CN113594472A - Ink for membrane electrode of proton exchange membrane fuel cell and preparation method thereof - Google Patents

Ink for membrane electrode of proton exchange membrane fuel cell and preparation method thereof Download PDF

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CN113594472A
CN113594472A CN202111085531.1A CN202111085531A CN113594472A CN 113594472 A CN113594472 A CN 113594472A CN 202111085531 A CN202111085531 A CN 202111085531A CN 113594472 A CN113594472 A CN 113594472A
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catalyst
ink
membrane electrode
fuel cell
surfactant
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刘凯
许笑目
刘敏
张义煌
陈杰
李刚
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Wuxi Weifu High Technology Group Co Ltd
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Wuxi Weifu High Technology Group Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention belongs to the technical field of fuel cells, and particularly relates to ink for a membrane electrode of a proton exchange membrane fuel cell and a preparation method thereof. The catalyst ink for the membrane electrode of the proton exchange membrane fuel cell comprises a catalyst, a resin solution, a surfactant and ultrapure water, wherein the catalyst is a platinum-carbon catalyst, a platinum-cobalt alloy catalyst or a platinum-containing ternary alloy catalyst with platinum loading capacity of 40-60%; the resin solution is a perfluorosulfonic acid resin solution; the surfactant is a cationic surfactant or a nonionic surfactant. The invention adjusts the distribution state of the catalyst in the ink by adjusting the proportion of the catalyst, the resin solution and the ultrapure water and adopting a step-by-step dispersion process, thereby reducing the production cost of the fuel cell. Compared with the traditional membrane electrode, the membrane electrode of the invention does not use alcohols, thereby greatly reducing the production cost, being easy to enlarge and being beneficial to batch production.

Description

Ink for membrane electrode of proton exchange membrane fuel cell and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to ink for a membrane electrode of a proton exchange membrane fuel cell and a preparation method thereof.
Background
Low contamination and even non-contamination of Proton Exchange Membrane Fuel Cells (PEMFCs) are of great global concern. With the development of fuel cell technology and the advancement of global industrialization, low-cost, high-power density and long-life fuel cell products have been initially scaled, and the continuous reduction of the cost of the stack becomes a key factor for the commercialization of the fuel cell. The membrane electrode plays a key role as one of the key materials of the fuel cell, and the preparation of the ink directly determines the performance and the cost of the cell.
In the process of preparing the membrane electrode, the use of reducing volatile components can reduce the production cost and the environmental pressure. The prior art mainly improves the dispersibility and volatility of the catalyst ink by adding alcohols, is beneficial to the dispersion of the catalyst and the quick drying of the ink, and improves the production efficiency, but has large environmental pressure and high cost.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide ink for a membrane electrode of a proton exchange membrane fuel cell and a preparation method thereof. The invention uses ultrapure water as solvent, adds a trace amount of surfactant, enables the resin to exist in a specific form (spherical shape), prevents the film formation in the catalyst layer from influencing the transmission of gas (hydrogen and air) and liquid (water), and can effectively improve the internal microstructure of the catalyst layer; alcohols are not used, so that the potential safety hazard of production can be reduced, and the production cost can be reduced at the same time.
In order to achieve the technical purpose, the embodiment of the invention adopts the technical scheme that:
on one hand, the embodiment of the invention provides catalyst ink for a membrane electrode of a proton exchange membrane fuel cell, which comprises a catalyst, a resin solution, a surfactant and ultrapure water, wherein the catalyst is a platinum-carbon catalyst, a platinum-cobalt alloy catalyst or a platinum-containing ternary alloy catalyst with platinum loading capacity of 40-60%;
the resin solution is a perfluorosulfonic acid resin solution; the surfactant is a cationic surfactant or a nonionic surfactant.
Further, the perfluorinated sulfonic acid resin is one or more of dupont D520, dupont D2020, solvay D72 or solvay D79 perfluorinated sulfonic acid resin.
On the other hand, the embodiment of the invention also provides a preparation method of the ink for the membrane electrode of the proton exchange membrane fuel cell, which comprises the following steps:
(1) weighing a certain amount of catalyst, ultrapure water, resin solution and surfactant, and mixing according to the mass ratio of 1:8-1000:6-12: 0.01-0.1;
(2) stirring the mixed solution in the step (1) by adopting a cantilever type stirrer or a magnetic stirrer to obtain catalyst ink, wherein the cantilever type stirrer is provided with a polytetrafluoroethylene stirring rod, the stirring speed is 100-; when the catalyst ink is stirred in the step (2), the stirring speed cannot be too slow, and the catalyst cannot be dispersed into nano particles and cannot be stirred too fast when the stirring is too slow, so that a large amount of foam is prevented from being generated; the stirring time cannot be too short, and the stirring time cannot be too short to disperse uniformly; the stirring time is not too long, which can cause the catalyst to re-agglomerate, and preferably, the stirring speed is 300-.
(3) Dispersing the catalyst ink prepared in the step (2) for 2-6 times by adopting a homogenizer, wherein the pressure of the homogenizer is 1000-30000 psi;
(4) and (4) performing anti-settling stirring on the catalyst ink obtained by secondary dispersion in the step (3) by adopting magnetic stirring, wherein the stirring speed is 100-400 r/min.
Further, the solid content of the catalyst ink in the step (2) is 1-12%.
Further, the adding sequence of the materials during mixing in the step (1) is as follows in sequence: catalyst, ultrapure water, resin solution and surfactant.
Further, the surfactant is a fluorine-containing surfactant, and one or more of DuPont FS30, FS3100, FS10 and FS31 are adopted.
Further, the homogeneous dispersion pressure in step (3) is 3000-25000psi, and the number of dispersions is 3-5. The number of times of homogeneous dispersion cannot be too small, too small catalyst has too wide particle size distribution, too much catalyst has too small particle size distribution, the performance is deteriorated, and even platinum particles or alloy particles are separated from the carbon surface.
Further, the anti-settling stirring in the step (4) is carried out until the catalyst ink is completely used up.
Further, the whole process in the steps (1) to (4) is carried out under the conditions of minus 7 to minus 5 ℃.
Compared with the prior art, the invention has the following advantages:
the invention uses ultrapure water as solvent, adds a trace amount of surfactant, enables the resin to exist in a specific form (spherical shape), prevents the film formation in the catalyst layer from influencing the transmission of gas (hydrogen and air) and liquid (water), and can effectively improve the internal microstructure of the catalyst layer; alcohols are not used, so that the potential safety hazard of production can be reduced, and the production cost can be reduced at the same time.
The catalyst ink dispersing process for the membrane electrode adopts pre-dispersion, homogeneous dispersion and anti-settling dispersion, and solves the problems of difficult dispersion and uneven dispersion of catalyst slurry.
The catalyst ink for the membrane electrode of the fuel cell adopts the catalyst ink without adding any alcohol material (except a solvent of a surfactant), so that the preparation cost of the membrane electrode ink of the fuel cell is reduced, and the production cost is reduced. Compared with the traditional membrane electrode, the ink for the membrane electrode provided by the invention adopts ultrapure water as a solvent, so that the cost of the catalyst ink can be effectively reduced, the environmental pressure can be reduced, the problems of insufficient membrane electrode performance and the like can be solved, the amplification is easy, and the mass production is facilitated.
Drawings
FIG. 1 is a graph comparing the performance of MEA's made with platinum carbon catalyst inks according to examples 1-3 of the present invention.
FIG. 2 is a comparison of the performance of the MEA's made with the inks of the platinum carbon catalysts of examples 1 and 4 of the present invention.
FIG. 3 is a comparison of the performance of MEA's made with inks of platinum alloy catalysts in examples 5 and 6 of the present invention.
FIG. 4 is a comparison of the performance of MEA's made with the catalyst inks of example 1 of the present invention and comparative example 1.
Fig. 5 is a graph showing the light transmission effect of the surface structure of the MEAs in example 1 of the present invention and comparative example 1.
Wherein, a is the light transmission effect of the MEA surface structure in example 1 under an optical microscope, and b is the light transmission effect of the MEA surface structure in comparative example 1 under an optical microscope.
Fig. 6 is a graph showing the light reflecting effect of the surface structure of the MEAs in example 1 of the present invention and comparative example 1.
Wherein, the graph a is the light reflection effect of the MEA surface structure under the optical microscope in the example 1, and the graph b is the light reflection effect of the MEA surface structure under the optical microscope in the comparative example 1.
FIG. 7 is a microstructure of an MEA according to example 1 of the present invention at different magnifications.
Wherein, figure a is the microstructure of the MEA in example 1 at a magnification of 1 ten thousand, and figure b is the microstructure of the MEA in example 1 at a magnification of 20 ten thousand.
FIG. 8 is a microstructure of an MEA according to comparative example 1 of the present invention at different magnifications.
Wherein, fig. a is a microstructure of the MEA in comparative example 1 at a magnification of 1 ten thousand, and fig. b is a microstructure of the MEA in comparative example 1 at a magnification of 20 ten thousand.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Weighing 1 g of Pt/C catalyst (60% of platinum loading capacity in Ming and Xin Wanfeng, England), putting the Pt/C catalyst into a beaker, adding 500mL of ultrapure water, 30 mu L of FS10 surfactant (fluorosulfonic acid solution of DuPont company) and 10mL of nafion resin mixed solution (DuPont D520), firstly mixing and dispersing at a stirring speed of 400 r/min by using a cantilever type stirrer, adopting a polytetrafluoroethylene stirring rod by using the cantilever type stirrer, then performing secondary dispersion at a pressure of 8000psi by using a homogenizer for 4 times to form catalyst ink, then performing magnetic stirring to prevent sedimentation, and stirring at a stirring speed of 400 r/min until the catalyst ink is completely used up; the ink is sprayed to the area of 75cm by ultrasonic spraying2Drying the front and back sides of the proton exchange membrane. The CCM was packaged into an MEA by attaching GDL (German Codebao H54CX653 gas diffusion layer), and the MEA was placed in a cell holder for performance test, wherein the performance graph is shown in FIG. 1.
Example 2
Weighing 1 g of Pt/C catalyst (60% of platinum loading capacity in Kangxinwan), putting the Pt/C catalyst into a beaker, adding 800mL of ultrapure water, 20 mu L of FS10 surfactant (fluorosulfonic acid solution of DuPont company) and 10mL of nafion resin mixed solution (DuPont D520), firstly mixing and dispersing at a stirring speed of 400 revolutions per minute by using a cantilever type stirrer, then performing secondary dispersion at a pressure of 8000psi by using a homogenizer for 4 times to form catalyst ink, then performing anti-settling by using magnetic stirring, and stirring at a stirring speed of 400 revolutions per minute until the catalyst ink is completely used up; the ink is sprayed to the area of 75cm by ultrasonic spraying2Drying the front and back sides of the proton exchange membrane. The CCM is packaged into MEA by attaching GDL (German Codebao H54CX653 gas diffusion layer), and the MEA is put into a battery clamp for performance test and life test comparison test, and the performance curve chart is shown in figure 2.
Example 3
1 g of Pt/C catalyst (60% platinum loading, Mingkuanxinwan) was weighed into a beaker, 1000mL of ultrapure water, 10. mu.L of FS10 surfactant (fluorosulfonic acid solution from DuPont corporation) and 10mL of nafion resin mixed solution (DuPont D520) were addedFirstly, mixing and dispersing at a stirring speed of 400 revolutions per minute by using a cantilever type stirrer, then carrying out secondary dispersion at a pressure of 8000psi by using a homogenizer for 4 times to form catalyst ink, then adopting magnetic stirring to prevent sedimentation, and stirring at a stirring speed of 400 revolutions per minute until the catalyst ink is completely used up; the ink is sprayed to the area of 75cm by ultrasonic spraying2Drying the front and back sides of the proton exchange membrane. The CCM was packaged into an MEA by attaching GDL (German Codebao H54CX653 gas diffusion layer), and the MEA was placed in a cell holder for performance test, wherein the performance graph is shown in FIG. 3.
Example 4
Weighing 1 g of Pt/C catalyst (60% of platinum loading capacity in Kangxinwan), putting the Pt/C catalyst into a beaker, adding 500mL of ultrapure water, 30 mu L of FS31 surfactant (fluorosulfonic acid solution of DuPont company) and 10mL of nafion resin mixed solution (DuPont D520), firstly mixing and dispersing at a stirring speed of 400 revolutions per minute by using a cantilever type stirrer, then performing secondary dispersion at a pressure of 8000psi of a homogenizer for 4 times to form catalyst ink, then performing magnetic stirring to prevent sedimentation, and stirring at a stirring speed of 400 revolutions per minute until the catalyst ink is completely used up; the ink is sprayed to the area of 75cm by ultrasonic spraying2Drying the front and back sides of the proton exchange membrane. The CCM was packaged into an MEA by attaching GDL (German Codebao H54CX653 gas diffusion layer), and the MEA was placed in a cell holder for performance test, wherein the performance graph is shown in FIG. 4.
Example 5
Weighing 1 g of platinum-cobalt alloy catalyst (48% of platinum, 3% of cobalt and the balance of carbon carrier, TKK company in Japan), placing the platinum-cobalt alloy catalyst in a beaker, adding 500mL of ultrapure water, 30 μ L of FS10 surfactant (fluorosulfonic acid solution of DuPont company) and 10mL of nafion resin mixed solution (DuPont D520), firstly mixing and dispersing at a stirring speed of 400 r/min by using a cantilever type stirrer, then performing secondary dispersion at a pressure of 8000psi of a homogenizer for 4 times to form catalyst ink, then performing magnetic stirring to prevent sedimentation, and stirring at a stirring speed of 400 r/min until the catalyst ink is completely used up; the ink is sprayed to the area of 75cm by ultrasonic spraying2Is a proton exchange membraneAnd drying the front side and the back side. The CCM was packaged into an MEA by attaching GDL (German Codebao H54CX653 gas diffusion layer), and the MEA was placed in a cell holder for performance test, wherein the performance graph is shown in FIG. 5.
Example 6
Weighing 1 g of platinum-cobalt alloy catalyst (48% of platinum, 3% of cobalt and the balance of carbon carrier, TKK company in Japan), placing the platinum-cobalt alloy catalyst in a beaker, adding 500mL of ultrapure water, 30 μ L of FS31 surfactant (fluorosulfonic acid solution of DuPont company) and 10mL of nafion resin mixed solution (DuPont D520), firstly mixing and dispersing at a stirring speed of 400 r/min by using a cantilever type stirrer, then performing secondary dispersion at a pressure of 8000psi of a homogenizer for 4 times to form catalyst ink, then performing magnetic stirring to prevent sedimentation, and stirring at a stirring speed of 400 r/min until the catalyst ink is completely used up; the ink is sprayed to the area of 75cm by ultrasonic spraying2Drying the front and back sides of the proton exchange membrane. The CCM was packaged into an MEA by attaching GDL (German Codebao H54CX653 gas diffusion layer), and the MEA was placed in a cell holder for performance test, wherein the performance graph is shown in FIG. 6.
Comparative example 1
Weighing 1 g of Pt/C catalyst (60% of platinum loading capacity in Mingkuangyi Funweng) and placing the Pt/C catalyst in a beaker, adding 500mL of ultrapure water, 100mL of isopropanol and 10mL of nafion resin mixed solution (DuPont D520), firstly adopting a cantilever type stirrer to mix and disperse at the stirring speed of 400 revolutions per minute, then adopting a homogenizer to carry out secondary dispersion at the pressure of 8000psi, dispersing for 4 times to form catalyst ink, then carrying out magnetic stirring to prevent sedimentation, and stirring at the stirring speed of 400 revolutions per minute until the catalyst ink is completely used up; the ink is sprayed to the area of 75cm by ultrasonic spraying2Drying the front and back sides of the proton exchange membrane. The CCM was packaged into an MEA by attaching GDL (German Codebao H54CX653 gas diffusion layer), and the MEA was placed in a cell holder for performance test, wherein the performance graph is shown in FIG. 7.
Comparative example 2
1 g of a platinum-cobalt alloy catalyst (48% platinum, 3% cobalt, and the balance carbon carrier, TKK Co., Japan) was weighed in a beaker, and 500mL of ultrapure water and 100mL of isopropyl alcohol were addedAnd 10mL of nafion resin mixed solution (DuPont D520), firstly adopting a cantilever type stirrer to mix and disperse at the stirring speed of 400 revolutions per minute, then adopting a homogenizer to carry out secondary dispersion at the pressure of 8000psi, dispersing for 4 times to form catalyst ink, then carrying out magnetic stirring to prevent sedimentation, and stirring at the stirring speed of 400 revolutions per minute until the catalyst ink is completely used up; the ink is sprayed to the area of 75cm by ultrasonic spraying2Drying the front and back sides of the proton exchange membrane. The CCM was packaged into an MEA by attaching GDL (German Codebao H54CX653 gas diffusion layer), and the MEA was placed in a cell holder for performance test, wherein the performance graph is shown in FIG. 8.
In examples 1 to 3, the influence of the performance of the membrane electrode was examined by changing the amounts of the surfactant and ultrapure water added to the catalyst ink (using the same surfactant), and it was compared with the performance of the membrane electrode shown in fig. 1, and it was found from fig. 1 that the addition of FS10 surfactant (fluorosulfonic acid solution from dupont) can effectively reduce the amount of water used, increase the solid content of the slurry, and simultaneously exert the electrochemical performance of the platinum-carbon catalyst on the membrane electrode.
Fig. 2 is a comparison of the membrane electrode performance of different catalyst inks in example 1 and example 4 (the inks are optimized by adding different surfactants), and fig. 2 shows that different kinds of surfactants have different effects on the electrochemical performance of the platinum-carbon catalyst on the membrane electrode, wherein the performance of FS10 surfactant (fluorosulfonic acid solution from dupont) is more excellent.
Examples 5-6 are the effect of this ink scheme on the performance of the membrane electrode of the platinum alloy catalyst ink formulation (cathode catalyst layer prepared from platinum alloy catalyst), and fig. 3 is a comparison of the performance of the membrane electrode, and fig. 2 shows that different types of surfactants have different effects on the electrochemical performance of platinum carbon catalyst on the membrane electrode, and that FS10 surfactant (fluorosulfonic acid solution from dupont) is more effective in exerting the electrochemical performance of platinum alloy catalyst on the membrane electrode than FS31 surfactant (anion solution from dupont).
The effect of the comparative example 1 and the platinum carbon catalyst ink containing isopropanol on the performance of the membrane electrode is shown, and the corresponding figure 4 is a comparison of the performance of the membrane electrode prepared in the comparative example 1 and the membrane electrode prepared in the example 1, which shows that the addition of the surfactant is beneficial to improving the performance of the membrane electrode (the performance of the membrane electrode is slightly improved), so that the prepared catalyst ink and the catalyst ink prepared by using alcohol have similar or even higher performance.
Fig. 5 is a comparison of the surface structures of the light transmission effect of the MEA in example 1 and comparative example 1 under an optical microscope, and it can be seen that the alcohol system (conventional ink formulation) in comparative example 1 forms a catalytic layer with a large amount of pore structures inside, which results in poor conductivity of the catalytic layer.
FIG. 6 is a surface texture comparison of light reflection effect under an optical microscope of MEA in example 1 and comparative example 1,
it can be seen from the figure that the alcohol system (conventional ink formulation) forms a rough surface of the catalytic layer, which results in poor contact between the catalytic layer and the GDL (gas diffusion layer).
Fig. 7 shows the microstructures of the MEA (membrane electrode prepared by ultra-low alcohol aqueous ink formulation and specific dispersion process) in example 1 at different magnifications, and fig. 8 shows the microstructures of the MEA (membrane electrode prepared by conventional ink formulation and dispersion process) in comparative example 1 at different magnifications, and it can be seen from the structural comparison between fig. 7 and fig. 8 that the ink formulation using surfactant can make the resin exist in the catalyst layer in an agglomerated form at high magnification, which is beneficial to proton conduction in the catalyst layer.
As can be seen by comparison, the alcohol can dissolve the resin, so that proton transmission in the catalyst layer is hindered, and the electrocatalytic performance of the catalyst is affected. The reason is as follows: the alcohol can dissolve the resin and wrap the resin on the surface of the catalyst, the resin film can block the transmission of water, gas and protons in the catalyst layer, the water and the gas can not reach the surface of the catalyst layer to react, and the performance of the membrane electrode can be greatly influenced; the resin in the new ink formula exists in the form of particles, so that the transmission of water and gas cannot be influenced, and the performance of the membrane electrode is obviously improved. The catalyst ink of the membrane electrode adopts a pure water system, adopts a characteristic dispersion process, and has the advantages of small environmental pressure, low cost and relatively simple equipment requirement because of no addition of substances such as alcohols and the like.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.

Claims (9)

1. A catalyst ink for a membrane electrode of a proton exchange membrane fuel cell is characterized by comprising a catalyst, a resin solution, a surfactant and ultrapure water, wherein the catalyst is a platinum-carbon catalyst, a platinum-cobalt alloy catalyst or a platinum-containing ternary alloy catalyst with the platinum loading of 40-60%; the resin solution is a perfluorosulfonic acid resin solution; the surfactant is a cationic surfactant or a nonionic surfactant.
2. The catalyst ink for a proton exchange membrane fuel cell membrane electrode assembly according to claim 1, wherein the perfluorosulfonic acid resin is one or more of dupont D520, dupont D2020, solvay D72, or solvay D79 perfluorosulfonic acid resin.
3. The preparation method of the ink for the membrane electrode of the proton exchange membrane fuel cell according to claim 1, which is characterized by comprising the following steps:
(1) weighing a certain amount of catalyst, ultrapure water, resin solution and surfactant, and mixing according to the mass ratio of 1:8-1000:6-12: 0.01-0.1;
(2) stirring the mixed solution in the step (1) by adopting a cantilever type stirrer or a magnetic stirrer to obtain catalyst ink, wherein the cantilever type stirrer is provided with a polytetrafluoroethylene stirring rod, the stirring speed is 100-;
(3) dispersing the catalyst ink prepared in the step (2) for 2-6 times by adopting a homogenizer, wherein the pressure of the homogenizer is 1000-30000 psi;
(4) and (4) performing anti-settling stirring on the catalyst ink obtained by secondary dispersion in the step (3) by adopting magnetic stirring, wherein the stirring speed is 100-400 r/min.
4. The method for preparing an ink formulation for a membrane electrode assembly of a proton exchange membrane fuel cell according to claim 3, wherein the solid content of the catalyst ink in the step (2) is 1% to 12%.
5. The preparation method of the ink formula for the membrane electrode of the proton exchange membrane fuel cell according to claim 3, wherein the adding sequence of the materials during the mixing in the step (1) is as follows in sequence: catalyst, ultrapure water, resin solution and surfactant.
6. The preparation method of the ink formula for the membrane electrode of the proton exchange membrane fuel cell according to claim 3, wherein the surfactant is a fluorine-containing surfactant, and one or more of DuPont FS30, FS3100, FS10 and FS31 are adopted.
7. The method for preparing the ink formulation for the membrane electrode of the proton exchange membrane fuel cell according to claim 3, wherein the pressure for homogeneous dispersion in the step (3) is 3000-25000psi, and the number of times of dispersion is 3-5.
8. The method for preparing an ink formulation for a membrane electrode assembly of a proton exchange membrane fuel cell according to claim 3, wherein the anti-settling agitation in step (4) is performed until the catalyst ink is completely used up.
9. The preparation method of the ink formula for the membrane electrode of the proton exchange membrane fuel cell according to claim 3, wherein the whole process in the steps (1) to (4) is carried out at the temperature of-7 to-5 ℃.
CN202111085531.1A 2021-09-16 2021-09-16 Ink for membrane electrode of proton exchange membrane fuel cell and preparation method thereof Pending CN113594472A (en)

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CN106654309A (en) * 2016-11-25 2017-05-10 清华大学 Preparation method of catalyst slurry for membrane electrode of fuel cell

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US20130252134A1 (en) * 2010-12-20 2013-09-26 Toyota Jidosha Kabushiki Kaisha High molecular weight ionomers and ionically conductive compositions for use as one or more electrode of a fuel cell
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Application publication date: 20211102