CN114725457B - Membrane electrode preparation method for accelerating local oxygen mass transfer - Google Patents
Membrane electrode preparation method for accelerating local oxygen mass transfer Download PDFInfo
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- CN114725457B CN114725457B CN202210320223.0A CN202210320223A CN114725457B CN 114725457 B CN114725457 B CN 114725457B CN 202210320223 A CN202210320223 A CN 202210320223A CN 114725457 B CN114725457 B CN 114725457B
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- 239000012528 membrane Substances 0.000 title claims abstract description 59
- 238000012546 transfer Methods 0.000 title claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000001301 oxygen Substances 0.000 title claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 35
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000029087 digestion Effects 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims abstract description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000557 Nafion® Polymers 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000007590 electrostatic spraying Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000000446 fuel Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- SIIVGPQREKVCOP-UHFFFAOYSA-N but-1-en-1-ol Chemical compound CCC=CO SIIVGPQREKVCOP-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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]
-
- 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
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
-
- 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
- H01M4/90—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
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a preparation method of a membrane electrode for accelerating local oxygen mass transfer, which comprises the following steps: mixing a catalyst, an ionic resin and a dispersion solvent to obtain anode catalyst slurry; mixing a catalyst, an ionic resin, a polyvinyl alcohol solution and a dispersion solvent to obtain a cathode catalyst slurry; spraying the cathode catalyst slurry on two sides of a proton exchange membrane; and (3) placing the membrane electrode in hot water for digestion, and drying to form the membrane electrode. The invention uses the polyvinyl alcohol to micro-adjust the internal structure and the distribution state of the ionic resin in the catalytic layer, thereby accelerating the local oxygen mass transfer on the surface of the catalyst and improving the performance of the battery.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a membrane electrode preparation method for accelerating local oxygen mass transfer.
Background
Fuel cells are a highly efficient energy conversion device that can directly convert chemical energy stored in fuel into usable electrical energy through electrochemical reactions. Although proton exchange membrane fuel cells have reached the standards for large-scale applications in terms of performance, lifetime, etc., the high cost has still prevented the industrial development of fuel cell stacks. The high Pt content in the catalytic layer is a bottleneck that limits the further expansion of the industry for proton exchange membrane fuel cells. Most of the new catalysts showed extremely high ORR catalytic performance in the rotating disk electrode test, but did not perform satisfactorily in the actual cell test. This is because the microstructure inside the electrode is complex, the performance of the novel catalyst is difficult to fully exert, and the main reason is diffusion polarization loss caused by slow mass transfer of reactants
It is worth noting that with the decrease of Pt loading, the oxygen local mass transfer resistance of the cathode increases significantly, so that the solution of the oxygen mass transfer resistance of the cathode, especially the oxygen mass transfer resistance in the catalytic layer, of the low Pt membrane electrode under high current is the key to improve the performance of the proton exchange membrane fuel cell and solve the cost problem.
Disclosure of Invention
The invention aims at solving the problems existing in the prior art and provides a membrane electrode preparation method for accelerating local oxygen mass transfer. In view of the above, the technical problem to be solved by the invention is to provide a membrane electrode preparation process for accelerating local oxygen mass transfer, and the porous membrane electrode is prepared by using an ice template method, so that the local oxygen mass transfer on the surface of a catalyst can be accelerated, and the performance of a battery is improved. The invention aims at a cathode catalyst layer, solves the problem of strengthening the local oxygen mass transfer of a cathode, and removes the added polyvinyl alcohol.
The aim of the invention can be achieved by the following scheme:
the invention provides a preparation method of a membrane electrode for accelerating local oxygen mass transfer, which comprises the following steps:
s1, mixing a catalyst, an ionic resin and a dispersing solvent, stirring, and then ball-milling and dispersing to obtain anode catalyst slurry;
s2, dissolving polyvinyl alcohol particles to obtain a polyvinyl alcohol solution;
s3, mixing the catalyst, the ionic resin, the polyvinyl alcohol solution and the dispersing solvent, stirring, and then ball-milling and dispersing to obtain cathode catalyst slurry;
s4, spraying the cathode and anode catalyst slurry in the steps S1 and S3 on two sides of the proton exchange membrane;
s5, placing the paper exchange membrane obtained in the step S4 into hot water for digestion, and drying to obtain the membrane electrode.
As an embodiment of the present invention, the catalyst in step S1 is a Pt/C catalyst; the ionic resin is Nafion resin; the dispersion solvent comprises one or more of deionized water, isopropanol and ethanol. The mass ratio of the catalyst to the ion resin to the dispersion solvent is 1:2:280. preferably, the dispersing solvent is deionized water, a mixed solution of isopropanol or a mixed solution of deionized water and ethanol, and the mass ratio of the Pt/C catalyst to the deionized water to the Nafion resin to the isopropanol is 1:40:2:240.
as one embodiment of the invention, the stirring in the step S1 is ultrasonic stirring, and the stirring time is 10-30 minutes.
As an embodiment of the present invention, the time of the ball milling in step S1 is 4 to 6 hours.
As an embodiment of the present invention, the mass fraction of the polyvinyl alcohol solution in step S2 is 5% to 10%. The solvent used for dissolution was ultrapure water. The polyvinyl alcohol must be added to the catalyst slurry in the form of a solution, but cannot be added to the catalyst slurry in the form of solid particles. Too low a mass fraction will result in too large a solvent ratio in the polyvinyl alcohol solution. If the invention adopts a polyvinyl alcohol solution with lower concentration (such as 1 per mill-1 percent), even if other solvents are not added when preparing catalyst slurry, the mass ratio of the catalyst, the ion resin, the polyvinyl alcohol and the dispersion solvent can reach 1:2:1:100-1000, obviously if 1% polyvinyl alcohol solution is used, 1:2:1: the 1000 ratio is far greater than the one intended by the invention to 1:2:1:280; even with a 1% polyvinyl alcohol solution, the ratio has reached 1:2:1:100, the tuning space left for additional slurry is also very limited, which can become difficult if the subsequent experiments require tuning of the slurry comparisons.
As an embodiment of the present invention, the catalyst in step S3 is a Pt/C catalyst; the ionic resin is Nafion resin; the dispersion solvent comprises one or more of deionized water, isopropanol and ethanol. The mass ratio of the catalyst, the ionic resin, the polyvinyl alcohol and the dispersing solvent in the cathode catalyst slurry is 1:2:1:200-500. Preferably, the dispersing solvent is deionized water, a mixed solution of isopropanol or a mixed solution of deionized water and ethanol. Preferably, the mass ratio of the Pt/C catalyst, deionized water, the ionic resin, the polyvinyl alcohol solution and the isopropanol in the cathode catalyst slurry is 1:40:2:1:240.
as one embodiment of the invention, the stirring in the step S3 is ultrasonic stirring, and the stirring time is 15-25 minutes.
As an embodiment of the present invention, the time of the ball milling in step S3 is 4 to 6 hours. When the dispersion time is short, slurry is unevenly dispersed, and excessive catalyst agglomeration exists in the slurry, so that the catalyst agglomeration occurs in the catalyst layer, thereby not only reducing the available active area of the catalyst, but also seriously preventing the transmission of cathode oxygen.
In one embodiment of the present invention, the slurry spraying in step S4 is to spray the cathode and anode catalyst slurries on the surface of the proton exchange membrane using an electrostatic spraying apparatus. The platinum loading of the cathode catalytic layer is controlled to be 0.1-0.2mg during spraying Pt /cm 2 。
As one embodiment of the present invention, the hot water temperature in step S5 is 95-99℃and the digestion time is 2-3 hours. The soaking and boiling are repeated for 8-12 times. The polyvinyl alcohol cannot be dissolved when the temperature is too low; too high a temperature may accelerate evaporation of water, possibly leading to hot water drying, and at the same time, polyvinyl alcohol may discolor and embrittle, and especially when the heating temperature is higher than 220 ℃, polyvinyl alcohol may decompose to form acetic acid, acetaldehyde, butenol and water, wherein acetic acid may react with ionomer, reducing its proton conductivity, and acetaldehyde and vinyl alcohol may contaminate the catalytically active sites. Meanwhile, the temperature is higher than 220 ℃, and the proton conduction property and durability of the proton exchange membrane are damaged by the exchange membrane. Too short a time may result in insufficient dissolution of the polyvinyl alcohol and too long a time may result in wasted time.
First, the membrane electrode is put into hot water for digestion, and the membrane electrode is not only a proton exchange membrane. In fact, the membrane electrode is a multi-layer structure comprising three parts, namely a cathode catalytic layer, an anode catalytic layer and a proton exchange membrane. Secondly, the polyvinyl alcohol added into the cathode catalytic layer is removed, so that holes on the surface or inside of the ultrathin ionic resin film on the surface of the catalyst are left, and the local oxygen mass transfer is enhanced. Thirdly, the multi-time digestion is used for fully washing off the polyvinyl alcohol in the catalytic layer, so that the catalytic layer is ensured to have no polyvinyl alcohol residue. The invention does not adopt high temperature treatment of proton exchange membrane, if solvent such as acid is used for cleaning the membrane covered with catalyst, partial insoluble still exists in the catalytic layer, which can cause acid residue in the catalytic layer and pollute the catalytic active site.
As an embodiment of the present invention, the drying in step S5 is drying in air.
The existing pore-forming technology mainly adopts nano oxide nano particles or calcium carbonate nano particles, the pore-forming agent is more than 50nm in size, and pore-forming can only be carried out aiming at the space between particles in the catalytic layer, so as to reduce the bulk oxygen mass transfer resistance in the catalytic layer. The invention aims at pore-forming of the ultra-thin ionomer film (5-10 nm) on the surface of the catalyst, converts the traditional multi-step mass transfer of adsorption-diffusion-re-adsorption into surface mass transfer, increases the free volume inside the ion resin, and reduces the mass transfer resistance of local oxygen.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the internal structure and the distribution state of the ionic resin in the catalytic layer are subjected to microscopic adjustment by using the polyvinyl alcohol, on one hand, the multi-step mass transfer of adsorption, diffusion and re-adsorption is converted into surface mass transfer, on the other hand, the free volume of the interior of the ionic resin is increased, the mass transfer resistance is reduced, the local oxygen mass transfer on the surface of the catalyst can be obviously accelerated, and the battery performance is improved.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a graph of membrane electrode performance test prepared in example 1;
FIG. 2 is a graph of membrane electrode performance test prepared in example 2;
FIG. 3 is a graph of membrane electrode performance test prepared in comparative example 1;
FIG. 4 is a graph of membrane electrode performance test prepared in comparative example 2.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
The embodiment provides a preparation method of a membrane electrode for accelerating local oxygen mass transfer, which comprises the following steps:
1. adding a commercial Pt/C catalyst, deionized water, nafion solution and isopropanol in sequence, carrying out ultrasonic stirring for 20 minutes, and then carrying out ball milling and dispersing for 5 hours to prepare anode catalyst slurry, wherein the mass ratio of the Pt/C catalyst to the deionized water to the Nafion resin to the isopropanol in the slurry is 1:40:2:240, a step of;
2. preparing an aqueous solution with the mass fraction of 5% of a polyvinyl alcohol solution, sequentially adding a commercial Pt/C catalyst, deionized water, nafion resin, the polyvinyl alcohol solution and isopropanol, and mixing to prepare a cathode catalyst slurry, wherein the mass ratio of the Pt/C catalyst, the deionized water, the Nafion resin, the polyvinyl alcohol and the isopropanol in the slurry is 1:40:2:1:240, a step of; after mixing, the mixture was stirred ultrasonically for 20 minutes, and then dispersed for 5 hours using a ball mill.
3. Spraying cathode-anode catalyst slurry on the surface of a proton exchange membrane by using an electrostatic spraying instrument, and controlling the platinum loading of a cathode catalytic layer to be 0.1mg Pt /cm 2 。
4. The membrane electrode was immersed in 95℃water for 2h and repeated 10 times.
5. Drying the membrane electrode in air.
The performance test conditions of the prepared membrane electrode are as follows: the anode and the cathode are respectively filled with hydrogen and air, the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100 percent. The test results are shown in FIG. 1.
Example 2
The embodiment provides a preparation method of a membrane electrode for accelerating local oxygen mass transfer, which comprises the following steps:
1. sequentially adding a commercial Pt/C catalyst, deionized water, nafion solution and isopropanol, ultrasonically stirring for 25 minutes, and then ball-milling and dispersing for 6 hours, wherein the mass ratio of the 4 components is 1:40:2:240, preparing anode catalyst slurry;
2. preparing an aqueous solution with the mass fraction of 5% of the polyvinyl alcohol solution, sequentially adding a commercial Pt/C catalyst, deionized water, nafion resin, the polyvinyl alcohol solution and isopropanol, and mixing, wherein the mass ratio of the 4 components is 1:40:2:1.1:240, preparing a cathode catalyst slurry therein; after mixing, the mixture was stirred ultrasonically for 20 minutes, and then dispersed for 5 hours using a ball mill.
3. Spraying cathode-anode catalyst slurry on the surface of a proton exchange membrane by using an electrostatic spraying instrument, and controlling the platinum loading of a cathode catalytic layer to be 0.1mg Pt /cm 2 。
4. The membrane electrode was immersed in water at 99℃for 2h and repeated 10 times.
5. Drying the membrane electrode in air.
The performance test conditions of the prepared membrane electrode are as follows: the anode and the cathode are respectively filled with hydrogen and air, the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100 percent. The test results are shown in fig. 2.
Comparative example 1
This comparative example provides a membrane electrode preparation method that accelerates local oxygen mass transfer, which is substantially similar to example 1, except that: the polyvinyl alcohol was not prepared as a solution and was added in equal amounts to mix.
The test conditions of the prepared membrane electrode are as follows: the anode and the cathode are respectively filled with hydrogen and air, the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100 percent. The test results are shown in FIG. 3.
Comparative example 2
This comparative example provides a membrane electrode preparation method that accelerates local oxygen mass transfer, which is substantially similar to example 1, except that: the digestion treatment is not carried out.
The test conditions of the prepared membrane electrode are as follows: the anode and the cathode are respectively filled with hydrogen and air, the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100 percent. The test results are shown in fig. 4.
Comparative example 3
This comparative example provides a membrane electrode preparation method that accelerates local oxygen mass transfer, which is substantially similar to the examples, except that: the temperature of the digested hot water was 120 ℃. The polyvinyl alcohol partially remains after embrittlement.
The test conditions of the prepared membrane electrode are as follows: the anode and the cathode are respectively filled with hydrogen and air, the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100 percent.
Comparative example 4
This comparative example provides a membrane electrode preparation method that accelerates local oxygen mass transfer, which is substantially similar to the examples, except that: the mass fraction of the polyvinyl alcohol solution is 1%.
The test conditions of the prepared membrane electrode are as follows: the anode and the cathode are respectively filled with hydrogen and air, the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100 percent.
Comparative example 5
This comparative example provides a membrane electrode preparation method that accelerates local oxygen mass transfer, which is substantially similar to the examples, except that: the membrane electrode was heated at 200℃for 10min without digestion, and then placed in 1M sulfuric acid for 20 min.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the invention. The embodiments of the present application and features in the embodiments may be combined with each other arbitrarily without conflict.
Claims (8)
1. The preparation method of the membrane electrode for accelerating the local oxygen mass transfer is characterized by comprising the following steps of:
s1, mixing a catalyst, an ionic resin and a dispersing solvent, stirring, and then ball-milling and dispersing to obtain anode catalyst slurry;
s2, dissolving polyvinyl alcohol particles to obtain a polyvinyl alcohol solution;
s3, mixing the catalyst, the ionic resin, the polyvinyl alcohol solution and the dispersing solvent, stirring, and then ball-milling and dispersing to obtain cathode catalyst slurry;
s4, spraying the cathode and anode catalyst slurry in the steps S1 and S3 on two sides of the proton exchange membrane;
s5, placing the proton exchange membrane obtained in the step S4 into hot water for digestion, and drying to obtain the membrane electrode;
the mass fraction of the polyvinyl alcohol solution in the step S2 is 5% -10%;
in the step S5, the temperature of the hot water is 95-99 ℃, and the digestion time is 2-3h.
2. The method according to claim 1, wherein the catalyst in step S1 is a Pt/C catalyst; the ionic resin is Nafion resin; the dispersion solvent comprises one or more of deionized water, isopropanol and ethanol.
3. The method according to claim 1, wherein the stirring in step S1 is ultrasonic stirring for 10 to 30 minutes.
4. The method of preparing a membrane electrode according to claim 1, wherein the time of ball milling in step S1 is 4 to 6 hours.
5. The method according to claim 1, wherein the catalyst in step S3 is a Pt/C catalyst; the ionic resin is Nafion resin; the dispersion solvent comprises one or more of deionized water, isopropanol and ethanol.
6. The method according to claim 1, wherein the stirring in step S3 is ultrasonic stirring for 15 to 25 minutes.
7. The method of preparing a membrane electrode according to claim 1, wherein the time of ball milling in step S3 is 4 to 6 hours.
8. The method according to claim 1, wherein the slurry spraying in step S4 is to spray the cathode and anode catalyst slurries on the surface of the proton exchange membrane by using an electrostatic spraying apparatus.
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| KR20080044492A (en) * | 2006-11-16 | 2008-05-21 | 삼성에스디아이 주식회사 | Membrane electrode assembly for fuel cell, preparing method for same, and fuel cell system comprising same |
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