CN116002665B - Catalyst carrier, composite catalyst, preparation method and application thereof - Google Patents

Catalyst carrier, composite catalyst, preparation method and application thereof Download PDF

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CN116002665B
CN116002665B CN202211592654.9A CN202211592654A CN116002665B CN 116002665 B CN116002665 B CN 116002665B CN 202211592654 A CN202211592654 A CN 202211592654A CN 116002665 B CN116002665 B CN 116002665B
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catalyst
layer
carbon nanotube
film layer
nano tube
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CN116002665A (en
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李然
冯红丽
袁想平
迟兴帅
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Shenzhen Cone Technology Co ltd
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Shenzhen Cone Technology Co ltd
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    • 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

Abstract

The application belongs to the technical field of catalysts, and particularly relates to a catalyst carrier, a composite catalyst, a preparation method and application thereof. The catalyst carrier comprises a carbon nano tube array film layer, wherein the surface of the carbon nano tube array film layer is combined with the carbon nano tube layer, and the porosity of the carbon nano tube array film layer is higher than that of the carbon nano tube layer. In the embodiment of the application, the carbon nano tube carrier with high corrosion resistance and high inertia is used for replacing the carbon black carrier which is easy to corrode, so that the catalyst carrier is prevented from being corroded, and the overall stability and the service life of the catalyst are improved. In addition, the porosity of the carbon nano tube array film layer and the carbon nano tube layer is higher than that of the carbon black carrier, which is favorable for improving the catalyst attachment site, and compared with the catalytic activity uniformly distributed in the existing carbon black carrier, the gradient distribution of the catalytic active center, the proton channel and the mass transfer channel is realized.

Description

Catalyst carrier, composite catalyst, preparation method and application thereof
Technical Field
The application belongs to the technical field of catalysts, and particularly relates to a catalyst carrier, a composite catalyst, a preparation method and application thereof.
Background
The high cost of fuel cells is a major cause of impeding commercialization of hydrogen-powered automobiles, and one of the major ways to reduce the cost is to reduce the amount of noble metal catalyst used. The membrane electrode is a core component of the fuel cell, is a place where the fuel cell performs oxidation-reduction reaction, and mainly comprises a gas diffusion layer, a catalyst layer, a proton exchange membrane and a sealing layer. The catalyst layer catalyzes an electrochemical reaction of hydrogen and oxygen, and is divided into a cathode catalyst layer (oxygen reduction reaction) and an anode catalyst layer (hydrogen oxidation reaction). The anode catalytic layer breaks down the hydrogen into protons and releases electrons, which pass through an external circuit to the cathode. The cathode catalytic layer catalyzes proton and oxygen to generate electrochemical reaction, and the obtained electrons generate water.
In the prior art, a catalyst layer is formed on both sides of a proton exchange membrane, and the catalyst layer contains catalyst-supported carbon obtained by supporting a platinum-based metal catalyst on carbon powder, and a polymer electrolyte having hydrogen ion conductivity. The anode and the cathode are constituted by a combination of a catalyst layer and a gas diffusion layer.
For example, the prior art discloses a low platinum cathode catalytic layer for fuel cells and its use. The preparation of the catalytic layer adopts a spraying method, and the first layer has a specific surface area of 800-1200 m 2 A catalyst prepared by a carbon black carrier per gram and a proton conductor; the second layer has a specific surface area of 50-300 m 2 Catalyst prepared by the carbon black carrier per gram and hydrophobic substance. The catalyst obtained by the method has the characteristics of small noble metal consumption, thin thickness and the like, mainly solves the problems of drainage in the catalyst layer and the utilization rate of the catalyst, but the structure of the catalyst layer needs to be further improved, and the preparation method needs to be optimized. However, the catalytic layer is typically composed of carbon black supported platinum (Pt/C) and an ionomer. Platinum is used as a catalyst to promote the electrochemical reaction process, while the ionic polymer is used as a bonding and transmission medium, so that the carbon black carrier of the Pt/C catalyst is easy to corrode, the Pt is separated from the carrier, dissolved and redeposited, and finally Pt particles are agglomerated on the surface of the carbon black carrier, so that the overall performance of the catalyst is attenuated, the service life of the catalyst is reduced, the effective utilization rate of the Pt catalyst is reduced, and the increase of the catalyst cost is further aggravated.
Disclosure of Invention
Aiming at the prior art, the application aims at providing a catalyst carrier and a preparation method thereof, a composite catalyst and a preparation method and application thereof, and aims at solving the problem that the existing carbon black carrier is corroded.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
the first aspect of the present application provides a catalyst carrier, including a carbon nanotube array film layer, a carbon nanotube layer is bonded to a surface of the carbon nanotube array film layer, and a porosity of the carbon nanotube array film layer is higher than a porosity of the carbon nanotube layer.
The carbon nano tube carrier with high corrosion resistance and high inertia for the catalyst carrier replaces the carbon black carrier which is easy to corrode, so that the catalyst carrier is prevented from being corroded, catalyst aggregation distributed in the catalyst carrier is further prevented, the stability and the service life of the catalyst carrier are improved, and the overall stability and the service life of the composite catalyst are further improved. In addition, the porosity of the carbon nano tube array film layer and the carbon nano tube layer is higher than that of the carbon black carrier, which is favorable for improving the catalyst attachment site, and the porosity of the carbon nano tube array film layer is higher than that of the carbon nano tube layer so as to form a gradient structure.
The second aspect of the present application provides a method for preparing the catalyst carrier in the above text, comprising the following steps:
and forming a carbon nano tube layer on the surface of the carbon nano tube array film layer by using the slurry containing the carbon nano tubes to obtain the catalyst carrier.
According to the preparation method of the catalyst carrier, the slurry containing the carbon nanotubes is formed into the carbon nanotube layer on the surface of the carbon nanotube array film layer, and the porosity of the carbon nanotube layer is smaller than that of the carbon nanotube array film layer, so that the catalyst carrier with a gradient structure can be prepared. The catalyst carrier prepared by the embodiment of the application has a gradient structure, so that the catalyst carrier can form gradient distribution of a catalytic active center, a proton channel and a mass transfer channel when being applied to a catalyst layer, further the utilization rate of the catalytic active center can be fully improved, and the entry of reaction raw materials and the discharge of products can be effectively promoted. In addition, the preparation method of the catalyst carrier has the advantages that the conditions are easy to control, and the stability of the prepared catalyst carrier can be ensured.
The third aspect of the present application provides a composite catalyst, which comprises the catalyst carrier or the catalyst carrier prepared by the preparation method, and further comprises a metal catalyst, wherein the metal catalyst is at least combined on carbon nanotubes in the carbon nanotube layer.
The catalyst carrier that this application contained composite catalyst just has gradient structure, and the quantity of existence of metal catalyst in carbon nanotube array rete is higher than the quantity of existence in the carbon nanotube rete, and then realized the gradient distribution of catalytic activity center, proton passageway, mass transfer passageway, can fully improve the utilization ratio of catalytic activity center, improve composite catalyst's efficiency and catalytic activity center durability, effectively promote the entering of reaction raw materials and the discharge of result, and can reduce composite catalyst's quantity effectively through improving catalytic activity center's utilization ratio, keep good catalytic performance simultaneously.
In a fourth aspect, a method for preparing a composite catalyst is provided, including the following steps:
providing the catalyst carrier or the catalyst carrier prepared by the preparation method;
and mixing the metal catalyst precursor solution with a catalyst carrier, and then carrying out reduction treatment to obtain the composite catalyst.
According to the preparation method of the composite catalyst, the catalyst carrier is immersed into the metal catalyst precursor solution, so that the metal catalyst precursor enters the carbon nanotube array film layer and the carbon nanotube layer and is subjected to in-situ reduction treatment, the porosity of the carbon nanotube array film layer is higher than that of the carbon nanotube layer, so that a gradient structure is formed, the active area and the active site in the carbon nanotube array film layer are higher than those in the carbon nanotube layer, the catalytic active sites, the proton channels and the mass transfer channels are distributed in a gradient manner, the conductivity and the nucleation sites are further improved, the three-phase reaction interface of the catalyst layer is optimized, the comprehensive treatment capacity of mass transfer, conductivity and water management of the catalyst layer is improved, and finally the whole catalytic reaction activity is improved.
A fifth aspect of the present application provides a fuel cell comprising a catalyst layer containing a composite catalyst as hereinbefore described or as prepared by a process for the preparation of a composite catalyst as hereinbefore described.
The fuel cell provided in the present application includes a catalyst layer containing the composite catalyst described above, and the catalyst layer is disposed between the gas diffusion layer and the polymer electrolyte membrane. The method is beneficial to improving the quantity of the catalytic active center, the proton channel and the mass transfer channel in the fuel cell, can prevent the pore canal from being blocked by liquid water in the reaction process in the fuel cell to block gas diffusion, and improves the electrical property and the service life of the fuel cell.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly explain the drawings needed in the description of the embodiments, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the surface of a CNT film according to one embodiment of the present disclosure;
FIG. 2 is an SEM image of the rear surface of a CNT film coating paste according to an embodiment of the present disclosure;
FIG. 3 is a TEM image of a Pt/CNT-MPL catalyst provided in an embodiment of the present application;
FIG. 4 is a TEM image of another Pt/CNT-MPL catalyst provided in embodiments of the present application;
FIG. 5 is a TEM image of a Pt/CNT catalyst provided in the comparative example of the present application;
fig. 6 is a TEM image of another Pt/CNT catalyst provided in the comparative example of the present application.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (a), b, or c)", or "at least one (a, b, and c)", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the specification of the present application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
The terms first and second are used for descriptive purposes only and are not to be construed as indicating or implying any relative importance or number of features indicated in order to distinguish one object from another. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of the embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
Carbon Nanotubes (CNT) are a promising carrier material as a novel carbon-based material due to their corrosion resistance, excellent pore size structure, high specific surface area, high conductivity and good mass transfer properties.
In a first aspect, embodiments of the present application provide a catalyst carrier, including a carbon nanotube array film layer, where the carbon nanotube array film layer is combined with a carbon nanotube layer on a surface of the carbon nanotube array film layer, and a porosity of the carbon nanotube array film layer is higher than a porosity of the carbon nanotube layer.
In order to prevent the catalyst carrier from being corroded, the embodiment of the application provides a catalyst carrier. On one hand, in the embodiment of the application, the carbon nano tube carrier which is corrosion-resistant and high in inertia is used for replacing the carbon black carrier which is easy to corrode, so that the catalyst carrier is prevented from being corroded, further, catalyst aggregation distributed in the catalyst carrier is prevented, and the overall stability and the service life of the composite catalyst are improved. On the other hand, the porosity of the carbon nano tube array film layer and the carbon nano tube layer is higher than that of the carbon black carrier, which is favorable for improving the catalyst attachment site, and the porosity of the carbon nano tube array film layer is higher than that of the carbon nano tube layer so as to form a gradient structure, and compared with the catalytic activity uniformly distributed in the existing carbon black carrier, the gradient distribution of the catalytic active center, the proton channel and the mass transfer channel is realized.
In some embodiments, the pore size of the carbon nanotube array film layer is 100-400 nm, such as 100nm, 200nm, 300nm, 400nm, etc., and the pore size of the carbon nanotube array film layer can be specifically adjusted to meet the requirement of catalyst loading.
In some embodiments, the thickness of the carbon nanotube array film layer is 8-30 μm, such as 8 μm, 10 μm, 15 μm, 30 μm, etc., and the thickness of the carbon nanotube array film layer can be specifically adjusted to meet the requirement of catalyst loading.
In some embodiments, the thickness of the carbon nanotube layer is 5-30 um, such as 10um, 20um, etc., but not limited thereto, and the thicknesses of the carbon nanotube array film layer and the carbon nanotube layer can be specifically adjusted to meet the requirement of catalyst loading.
In some embodiments, the pore size of the carbon nanotube array film layer is 100-400 nm, such as 100nm, 200nm, 400nm, but not limited thereto, and is larger than the pore size of the carbon black carrier, so that the active site amount can be increased, and the pore size of the carbon nanotube array film layer can be larger than the pore size of the carbon nanotube layer, thereby being beneficial to the porosity of the carbon nanotube array film layer being higher than the porosity of the carbon nanotube layer, and further forming a gradient structure.
In some embodiments, the porosity of the carbon nanotube array film layer is 65-80%, which is greater than the porosity of the carbon black support, so that the active site amount can be increased, and the porosity of the carbon nanotube array film layer can also be greater than the porosity of the carbon nanotube layer, thereby facilitating the formation of a gradient structure.
In some embodiments, the pore size of the carbon nanotube layer is 50-100 nm, such as 50nm, 100nm, etc., but not limited thereto, and is larger than the pore size of the carbon black carrier, so that the active site amount can be increased, and the pore size of the carbon nanotube layer can be smaller than the pore size of the carbon nanotube array film layer, so that the porosity of the carbon nanotube array film layer is higher than the porosity of the carbon nanotube layer, and a gradient structure can be formed.
In some embodiments, the carbon nanotubes contained in the carbon nanotube layer have a tube diameter of 5-30 nm, such as 5nm, 20nm, 30nm, etc., and a tube length of 10-50 μm, such as 10 μm, 40 μm, 50 μm, etc., but not limited thereto, and the CNT with strong corrosion resistance and hollow tubular structure is selected to replace the conventional activated carbon or carbon black as the carrier of the fuel cell catalyst, so that the stability of the catalyst carrier can be improved, the catalyst carrier is not easy to corrode, the problem of easy corrosion and agglomeration of the Pt/C catalyst is solved, the catalyst utilization rate is improved, and the production cost is further reduced.
In some embodiments, the porosity of the carbon nanotube layer is 50-70%, which is greater than the porosity of the carbon black support, so that the amount of active sites can be increased, and the porosity of the carbon nanotube layer can be smaller than the porosity of the carbon nanotube array film layer, thereby facilitating the formation of a gradient structure.
In some embodiments, the porosity of the carbon nanotube array film layer is higher than the porosity of the carbon nanotube layer, facilitating the formation of a gradient structure.
In a second aspect, an embodiment of the present application provides a method for preparing a catalyst carrier in the foregoing text, including the following steps:
s10: and forming a carbon nano tube layer on the surface of the carbon nano tube array film layer by using the slurry containing the carbon nano tubes to obtain the catalyst carrier.
In the embodiment of the application, the porosity of the film layer formed by the slurry containing the carbon nanotubes is smaller than the porosity of the carbon nanotube array film layer, so that the carbon nanotube layer is formed on the surface of the carbon nanotube array film layer by the slurry containing the carbon nanotubes, and the catalyst carrier with a gradient structure can be prepared. The catalyst carrier prepared by the embodiment of the application has a gradient structure, so that the catalyst carrier can be applied to a catalyst layer, the gradient distribution of a catalytic active center, a proton channel and a mass transfer channel can be formed, and the carbon nano tube carrier with corrosion resistance and higher inertia is used for replacing the carbon black carrier which is easy to corrode, so that the catalyst carrier can be prevented from being corroded, further, the catalyst distributed in the catalyst carrier is prevented from agglomerating, and the overall stability and the service life of the catalyst are improved. In addition, the preparation method of the catalyst carrier has the advantages that the conditions are easy to control, and the stability of the prepared catalyst carrier can be ensured.
In some embodiments, in order to further improve the corrosion resistance of the carbon nanotube array film layer, the tube diameter of the carbon nanotubes is 5-30 nm, such as 5nm, 20nm, 30nm, etc., the tube length is 10-50 μm, such as 10 μm, 40 μm, 50 μm, etc., and the CNT with strong corrosion resistance and hollow tubular structure is selected to replace the conventional activated carbon or carbon black as the carrier of the fuel cell catalyst, so that the stability of the catalyst carrier can be improved, the catalyst carrier is not easy to corrode, the problem of easy corrosion and agglomeration of the Pt/C catalyst is solved, the catalyst utilization rate is improved, and the production cost is further reduced.
In order to prepare a carbon nanotube array film layer having a higher porosity than the carbon nanotube layer, the method for preparing the carbon nanotube array film layer comprises the following steps:
and carrying out dry film-forming treatment on the carbon nanotube array to obtain a carbon nanotube array film layer, wherein the carbon nanotube array is prepared by a chemical vapor deposition method.
In an exemplary embodiment, the steps for preparing the carbon nanotube array film layer are as follows:
step S11: sequentially depositing a catalyst carrier layer and a catalyst layer on a substrate to obtain a first film layer;
step S12: introducing hydrogen, acetylene and argon into the first film layer for growth treatment to obtain a carbon tube vertical array;
Step S13: and (3) pulling out the carbon nanotube fiber bundles with a certain width in parallel from the carbon nanotube vertical array by using a dry film-making method, and circularly winding to obtain a carbon nanotube array film layer.
According to the method for preparing the carbon nanotube array film layer, the catalyst carrier layer and the catalyst layer are sequentially deposited on the substrate, further, the thickness of the catalyst layer is 0.5-1 nm, the material for forming the catalyst layer comprises Fe, the thickness of the catalyst carrier layer is 10-15 nm, and the material for forming the catalyst carrier layer comprises Al 2 O 3 The catalyst is a carrier of Fe catalyst and also plays a role of a buffer layer of the catalyst, so that a layer of carbon tube vertical array is formed on a substrate by catalyzing hydrogen, acetylene and argon conveniently, the flow of the hydrogen is 0.05L/min, the flow of the acetylene is 0.04L/min, the flow of the argon is 1.5L/min, the temperature of the growth treatment is 800-1000 ℃, and the temperature of the growth treatment is 800-1000 ℃ for 10-20 min. The carbon tube vertical array is obtained after the substrate is separated, the carbon tube vertical array is processed by a dry film drawing method to obtain a carbon nano tube array film layer, and the carbon nano tube prepared by the embodiment of the applicationThe porosity of the tube array film layer is higher than that of the carbon nanotube layer.
In some embodiments, the dry-farad film process comprises the steps of:
and pulling out the carbon nanotubes in parallel from the array, pouring the carbon nanotubes along the action direction of the pulling force, and forming a carbon nanotube array film layer between the carbon nanotubes through Van der Waals force.
Specifically, in the embodiment of the application, a carbon nanotube array with a certain width is selected, carbon nanotubes are pulled out from the array in parallel, and due to the fact that the carbon nanotubes have very strong van der waals force interactions, the carbon nanotubes are poured one by one along the action direction of the pulling force, and the pulled carbon nanotubes with consistent arrangement directions form a carbon nanotube array single film. Further, the carbon nano tube array film layer is formed by laminating 30-500 layers of carbon nano tube array single films densely, the thickness is 5-1000 um, and no angle difference exists between the carbon nano tube array single films during lamination.
In some embodiments, the CNT-containing slurry can be formulated as comprising the steps of:
step S14: carrying out first mixing treatment on the dispersing agent and the solvent to obtain a first solution;
step S15: adding CNT powder into the first solution to perform second mixing treatment to obtain a second solution;
step S16: and carrying out third mixing treatment on the second solution to obtain the slurry of the carbon nano tube.
According to the slurry method of the carbon nano tube, the dispersing agent and the solvent are subjected to the first mixing treatment, further, the temperature of the first mixing treatment is 50-80 ℃, the stirring speed is 40-200 rpm/min, the first solution with high dispersion can be obtained, and the subsequent dispersion of the CNT powder is facilitated. Adding CNT powder into the first solution for second mixing treatment, and further stirring at 8000-15000 rpm/min under normal temperature to obtain primarily dispersed second solution. And (3) carrying out third mixing treatment on the second solution, and further dispersing by using a high-pressure homogenizer, wherein the system pressure is 13-17 bar, the dispersing bin pressure is 1000-1600 bar, and the dispersing times are 5-10, so that the highly dispersed carbon nano tube slurry can be obtained.
In some embodiments, the method further comprises acid leaching the carbon nanotube array film prior to forming the carbon nanotube slurry on the surface of the carbon nanotube array film.
In an embodiment, the acid leaching treatment method for the carbon nanotube array film layer includes the following steps:
step S17: performing acid leaching treatment on the carbon nanotube array film layer by using concentrated sulfuric acid to obtain a second film layer;
step S18: washing the second film layer until the PH of the solution is neutral to obtain a third film layer;
Step S19: and drying the third film layer to obtain the carbon nanotube array film after impurity removal.
According to the acid leaching treatment method provided by the embodiment of the application, the concentrated sulfuric acid is used for carrying out acid leaching treatment on the carbon nanotube array film layer, so that the modification of the carbon nanotube array film layer can be realized, impurities inside the carbon nanotube array film layer are removed, the hydrophilicity of the carbon nanotube array film layer is improved, defects of the carbon nanotube array film layer and nucleation sites of a catalyst can be increased, and the catalyst can be conveniently dispersed. Further, the acid leaching treatment time is 15-30 min. And washing the second membrane substance until the pH of the solution is neutral, and drying the third membrane substance to avoid the impurities from affecting the catalysis effect of the carbon nanotube array membrane layer. Further, the temperature of the drying treatment is 50-80 ℃ and the time is 1-2 h.
In an embodiment, the method for forming the carbon nanotube layer on the surface of the carbon nanotube array film layer by using the slurry of the carbon nanotubes may be spraying. Of course, other ways of forming the film are also possible.
In the embodiment of the application, the carbon nano tube layer can be uniformly formed on the surface of the carbon nano tube array film layer by adopting a slurry spraying method. Further, spreading the carbon nanotube array film layer on a spraying flat plate, filling the slurry of the carbon nanotubes into a spray gun container, placing a spray gun opening right above the carbon nanotube array film layer, and spraying the carbon nanotube array film layer at a constant speed for 3-5 times to obtain a fifth film substance; and baking the fifth membrane material at 70-90 ℃ for 30-60 min to obtain the catalyst carrier.
In some embodiments, the slurry containing carbon nanotubes may form a carbon nanotube layer on one surface of the carbon nanotube array film layer, or may form carbon nanotube layers on two opposite surfaces of the carbon nanotube array film layer at the same time, where the thickness of the single-layer slurry is 10-30 μm, and may be set according to practical requirements.
In a third aspect, embodiments of the present application provide a composite catalyst, including the catalyst carrier described above or the catalyst carrier prepared by the preparation method described above, and further including a metal catalyst, where the metal catalyst is at least bonded to carbon nanotubes in the carbon nanotube layer.
The composite catalyst can realize gradient distribution of the catalytic active center, the proton channel and the mass transfer channel, so that the utilization rate of the catalytic active center can be fully improved, the entry of reaction raw materials and the discharge of products can be effectively promoted, for example, the blocking of pore channels by liquid water in the reaction process can be prevented to obstruct gas diffusion, the efficiency of a catalytic layer and the durability of the catalytic active center are improved, the loading capacity and the utilization rate of the catalyst are improved, the waste of the catalyst is reduced, and the cost is further reduced, for example, if the catalytic active center is noble metal, the consumption of the catalyst can be effectively reduced by improving the utilization rate of the catalytic active center, and meanwhile, the good catalytic performance is maintained, so that the raw material cost of the catalytic layer is effectively reduced.
In some embodiments, the metal catalyst comprises at least one of Pt, ru, rh, ir, which can be used in a fuel cell. Further, pt can catalyze electrochemical reactions of hydrogen and oxygen, oxygen reduction reactions and hydrogen oxidation reactions, hydrogen is decomposed into protons, electrons are released, the electrons reach a cathode through an external circuit, and a cathode catalytic layer catalyzes electrochemical reactions of protons and oxygen to obtain electrons to generate water.
In some embodiments, the catalyst carrier in the foregoing description is not corroded, the aggregation of catalyst particles is reduced, the particle size of the particles contained in the metal catalyst is 2-5 nm, the particle size of the metal catalyst particles is suitable for increasing the loading amount of the metal catalyst on the catalyst carrier, and a suitable catalytic activity surface area is provided, which is beneficial for improving the catalytic reaction rate and improving the electrochemical performance of the fuel cell. Further, the content of the metal catalyst is 10-60 wt%, such as 20wt%, and the content of the metal catalyst is suitable, which is beneficial to improving the catalytic reaction rate, improving the electrochemical performance of the fuel cell and facilitating the gas transmission.
In a fourth aspect, a method for preparing a catalyst is provided, including the following steps:
Step S20: providing the catalyst carrier or the catalyst carrier prepared by the preparation method;
step S30: and mixing the metal catalyst precursor solution with a catalyst carrier, and then carrying out reduction treatment to obtain the composite catalyst.
According to the preparation method of the composite catalyst, the catalyst carrier is immersed into the metal catalyst precursor solution, so that the metal catalyst precursor enters the carbon nano tube array film layer and the carbon nano tube layer and is subjected to in-situ reduction treatment, and as the porosity of the carbon nano tube array film layer is higher than that of the carbon nano tube layer, a gradient structure is formed, the active area and the active site in the carbon nano tube array film layer are higher than those in the carbon nano tube layer, and the catalytic active center, the proton channel and the mass transfer channel are distributed in a gradient manner, so that the conductivity and the nucleation site are improved, the three-phase reaction interface of the catalyst layer is optimized, the comprehensive treatment capacity of mass transfer, conductivity and water management of the catalyst layer is improved, and the whole catalytic reaction activity is finally improved.
Step S20:
in step S20, the catalyst carrier includes a carbon nanotube array film layer, and the carbon nanotube array film layer is bonded to the surface of the carbon nanotube array film layer, and the porosity of the carbon nanotube array film layer is higher than that of the carbon nanotube layer, but is not limited thereto.
Step S30:
in step S30, the metal catalyst precursor includes chloroplatinic acid, platinum acetylacetonate, platinum chloride, tetraamineplatinum acetate, and platinum nitrateAt least one of palladium dichloride, sodium tetrachloropalladate, chloroauric acid, gold chloride, triphenylphosphine gold chloride, rhodium acetate, rhodium nitrate, ruthenium chloride, ruthenium acetate, ruthenium nitrate, chloroiridic acid, ammonium chloroiridate and iridium nitrate. The platinum ion, the gold ion, the ruthenium ion and the iridium ion contained in the metal catalyst precursor can be reduced into Pt, ru, rh, ir simple substance, and can be used as a catalyst in subsequent reactions. For example, H 2 PtCl 6 The Pt ions contained in the catalyst can be reduced into Pt simple substance, and can be used as a catalyst for reaction in a fuel cell.
In some embodiments, an alkaline reagent is also used in the reduction reaction, and the alkali used in the alkaline reagent includes NaOH,
At least one of the KOH and the alkaline reagent can adjust the pH value in the reduction treatment system, for example, the pH value is adjusted to 9, and a proper reaction environment is provided for reducing Pt ions to generate Pt simple substance.
In some embodiments, the reduction reaction is further followed by a de-impurity treatment. Further, the impurity removal treatment 5 includes a drying treatment and a washing treatment.
In a fifth aspect, embodiments herein provide a fuel cell comprising a catalyst layer comprising a composite catalyst as described above or a composite catalyst prepared as described above by a method of preparing a composite catalyst.
The fuel cell provided in the embodiment of the present application includes a catalyst layer containing the composite catalyst described in the above 0, and the catalyst layer is provided between the gas diffusion layer and the polymer electrolyte membrane. The method is beneficial to improving the quantity of the catalytic active center, the proton channel and the mass transfer channel in the fuel cell, can prevent the pore canal from being blocked by liquid water in the reaction process in the fuel cell to block gas diffusion, and improves the electrical property and the service life of the fuel cell.
In some embodiments, a carbon nanotube layer is formed on one surface of the carbon nanotube array film layer, the carbon nanotube array 5 film layer is close to the polymer electrolyte membrane, and as the porosity of the carbon nanotube array film layer in the catalytic layer is higher than that of the carbon nanotube layer, the carbon nanotube array film layer is distributed with more catalyst sites, and further has relatively higher catalytic activity center density near the polymer electrolyte membrane than at the other end, so that the problem that the characteristic of heterogeneous chemical reaction in the catalytic layer requires relatively higher catalytic activity center density near the polymer electrolyte membrane than at the other end is solved.
0 is such that the implementation details and operation of the present application described above are clearly understood by those skilled in the art, and
the catalyst carrier and the preparation method thereof, the composite catalyst and the preparation method and application thereof have remarkable improvement performances, and the technical scheme is exemplified by a plurality of examples.
1 catalyst carrier and method for producing the same
Example A1
5 this example provides a catalyst support and a method of preparing the same. The catalyst carrier of this embodiment includes a carbon nanotube array film layer, a carbon nanotube layer is bonded on the surface of the carbon nanotube array film layer, the porosity of the carbon nanotube array film layer is 70%, the porosity of the carbon nanotube layer is 65%, wherein the aperture of the carbon nanotube array film layer is 150nm, the aperture of the carbon nanotube layer is 50nm, the thickness of the carbon nanotube layer is 40 μm, and the thickness of the carbon nanotube array film layer is 20 μm.
The catalyst carrier preparation method of this example is as follows:
s1, preparing a carbon nano tube array film:
step S11: al with thickness of 15nm is deposited on the silicon wafer substrate in sequence by utilizing the electron beam evaporation technology 2 O 3 And a Fe catalyst with the thickness of 1nm is added into a tube furnace, and hydrogen, acetylene and argon are introduced, wherein the air flow rates are respectively 0.05L/min, 0.04L/min and 1.5L/min, and the multi-wall carbon tube vertical array is prepared by growing for 20min at the high temperature of 800 ℃;
Step S12: and (3) pulling out the carbon nanotube fiber bundles with a certain width in parallel from the carbon nanotube vertical array by utilizing a dry film-making process, circularly rolling, and then compacting to obtain a carbon nanotube array film layer with the thickness of 20 mu m.
S2, preparing slurry containing carbon nano tubes:
step S21: the dispersing agent PVP accounts for 2 percent, the solvent NMP, the pipe diameter of the CNT powder is 7-15 nm, the pipe length is 10-20 mu m, and the dispersing agent PVP accounts for 5 percent, so as to obtain a first solution;
step S22: the PVP dispersing agent is added into the NMP to be stirred uniformly at a low speed, the temperature is 50 ℃, and the stirring speed is 200rpm/min, so that a second solution is obtained;
step S23: then adding CNT powder, stirring at high speed to finish preliminary dispersion under normal temperature condition, stirring at 10000rpm/min to obtain carbon nanotube slurry;
step S24: and then further dispersing by using a high-pressure homogenizer, wherein the system pressure is 17bar, the dispersing bin pressure is 1000bar, and the dispersing times are 5 times, so as to obtain the slurry of the carbon nano tube.
S3, pickling the carbon nanotube array film:
step S31: soaking the carbon nanotube array film layer in concentrated sulfuric acid for 20min, and removing impurities to obtain a second film substance;
step S32: repeatedly cleaning the CNT film with deionized water until the PH of the solution is neutral to obtain a third film substance;
Step S33: putting the cleaned CNT film into a baking oven, and baking at 80 ℃ for 1h to obtain a fourth film substance;
s4, forming a film on the carbon nano tube film by the slurry containing the carbon nano tubes;
step S41: spreading a carbon nano tube array film layer on a spraying flat plate, filling the slurry of the carbon nano tube into a spray gun container, placing a spray gun opening right above the CNT film, and spraying the carbon nano tube array film layer on one side of the CNT film at a constant speed for 10 times to obtain a fifth film substance, wherein the thickness of the carbon nano tube layer is 40 mu m;
step S42: and (3) putting the fifth film material into an oven, and baking at 90 ℃ for 60min to obtain the CNT gradient film, wherein the CNT gradient film is marked as CNT-MPL.
Example A2
The present embodiment provides a catalyst carrier and a method for preparing the same. The catalyst carrier of this embodiment includes a carbon nanotube array film layer, a carbon nanotube layer is bonded on the surface of the carbon nanotube array film layer, the porosity of the carbon nanotube array film layer is 80%, the porosity of the carbon nanotube layer is 60%, wherein the aperture of the carbon nanotube array film layer is 300nm, the aperture of the carbon nanotube layer is 75nm, the thickness of the carbon nanotube layer is 30 μm, and the thickness of the carbon nanotube array film layer is 20 μm.
The catalyst carrier preparation method of this example is as follows:
s1, preparing a carbon nano tube array film:
Step S11: al with thickness of 15nm is deposited on the silicon wafer substrate in sequence by utilizing the electron beam evaporation technology 2 O 3 And a Fe catalyst with the thickness of 1nm is added into a tube furnace, and hydrogen, acetylene and argon are introduced, wherein the air flow rates are respectively 0.05L/min, 0.04L/min and 1.5L/min, and the multi-wall carbon tube vertical array is prepared by growing for 20min at the high temperature of 800 ℃;
step S12: and (3) pulling out the carbon nanotube fiber bundles with a certain width in parallel from the carbon nanotube vertical array by utilizing a dry film-making process, circularly rolling, and then compacting to obtain a carbon nanotube array film layer with the thickness of 20 mu m.
S2, preparing slurry containing carbon nano tubes:
step S21: the dispersing agent PVP accounts for 2 percent, the solvent NMP and the CNT powder have the pipe diameter of 7-15 nm and the pipe length of 10-20 mu m and account for 4.95 percent, so as to obtain a first solution;
step S22: the PVP dispersing agent is added into the NMP to be stirred uniformly at a low speed, the temperature is 50 ℃, and the stirring speed is 200rpm/min, so that a second solution is obtained;
step S23: then adding CNT powder, stirring at high speed to finish preliminary dispersion under normal temperature condition, stirring at 10000rpm/min to obtain carbon nanotube slurry;
step S24: and then further dispersing by using a high-pressure homogenizer, wherein the system pressure is 17bar, the dispersing bin pressure is 1000bar, and the dispersing times are 5 times, so as to obtain the slurry of the carbon nano tube.
S3, pickling the carbon nanotube array film:
step S31: soaking the carbon nanotube array film layer in concentrated sulfuric acid for 20min, and removing impurities to obtain a second film substance;
step S32: repeatedly cleaning the CNT film with deionized water until the PH of the solution is neutral to obtain a third film substance;
step S33: putting the cleaned CNT film into a baking oven, and baking at 80 ℃ for 1h to obtain a fourth film substance;
s4, forming a film on the carbon nano tube film by the slurry containing the carbon nano tubes;
step S41: spreading a carbon nanotube array film layer on a spraying flat plate, filling the slurry of the carbon nanotubes into a spray gun container, placing a spray gun opening right above the CNT film, and spraying at a constant speed for 8 times against one side of the CNT film to obtain a fifth film substance, wherein the thickness of the carbon nanotube layer is 30 mu m;
step S42: and (3) putting the fifth film material into an oven, and baking at 90 ℃ for 60min to obtain the CNT gradient film, wherein the CNT gradient film is marked as CNT-MPL.
Example A3
The present embodiment provides a catalyst carrier and a method for preparing the same. The catalyst carrier of this embodiment includes a carbon nanotube array film layer, a carbon nanotube layer is bonded on the surface of the carbon nanotube array film layer, the porosity of the carbon nanotube array film layer is 75%, the porosity of the carbon nanotube layer is 65%, where the aperture of the carbon nanotube array film layer is 250nm, the aperture of the carbon nanotube layer is 100nm, the thickness of the carbon nanotube layer is 20 μm, and the thickness of the carbon nanotube array film layer is 20 μm.
The catalyst carrier preparation method of this example is as follows:
s1, preparing a carbon nano tube array film:
step S11: al with thickness of 15nm is deposited on the silicon wafer substrate in sequence by utilizing the electron beam evaporation technology 2 O 3 And a Fe catalyst with the thickness of 1nm is added into a tube furnace, and hydrogen, acetylene and argon are introduced, wherein the air flow rates are respectively 0.05L/min, 0.04L/min and 1.5L/min, and the multi-wall carbon tube vertical array is prepared by growing for 20min at the high temperature of 800 ℃;
step S12: and (3) pulling out the carbon nanotube fiber bundles with a certain width in parallel from the carbon nanotube vertical array by utilizing a dry film-making process, circularly rolling, and then compacting to obtain a carbon nanotube array film layer with the thickness of 30 mu m.
S2, preparing slurry containing carbon nano tubes:
step S21: the dispersing agent PVP accounts for 2 percent, the solvent NMP, the pipe diameter of the CNT powder is 7-15 nm, the pipe length is 10-20 mu m, and the proportion is 4.9 percent, so as to obtain a first solution;
step S22: the PVP dispersing agent is added into the NMP to be stirred uniformly at a low speed, the temperature is 50 ℃, and the stirring speed is 200rpm/min, so that a second solution is obtained;
step S23: then adding CNT powder, stirring at high speed to finish preliminary dispersion under normal temperature condition, stirring at 10000rpm/min to obtain carbon nanotube slurry;
step S24: and then further dispersing by using a high-pressure homogenizer, wherein the system pressure is 17bar, the dispersing bin pressure is 1000bar, and the dispersing times are 5 times, so as to obtain the slurry of the carbon nano tube.
S3, pickling the carbon nanotube array film:
step S31: soaking the carbon nanotube array film layer in concentrated sulfuric acid for 20min, and removing impurities to obtain a second film substance;
step S32: repeatedly cleaning the CNT film with deionized water until the PH of the solution is neutral to obtain a third film substance;
step S33: putting the cleaned CNT film into a baking oven, and baking at 80 ℃ for 1h to obtain a fourth film substance;
s4, forming a film on the carbon nano tube film by the slurry containing the carbon nano tubes;
step S41: spreading a carbon nano tube array film layer on a spraying flat plate, filling the slurry of the carbon nano tube into a spray gun container, placing a spray gun opening right above the CNT film, and spraying the single surface of the CNT film at a constant speed for 5 times to obtain a fifth film substance, wherein the thickness of the carbon nano tube layer is 20 mu m;
step S42: and (3) putting the fifth film material into an oven, and baking at 90 ℃ for 60min to obtain the CNT gradient film, wherein the CNT gradient film is marked as CNT-MPL.
2 composite catalyst carrier and preparation method thereof
Comparative example A1
The carbon nanotube array film was prepared according to step S1 of example A1.
Comparative example A2
The carbon nanotube-containing paste was coated into a carbon nanotube layer according to step S2 of example A1.
Comparative example A3
Black carbon.
Example B1
The embodiment provides a Pt/CNT-MPL catalyst and a preparation method thereof.
The Pt/CNT-MPL catalyst of this embodiment includes the catalyst carrier and the combined metal catalyst provided in embodiment A1, the catalyst carrier includes a carbon nanotube array film layer and a carbon nanotube layer, the metal catalyst is at least combined on carbon nanotubes in the carbon nanotube array film layer, the carbon nanotube array film layer has a surface combined with the carbon nanotube layer, the porosity of the carbon nanotube array film layer is higher than that of the carbon nanotube layer, wherein the aperture of the carbon nanotube array film layer is 200nm, the thickness of the carbon nanotube layer is 30 μm, the metal catalyst includes Pt, the particle size of the metal catalyst particles is 3-5 nm, and the content of the metal catalyst is 20wt%.
The preparation method of the composite catalyst of the embodiment is as follows:
step S51: providing the catalyst support of example A1;
step S61: 50ml of ethylene glycol, 4.56ml of 0.01mol/L H are added in sequence 2 PtCl 6 The solution was placed in a beaker and the pH was adjusted to 9 with 1mol/L NaOH aqueous solution;
step S62: adding 80mg of CNT-MPL, and performing ultrasonic treatment until the mixture is uniformly dispersed;
step S63: heating by adopting a modified microwave oven (adding 10 times, heating for 30s each time);
step S64: after the reaction was completed, the product was filtered, washed with acetone and deionized water, and dried overnight at 80 ℃ for use, labeled Pt/CNT-MPL.
Example B2
The embodiment provides a Pt/CNT-MPL catalyst and a preparation method thereof.
The Pt/CNT-MPL catalyst of this embodiment includes the catalyst carrier and the combined metal catalyst provided in embodiment A1, the catalyst carrier includes a carbon nanotube array film layer and a carbon nanotube layer, the metal catalyst is at least combined on carbon nanotubes in the carbon nanotube array film layer, the carbon nanotube array film layer has a surface combined with the carbon nanotube layer, the porosity of the carbon nanotube array film layer is higher than that of the carbon nanotube layer, wherein the aperture of the carbon nanotube array film layer is 250nm, the thickness of the carbon nanotube layer is 30 μm, the metal catalyst includes Pt, the particle size of the metal catalyst particles is 3-5 nm, and the content of the metal catalyst is 30wt%.
The preparation method of the composite catalyst of the embodiment is as follows:
step S51: providing the catalyst support of example A1;
step S61: 50ml of ethylene glycol, 4.56ml of 0.015mol/L H are added in sequence 2 PtCl 6 The solution was placed in a beaker and the pH was adjusted to 9 with 1mol/L NaOH aqueous solution;
step S62: adding 80mg of CNT-MPL, and performing ultrasonic treatment until the mixture is uniformly dispersed;
step S63: heating by adopting a modified microwave oven (adding 10 times, heating for 30s each time);
step S64: after the reaction was completed, the product was filtered, washed with acetone and deionized water, and dried at 80℃for 5 overnight use, labeled Pt/CNT-MPL.
Example B3
The embodiment provides a Pt/CNT-MPL catalyst and a preparation method thereof.
The Pt/CNT-MPL catalyst of this embodiment includes the catalyst carrier and the combined metal catalyst provided in embodiment A1, the catalyst carrier includes a carbon nanotube array film layer and a carbon nanotube layer, the metal catalyst 0 is combined at least on carbon nanotubes in the carbon nanotube array film layer, the carbon nanotube array film layer has a surface combined with the carbon nanotube layer, the porosity of the carbon nanotube array film layer is higher than that of the carbon nanotube layer, wherein the aperture of the carbon nanotube array film layer is 300nm, the thickness of the carbon nanotube layer is 30 μm, the metal catalyst includes Pt, the particle size of the metal catalyst particles is 3-5 nm, and the content of the metal catalyst is 40wt%.
The preparation method of the composite catalyst of the embodiment is as follows: step 5S 51: providing the catalyst support of example A1;
step S61: 50ml of ethylene glycol, 4.56ml of 0.02mol/L H are added in sequence 2 PtCl 6 SolutionInto a beaker, the pH was adjusted to 9 with 1mol/L NaOH aqueous solution;
step S62: adding 80mg of CNT-MPL, and performing ultrasonic treatment until the mixture is uniformly dispersed;
step S63: heating by adopting a modified microwave oven (adding 10 times, heating for 30s each time); 0 step S64: after the reaction was completed, the product was filtered, washed with acetone and deionized water, and dried overnight at 80 ℃ for use, labeled Pt/CNT-MPL.
Comparative example B1
The Pt catalyst on the support of comparative example A1, pt/MPL, metal catalyst content was less than 20wt% according to the method of steps S61 to S64 in example B1.
Comparative example B2
The Pt catalyst on the support of comparative example A2, pt/MPL, metal catalyst content was less than 20wt% according to the method of steps S61 to S64 in example B2.
Comparative example B3
The Pt catalyst on the support of comparative example A3, pt/MPL, metal catalyst content was less than 20wt% according to the method of steps S61 to S64 in example B3.
In summary, in examples B1 to B3 and comparative examples B1 to B3, the content of the metal catalyst in examples B1 to B3 was higher than that in comparative examples B1 to B3, indicating that the content of the metal catalyst in examples B1 to B3 was higher.
Fig. 1 is an SEM image of the surface of the carbon nanotube array film in example B1, and fig. 2 is an SEM image of the surface of the carbon nanotube array film in example B1 after the coating slurry, in which the porosity of the carbon nanotube array film after the coating slurry is smaller than that of the carbon nanotube array film, thereby forming a gradient structure.
Fig. 3 is a TEM image of the Pt/CNT-MPL catalyst of example B1, and fig. 4 is a partial enlarged view of fig. 3, showing that the metal particles are well dispersed and uniform, and have a diameter of 10-20 nm, and the electrical properties of the catalyst are tested, which has good electrochemical characteristics, a high initial voltage of 0.89v and a half-wave voltage of 0.79v. Fig. 5 is a TEM image of the Pt/CNT catalyst of comparative example B1, and fig. 6 is a partial enlarged view of fig. 5, showing the occurrence of significant catalyst particle agglomerate grains, with some large catalyst particles of tens of nm or even nearly 200nm, and further, the Pt/CNT-MPL catalyst of example B1, which can increase the composite catalyst active area and active sites on the catalyst layer.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.

Claims (10)

1. The catalyst carrier is characterized by comprising a carbon nano tube array film layer, wherein the surface of the carbon nano tube array film layer is combined with a carbon nano tube layer, and the porosity of the carbon nano tube array film layer is higher than that of the carbon nano tube layer so as to form a gradient structure;
the porosity of the carbon nano tube array film layer is 65-80%;
the porosity of the carbon nano tube layer is 50-70%.
2. The catalyst support of claim 1, wherein the carbon nanotube array film layer has a thickness of 8 to 30 μm;
or/and the aperture of the carbon nano tube array film layer is 100-400 nm;
or/and the aperture of the carbon nano tube layer is 50-100 nm;
or/and the thickness of the carbon nano tube layer is 5-30 mu m;
or/and the pipe diameter of the carbon nano-tube contained in the carbon nano-tube layer is 5-30 nm, and the pipe length is 10-50 mu m;
or/and the porosity of the carbon nano tube array film layer is 10-16% higher than that of the carbon nano tube layer.
3. A method for preparing the catalyst carrier according to claim 1 or 2, comprising the steps of:
forming a carbon nanotube layer on the surface of the carbon nanotube array film layer by using the slurry containing the carbon nanotubes to obtain a catalyst carrier with a gradient structure;
the porosity of the carbon nano tube array film layer is 65-80%;
the porosity of the carbon nano tube layer is 50-70%.
4. The method for preparing a catalyst carrier according to claim 3, further comprising the step of preparing a carbon nanotube array film layer by:
and carrying out dry film-making treatment on the carbon nanotube array to obtain a carbon nanotube array film layer, wherein the carbon nanotube array is prepared by chemical vapor deposition.
5. The method of preparing a catalyst support according to claim 3 or 4, further comprising the step of acid leaching the carbon nanotube array film layer before forming the carbon nanotube layer.
6. The method for preparing a catalyst carrier according to claim 3 or 4, wherein the carbon nanotube layer is formed on the surface of the carbon nanotube array film layer by spraying the slurry.
7. A composite catalyst comprising the catalyst support of claim 1 or 2 or the catalyst support prepared by the method of any one of claims 3 to 6, and a metal catalyst bound to the catalyst support.
8. The composite catalyst of claim 7, wherein the metal catalyst comprises at least one of Pt, ru, rh, ir;
or/and the particle size of the particles contained in the metal catalyst is 2-5 nm;
or/and the content of the metal catalyst is 10-60 wt%.
9. The preparation method of the composite catalyst is characterized by comprising the following steps:
providing a catalyst support according to claim 1 or 2 or a catalyst support prepared by a method according to any one of claims 3 to 6;
and mixing the metal catalyst precursor solution with the catalyst carrier, and then carrying out reduction treatment to obtain the composite catalyst.
10. A fuel cell comprising a catalyst layer containing the composite catalyst according to claim 7 or 8 or the composite catalyst produced by the production method of the composite catalyst according to claim 9.
CN202211592654.9A 2022-12-08 2022-12-08 Catalyst carrier, composite catalyst, preparation method and application thereof Active CN116002665B (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1356260A (en) * 2001-09-26 2002-07-03 复旦大学 Process for preparing nano carbon tubes arranged in array
CN101239712A (en) * 2007-02-09 2008-08-13 清华大学 Carbon nano-tube thin film structure and preparation method thereof
CN101465434A (en) * 2007-12-19 2009-06-24 清华大学 Fuel battery membrane electrode and preparation method thereof
CN101471443A (en) * 2007-12-28 2009-07-01 汉能科技有限公司 Fuel battery gaseous diffusion layer, electrode, membrane electrode component, electric stack and preparation method thereof
CN102318111A (en) * 2009-07-17 2012-01-11 佛罗里达州立大学研究基金有限公司 Catalytic electrode with gradient porosity and catalyst density for fuel cells
CN103771387A (en) * 2012-10-19 2014-05-07 清华大学 Preparation method for carbon nanotube film
CN108539206A (en) * 2018-03-30 2018-09-14 江苏大学 A kind of Catalytic Layer orderly fuel cell electrode and membrane electrode entirely
CN110289423A (en) * 2019-05-17 2019-09-27 同济大学 A kind of membrane electrode with catalyst gradient

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1356260A (en) * 2001-09-26 2002-07-03 复旦大学 Process for preparing nano carbon tubes arranged in array
CN101239712A (en) * 2007-02-09 2008-08-13 清华大学 Carbon nano-tube thin film structure and preparation method thereof
CN101465434A (en) * 2007-12-19 2009-06-24 清华大学 Fuel battery membrane electrode and preparation method thereof
CN101471443A (en) * 2007-12-28 2009-07-01 汉能科技有限公司 Fuel battery gaseous diffusion layer, electrode, membrane electrode component, electric stack and preparation method thereof
CN102318111A (en) * 2009-07-17 2012-01-11 佛罗里达州立大学研究基金有限公司 Catalytic electrode with gradient porosity and catalyst density for fuel cells
CN103771387A (en) * 2012-10-19 2014-05-07 清华大学 Preparation method for carbon nanotube film
CN108539206A (en) * 2018-03-30 2018-09-14 江苏大学 A kind of Catalytic Layer orderly fuel cell electrode and membrane electrode entirely
CN110289423A (en) * 2019-05-17 2019-09-27 同济大学 A kind of membrane electrode with catalyst gradient

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张济忠等.《现代薄膜技术》.冶金工业出版社,2009,第349页. *

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