CN112259747A - Fuel cell membrane electrode assembly formed by growing whiskers and preparation method - Google Patents
Fuel cell membrane electrode assembly formed by growing whiskers and preparation method Download PDFInfo
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Abstract
The invention relates to the field of fuel cells, and discloses a fuel cell membrane electrode assembly formed by growing whiskers and a preparation method thereof. The preparation method comprises the following preparation processes: (1) spraying polytetrafluoroethylene emulsion on two sides of the carbon fiber paper, and drying for later use; (2) adding a porous nano catalyst, zinc chloride, a dispersing agent and a precipitating agent into water, and mixing and stirring to obtain slurry; (3) mixing the slurry, the Nafion solution and the carbon material, coating the mixture on one side of the carbon fiber paper, and heating to obtain the carbon fiber paper with the surface formed with the catalyst layer; (4) and spraying a Nafion solution on the surface of the proton exchange membrane, and then hot-pressing and attaching the proton exchange membrane with carbon fiber paper to obtain the fuel cell membrane electrode assembly formed by growing the whiskers. The invention loads zinc chloride in the microporous catalyst to gradually form zinc oxide whiskers and simultaneously form macroscopic fibrous catalyst fibers, the whiskers are uniformly distributed, the meshes of the whiskers are fine and uniform, and the preparation process is simple and controllable.
Description
Technical Field
The invention relates to the field of fuel cells, and discloses a fuel cell membrane electrode assembly formed by growing whiskers and a preparation method thereof.
Background
The proton exchange membrane fuel cell is also called a polymer electrolyte membrane fuel cell, is a new, high-efficiency and environment-friendly energy conversion application cell, and is widely applied in the fields of transportation, fixation and movable power supplies. Among them, a Membrane Electrode (MEA) is a core component of a fuel cell, and generally consists of a gas diffusion layer, a catalytic layer, and a proton exchange membrane.
In a membrane electrode, a catalyst layer is a place where electrochemical reaction occurs in a Membrane Electrode Assembly (MEA), the performance and stability of the catalyst layer greatly determine the electrochemical performance of the MEA, and the cost of an electrocatalyst in the catalyst layer also accounts for a large proportion of the total cost of the MEA. In order to reduce the cost of the catalyst, on one hand, the composite catalyst is continuously screened, and the reaction activity of the catalyst layer is improved; on the other hand, the stability of the catalyst and the proton exchange membrane is improved, the loss is reduced, and the dosage of the catalyst is reduced. The microstructure modification of the catalytic layer is improved, and particularly the ordered catalytic layer becomes another breakthrough for improving the performance of the catalytic layer.
The catalyst layer is usually adhered to the proton exchange membrane layer by ultrasonic atomization spraying after the catalyst, isopropanol solvent and adhesive are uniformly dispersed, and the formed catalyst thin layer has disordered micropores, thereby influencing the mass transfer effect. The introduction of an ordered interface into the carrier structure of the membrane electrode plays an important role in charge and material transport in the membrane electrode, and the ordered catalyst, proton conductor and conductor in the proton exchange membrane interface play a role in improving proton exchange, air permeability, water drainage and catalytic efficiency, and become the focus of research at present.
Chinese patent application No. 201611014780.0 discloses an ordered membrane electrode based on metal oxide nanobelts, and a preparation method and application thereof, which comprises the preparation of the metal oxide nanobelts, the modification of the surface of the metal oxide nanobelts and the assembly of the ordered membrane electrode. Firstly, growing Co-OH-CO with regular orientation on a substrate3Array, then with Co-OH-CO3Preparing metal oxide nanorod array by using nanorod array as template, loading catalyst on the surface of metal oxide nanorod array, and hot pressing the arrayThe membrane electrode is obtained on the ion exchange membrane and is purified, and the constructed ordered membrane electrode can be applied to fuel cells, solid polymer water electrolysis cells and integrated renewable fuel cells.
Chinese invention patent application number 201810296464.X discloses a preparation method of a fuel cell electrode and a membrane electrode with a full-ordered structure of a catalytic layer. The fully-ordered catalyst layer structure has a very high three-phase reaction interface, and can provide a high-efficiency electron, ion and substance transmission channel, so that the substance transmission resistance, the charge transmission resistance and the electrochemical polarization resistance in the electrode are effectively reduced, and the electrochemical reaction efficiency and the energy conversion efficiency in the electrode are effectively improved.
According to the above, the ordered design and preparation of the catalyst layer in the membrane electrode for the proton exchange membrane fuel cell in the existing scheme are complex, and lack of certain controllability, which restricts the further development of the membrane electrode.
Disclosure of Invention
In the membrane electrode of the proton exchange membrane fuel cell which is widely applied at present, the defects of complex preparation process, poor controllability, non-ideal performance and the like exist in the ordering process of the catalyst layer, and the invention provides a fuel cell membrane electrode component formed by growing whiskers and a preparation method thereof, which can effectively solve the technical problems.
In order to solve the problems, the invention adopts the following technical scheme:
a method for preparing a fuel cell membrane electrode assembly formed by growing whiskers comprises the following specific steps:
(1) uniformly spraying polytetrafluoroethylene emulsion on two sides of the carbon fiber paper, and drying to obtain pretreated carbon fiber paper;
(2) adding a porous nano catalyst, zinc chloride and a dispersing agent into water, ultrasonically dispersing for 30-45 min at room temperature, slowly adding a precipitating agent, adjusting the pH value to 8-9, mixing and stirring uniformly to enable the zinc chloride to form a precursor in micropores of the porous nano catalyst to obtain a slurry;
(3) adding a Nafion solution and a carbon material into the slurry obtained in the step (2), uniformly stirring at the speed of 300-500 r/min to obtain a coating liquid, uniformly coating one side of the pretreated carbon fiber paper prepared in the step (1), treating at 80-100 ℃ for 10-15 min to stabilize pre-curing, transferring the carbon fiber paper into a hydrothermal reaction device, carrying out hydrothermal reaction at 150-200 ℃ for 1-3 h to gradually form zinc oxide whiskers, arranging the porous nano catalyst along the direction of the zinc oxide whiskers, washing after the reaction is finished, and drying to obtain the carbon fiber paper with the surface on which the catalyst layer is formed;
(4) uniformly spraying a Nafion solution on the surface of the proton exchange membrane, and then hot-pressing and attaching the carbon fiber paper with the surface formed with the catalyst layer prepared in the step (3) and the proton exchange membrane to form a fuel cell membrane electrode which sequentially comprises the carbon fiber paper layer, the catalyst layer and the proton exchange membrane from bottom to top, namely the fuel cell membrane electrode assembly formed by growing whiskers.
The carbon fiber paper is functional paper with special performance produced by mixing carbon fiber or activated carbon fiber and carbon fiber or activated carbon fiber with other plant or non-plant fiber. The carbon fiber paper has excellent performance of carbon fiber as a functional material of the carbon fiber, and the carbon fiber exists in the carbon fiber paper in a random form of short fiber, so that the isotropy is incomparable to a long fiber composite molding material, and the specific performance of the carbon fiber paper is as follows.
(l) Excellent electric heating performance as a heating device;
(2) the conductivity, the self resistance, density, thickness and processing technology of the carbon fiber paper can influence the conductivity of the carbon fiber paper to change the resistance of the carbon fiber; the carbon fiber paper with different conductivities can be obtained by controlling the production process and applied to different fields;
(3) the porous carbon fiber is a uniform porous material and the specific surface area of the surface of the carbon fiber is large, and the carbon fiber paper is an important breathable and water-permeable material.
Preferably, the thickness of the carbon fiber paper in the step (1) is 0.2-0.3 mm, and the porosity is more than 70%.
Preferably, the porous nano-catalyst in the step (2) is Pt/C catalyst particles with micropores and the particle size of 10-100 nm.
Preferably, the dispersant in step (2) is at least one of ammonium carbonate and ammonium bicarbonate.
Preferably, the precipitant in step (2) is one of sodium hydroxide and ammonia water.
Preferably, in step (2): 30-35 parts of porous nano catalyst, 12-16 parts of zinc chloride, 1-3 parts of dispersing agent, 40-54 parts of water and 3-6 parts of precipitator.
Preferably, the mass concentration of the Nafion solution in the step (3) is 5-10%.
Preferably, the carbon material in step (3) is at least one of microporous acetylene black carbon powder, carbon nanotubes, carbon nanofibers, and graphene.
Preferably, in step (3): 50-65 parts of slurry, 20-30 parts of Nafion solution and 15-20 parts of carbon material.
Preferably, the coating in the step (3) can be blade coating or ultrasonic spraying, and the coating thickness is 50-500 μm.
Preferably, the proton exchange membrane in the step (4) is a perfluorosulfonic acid type proton exchange membrane.
Further preferably, the perfluorosulfonic acid type proton exchange membrane is a Nafion series membrane commonly available from Du Pont.
Still more preferably, the Nafion series membrane is one of Nafion 117, Nafion 115, Nafion 112, Nafion 1135, and Nafion 105.
Preferably, the mass concentration of the Nafion solution in the step (4) is 5-10%.
Preferably, the hot-pressing and attaching in the step (4) are carried out at the temperature of 120-130 ℃, under the pressure of 8-10 MPa and under the pressure maintaining time of 60-70 s.
Spraying polytetrafluoroethylene emulsion on two surfaces of carbon fiber paper, and drying for later use; ultrasonically dispersing a porous nano catalyst, zinc chloride, water and a dispersing agent at room temperature, slowly adding a precipitating agent, adjusting the pH value, and forming a precursor of the zinc chloride in micropores of the porous nano catalyst to obtain a slurry; adding a Nafion solution and a carbon material into the slurry, stirring at a high speed, coating on one side of the pretreated carbon fiber paper by a coating process, heating for pretreatment, solidifying stably, transferring into a hydrothermal reaction device for hydrothermal reaction to gradually form zinc oxide whiskers, arranging the porous nano catalyst along the direction of the zinc oxide whiskers, washing and drying to form a catalyst layer; spraying Nafion solution on the surface of the proton exchange membrane, then attaching the carbon fiber paper coated with the catalyst layer to the proton exchange membrane, and hot pressing to form the fuel cell membrane electrode assembly sequentially comprising the carbon fiber paper layer, the catalyst layer and the proton exchange membrane from bottom to top.
Compared with the prior art, the invention provides a fuel cell membrane electrode assembly formed by growing whiskers and a preparation method thereof, and the outstanding characteristics and excellent effects are as follows:
1. methods for preparing whisker-grown fuel cell membrane electrode assemblies by precipitating zinc chloride in a microporous catalyst to gradually form zinc oxide whiskers are presented.
2. By selecting a porous nano catalyst, zinc chloride is dissolved and pre-loaded in micropores of the porous nano catalyst, and a process of forming zinc oxide whiskers by utilizing hydrothermal is utilized.
3. The catalyst fiber prepared by the method of the invention gradually grows whiskers after precoating, the formed whiskers are uniformly distributed, and the meshes of the whiskers are fine and uniform.
4. In the membrane electrode prepared by the invention, the zinc oxide crystal grows into a fiber in a single crystal form, the diameter is small, the fiber has a highly oriented structure, the strength is high, the hydrophobicity is excellent, the catalyst is arranged in a fiber shape, the electron and proton transmission is provided, and a network micro-channel is convenient for the hydrophobic transmission of gas and the removal of water. The membrane electrode is an ordered structure of a catalyst forming network, so that the material transmission resistance, the charge transmission resistance and the electrochemical polarization resistance in the electrode are effectively reduced, and the electrochemical catalytic reaction efficiency and the energy conversion efficiency are improved.
Drawings
FIG. 1 is a schematic diagram of a fuel cell membrane electrode assembly according to the present invention; wherein, 1-carbon fiber paper layer; 2-a catalytic layer for growing whiskers; 3-proton exchange membrane layer.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Uniformly spraying polytetrafluoroethylene emulsion with the mass concentration of 8% on two sides of the carbon fiber paper to enable polytetrafluoroethylene to permeate into the carbon fiber paper to form a hydrophobic microfilm, and drying to obtain pretreated carbon fiber paper; the thickness of the carbon fiber paper is 0.25mm, and the porosity is 76%;
(2) adding a porous nano catalyst, zinc chloride and a dispersing agent into water, ultrasonically dispersing for 42min at room temperature, slowly adding a precipitating agent, adjusting the pH value to 8.8, mixing and stirring uniformly to enable the zinc chloride to form a precursor in micropores of the porous nano catalyst to obtain a slurry; the porous nano catalyst is Pt/C catalyst particles with micropores and the average particle size of 90 nm; dispersant ammonium carbonate; the precipitant is sodium hydroxide;
wherein: 34 parts of porous nano catalyst, 15 parts of zinc chloride, 2 parts of dispersant, 44 parts of water and 5 parts of precipitator;
(3) adding a Nafion solution and a carbon material into the slurry obtained in the step (2), uniformly stirring at the speed of 400r/min to obtain a coating liquid, uniformly coating one side of the pretreated carbon fiber paper prepared in the step (1), treating at 95 ℃ for 11min to stabilize pre-curing, transferring into a hydrothermal reaction device, carrying out hydrothermal reaction at 190 ℃ for 1.5h to gradually form zinc oxide whiskers, arranging the porous nano catalyst along the direction of the zinc oxide whiskers, washing after the reaction is finished, and drying to obtain the carbon fiber paper with the surface formed with the catalyst layer; the mass concentration of the Nafion solution is 9 percent; the carbon material is microporous acetylene black carbon powder; the coating is blade coating, and the coating thickness is 400 mu m;
wherein: 54 parts by weight of the slurry, 28 parts by weight of the Nafion solution, and 18 parts by weight of the carbon material;
(4) uniformly spraying a Nafion solution on the surface of a proton exchange membrane, and then hot-pressing and attaching the carbon fiber paper with the surface formed with the catalyst layer prepared in the step (3) and the proton exchange membrane to form a fuel cell membrane electrode which sequentially comprises the carbon fiber paper layer, the catalyst layer and the proton exchange membrane from bottom to top, namely a fuel cell membrane electrode assembly formed by growing whiskers; the proton exchange membrane is a Nafion 117 perfluorosulfonic acid type proton exchange membrane; the mass concentration of the Nafion solution is 8 percent; the temperature of hot pressing and bonding is 128 ℃, the pressure is 9.5MPa, and the pressure maintaining time is 62 s.
Example 2
(1) Uniformly spraying polytetrafluoroethylene emulsion with the mass concentration of 8% on two sides of the carbon fiber paper to enable polytetrafluoroethylene to permeate into the carbon fiber paper to form a hydrophobic microfilm, and drying to obtain pretreated carbon fiber paper; the thickness of the carbon fiber paper is 0.25mm, and the porosity is 76%;
(2) adding a porous nano catalyst, zinc chloride and a dispersing agent into water, ultrasonically dispersing for 35min at room temperature, slowly adding a precipitating agent, adjusting the pH value to 8.2, mixing and stirring uniformly to enable the zinc chloride to form a precursor in micropores of the porous nano catalyst to obtain a slurry; the porous nano catalyst is Pt/C catalyst particles with micropores and an average particle size of 30 nm; dispersing agent ammonium bicarbonate; the precipitator is ammonia water;
wherein: 31 parts of porous nano catalyst, 13 parts of zinc chloride, 1 part of dispersant, 51 parts of water and 4 parts of precipitator;
(3) adding a Nafion solution and a carbon material into the slurry obtained in the step (2), uniformly stirring at the speed of 300r/min to obtain a coating liquid, uniformly coating one side of the pretreated carbon fiber paper prepared in the step (1), treating at 95 ℃ for 12min to stabilize pre-curing, transferring into a hydrothermal reaction device, carrying out hydrothermal reaction at 190 ℃ for 1.5h to gradually form zinc oxide whiskers, arranging the porous nano catalyst along the direction of the zinc oxide whiskers, washing and drying after the reaction is finished, and preparing the carbon fiber paper with the surface formed with the catalyst layer; the mass concentration of the Nafion solution is 6 percent; the carbon material is a carbon nano tube; the coating is ultrasonic spraying, and the coating thickness is 100 mu m;
wherein: 55 parts by weight of slurry, 23 parts by weight of Nafion solution and 12 parts by weight of carbon material;
(4) uniformly spraying a Nafion solution on the surface of a proton exchange membrane, and then hot-pressing and attaching the carbon fiber paper with the surface formed with the catalyst layer prepared in the step (3) and the proton exchange membrane to form a fuel cell membrane electrode which sequentially comprises the carbon fiber paper layer, the catalyst layer and the proton exchange membrane from bottom to top, namely a fuel cell membrane electrode assembly formed by growing whiskers; the proton exchange membrane is a Nafion 115 perfluorosulfonic acid type proton exchange membrane; the mass concentration of the Nafion solution is 6 percent; the temperature of hot pressing and bonding is 122 ℃, the pressure is 8.5MPa, and the pressure maintaining time is 68 s.
Example 3
(1) Uniformly spraying polytetrafluoroethylene emulsion with the mass concentration of 8% on two sides of the carbon fiber paper to enable polytetrafluoroethylene to permeate into the carbon fiber paper to form a hydrophobic microfilm, and drying to obtain pretreated carbon fiber paper; the thickness of the carbon fiber paper is 0.25mm, and the porosity is 76%;
(2) adding a porous nano catalyst, zinc chloride and a dispersing agent into water, ultrasonically dispersing for 37min at room temperature, slowly adding a precipitating agent, adjusting the pH value to 8-9, mixing and stirring uniformly to enable the zinc chloride to form a precursor in micropores of the porous nano catalyst to obtain a slurry; the porous nano catalyst is Pt/C catalyst particles with micropores and an average particle size of 50 nm; dispersant ammonium carbonate; the precipitator is ammonia water;
wherein: 33 parts of porous nano catalyst, 13 parts of zinc chloride, 2 parts of dispersant, 48 parts of water and 4 parts of precipitator;
(3) adding a Nafion solution and a carbon material into the slurry obtained in the step (2), uniformly stirring at the speed of 500r/min to obtain a coating liquid, uniformly coating one side of the pretreated carbon fiber paper prepared in the step (1), treating at 88 ℃ for 13min to stabilize pre-curing, transferring into a hydrothermal reaction device, carrying out hydrothermal reaction at 170 ℃ for 2h to gradually form zinc oxide whiskers, arranging the porous nano catalyst along the direction of the zinc oxide whiskers, washing and drying after the reaction is finished, and preparing the carbon fiber paper with the surface formed with the catalyst layer; the mass concentration of the Nafion solution is 7 percent; the carbon material is carbon nanofiber; the coating is blade coating, and the coating thickness is 300 mu m;
wherein: 59 parts of slurry, 4 parts of Nafion solution and 17 parts of carbon material;
(4) uniformly spraying a Nafion solution on the surface of a proton exchange membrane, and then hot-pressing and attaching the carbon fiber paper with the surface formed with the catalyst layer prepared in the step (3) and the proton exchange membrane to form a fuel cell membrane electrode which sequentially comprises the carbon fiber paper layer, the catalyst layer and the proton exchange membrane from bottom to top, namely a fuel cell membrane electrode assembly formed by growing whiskers; the proton exchange membrane is a Nafion 112 perfluorosulfonic acid type proton exchange membrane; the mass concentration of the Nafion solution is 7 percent; the temperature of hot pressing and bonding is 1206 ℃, the pressure is 9MPa, and the dwell time is 66 s.
Example 4
(1) Uniformly spraying polytetrafluoroethylene emulsion with the mass concentration of 8% on two sides of the carbon fiber paper to enable polytetrafluoroethylene to permeate into the carbon fiber paper to form a hydrophobic microfilm, and drying to obtain pretreated carbon fiber paper; the thickness of the carbon fiber paper is 0.25mm, and the porosity is 76%;
(2) adding a porous nano catalyst, zinc chloride and a dispersing agent into water, ultrasonically dispersing for 45min at room temperature, slowly adding a precipitating agent, adjusting the pH value to 9, mixing and stirring uniformly to enable the zinc chloride to form a precursor in micropores of the porous nano catalyst to obtain a slurry; the porous nano catalyst is Pt/C catalyst particles with micropores and an average particle size of 100 nm; dispersing agent ammonium bicarbonate; the precipitant is sodium hydroxide;
wherein: 35 parts of porous nano catalyst, 16 parts of zinc chloride, 3 parts of dispersant, 40 parts of water and 6 parts of precipitator;
(3) adding a Nafion solution and a carbon material into the slurry obtained in the step (2), uniformly stirring at the speed of 350r/min to obtain a coating liquid, uniformly coating one side of the pretreated carbon fiber paper prepared in the step (1), treating at 100 ℃ for 10min to stabilize pre-curing, transferring into a hydrothermal reaction device, carrying out hydrothermal reaction at 200 ℃ for 1h to gradually form zinc oxide whiskers, arranging the porous nano catalyst along the direction of the zinc oxide whiskers, washing and drying after the reaction is finished, and preparing the carbon fiber paper with the surface formed with the catalyst layer; the mass concentration of the Nafion solution is 10 percent; the carbon material is graphene; the coating is ultrasonic spraying, and the coating thickness is 500 mu m;
wherein: 50 parts by weight of slurry, 30 parts by weight of Nafion solution and 20 parts by weight of carbon material;
(4) uniformly spraying a Nafion solution on the surface of a proton exchange membrane, and then hot-pressing and attaching the carbon fiber paper with the surface formed with the catalyst layer prepared in the step (3) and the proton exchange membrane to form a fuel cell membrane electrode which sequentially comprises the carbon fiber paper layer, the catalyst layer and the proton exchange membrane from bottom to top, namely a fuel cell membrane electrode assembly formed by growing whiskers; the proton exchange membrane is a Nafion 1135 perfluorosulfonic acid type proton exchange membrane; the mass concentration of the Nafion solution is 10 percent; the temperature of hot-pressing and laminating is 130 ℃, the pressure is 10MPa, and the pressure maintaining time is 60 s.
Example 5
(1) Uniformly spraying polytetrafluoroethylene emulsion with the mass concentration of 8% on two sides of the carbon fiber paper to enable polytetrafluoroethylene to permeate into the carbon fiber paper to form a hydrophobic microfilm, and drying to obtain pretreated carbon fiber paper; the thickness of the carbon fiber paper is 0.25mm, and the porosity is 76%;
(2) adding a porous nano catalyst, zinc chloride and a dispersing agent into water, ultrasonically dispersing for 30min at room temperature, slowly adding a precipitating agent, adjusting the pH value to 8, mixing and stirring uniformly to enable the zinc chloride to form a precursor in micropores of the porous nano catalyst to obtain a slurry; the porous nano catalyst is Pt/C catalyst particles with micropores and an average particle size of 10 nm; dispersant ammonium carbonate; the precipitant is sodium hydroxide;
wherein: 30 parts of porous nano catalyst, 12 parts of zinc chloride, 1 part of dispersant, 54 parts of water and 3 parts of precipitator;
(3) adding a Nafion solution and a carbon material into the slurry obtained in the step (2), uniformly stirring at the speed of 450r/min to obtain a coating liquid, uniformly coating one side of the pretreated carbon fiber paper prepared in the step (1), treating at 80 ℃ for 15min to stabilize pre-curing, transferring into a hydrothermal reaction device, carrying out hydrothermal reaction at 150 ℃ for 3h to gradually form zinc oxide whiskers, arranging the porous nano catalyst along the direction of the zinc oxide whiskers, washing and drying after the reaction is finished, and preparing the carbon fiber paper with the surface formed with the catalyst layer; the mass concentration of the Nafion solution is 5 percent; the carbon material is microporous acetylene black carbon powder; the coating is blade coating, and the coating thickness is 50 mu m;
wherein: 65 parts by weight of slurry, 20 parts by weight of Nafion solution and 15 parts by weight of carbon material;
(4) uniformly spraying a Nafion solution on the surface of a proton exchange membrane, and then hot-pressing and attaching the carbon fiber paper with the surface formed with the catalyst layer prepared in the step (3) and the proton exchange membrane to form a fuel cell membrane electrode which sequentially comprises the carbon fiber paper layer, the catalyst layer and the proton exchange membrane from bottom to top, namely a fuel cell membrane electrode assembly formed by growing whiskers; the proton exchange membrane is a Nafion105 perfluorosulfonic acid type proton exchange membrane; the mass concentration of the Nafion solution is 5 percent; the temperature of hot pressing and bonding is 120 ℃, the pressure is 8MPa, and the pressure maintaining time is 70 s.
Example 6
(1) Uniformly spraying polytetrafluoroethylene emulsion with the mass concentration of 8% on two sides of the carbon fiber paper to enable polytetrafluoroethylene to permeate into the carbon fiber paper to form a hydrophobic microfilm, and drying to obtain pretreated carbon fiber paper; the thickness of the carbon fiber paper is 0.25mm, and the porosity is 76%;
(2) adding a porous nano catalyst, zinc chloride and a dispersing agent into water, ultrasonically dispersing for 38min at room temperature, slowly adding a precipitating agent, adjusting the pH value to 8.5, mixing and stirring uniformly to enable the zinc chloride to form a precursor in micropores of the porous nano catalyst to obtain a slurry; the porous nano catalyst is Pt/C catalyst particles with micropores and an average particle size of 60 nm; dispersing agent ammonium bicarbonate; the precipitator is ammonia water;
wherein: 32 parts of porous nano catalyst, 14 parts of zinc chloride, 2 parts of dispersant, 47 parts of water and 5 parts of precipitator;
(3) adding a Nafion solution and a carbon material into the slurry obtained in the step (2), uniformly stirring at the speed of 380r/min to obtain a coating liquid, uniformly coating one side of the pretreated carbon fiber paper prepared in the step (1), treating at 90 ℃ for 12min to stabilize pre-curing, transferring into a hydrothermal reaction device, carrying out hydrothermal reaction at 180 ℃ for 2h to gradually form zinc oxide whiskers, arranging the porous nano catalyst along the direction of the zinc oxide whiskers, washing and drying after the reaction is finished, and preparing the carbon fiber paper with the surface formed with the catalyst layer; the mass concentration of the Nafion solution is 8 percent; the carbon material is a carbon nano tube; the coating is ultrasonic spraying, and the coating thickness is 400 mu m;
wherein: 57 parts by weight of the slurry, 25 parts by weight of a Nafion solution, and 18 parts by weight of a carbon material;
(4) uniformly spraying a Nafion solution on the surface of a proton exchange membrane, and then hot-pressing and attaching the carbon fiber paper with the surface formed with the catalyst layer prepared in the step (3) and the proton exchange membrane to form a fuel cell membrane electrode which sequentially comprises the carbon fiber paper layer, the catalyst layer and the proton exchange membrane from bottom to top, namely a fuel cell membrane electrode assembly formed by growing whiskers; the proton exchange membrane is a Nafion 117 perfluorosulfonic acid type proton exchange membrane; the mass concentration of the Nafion solution is 8 percent; the temperature of hot-pressing and laminating is 125 ℃, the pressure is 9MPa, and the pressure maintaining time is 65 s.
Comparative example 1
(1) Uniformly spraying polytetrafluoroethylene emulsion with the mass concentration of 8% on two sides of the carbon fiber paper to enable polytetrafluoroethylene to permeate into the carbon fiber paper to form a hydrophobic microfilm, and drying to obtain pretreated carbon fiber paper; the thickness of the carbon fiber paper is 0.25mm, and the porosity is 76%;
(2) adding a porous nano catalyst and a dispersing agent into water, ultrasonically dispersing for 38min at room temperature, adjusting the pH value to 8.5, and uniformly mixing and stirring to obtain a slurry; the porous nano catalyst is Pt/C catalyst particles with micropores and an average particle size of 60 nm; dispersing agent ammonium bicarbonate;
wherein: 32 parts of porous nano catalyst, 2 parts of dispersant and 47 parts of water;
(3) adding a Nafion solution and a carbon material into the slurry obtained in the step (2), uniformly stirring at the speed of 380r/min to obtain a coating liquid, uniformly coating one side of the pretreated carbon fiber paper prepared in the step (1), treating at 90 ℃ for 12min to ensure that the carbon fiber paper is pre-cured stably, and drying to obtain carbon fiber paper with a catalytic layer formed on the surface; the mass concentration of the Nafion solution is 8 percent; the carbon material is a carbon nano tube; the coating is ultrasonic spraying, and the coating thickness is 400 mu m;
wherein: 57 parts by weight of the slurry, 25 parts by weight of a Nafion solution, and 18 parts by weight of a carbon material;
(4) uniformly spraying a Nafion solution on the surface of a proton exchange membrane, and then hot-pressing and attaching the carbon fiber paper with the surface formed with the catalyst layer prepared in the step (3) and the proton exchange membrane to form a fuel cell membrane electrode which sequentially comprises the carbon fiber paper layer, the catalyst layer and the proton exchange membrane from bottom to top, namely a fuel cell membrane electrode assembly; the proton exchange membrane is a Nafion 117 perfluorosulfonic acid type proton exchange membrane; the mass concentration of the Nafion solution is 8 percent; the temperature of hot-pressing and laminating is 125 ℃, the pressure is 9MPa, and the pressure maintaining time is 65 s.
The membrane electrode catalysts obtained in example 6 and comparative example 1 were tested for their catalytic energy conversion effect. The specific test method comprises cutting and packaging the membrane electrode in a small test device of the fuel cell, fixing with a fixture, using 2.0M methanol solution as anode, free air as cathode, and testing at 45 deg.C. The maximum power of the fuel cell test apparatus was tested as shown in table 1:
table 1:
through tests, the catalyst layer of the membrane electrode disclosed by the invention promotes the catalyst to be distributed in a fiber whisker shape into an ordered network by forming the zinc oxide whiskers, so that the material transmission resistance, the charge transmission resistance and the electrochemical polarization resistance in the electrode are effectively reduced, the electrochemical catalytic reaction efficiency and the energy conversion efficiency are improved, and larger power is generated in unit area. Comparative example 1 since zinc oxide whiskers were not formed, the catalyst was distributed in fine particles, and the energy efficiency of the catalyst was exerted to a limited extent.
Claims (10)
1. A preparation method of a fuel cell membrane electrode component formed by growing whiskers is characterized by comprising the following specific steps:
(1) uniformly spraying polytetrafluoroethylene emulsion on two sides of the carbon fiber paper, and drying to obtain pretreated carbon fiber paper;
(2) adding a porous nano catalyst, zinc chloride and a dispersing agent into water, ultrasonically dispersing for 30-45 min at room temperature, slowly adding a precipitating agent, adjusting the pH value to 8-9, mixing and stirring uniformly to enable the zinc chloride to form a precursor in micropores of the porous nano catalyst to obtain a slurry;
(3) adding a Nafion solution and a carbon material into the slurry obtained in the step (2), uniformly stirring at the speed of 300-500 r/min to obtain a coating liquid, uniformly coating one side of the pretreated carbon fiber paper prepared in the step (1), treating at 80-100 ℃ for 10-15 min to stabilize pre-curing, transferring the carbon fiber paper into a hydrothermal reaction device, carrying out hydrothermal reaction at 150-200 ℃ for 1-3 h to gradually form zinc oxide whiskers, arranging the porous nano catalyst along the direction of the zinc oxide whiskers, washing after the reaction is finished, and drying to obtain the carbon fiber paper with the surface on which the catalyst layer is formed;
(4) uniformly spraying a Nafion solution on the surface of the proton exchange membrane, and then hot-pressing and attaching the carbon fiber paper with the surface formed with the catalyst layer prepared in the step (3) and the proton exchange membrane to form a fuel cell membrane electrode which sequentially comprises the carbon fiber paper layer, the catalyst layer and the proton exchange membrane from bottom to top, namely the fuel cell membrane electrode assembly formed by growing whiskers.
2. A method of making a whisker-grown fuel cell membrane electrode assembly according to claim 1, wherein: the thickness of the carbon fiber paper in the step (1) is 0.2-0.3 mm, and the porosity is more than 70%.
3. A method of making a whisker-grown fuel cell membrane electrode assembly according to claim 1, wherein: the porous nano catalyst in the step (2) is Pt/C catalyst particles with micropores and the particle size of 10-100 nm, the dispersant is at least one of ammonium carbonate and ammonium bicarbonate, and the precipitant is one of sodium hydroxide and ammonia water.
4. A method of making a whisker-grown fuel cell membrane electrode assembly according to claim 1, wherein: in the step (2), 30-35 parts by weight of porous nano catalyst, 12-16 parts by weight of zinc chloride, 1-3 parts by weight of dispersant, 40-54 parts by weight of water and 3-6 parts by weight of precipitator.
5. A method of making a whisker-grown fuel cell membrane electrode assembly according to claim 1, wherein: and (3) the mass concentration of the Nafion solution in the step (3) is 5-10%, and the carbon material is at least one of microporous acetylene black carbon powder, carbon nano tubes, carbon nano fibers and graphene.
6. A method of making a whisker-grown fuel cell membrane electrode assembly according to claim 1, wherein: in the step (3), 50-65 parts by weight of the slurry, 20-30 parts by weight of the Nafion solution and 15-20 parts by weight of the carbon material are added.
7. A method of making a whisker-grown fuel cell membrane electrode assembly according to claim 1, wherein: and (3) blade coating or ultrasonic spraying is adopted as the coating, and the coating thickness is 50-500 mu m.
8. A method of making a whisker-grown fuel cell membrane electrode assembly according to claim 1, wherein: the proton exchange membrane in the step (4) is a perfluorosulfonic acid type proton exchange membrane, and can be a Nafion series membrane provided by Du Pont, which is commonly used, specifically one of Nafion 117, Nafion 115, Nafion 112, Nafion 1135 and Nafion105, and the mass concentration of the Nafion solution is 5-10%.
9. A method of making a whisker-grown fuel cell membrane electrode assembly according to claim 1, wherein: and (4) performing hot-pressing lamination at the temperature of 120-130 ℃, under the pressure of 8-10 MPa, and keeping the pressure for 60-70 s.
10. A whisker-grown fuel cell membrane electrode assembly prepared by the method of any one of claims 1 to 8.
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