.5A CN202110962987A CN113839048B CN 113839048 B CN113839048 B CN 113839048B CN 202110962987 A CN202110962987 A CN 202110962987A CN 113839048 B CN113839048 B CN 113839048B
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catalyst
proton exchange
exchange membrane
catalyst slurry
glycol
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CN113839048A (en
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耿凯明
倪海芳
陈琳琳
刘颖
周明正
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Spic Hydrogen Energy Technology Development Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a catalyst slurry for a proton exchange membrane, which comprises the following components: the catalyst comprises a catalyst, perfluorinated sulfonic acid resin, a solvent and an additive, wherein the additive is a dispersion liquid containing carbon nano tubes, and the dispersion liquid is a water-soluble amide organic solvent. The mass of the carbon nano tube is 1-10% of the total mass of the catalyst and the perfluorosulfonic acid resin, wherein the solid content of the carbon nano tube in the dispersion liquid containing the carbon nano tube is 5-10%. According to the catalyst slurry for the proton exchange membrane, a three-dimensional conductive network is constructed on the catalyst layer of the proton exchange membrane fuel cell, so that the contact between the catalyst layer and the proton exchange membrane is improved, the swelling of the proton exchange membrane is reduced, and the utilization rate of the catalyst is improved.

Description

Catalyst slurry for proton exchange membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cells, particularly relates to catalyst slurry for a proton exchange membrane, and particularly relates to a preparation method of the catalyst slurry for the proton exchange membrane.
Background
The CCM is a core component of the membrane electrode, plays an important role in the cost and the performance of the proton membrane fuel cell, and is a three-in-one structure consisting of an anode catalyst layer, a proton exchange membrane and a cathode catalyst layer. At present, most CCMs are prepared by a hot-pressing transfer method. The hot-pressing transfer printing method is that catalyst slurry is first coated onto the back film and transferred to the proton exchange film from the back film at certain temperature and pressure. There are also a few CCMs that are commercially difficult to apply due to the low efficiency and waste of slurry sputtering by spraying the catalyst slurry directly onto the proton exchange membrane.
Compared with a hot-pressing transfer printing method, if the catalyst slurry can be directly coated on the membrane electrode prepared by the proton exchange membrane, because the interface contact resistance between the catalyst layer and the proton exchange membrane is smaller, the production procedures are fewer, the batch stability of the membrane electrode can be ensured, and the cost is reduced. However, the conventional catalyst slurry is directly coated on the proton exchange membrane to prepare the CCM, and the catalyst layer is easy to crack after drying, so that the performance of the MEA is influenced finally.
In the related art, publication No. CN 112259753A discloses a method for preparing CCM by directly coating a catalyst slurry on a proton exchange membrane, in which the components of the catalyst slurry for CCM include a catalyst, a perfluorosulfonic acid resin, a solvent and an additive, wherein the additive is a compound or a polymer containing at least two nitrogen functional groups, and the adopted additive ethylenediamine has a high boiling point, and in order to remove the ethylenediamine in the catalyst layer, the drying is performed at a high temperature of 160 ℃ or higher, and an excessively high temperature may cause dehydration of the proton membrane, thereby affecting the performance of the membrane electrode. In addition, ethylenediamine is a highly toxic solvent, and three wastes need to be treated, so that the production cost is increased.
CN1477724A discloses a method for preparing a membrane electrode assembly of a proton exchange membrane fuel cell, which uses low boiling point and low viscosity alcohol as a dispersant and high boiling point and high viscosity alcohol as a stabilizer to prepare a catalyst slurry directly coated on the proton exchange membrane, wherein in the method, firstly, resin and a proton exchange membrane Na are mixed + Forming, and soaking in high boiling point alcohol solution to obtain Na + The proton exchange membrane is shaped, the CCM prepared subsequently is dried at high temperature, and finally the membrane is reprotonated. CCM preparation process procedure is loaded down with trivial details in this patent, has increased many uncontrollable factors, is unfavorable for the quality control of industrial production line.
Therefore, there is a need to develop a catalyst slurry for direct coating of proton exchange membranes, which is low in cost, simple in operation, and excellent in performance.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: because the conventional catalyst slurry mainly adopts lower alcohol as a solvent, and the proton exchange membrane is an ionomer, the catalyst slurry is directly coated on the proton exchange membrane, the membrane can absorb the lower alcohol in the catalyst slurry to swell, and the volatilization of the lower alcohol and water can promote the proton exchange membrane to shrink in the heating and drying process of the catalyst layer, so that the cracking phenomenon of the catalyst layer is caused, and the integral performance and the durability of the electrode are not facilitated.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides the catalyst slurry for the proton exchange membrane, a three-dimensional conductive network is constructed on the catalyst layer of the proton exchange membrane fuel cell, the contact between the catalyst layer and the proton exchange membrane is improved, the swelling of the proton exchange membrane is reduced, the utilization rate of the catalyst is improved, the catalyst slurry can be directly coated on the proton exchange membrane, and the CCM with few cracks and excellent performance can be prepared.
The catalyst slurry for proton exchange membranes according to an embodiment of the present invention includes: the catalyst comprises a catalyst, perfluorinated sulfonic acid resin, a solvent and an additive, wherein the additive is a dispersion liquid containing carbon nano tubes, and the dispersion liquid is a water-soluble amide organic solvent.
The catalyst slurry for the proton exchange membrane provided by the embodiment of the invention has the following advantages and technical effects: 1. in the embodiment of the invention, the additive containing the carbon nano tube is added, and the carbon nano tube promotes the winding between the carbon nano tube and the catalyst and the resin due to the conjugated pi bond effect and the higher length-diameter ratio, so that the catalyst slurry is not easy to generate cracks in the process of drying the catalyst layer after being coated on the proton exchange membrane; 2. in the embodiment of the invention, the dispersion liquid containing the carbon nano tubes is added, so that the system viscosity of the catalyst slurry is improved, the fluidity of the slurry is reduced, and a catalyst layer with uniform thickness and flat appearance can be obtained after the catalyst layer is coated on a proton exchange membrane; 3. the catalyst slurry of the embodiment of the invention can be directly coated on a proton exchange membrane, so that the contact area of a three-phase interface is increased, and the contact resistance is reduced, thereby improving the overall performance of the membrane electrode.
In some embodiments, the dispersion is selected from at least one of N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), N-diethylacetamide, or N-methylcaprolactam.
In some embodiments, the dispersion is selected from at least one of N-methyl pyrrolidone or N-ethyl pyrrolidone.
In some embodiments, the mass of the carbon nanotubes is 1 to 10% of the total mass of the catalyst and the perfluorosulfonic acid resin, wherein the carbon nanotube content in the carbon nanotube-containing dispersion is 5 to 10%.
In some embodiments, the viscosity of the catalyst ink is greater than 200cP (shear rate: 10S) -1 Temperature: at 25 deg.C).
In some embodiments, the catalyst is a Pt and carbon particulate catalyst, the Pt mass content being 20-60%; and/or the solvent comprises water and alcohol, wherein the alcohol is selected from at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexylene glycol, pentylene glycol, glycerol, hexanetriol and thiodiglycol.
In some embodiments, the catalyst slurry comprises 1 to 10 parts by weight of the catalyst, 80 to 95 parts by weight of the solvent, 1 to 10 parts by weight of the perfluorosulfonic acid resin, and the additive carbon nanotubes are added in an amount of 1 to 10% of the total mass of the catalyst and the perfluorosulfonic acid resin.
The embodiment of the invention also provides a preparation method of the catalyst slurry for the proton exchange membrane, which comprises the following steps: uniformly mixing the catalyst and the solvent, then adding the additive, adding the perfluorosulfonic acid resin after ball milling, and continuing ball milling to obtain the catalyst slurry.
According to the advantages and technical effects brought by the preparation method of the catalyst slurry for the proton exchange membrane, 1, in the method, the additive containing the carbon nano tube is added, and the carbon nano tube promotes the winding among the carbon nano tube, the catalyst and the resin due to the conjugated pi bond effect and the higher length-diameter ratio, so that the prepared catalyst slurry is not easy to generate cracks in the process of drying the catalyst layer after being coated on the proton exchange membrane; 2. in the method of the embodiment of the invention, the additive containing the carbon nano tube is added, so that the system viscosity of the catalyst slurry is improved, the fluidity of the slurry is reduced, and the catalyst layer with uniform thickness and flat appearance can be obtained after the prepared catalyst slurry is coated on the proton exchange membrane; 3. the catalyst slurry prepared by the method of the embodiment of the invention can be directly coated on a proton exchange membrane, so that the contact area of a three-phase interface is increased, and the contact resistance is reduced, thereby improving the overall performance of the membrane electrode.
The embodiment of the invention also provides a membrane electrode CCM of a fuel cell, which comprises a proton exchange membrane, and an anode catalyst layer and a cathode catalyst layer which are arranged on two sides of the proton exchange membrane, wherein the anode catalyst layer and/or the cathode catalyst layer are/is prepared by coating the catalyst slurry of the embodiment of the invention.
According to the advantages and technical effects brought by the membrane electrode CCM of the fuel cell provided by the embodiment of the invention, the CCM provided by the embodiment of the invention can be prepared by directly coating the catalyst slurry provided by the embodiment of the invention on a proton exchange membrane, and the catalyst layer has the advantages of uniform thickness, flat appearance, high activity, high stability and excellent performance of few cracks.
Embodiments of the invention also provide a membrane electrode comprising a CCM of an embodiment of the invention.
According to the advantages and technical effects brought by the membrane electrode of the embodiment of the invention, the membrane electrode of the embodiment of the invention has all the advantages brought by the CCM of the embodiment of the invention, and details are not repeated herein.
Drawings
FIG. 1 is an I-V curve for examples 1-3 and comparative examples 1-2;
FIG. 2 is an optical microscope photograph of the CCM made in example 1;
FIG. 3 is an optical microscope photograph of a CCM made in example 2;
FIG. 4 is an optical microscope photograph of a CCM made in example 3;
FIG. 5 is an optical microscope photograph of a CCM prepared in comparative example 1;
FIG. 6 is an optical microscope photograph of a CCM prepared in comparative example 2.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The catalyst slurry for proton exchange membranes according to an embodiment of the present invention includes: the catalyst comprises a catalyst, perfluorinated sulfonic acid resin, a solvent and an additive, wherein the additive is a dispersion liquid containing carbon nano tubes, and the dispersion liquid is a water-soluble amide organic solvent.
According to the catalyst slurry for the proton exchange membrane, disclosed by the embodiment of the invention, the additive containing the carbon nano tube is added, and the carbon nano tube is promoted to be wound with the catalyst and the resin due to the conjugated pi bond effect and the higher length-diameter ratio, so that the catalyst slurry is not easy to crack in the process of drying the catalyst layer after being coated on the proton exchange membrane; in the embodiment of the invention, the dispersion liquid containing the carbon nano tubes is added, so that the system viscosity of the catalyst slurry is improved, the fluidity of the slurry is reduced, and the catalyst layer with uniform thickness and flat appearance can be obtained after the catalyst layer is coated on a proton exchange membrane; the catalyst slurry of the embodiment of the invention can be directly coated on a proton exchange membrane, so that the contact area of a three-phase interface is increased, and the contact resistance is reduced, thereby improving the overall performance of the membrane electrode.
In some embodiments, the dispersion is selected from at least one of N-methylpyrrolidone, N-ethylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide, or N-methylcaprolactam, preferably the dispersion is selected from at least one of N-methylpyrrolidone or N-ethylpyrrolidone. In the embodiment of the invention, N-methyl pyrrolidone with a high boiling point is preferably used as a dispersion liquid, the dispersion liquid can play a role of a stabilizer, the carbon nano tube is dispersed in the N-methyl pyrrolidone, a catalytic layer can be prevented from generating cracks in the drying process, and the N-methyl pyrrolidone is added to improve the wetting of the catalyst and water due to the poor hydrophilicity of the catalyst in the catalyst slurry, so that the catalyst and resin can be better mixed, the coating quality is improved, and the CCM with excellent performance is obtained.
In some embodiments, the mass of the carbon nanotube is preferably 1 to 10%, and more preferably 5% of the sum of the mass of the catalyst and the mass of the perfluorosulfonic acid resin, and the solid content of the carbon nanotube in the carbon nanotube-containing dispersion is preferably 5 to 10%. In the embodiment of the invention, the addition amount of the carbon nano tube and the solid content of the carbon nano tube in the additive are preferably selected, and if the use amount is too small, the anti-crack effect of the prepared CCM is not obvious; if the amount is too large, the viscosity will be too high, which will affect the dispersibility of the catalyst.
In some embodiments, the viscosity of the catalyst ink is greater than 200cP (shear rate: 10S) -1 Temperature: at 25 deg.C). In the embodiment of the invention, the viscosity of the catalyst slurry is optimized, and the catalyst layer with uniform thickness and flat appearance can be obtained after being coated on the proton exchange membrane, so that CCM with less cracks and excellent performance can be obtained.
In some embodiments, the catalyst is Pt and carbon particle catalyst, the Pt content is 20-60% by mass, and the solvent comprises water and alcohol, wherein the alcohol may be at least one selected from monohydric alcohol or polyhydric alcohol, and the monohydric alcohol is at least one selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, and benzyl alcohol; the polyalcohol is at least one selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, hexanediol, pentanediol, glycerol, hexanetriol and thiodiglycol. The embodiment of the invention has no special limitation on the catalyst and the solvent, can be suitable for Pt-C catalysts with various loading amounts, and has wide application range.
In some embodiments, the catalyst slurry comprises 1 to 10 parts by weight of the catalyst, 80 to 95 parts by weight of the solvent, and 1 to 10 parts by weight of the perfluorosulfonic acid resin, wherein the carbon nanotubes are added in an amount of 1 to 10% of the total mass of the catalyst and the perfluorosulfonic acid resin in the additive. In the embodiment of the invention, the proportion of each raw material of the catalyst slurry is optimized, and the comprehensive performance of CCM obtained after the catalyst slurry is coated is further improved.
The embodiment of the invention also provides a preparation method of the catalyst slurry for the proton exchange membrane, which comprises the following steps: uniformly mixing a catalyst and a solvent, adding an additive, performing ball milling treatment, preferably, the ball milling rotation speed is 300-500r/min, the ball milling time is 2-6h, adding perfluorinated sulfonic acid resin, and continuing ball milling, preferably, the ball milling rotation speed is 300-500r/min, and the ball milling time is 6-18h to obtain catalyst slurry.
According to the preparation method of the catalyst slurry for the proton exchange membrane, disclosed by the embodiment of the invention, the additive containing the carbon nano tube is added, and the carbon nano tube promotes the winding among the carbon nano tube, the catalyst and the resin due to the conjugated pi bond effect and the higher length-diameter ratio, so that the prepared catalyst slurry is not easy to generate cracks in the process of drying the catalyst layer after being coated on the proton exchange membrane; in the method of the embodiment of the invention, the additive containing the carbon nano tube is added, so that the system viscosity of the catalyst slurry is improved, the fluidity of the slurry is reduced, and the catalyst layer with uniform thickness and flat appearance can be obtained after the prepared catalyst slurry is coated on a proton exchange membrane; the catalyst slurry prepared by the method of the embodiment of the invention can be directly coated on a proton exchange membrane, so that the contact area of a three-phase interface is increased, and the contact resistance is reduced, thereby improving the overall performance of the membrane electrode.
The embodiment of the invention also provides a membrane electrode CCM of a fuel cell, which comprises a proton exchange membrane, and an anode catalyst layer and a cathode catalyst layer which are arranged on two sides of the proton exchange membrane, wherein the anode catalyst layer and/or the cathode catalyst layer are/is prepared by coating the catalyst slurry of the embodiment of the invention.
The CCM provided by the embodiment of the invention can be prepared by directly coating the catalyst slurry provided by the embodiment of the invention on a proton exchange membrane, and the catalyst layer has the advantages of uniform thickness, flat appearance, high activity, high stability and less cracks.
Embodiments of the invention also provide a membrane electrode comprising a CCM of an embodiment of the invention. The membrane electrode of the embodiment of the invention has all the advantages brought by the CCM of the embodiment of the invention, and is not described in detail herein.
The present invention is described in detail below with reference to the drawings and examples.
Example 1
(1) Preparation of catalyst slurry:
the catalyst slurry prepared included: 8 parts by weight of Pt/C,86 parts by weight of solvent, 6 parts by weight of perfluorinated sulfonic acid resin, and 0.7 part by weight of N-methylpyrrolidone (NMP) dispersion liquid of which the additive is carbon nano tubes and the mass of which is 5 percent of the mass of the Pt/C catalyst and the mass of the perfluorinated sulfonic acid resin, wherein the solvent comprises 50 parts by weight of deionized water and 36 parts by weight of N-propanol, and the solid content of the carbon nano tubes in the carbon nano tube NMP dispersion liquid is 8 percent.
Weighing Pt/C (50%) catalyst, putting the Pt/C catalyst into a ball milling tank, adding deionized water to fully wet the catalyst, uniformly mixing, and sequentially adding n-propanol, NMP dispersion liquid containing carbon nano tubes and ZrO 2 Grinding balls, and after the ball milling tank is sealed, putting the ball into an automatic ball mill for ball milling, wherein the rotating speed is 400r/min, and the ball milling time is 3h; and then taking out the ball milling tank, adding the perfluorinated sulfonic acid resin dispersion liquid into the slurry, resealing, 300r/min, and continuing ball milling for 6 hours to prepare the catalyst slurry.
(2) Preparation of CCM:
the catalyst slurry prepared in the embodiment is coated on the cathode side and the anode side of a proton exchange membrane respectively by a small automatic coater or a slit coater, and after being naturally dried, the catalyst slurry is put into a vacuum drying oven and is kept at 80 ℃ for 3h and 130 ℃ for 10min. Wherein the platinum loading of the catalyst of the cathode catalyst layer is 0.3mg/cm 2 The platinum loading of the anode catalyst layer is 0.05mg/cm 2 。
(3) Preparation and testing of membrane electrode:
the CCM obtained in this example was cut into 5X 5cm pieces 2 And the size of the diffusion layer is directly clamped between two diffusion layers, and the diffusion layer is tested on a fuel cell test fixture with a snake-shaped flow field. The temperature of the battery is 80 ℃, the humidification and activation are carried out for 40 percent, and H 2 The initial flow rates on the side and air side were set at 300/700sccm, the excess factor was 1.5/2.0, and the back pressure was 100kPa/40kPa.
This example produced a catalyst paste having a viscosity of 356cP (shear rate: 10S) -1 Temperature: 25℃)。
The results of the performance test of the membrane electrode obtained in this example are shown in FIG. 1.
The crack behavior of the CCM made in this example is shown in fig. 2.
Example 2
The same procedure as in example 1 was followed, except that the additive in the catalyst slurry was an N-ethylpyrrolidone (NEP) dispersion of carbon nanotubes, and the amount of carbon nanotubes added was 10% by mass, i.e., 1.4 parts by weight, of the mass of the Pt/C catalyst and the perfluorosulfonic acid resin.
The viscosity of the catalyst paste prepared in this example was 1353cP (shear rate: 10S) -1 Temperature: at 25 deg.C).
The results of the performance test of the membrane electrode obtained in this example are shown in FIG. 1.
The CCM cracking performance of this example is shown in fig. 3.
Example 3
The same procedure as in example 1 was conducted except that the carbon nanotubes in the catalyst slurry were added in an amount of 1% by mass, that is, 0.14 part by weight, based on the mass of the Pt/C catalyst and the perfluorosulfonic acid resin.
This example produced a catalyst slurry having a viscosity of 135cP (shear rate: 10S) -1 Temperature: at 25 deg.C).
The results of the performance test of the membrane electrode obtained in this example are shown in FIG. 1.
The CCM cracking performance obtained in this example is shown in fig. 4.
Comparative example 1
The same procedure as in example 1 was followed, except that no carbon nanotubes were added to the catalyst slurry.
The viscosity of the catalyst slurry prepared in comparative example 1 was: 35cP (shear rate: 10S) -1 Temperature: at 25 deg.C).
The results of the performance test of the membrane electrode obtained in comparative example 1 are shown in FIG. 1.
The crack behavior of CCM made in comparative example 1 is shown in fig. 5.
Comparative example 2
The same procedure as in example 1 was followed, except that the additive was added in the form of an aqueous dispersion containing carbon nanotubes.
The viscosity of the catalyst slurry prepared in comparative example 2 was: 335cP (shear Rate: 10S) -1 Temperature: at 25 deg.C).
The results of the membrane electrode performance test obtained in comparative example 2 are shown in FIG. 1
The CCM crack behavior obtained in comparative example 2 is shown in fig. 6.
As can be seen from fig. 1, in examples 1 to 3 according to the present invention, the addition of the water-soluble amide dispersion containing carbon nanotubes to the catalyst slurry effectively improved the output voltage of the battery in the high current density region as compared to comparative examples 1 and 2, and as shown in fig. 2 to 4, the CCMs prepared in examples 1 to 3 did not crack, while the CCMs prepared in comparative example 1 did not crack significantly as compared to comparative example 1, and as shown in fig. 5, the dispersion used was water and cracks were generated in comparative example 2 although carbon nanotubes were added.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (7)

1. The catalyst slurry for the proton exchange membrane is characterized by comprising 1-10 parts by weight of a catalyst, 1-10 parts by weight of a perfluorinated sulfonic acid resin, 80-95 parts by weight of a solvent and an additive, wherein the additive is a dispersion liquid containing carbon nano tubes, and the dispersion liquid is at least one selected from N-methylpyrrolidone, N-ethylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide or N-methylcaprolactam; the mass of the carbon nano tube is 1-10% of the total mass of the catalyst and the perfluorosulfonic acid resin, wherein the solid content of the carbon nano tube in the dispersion liquid containing the carbon nano tube is 5-10%.
2. The catalyst slurry for a proton exchange membrane according to claim 1, wherein the dispersion liquid is at least one selected from N-methylpyrrolidone and N-ethylpyrrolidone.
3. The catalyst paste for a proton exchange membrane according to claim 1, wherein the viscosity of the catalyst paste is greater than 200cP.
4. The catalyst slurry for a proton exchange membrane according to claim 1, wherein the catalyst is a Pt and carbon particle catalyst, and the Pt mass content is 20-60%; and/or the solvent comprises water and alcohol, wherein the alcohol is selected from at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexylene glycol, pentylene glycol, glycerol, hexanetriol and thiodiglycol.
5. A method for preparing a catalyst slurry for a proton exchange membrane according to any one of claims 1 to 4, comprising: uniformly mixing the catalyst and the solvent, adding the additive, adding the perfluorinated sulfonic acid resin after ball milling, and continuing ball milling to obtain the catalyst slurry.
6. A membrane electrode CCM for a fuel cell, which is characterized by comprising a proton exchange membrane and an anode catalytic layer and a cathode catalytic layer which are arranged on two sides of the proton exchange membrane, wherein the anode catalytic layer and/or the cathode catalytic layer are/is prepared by coating the catalyst slurry in any one of claims 1 to 4 on the proton exchange membrane.
7. A membrane electrode comprising the CCM of claim 6.
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