CN111117349A - Catalyst ink, preparation method thereof, fuel cell and vehicle - Google Patents

Catalyst ink, preparation method thereof, fuel cell and vehicle Download PDF

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Publication number
CN111117349A
CN111117349A CN201811278676.1A CN201811278676A CN111117349A CN 111117349 A CN111117349 A CN 111117349A CN 201811278676 A CN201811278676 A CN 201811278676A CN 111117349 A CN111117349 A CN 111117349A
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Prior art keywords
catalyst
solvent
carbon
linking agent
catalyst ink
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CN201811278676.1A
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金东一
黄仁哲
张家海
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Great Wall Motor Co Ltd
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Great Wall Motor Co Ltd
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Priority to CN201811278676.1A priority Critical patent/CN111117349A/en
Publication of CN111117349A publication Critical patent/CN111117349A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/108—Hydrocarbon resins
    • 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
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention provides catalyst ink, a preparation method thereof, a fuel cell and an automobile. The catalyst ink includes: the catalyst comprises a carbon-based carrier with a porous structure and an active metal loaded on the carbon-based carrier, wherein the connecting agent is attached to the outer surface of the catalyst and the porous structure. After the catalyst layer is formed by spraying and other methods, the connecting agent can be uniformly loaded on the surface layer and the porous structure of the catalyst particles or uniformly distributed among the catalyst particles. Thus, the catalytic performance of the catalyst layer prepared by using the catalyst ink can be improved.

Description

Catalyst ink, preparation method thereof, fuel cell and vehicle
Technical Field
The invention relates to the field of energy and materials, in particular to catalyst ink and a preparation method thereof, a fuel cell and a vehicle.
Background
With the exhaustion and consumption of traditional energy sources, green energy storage devices and various green batteries have received extensive attention from researchers. The fuel cell converts chemical energy of fuel into electric energy through electrochemical reaction without the limitation of Carnot cycle effect, so that the fuel cell has the advantages of high energy conversion efficiency, less harmful gas pollution and the like. Although fuel cells are currently commercialized, there is still a need for further cost reduction. Since the fuel cell needs to convert chemical energy in fuel through an electrochemical oxidation-reduction reaction, it is necessary to use a catalyst capable of catalyzing the corresponding oxidation-reduction reaction. The active metal of the catalyst is generally a noble metal, so that one direction of reducing the production cost of the fuel cell is to reduce the catalyst content of the catalyst layer in the electrode of the cell. For example, the catalyst may be formed by using a support having a nanostructure to increase the contact area of an active catalytic component with an ion conductor, thereby increasing the catalytic effect, or the catalytic performance of a porous catalyst on which an active metal is supported may be increased by adding a particle conductor formed of a functionalized polymer. The catalyst mixture having the above structure and composition can be generally prepared into a catalyst ink which facilitates film formation by a process such as spraying. Therefore, in a large-scale production process, it is very important to ensure long-term stability of the catalytic ink (catalyst ink).
However, the catalyst ink for fuel cells, and the method of preparing the electrode catalyst layer, have yet to be improved.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a catalyst ink and a method for preparing a catalyst layer using the same, so as to form a catalyst layer having a catalyst that can be uniformly covered with a linking agent.
To achieve the above object, in one aspect of the present invention, a catalyst ink is provided. The catalyst ink includes: the catalyst comprises a carbon-based carrier with a porous structure and an active metal loaded on the carbon-based carrier, and the connecting agent is attached to the outer surface of the catalyst and the porous structure.
Further, the solvent has a boiling point of 70-150 ℃, a viscosity of 0.5-5mPa & s, and is miscible in water or soluble in water more than 150g/dm3。
Further, the monohydric alcohol includes a straight or branched chain monohydric alcohol having 1 to 10 carbon atoms, and the dihydric alcohol includes a straight or branched chain dihydric alcohol having 1 to 15 carbon atoms.
Further, the solvent further comprises at least one of dimethyl sulfoxide, sulfolane, N-dimethylformamide, N-methylacetamide, N-methylpyrrolidone and methylethylketone.
Further, the linking agent includes a polymer including at least one of O, S, F.
Further, the polymer has a density of 1.6 to 2.2g/cm3。
Further, the linking agent includes at least one of fluorinated ethylene propylene copolymer, polytetrafluoroethylene, polyvinylidene fluoride, perfluorosulfonic acid, and perfluoroimide acid.
Further, the polymer further comprises at least one of the following structures: a branch containing 1-10 carbon atoms, and an electron-rich functional group, wherein the equivalent value of the electron-rich functional group is 500-1000.
Further, the catalyst ink includes an additive, the solvent may form an azeotropic mixture with the catalyst, the linking agent, and the additive, the additive includes at least one of a viscosity reducer, a tackifier, a stabilizer, and a scavenger, and the additive is included in an amount of 0.01 wt% to 1 wt% based on the total mass of the catalyst ink.
Further, in the above-mentioned case,the additive comprises benzyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxymethyl cellulose, glycerol-26, propylene carbonate and TiO2、RuO2、CeO2、IrO2、SiO2、ZrO2、WO3、CeZrO2、OsO2、VxOy、NiO、Fe2O3、CoO、Al2O3、Rb2O、NdxOy、Rh2O3、YxOy、YbxOy、TbO2、CrOyMoO and MnxOyWherein x and y are determined according to the chemical valence of the above-mentioned metal element and oxygen element, and, as specific, x may be 1 to 2 and y may be 1 to 3, in other words, 1. ltoreq. x.ltoreq.2 and 1. ltoreq. y.ltoreq.3.
Compared with the prior art, the catalyst ink provided by the invention has at least the following advantages:
after the catalyst layer is formed by spraying or other methods, the connecting agent can be uniformly loaded on the surface layer and the porous structure of the catalyst particles or uniformly distributed among the catalyst particles. Thus, the catalytic performance of the catalyst layer prepared by using the catalyst ink can be improved.
In another aspect of the present invention, the present invention provides a method of preparing the catalyst ink set forth above. The method comprises the following steps: mixing a catalyst, a linking agent and a first solvent to form an azeotropic mixture and drying, the catalyst comprising a carbon-based support having a porous structure, and an active metal supported on the carbon-based support, to remove the first solvent and allow the linking agent to adhere to an outer surface of the catalyst and the porous structure, obtaining a catalyst block; and crushing the catalyst block in a second solvent containing the connecting agent, and stirring and mixing the crushed catalyst and the second solvent to obtain the catalyst ink.
Further, the step of obtaining a catalyst block further comprises: mixing a solution containing the catalyst, the connecting agent and the first solvent, and stirring under the conditions of constant temperature and constant pressure, wherein the mass ratio of carbon elements in the connecting agent to carbon elements in the catalyst is 0.5-0.9, and the solid content of the mixture formed after mixing is 5-50%; drying the mixture, and enabling the solid content of the catalyst block obtained after drying to be 10% -92%.
Further, the first solvent includes at least one of water, monohydric alcohol and dihydric alcohol, and the first solvent may form an azeotropic mixture with the catalyst and the linking agent, and the first solvent further includes an optional additive.
Further, the second solvent has the same chemical composition as the first solvent.
In yet another aspect of the present invention, a catalyst layer for a fuel cell is provided. The catalyst layer is obtained on the basis of the catalyst ink described above.
In yet another aspect of the present invention, a fuel cell is provided. The fuel cell includes the catalyst layer described above.
In yet another aspect of the present invention, a vehicle is presented. The vehicle includes the fuel cell described above.
Drawings
Fig. 1 shows a schematic flow diagram of a method of preparing a catalyst ink according to one embodiment of the present invention.
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. Unless otherwise specified, the following percentage contents are all mass percentage contents.
In one aspect of the invention, a catalyst ink is provided. According to an embodiment of the present invention, the catalyst ink includes: a catalyst, a linking agent, and a solvent. Wherein the solvent comprises at least one of water, monohydric alcohol and dihydric alcohol, and the solvent can form an azeotropic mixture with the catalyst and the connecting agent.
For the sake of easy understanding, the specific composition of the catalyst ink and the principle of exerting the above-described advantageous effects will be briefly described below.
As described above, in order to obtain a better catalyst layer without increasing the cost, it is theoretically possible to improve the catalytic performance of the catalyst by adding a connecting agent having an ion/proton conductor function to the catalyst ink, so that the entire surface of the catalyst particles (including the porous support and the active metal dispersed on the surface thereof) has a more uniform catalytic performance rather than being concentrated at individual sites to which the active metal is attached. The catalytic performance of the catalyst layer actually obtained by this strategy is still not ideal enough. The inventors have found that this is mainly caused by the difficulty in making the linking agent cover the surface of the catalyst particles relatively uniformly due to the influence of the process such as solvent evaporation during the preparation of the catalyst layer using the catalyst ink. Namely: on one hand, due to the influence of solvent evaporation in the drying process, the chemical components of the residual catalyst ink are actually changed, so that the surface of the carrier with the porous structure and the inner pore diameter are difficult to be adhered with the connecting agent, and the catalytic performance of the catalyst particles only covered by the connecting agent in the obtained catalyst layer can be improved; on the other hand, due to the effect of coffee rings and the like in the drying process, it is difficult to ensure that the catalyst particles in the finally obtained catalyst layer can be uniformly covered by the connecting agent. The linking agent can be uniformly covered on the surface layer and the inner part (in the nano-pores) of the catalyst particles. Specifically, the solvent mixture in the catalyst ink according to the embodiment of the present invention may be vaporized simultaneously at a constant ratio, so that the inside and outside of the nano-pores in the dried catalyst may be uniformly covered with the linking agent. In other words, the effective utilization rate of the active metal (such as platinum) on the outer surface and the inner surface of the nano-pores can be improved, and the resistance of oxygen close to the catalyst particles can be reduced, so that oxygen and hydrogen can easily enter the catalyst (inside the nano-pores) to perform electrochemical reaction, thereby achieving the effect of improving the performance of the catalyst layer. The inventor finds that when the solvent can make the catalyst ink form an azeotropic mixture, a layer of more uniform connecting agent is attached to the surface of the catalyst particles and the inside of the porous structure in the process of preparing the catalyst layer by the catalyst ink, and the catalytic performance of the catalyst layer is further improved.
According to an embodiment of the present invention, a catalyst may include a carbon-based support having a porous structure, and an active metal supported on the carbon-based support. The active metal may be located on the surface of the carbon-based support and inside the pores of the porous structure. Since the active center of the catalytic reaction is the position of the active metal, in order to improve the catalytic performance of the catalyst layer, a sufficient amount of the active metal needs to be supported on the carbon-based support. However, since the active metal is mostly a noble metal such as Pt, increasing the amount of the active metal supported increases the cost of the catalyst ink. As described above, although the catalytic performance of the catalyst can be improved by adding a linking agent composed of an ion/proton conductor to the catalyst ink, for example, by improving the ability of the catalyst surface to receive a redox reactant, it is difficult to ensure that the linking agent is uniformly adhered to both the surface and the internal porous structure of the catalyst particles after the catalyst ink is dried, and thus the function of the linking agent cannot be fully exerted. According to the catalyst ink provided by the embodiment of the invention, the solvent is an azeotropic mixture, or the solvent and other components in the catalyst ink can jointly form an azeotropic mixture, so that in the drying process of the catalyst ink, the solvent (or called as a volatile component) is volatilized and dried by a fixed chemical composition, and further, on one hand, the connecting agent is attached to the outer surface of the catalyst and the porous structure, and on the other hand, the solvent is volatilized by the fixed chemical composition, namely, in the whole preparation process of the catalyst layer, the dissolving and dispersing conditions of the solvent to the connecting agent are not changed. Therefore, the connecting agent layer with uniform thickness can be formed at different positions of the catalyst layer. That is, after the catalyst layer is formed by spraying or the like, the linking agent can be uniformly loaded on the surface layer and the porous structure of the catalyst particles or uniformly distributed among the catalyst particles.
According to the embodiment of the present invention, the specific chemical composition of the above solvent is not particularly limited as long as an azeotropic mixture can be formed. For example, according to some examples of the invention, the boiling point of the solvent may be 70-150 degrees celsius. According to some examples of the invention, the solvent may have a viscosity of 0.5 to 5mPa · s. According to some examples of the invention, the solvent is miscible in water or has a solubility in water of greater than 150g/dm3. Specifically, when the boiling point of the solvent is within the above range, the process of removing the solvent does not affect other components in the catalyst ink; when the viscosity is within the above range, the problem of dispersion due to excessive viscosity can be avoided, and formation of bubbles which are not easily removed in a solvent during the process of preparing the catalyst layer (such as mixing, stirring, blade coating, and the like) can be avoided, thereby preventing the failure of the preparation of the catalyst layer. In particular, when a catalyst layer having a thickness of 10 μm or less is prepared, the problem caused by excessive viscosity can be avoided.
According to an embodiment of the present invention, the solvent may include at least one of water, monohydric alcohol, and dihydric alcohol. For example, water and monohydric alcohols may be included, water and dihydric alcohols may be included, and water, monohydric alcohols, and dihydric alcohols may also be included. The solvent may comprise one or more monohydric alcohols, such as two, three, four or even more monohydric alcohols, and may comprise one or more dihydric alcohols, such as two, three, four or even more dihydric alcohols. More specifically, the solvent may include water, and liquid compounds having physical properties similar to water. For example, a mixed solvent composed of a ternary compound (water, monohydric alcohol and dihydric alcohol) in which the above-mentioned linking agent can be dispersed may be used.
According to an embodiment of the present invention, the monohydric alcohol may include a straight or branched chain monohydric alcohol having 1 to 10 carbon atoms, and the dihydric alcohol includes a straight or branched chain dihydric alcohol having 1 to 15 carbon atoms. More specifically, the monohydric alcohol may include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, and cyclopentanol, and when the cyclopentanol has other substituents in the six-membered ring skeleton, the position of the hydroxyl group may be the 1-position, the 2-position, the 3-position, and the like. The monohydric alcohol may further include 2-propanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 3-methyl-1-butanol, 2-dimethyl-1-propanol, 2-pentanol, 3-methyl-2-butanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2-dimethyl-1-butanol, 2, 3-dimethyl-1-butanol, 3-dimethyl-1-butanol, 2-methyl-2-pentano, 2, 3-dimethyl-2-butanol, 3-dimethyl-2-butanol, 2-ethyl-1-butanol, and the like.
The dihydric alcohol may include 1, 2-ethanediol, 1, 2-propanediol, 1, 2-butanediol, 2, 3-butanediol, 2-methyl-2, 4-pentanediol, 4-oxo-2, 6-hexanediol (dipropylene glycol), 2- (2-hydroxypropoxy) -1-propanol, and 2- (2-hydroxy-1-methylethoxy) -1-propanol, and the like.
It should be noted that the above-mentioned types of monohydric alcohol and dihydric alcohol are only used for explaining the present invention and should not be construed as limiting the present invention. Monohydric and dihydric alcohols according to embodiments of the present invention may also include, but are not limited to, isomers of the alcohols listed above, such as may include structural isomers and stereoisomers.
According to an embodiment of the present invention, the solvent may further include at least one of dimethyl sulfoxide, sulfolane, N-dimethylformamide, N-methylacetamide, N-methylpyrrolidone, and methylethylketone. Thus, the solvent can be further improved in the dissolving and dispersing ability with respect to other components (such as a linking agent, an additive, etc.) in the catalyst ink, and an azeotropic mixture can be formed better.
According to an embodiment of the present invention, in order to ensure that the chemical properties of other components in the ink are not changed during the drying of the catalyst ink, the boiling point of the solvent may not be higher than 150 ℃. Specifically, the solvent may include at least a monohydric alcohol, in which case the monohydric alcohol may include, but is not limited to, methanol, ethanol, 1-propanol, 2-butanol, 1-methyl 2-propanol, 2-methyl 2-propanol, 3-methyl 1-butanol, 2-methyl 2-butanol, 2-methyl 1-butanol, 2-dimethyl 1-propanol, 3-pentanol, 2-pentanol, 3-methyl 2-butanol, 2-hexanol, 3-hexanol, 2-methyl 1-pentanol, 2-methyl 2-pentanol, 3-methyl 2-pentanol, 4-methyl 2-pentanol, 2-methyl 3-pentanol, 3-methyl 3-pentanol, 2-methyl 2-pentanol, and mixtures thereof, 2, 2-dimethyl-1-butanol, 2, 3-dimethyl-1-butanol, 3-dimethyl-1-butanol, 2, 3-dimethyl-2-butanol, 3-dimethyl-2-butanol, 2-ethyl-1-butanol, and the like. According to other embodiments of the present invention, the solvent may be removed from the coating of the catalyst ink at a constant chemical composition ratio under constant temperature conditions without affecting the performance of the binder. Specifically, the solvent may preferably include methanol, ethanol, propanol, isopropanol (isomer of propanol), 1-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol (isomer of butanol), 2, 2-dimethyl-1-propanol, 3-pentanol, 2-pentanol, 3-methyl-2-butanol, 2-methyl-2-butanol, 3-dimethyl-2-butanol and 2, 3-dimethyl-2-butanol.
According to an embodiment of the present invention, the specific content of the solvent in the catalyst ink is not particularly limited as long as an azeotropic mixture can be formed during the process of preparing the catalyst layer by drying the catalyst ink, that is, each component in the solvent can be removed simultaneously during the drying process, and the linking agent (or proton conductor) in the catalyst ink can be attached to the surface of the catalyst carbon-based carrier and the inside of the pore channel more uniformly.
According to the embodiment of the present invention, the specific chemical composition and content of the connecting agent are not particularly limited as long as the connecting agent is a good proton conductor. For example, according to particular embodiments of the present invention, the linking agent may include a polymer including at least one of O, S, F. According to some examples of the invention, the polymer has a density of 1.6 to 2.2g/cm3. The linking agent includes at least one of fluorinated ethylene propylene copolymer, polytetrafluoroethylene, polyvinylidene fluoride, perfluorosulfonic acid, and perfluoroimide acid. The polymer further comprises at least one of the following structures: a branch containing 1-10 carbon atoms, and an electron-rich functional group, wherein the equivalent value of the electron-rich functional group is 500-1000. For example, it may contain a sulfonic acid group.
Specifically, the linking agent may be a polymer capable of transferring hydrogen ions or protons, and may be reliably attached to the surface of the catalyst (which has a strong binding force with the catalyst carbon-based carrier, such as a certain functional group). For example, it may be a functional group containing water, or have a certain gas permeability. Specifically, it may be a resin-based material. Such as a cation conductive membrane. More specifically, a copolymer having a sulfonic acid group, a carboxyl group, a fluorinated sulfonic acid, and a hydrocarbon polymer containing a sulfonic acid group may be contained. For example, sulfonated polyarylethersulfones, sulfonated polyetheretherketones, sulfonated polyvinyl acids, sulfonated polyamide resins, sulfonated polyarylethersulfone block copolymers, polysulfonated polyarylethersulfone block copolymers, polytrifluorostyrene sulfonic acid, and the like may be included. In the process of manufacturing the thin film battery, since compatibility between the linking agent in the catalyst layer and the substrate supporting the catalyst layer needs to be considered, the linking agent may be selected in consideration of compatibility between the linking agent and the substrate supporting the catalyst layer, which is commonly used. Common support substrates include ePTFE membranes with micropores and polymer membranes that can be used to support the ePTFE membrane. For example, specifically, Polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polyimide (PI), Fluorinated Ethylene Propylene (FEP), polyvinylidene fluoride (PVDF), and the like are included. The fluorinated sulfonic acid group copolymer and the polytetrafluoroethylene skeleton compound have certain commonality, are different in the carbon number of the side chain and have sulfonic acid group modification, so that the compatibility degree between the catalyst ink and the polytetrafluoroethylene supporting substrate can be improved by including the polymer in the connecting agent. For example, the linking agent may comprise a fluorinated copolymer (polytetrafluoroethylene-perfluorovinylether sulfonic acid copolymer) including commercially available Nafion.
According to particular embodiments of the present invention, the linking agent may include a carboxylic acid-containing copolymer. Specifically, the linking agent may comprise, but is not limited to, tetrafluoroethylene-perfluorovinylether carboxylic acid copolymer, polyvinylbenzoic acid, crosslinked polyvinylbenzoic acid, ethylene tetrafluoroethylene copolymer-g-polyvinylbenzoic acid, carboxylated polyvinylether ketone, carboxylated polyvinylether sulfone, polytrifluorostyrene carboxylic acid, carboxylated poly (2, 3-diphenyl-1, 4-phenyl oxide), carboxylated polybenzylsilane, and carboxylated polyimide. The linking agent may include a copolymer having an imide group, and may include, for example, tetrafluoroethylene-perfluorovinyl ether sulfamide acid copolymer and polystyrene trifluoromethyl sulfamide.
The inventors have found that the solubility constants of polymers containing sulfonic acid groups, F and O elements are relatively large (compared to other polymers not containing fluoride and oxygen atoms), mainly because F and O elements have relatively abundant electrons, and when adjacent to sulfonic acid groups, the electron-rich oxygen and fluorine can act as electron donors, thereby improving proton conductivity of the binder and facilitating the formation of ion channels. Furthermore, fluorinated copolymers are more permeable to hydrogen and oxygen than hydrocarbon-based copolymers, and therefore linkers containing this type of polymer allow the redox reactants to react better close to the catalyst surface. Further, the fluorinated copolymer is less likely to be stacked or less crystalline than the hydrocarbon-based copolymer. Therefore, the amount of the linking agent can be reduced, and a good catalytic activity promoting effect can also be obtained. In conclusion, the connecting agent containing S, O, F element polymer has more remarkable advantages in the process of preparing the catalyst layer of the MEA membrane electrode.
According to an embodiment of the present invention, the catalyst ink may further include an additive. When the catalyst ink has an additive, the aforementioned solvent may form an azeotropic mixture with the catalyst, the linking agent, and the additive. According to some examples of the invention, the additive may include at least one of a viscosity reducer, a tackifier, a stabilizer, and a scavenger.
According to some embodiments of the invention, the additive is present in an amount of 0.01 to 1 wt% based on the total mass of the catalyst ink.
According to an embodiment of the present invention, the specific kind of the additive is not particularly limited, and for example, may include inorganic additives as well as organic additives. Wherein the organic additive may comprise benzyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxymethyl celluloseGlycerin-26, propylene carbonate, etc., and the inorganic additive may include TiO2、RuO2、CeO2、IrO2、SiO2、ZrO2、WO3、CeZrO2、OsO2、VxOy、NiO、Fe2O3、CoO、Al2O3、Rb2O、NdxOy、Rh2O3、YxOy、YbxOy、TbO2、CrOyMoO and MnxOyWherein x and y are determined according to the chemical valence of the above-mentioned metal element and oxygen element, and, as specific, x may be 1 to 2 and y may be 1 to 3, in other words, 1. ltoreq. x.ltoreq.2 and 1. ltoreq. y.ltoreq.3.
The specific type of the catalyst according to the embodiment of the present invention is not particularly limited, and those skilled in the art can select the catalyst according to the actual situation, for example, a commercial catalyst can be selected, or the catalyst can be adjusted and selected according to the actual situation. According to an embodiment of the present invention, a supported catalyst may be used, and the catalyst support of the supported catalyst may be electrically conductive so that the catalyst support may act as an electron conductor to transfer electrons to the active component in the catalyst. Materials having a certain surface area, a suitable dispersion state, and sufficient electron conductivity can be used as the catalyst support according to the embodiment of the present invention. According to particular embodiments of the present invention, carbon-based supports may be employed. For example, the carbon-based support may include carbon black, graphitized carbon black, carbon nanotubes, carbon fibers, graphite fibers, graphene, and the like.
According to embodiments of the present invention, the specific surface area of the carbon-based support may be 50 to 1000m2(ii) in terms of/g. When the specific surface area of the conductive substrate has a value within this range, it is possible to properly control the balance between the dispersion characteristics of platinum on the conductive substrate and the effective utilization of the catalyst. According to the embodiment of the invention, the average particle diameter of the carbon-based carrier can be in the range of 30-500 nm, such as in the range of 100-300 nm, so that the catalyst can be well dispersed, and the thickness of the catalyst layer can be well controlled. In particular, the average particle diameter of the carbon-based carrier herein refers to the size of the medium-sized particles obtained by polymerizing the primary particles. The specific method for detecting the average particle diameter is not particularly limited, and a person skilled in the art can select a familiar method for the measurement. Specifically, the average value of the crystals can be calculated by a Brag equation, and can be determined by the full width at half maximum of the diffraction peak of platinum in an XRD detection result or determined by a transmission electron microscope image.
The surface of the carbon-based catalyst may have a porous structure, and the pore size of the porous structure may vary from several nanometers to several tens of nanometers, and may specifically be 1 to 30 nanometers. According to an embodiment of the present invention, the content of the active metal may be 5 to 55 wt% based on the total mass of the catalyst.
According to an embodiment of the present invention, the active metal may be a noble metal, such as noble metals including but not limited to platinum, palladium, iridium, and may further include an alloy or an oxide type alloy of transition metals, such as ruthenium, rhodium, osmium, tungsten, iron, chromium, cobalt, nickel, manganese, vanadium, molybdenum, zirconium, silicon, titanium, cerium, molybdenum, rhodium, tin, and rhenium. Further, among these materials, a material containing platinum may be preferably used in order to improve the activity of the catalyst having thermal resistance and the poisoning resistance of the catalyst to carbon monoxide.
According to a particular embodiment of the invention, the reactive metal may be an alloy. The alloy may include 50 to 95.5 atomic percent platinum and when the alloy includes the transition metal, the alloy may include a different percentage of platinum from 4.5 to 50 atomic percent. When the catalyst ink is used to prepare a cathode catalyst layer, i.e., the alloy serves as a cathode catalyst, the specific content of the above-mentioned platinum atom may be changed according to the kind of transition metal in the alloy. According to some preferred embodiments of the present invention, the alloy catalyst may include 50 atomic% to 95.5 atomic% of platinum, and the transition metal-containing alloy may include 4.5 atomic% to 50 atomic% of platinum.
According to an embodiment of the present invention, the supported amount of platinum on a carbon support (carbon-based support) may be 5 to 95 wt%, and the catalyst may be used for a catalyst ink for preparing an anode catalyst layer or a cathode catalyst layer. The specific loading of the active metal in the catalyst can be adjusted according to the polarity of the electrode (anode or cathode) and the specific reaction to be catalyzed.
According to the embodiment of the present invention, the shape and size of the catalyst are also not particularly limited. According to a preferred embodiment of the present invention, the catalysts included in the catalyst ink may have the same shape, size, and chemical composition. Namely: the catalyst in the catalyst ink may be a single type of catalyst. According to a preferred embodiment of the invention, the catalyst may be selected in the form of particles. Specifically, the average particle size of platinum on the carbon-based support may be 1 to 10 nm, for example, 2 to 5 nm. In this case, when the average particle diameter of platinum on the carbon support is within the above range, the utilization rate of platinum in the catalyst and the effective electrode area generated by the electrochemical reaction can be well balanced. The specific method for detecting the average particle diameter of platinum on the carbon-based support is not particularly limited, and the aforementioned method for measuring the average particle diameter of the carbon-based support can be employed.
According to the embodiment of the present invention, the content of the catalyst in the catalyst ink may be 10% to 90% (by mass), and for example, may be 40% to 70% (by mass). When the content of the catalyst in the catalyst ink is within the above range, the dispersibility of the catalyst and the catalytic performance of the catalyst layer can be well balanced.
According to some embodiments of the invention, the catalyst may contain carbon, platinum or a platinum alloy, and the platinum content may be 20% to 60% by mass. The carbon may be a carbon-based support, and specifically may include Vulcan, ketjen black, acetylene black, black pearl, carbon nanotube, carbon nanohorn, carbon fiber, mesoporous carbon, and double-pore carbon composed of mesopores and nanopores, graphitized carbon by high-temperature treatment, for example, graphitized ketjen black and graphitized acetylene black may be used.
In another aspect of the present invention, the present invention provides a method of preparing the catalyst ink set forth above. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: forming a catalyst block
According to an embodiment of the present invention, in this step, a catalyst, a linking agent, and a first solvent are mixed to form an azeotropic mixture, the catalyst including a carbon-based support having a porous structure, and an active metal supported on the carbon-based support. Drying the azeotropic mixture to remove the first solvent and to allow the linking agent to adhere to the outer surface of the catalyst and the porous structure to obtain a catalyst block. Therefore, a layer of connecting agent can be uniformly adhered to the surface of the obtained catalyst block, so that the function of the connecting agent (proton conductor) is favorably exerted, and the catalytic performance of the finally obtained catalyst layer is improved.
According to an embodiment of the present invention, the step of obtaining the catalyst block may specifically include: mixing the solution containing the catalyst, the connecting agent and the first solvent, and stirring under the conditions of constant temperature and constant pressure, wherein the mass ratio of the carbon elements in the connecting agent and the catalyst is 0.5-0.9. The first solvent includes at least one of water, a monohydric alcohol, and a dihydric alcohol, and the first solvent may form an azeotropic mixture with the catalyst and the linking agent. Therefore, in the process of preparing the catalyst block, the first solvent is volatilized in a fixed chemical ratio, so that a uniform connecting agent attaching structure is formed in the solidified catalyst block, and the connecting agent can be attached to the surface of the catalyst and the internal porous structure. Also, the content of the linking agent attached to different positions in the catalyst block may be relatively uniform. The principle of obtaining a more uniform adhesive structure of the connecting agent by evaporation of the azeotropic solvent has been described in detail above, and will not be described herein again.
According to a specific embodiment of the present invention, the first solvent may further include an additive. The mixture used to prepare the catalyst block may include a first solvent (which may include water, isopropanol, monohydric alcohol), a catalyst, a linking agent, and additives. In detail, the catalyst, the linking agent and the additive may be first mixed with the monohydric alcohol. The catalyst is preferably thoroughly wetted with water before being mixed with the other components. Subsequently, a linking agent solution and a monohydric alcohol may be added to the impregnated catalyst. The linker solution may be formulated from the first solvent described above.
According to the embodiment of the invention, the content of the connecting agent in the mixture can be adjusted according to the content of the catalyst and the content of the active metal in the catalyst, so that the active center of the catalyst is better covered, and the catalytic performance is improved. Specifically, when the content of the active metal (in the case of Pt) is larger, the content of the added linking agent is smaller. In contrast, when the content of the active metal is small, the content of the linking agent is large. The specific composition of the linking agent has been described in detail above and will not be described further herein. Since the connecting agent is mostly formed of a polymer, an increase in the connecting agent may result in a change in the viscosity of the mixture. The inventors have found that when the viscosity of the mixture is greater than 5mPa · s, bubbles in the mixture are caused to be difficult to remove, thereby affecting the quality of the obtained catalyst cake. Specifically, in this step, the viscosity of the mixture may be adjusted to 0.5 to 5 mPas. Specifically, the content of the first solvent, the linking agent, and the additive to be added is smaller as the content of the active metal (in the case of Pt) is larger. In contrast, when the content of the active metal is small, the content of the first solvent, the linking agent, and the additive to be added is large. Specifically, the content of the linking agent and the additive having a binding function in the mixture for forming the catalyst block may be 1 to 35%, for example, 5 to 30%, and preferably 10 to 25%.
According to an embodiment of the present invention, the first solvent may include any one or more of water, monohydric alcohol and dihydric alcohol. The specific composition of the monohydric alcohol and the dihydric alcohol may be the monohydric alcohol and the dihydric alcohol in the catalyst ink solvent, which are not described herein again. According to a specific embodiment of the present invention, the first solvent may be the solvent in the catalyst ink described above.
According to an embodiment of the present invention, the specific conditions of the constant temperature and constant pressure stirring may be: the stirring speed is 10-1500rpm, the temperature is kept below 30 ℃, and the pressure is 1-1.1 atm. The specific manner of carrying out the above-mentioned mixing and stirring is not particularly limited, and those skilled in the art can select the mixing and stirring according to the actual situation. For example, the mixing process can be achieved by means of a stirrer, an ultrasonic device, a ball mill, etc. The mixing and stirring time may be 15 to 240 minutes. The specific temperature may be 10-30 degrees celsius. During the mixing process, a medium such as a stirrer, magnetic beads, ball milling balls, etc. may be added to mix the catalyst and the solution containing the linking agent uniformly, and the stirring medium may be separated by including but not limited to a screen, etc. When the nano dispersing agent is adopted, the nano dispersing agent can not be additionally separated, and the nano dispersing agent in the mixture can also play a role in preventing catalyst agglomeration. Alternatively, an additive having the function of preventing agglomeration of nanoparticles may be added to achieve the effect of the above-described nano-dispersant. According to particular embodiments of the present invention, the solids content of the mixture used to prepare the catalyst block may range from 5 to 30%, more particularly, from 10 to 25%.
The mixture used to prepare the catalyst block in this step may have viscoelastic properties according to an embodiment of the present invention. According to other embodiments of the present invention, the mixture is formed by mixing a solid and a liquid, and the mixture may have a thixotropic effect, and may be transformed from a gel to a sol in a gel state by external disturbance. Thus, the catalytic performance of the catalyst block can be maintained well after the catalyst block is formed.
As mentioned above, since the mixture is an "azeotropic mixture", the content of the linking agent in the remaining solution (mixture) is constant during the process of removing the first solvent to obtain the catalytic mass, while the solvent is continuously removed: while the first solvent is continuously evaporated, the linking agent is continuously attached to the dried catalyst surface. Therefore, the linking agent adsorbed on the surface of the catalyst is not easily dissolved again in the subsequent process of dissolving and breaking the catalyst block. Therefore, the connector structure with uniform adhesion is conveniently obtained finally.
According to the embodiment of the present invention, the solid content in the catalyst block obtained in this step can be increased to 92% by mass. After removal of the solvent, the solid content of the catalytic mass may be 10% to 92% by mass. The range of the solid content affects the adhesive force between the catalyst component and the linking agent, and when the solid content of the catalyst block is within the above range, it is advantageous to prevent the linking agent having adhered to the surface of the catalyst from being secondarily dissolved in the subsequent treatment step. The method for removing the solvent is not particularly limited, and for example, a thermal distillation method, a centrifugal method, a vacuum distillation method, a freeze-drying method, etc. may be used for preparing the catalyst block. Further, the equipment used in the removal process is also not particularly limited, and known equipment such as a rotary evaporator or a freeze dryer can be used. The preparation of the catalytic block (drying process) may be carried out by using a freeze-drying system equipped with a pressure-reducing device.
S200: forming catalyst ink
According to an embodiment of the present invention, in this step, the catalyst block is subjected to pulverization treatment in the second solvent containing the linking agent, and the pulverized catalyst and the second solvent are stirred and mixed to obtain the catalyst ink. Thus, in the process of crushing and redispersing the catalyst in the solvent, the catalyst block is crushed again, so that a part of the catalyst surface not covered with the linking agent can be exposed, and the linking agent is further attached at the position in this step, so that the catalytic performance of the obtained catalyst ink can be further improved. According to an embodiment of the present invention, the linking agent mixed in the second solvent in this step may be the linking agent previously added when the catalyst block is formed.
Thus, the catalytic layer manufactured using such a catalyst ink can have excellent proton conductivity, and redox reactants can more easily approach the surface of the catalyst, so that the catalytic layer can exhibit the best performance of its own catalyst and contribute to the improvement of the output effect of a polymer electrolyte membrane fuel cell using the catalytic layer.
According to an embodiment of the present invention, the catalytic mass may be pulverized into nanoparticles in the second solvent dispersion solution containing the linking agent by means of stirring, ultrasound, or high-speed mixing. Specifically, stirring may be performed using an apparatus equipped with a pulsed ultrasonic generator and a rotary high-speed mixer. After the catalyst mass is pulverized in the dispersion solution, the average particle diameter and average volume of the binder-coated catalyst are smaller than the size before pulverization. This also means that the average particle size and average volume of the catalyst coated with the binder is at least equal to or less than the size in the catalytic solution before the preparation of the catalytic mass. The particle size can be measured by laser diffraction scattering.
According to an embodiment of the invention, the second solvent is identical in chemical composition to the first solvent. For example, where the linking agent has proton conductivity, the second solvent may include one or more monohydric alcohols, such as ethanol, 1-propanol, 2-propanol, and the like.
According to embodiments of the present invention, although the amount of the second solvent added in this step is not particularly limited, according to some preferred embodiments of the present invention, the amount of the second solvent added may be 100-500% of the mass of the first solvent added for the first time when the formation catalyst block is prepared. The second solvent in this step may be a three component solution "azeotrope" (e.g., containing water, isopropanol, and one of the other solvents previously described). According to some preferred embodiments of the present invention, the time and temperature of the mixing may be 15-60 minutes and 10-30 ℃.
According to an embodiment of the present invention, the catalyst ink obtained by the above method can be prepared by a conventional method in preparing a catalyst layer, i.e., the catalyst ink has an advantage that a catalyst layer can be formed by a simple method. For example, a catalyst ink may be applied to a substrate by various methods such as a spray method, a blade method, a slit coating method, a dot coating method, a screen printing method, an ink jet printing method, etc., and the resulting catalyst layer may be used for a solid polymer electrolyte fuel cell.
In yet another aspect of the present invention, a catalyst layer for a fuel cell is provided. The catalyst layer is obtained on the basis of the catalyst ink described above. Thus, the catalyst layer has at least one of the following advantages: the preparation process is simple, and the ink can be formed by a simple ink spraying or printing method. In addition, in the formed catalyst layer, the catalytic performance of the catalyst particles is better, the surfaces of the catalyst particles and the porous structure have uniform catalytic performance, and the reaction sites with high catalytic activity are not only positioned on the local surfaces of the catalyst particles.
In yet another aspect of the present invention, a fuel cell is provided. The fuel cell includes the catalyst layer described above.
In yet another aspect of the present invention, a vehicle is presented. The vehicle includes a fuel cell. For example, specifically, the vehicle includes a housing, and a fuel cell disposed in the housing. The vehicle is provided with a power system, and the fuel cell is electrically connected with the power system to provide energy for the power system.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. 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 is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, 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 (12)

1. A catalyst ink, comprising:
a catalyst, a linking agent, and a solvent, the solvent including at least one of water, a monohydric alcohol, and a dihydric alcohol, the solvent forming an azeotropic mixture with the catalyst and the linking agent,
the catalyst comprises a carbon-based carrier with a porous structure and an active metal loaded on the carbon-based carrier, wherein the connecting agent is attached to the outer surface of the catalyst and the porous structure.
2. The catalyst ink according to claim 1 wherein the solvent has a boiling point of 70-150 degrees celsius, a viscosity of 0.5-5 mPa-s, is miscible in water or has a solubility in water of more than 150g/dm3。
3. The catalyst ink according to claim 1 wherein the monohydric alcohol comprises a straight or branched chain monohydric alcohol containing 1-10 carbon atoms,
the dihydric alcohol includes a straight or branched chain dihydric alcohol having 1 to 15 carbon atoms.
4. The catalyst ink of claim 3 wherein the solvent further comprises at least one of dimethyl sulfoxide, sulfolane, N-dimethylformamide, N-methylacetamide, N-methylpyrrolidone, and methylethylketone.
5. The catalyst ink of claim 1 wherein the linking agent comprises a polymer comprising at least one of O, S, F, the polymer having a density of 1.6-2.2g/cm3。
6. The catalyst ink of claim 5 wherein the polymer further comprises at least one of the following structures:
a branch chain containing 1-10 carbon atoms, and an electron-rich functional group,
wherein the equivalent value of the electron-rich functional group is 500-1000.
7. The catalyst ink according to claim 1, further comprising: an additive, the solvent being capable of forming an azeotrope with the catalyst, the linking agent, and the additive, the additive comprising at least one of a viscosity depressant, a tackifier, a stabilizer, and a scavenger,
the additive is contained in an amount of 0.01 to 1 wt% based on the total mass of the catalyst ink,
optionally, the additives include benzyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxymethyl cellulose, glycerol-26, and propylene carbonate, TiO2、RuO2、CeO2、IrO2、SiO2、ZrO2、WO3、CeZrO2、OsO2、VxOy、NiO、Fe2O3、CoO、Al2O3、Rb2O、NdxOy、Rh2O3、YxOy、YbxOy、TbO2、CrOyMoO and MnxOyAt least one of the above-mentioned (B),
wherein x is more than or equal to 1 and less than or equal to 2, and y is more than or equal to 1 and less than or equal to 3.
8. A method of preparing the catalyst ink of any one of claims 1 to 7, comprising:
mixing a catalyst, a linking agent and a first solvent to form an azeotropic mixture and drying, the catalyst comprising a carbon-based support having a porous structure, and an active metal supported on the carbon-based support, to remove the first solvent and allow the linking agent to adhere to an outer surface of the catalyst and the porous structure, obtaining a catalyst block;
and crushing the catalyst block in a second solvent containing the connecting agent, and stirring and mixing the crushed catalyst and the second solvent to obtain the catalyst ink.
9. The method of claim 8, wherein the step of obtaining a catalyst block further comprises:
mixing a solution containing the catalyst, the connecting agent and the first solvent, and stirring under the conditions of constant temperature and constant pressure, wherein the mass ratio of carbon elements in the connecting agent to carbon elements in the catalyst is 0.5-0.9, and the solid content of the mixture formed after mixing is 5-50%;
drying the mixture, and enabling the solid content of the catalyst block obtained after drying to be 10% -92%.
10. The method of claim 8, wherein the second solvent is the same chemical composition as the first solvent.
11. A fuel cell comprising a catalyst layer obtained on the basis of the catalyst ink according to any one of claims 1 to 7.
12. A vehicle characterized by comprising the fuel cell according to claim 11.
CN201811278676.1A 2018-10-30 2018-10-30 Catalyst ink, preparation method thereof, fuel cell and vehicle Pending CN111117349A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113871761A (en) * 2021-09-23 2021-12-31 嘉兴南湖学院 Air cathode catalyst layer ink suitable for aerosol printing and preparation method thereof
CN113921831A (en) * 2021-09-22 2022-01-11 一汽解放汽车有限公司 Electrode catalyst slurry, method for producing the same, catalyst coated membrane, and fuel cell

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004281305A (en) * 2003-03-18 2004-10-07 Matsushita Electric Ind Co Ltd Fuel cell and its manufacturing method
CN103782430A (en) * 2011-09-26 2014-05-07 日产自动车株式会社 Catalytic ink adjustment method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004281305A (en) * 2003-03-18 2004-10-07 Matsushita Electric Ind Co Ltd Fuel cell and its manufacturing method
CN103782430A (en) * 2011-09-26 2014-05-07 日产自动车株式会社 Catalytic ink adjustment method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张克立等: "《无机合成化学》", 31 January 2012, 武汉大学出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113921831A (en) * 2021-09-22 2022-01-11 一汽解放汽车有限公司 Electrode catalyst slurry, method for producing the same, catalyst coated membrane, and fuel cell
CN113871761A (en) * 2021-09-23 2021-12-31 嘉兴南湖学院 Air cathode catalyst layer ink suitable for aerosol printing and preparation method thereof

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