CN114725457A - Method for preparing membrane electrode for accelerating local oxygen mass transfer - Google Patents
Method for preparing membrane electrode for accelerating local oxygen mass transfer Download PDFInfo
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- CN114725457A CN114725457A CN202210320223.0A CN202210320223A CN114725457A CN 114725457 A CN114725457 A CN 114725457A CN 202210320223 A CN202210320223 A CN 202210320223A CN 114725457 A CN114725457 A CN 114725457A
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- 239000012528 membrane Substances 0.000 title claims abstract description 63
- 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
- 238000000034 method Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 34
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 4
- 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
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000007654 immersion Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 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
- 229910052697 platinum Inorganic materials 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
- 230000029087 digestion Effects 0.000 description 2
- 238000007590 electrostatic spraying Methods 0.000 description 2
- 229920000554 ionomer Polymers 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
- 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
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- 238000011161 development Methods 0.000 description 1
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- 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
- 239000000203 mixture Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 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
Images
Classifications
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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
- 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
Abstract
The invention discloses a membrane electrode preparation method for accelerating local oxygen mass transfer, which comprises the following steps: mixing a catalyst, an ionic resin and a dispersing solvent to obtain anode catalyst slurry; mixing a catalyst, ionic resin, a polyvinyl alcohol solution and a dispersing solvent to obtain cathode catalyst slurry; spraying the cathode and anode catalyst slurry on two sides of a proton exchange membrane; and (3) putting the membrane electrode into hot water for immersion and boiling, and drying to form the membrane electrode. The invention uses polyvinyl alcohol to carry out microscopic adjustment on the internal structure and the distribution state of the ionic resin in the catalyst layer, can accelerate the local oxygen mass transfer on the surface of the catalyst, and improves 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 highly efficient energy conversion devices that can directly convert chemical energy stored in fuel into usable electrical energy through electrochemical reactions. Although pem fuel cells have achieved the standards of large-scale application in terms of performance, lifetime, etc., the high cost still hinders the industrialization of fuel cell stacks. The high Pt content in the catalytic layer is a bottleneck that restricts the further expansion of the industrial development of the proton exchange membrane fuel cell. 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 be fully exerted, and the main reason is due to the diffusion polarization loss caused by the slow mass transfer of the reactants
It is worth noting that the cathode oxygen local mass transfer resistance is obviously increased along with the reduction of the Pt loading capacity, so that the solving of the cathode oxygen mass transfer resistance of the low Pt membrane electrode under a large current, especially the oxygen mass transfer resistance in the catalytic layer 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 to provide a membrane electrode preparation method for accelerating local oxygen mass transfer, aiming at the problems in the prior art. In view of the above, the technical problem to be solved by the present invention is to provide a membrane electrode preparation process for accelerating local oxygen mass transfer, wherein an ice template method is used to prepare a porous membrane electrode, so that local oxygen mass transfer on the surface of a catalyst can be accelerated, and the performance of a battery can be improved. The invention aims at a cathode catalyst layer, solves the problem of strengthening the oxygen mass transfer of a cathode local area, and removes the added polyvinyl alcohol.
The purpose of the invention can be realized by the following scheme:
the invention provides a membrane electrode preparation method for accelerating local oxygen mass transfer, which comprises the following steps:
s1, mixing the catalyst, the ionic resin and the dispersing solvent, stirring, and then performing ball milling dispersion 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 performing ball milling dispersion to obtain cathode catalyst slurry;
s4, spraying the cathode and anode catalyst slurry obtained in the step S1 and the step S3 on two sides of the proton exchange membrane;
and S5, soaking and boiling the paper exchange membrane obtained in the step S4 in hot water, 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 dispersing solvent comprises one or more of deionized water, isopropanol and ethanol. The mass ratio of the catalyst to the ionic resin to the dispersing solvent is 1: 2: 280. preferably, the dispersion solvent is deionized water, isopropanol mixed solution or deionized water and ethanol mixed solution, and the mass ratio of the Pt/C catalyst, the deionized water, the Nafion resin and the isopropanol is 1: 40: 2: 240.
as an embodiment of the present invention, the stirring in step S1 is ultrasonic stirring, and the stirring time is 10 to 30 minutes.
As one embodiment of the present invention, the time for 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 dissolving is ultrapure water. The polyvinyl alcohol must be added to the catalyst slurry in solution, but not in solid particulate form. Too low a mass fraction may result in too high a solvent ratio in the polyvinyl alcohol solution. If the invention adopts the polyvinyl alcohol solution with lower concentration (such as 1 per thousand-1%), even if no other solvent is added during the preparation of the catalyst slurry, the mass ratio of the catalyst, the ionic resin, the polyvinyl alcohol and the dispersing solvent can reach 1: 2: 1: 100-: 2: 1: the 1000 ratio is far beyond what the present invention is intended to achieve to 1: 2: 1: 280 parts of; even with 1% polyvinyl alcohol solution, the ratio has reached 1: 2: 1: 100, the adjustment space for the extra slurry is also very limited, which becomes very difficult if subsequent experiments require adjustment of the slurry comparison.
As an embodiment of the present invention, the catalyst in step S3 is a Pt/C catalyst; the ionic resin is Nafion resin; the dispersing 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 dispersion 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, the deionized water, the ionic resin, the polyvinyl alcohol solution and the isopropanol in the cathode catalyst slurry is 1: 40: 2: 1: 240.
as an embodiment of the present invention, the stirring in step S3 is ultrasonic stirring, and the stirring time is 15 to 25 minutes.
As one embodiment of the present invention, the time for the ball milling in step S3 is 4 to 6 hours. When the dispersion time is short, the slurry is not uniformly dispersed, and overlarge catalyst agglomeration exists in the slurry, so that the catalyst agglomeration occurs in the catalyst layer, the available active area of the catalyst is reduced, and the transmission of cathode oxygen is seriously hindered.
In one embodiment of the present invention, the slurry spraying in step S4 is to spray the cathode and anode catalyst slurry on the surface of the proton exchange membrane by using an electrostatic sprayer. Controlling the platinum loading of the cathode catalyst layer to be 0.1-0.2mg during sprayingPt/cm2。
As an embodiment of the present invention, the hot water temperature in step S5 is 95-99 deg.C, and the cooking time is 2-3 h. The soaking and decocting are repeated for 8-12 times. When the temperature is too low, the polyvinyl alcohol can not be dissolved; the evaporation of water is accelerated by the over-high temperature, which may cause the hot water to be dried, and the polyvinyl alcohol may be discolored and embrittled, especially when the heating temperature is higher than 220 ℃, the polyvinyl alcohol may be decomposed to generate acetic acid, acetaldehyde, butenol and water, wherein the acetic acid may react with the ionomer to reduce the proton conductivity, and the acetaldehyde and the vinyl alcohol may pollute the catalytic active sites. At the same time, temperatures above 220 ℃ can compromise the proton conductivity and durability of the proton 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 present invention places the membrane electrode in hot water to be soaked and boiled, not just the proton exchange membrane. In fact, the membrane electrode is a multi-layer structure, comprising a cathode catalytic layer, an anode catalytic layer and a proton exchange membrane. And secondly, the polyvinyl alcohol which is added into the cathode catalyst layer before is removed, holes on the surface or inside the ultrathin ionic resin film on the surface of the catalyst are left, and the local oxygen mass transfer is enhanced. Thirdly, the multiple times of immersion boiling are used for fully washing off the polyvinyl alcohol in the catalyst layer, and the catalyst layer is ensured not to have polyvinyl alcohol residue. The invention does not adopt high-temperature treatment to the proton exchange membrane, if the membrane covered with the catalyst is cleaned by using solvents such as acid and the like, the inside of the catalytic layer still has partial insolubility, which can cause the residue of acid and the like in the catalytic layer to pollute catalytic active sites.
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 size of the pore-forming agent is more than 50nm, and the pore-forming can only be carried out aiming at the space between particles in a catalytic layer, so that the bulk phase oxygen mass transfer resistance in the catalytic layer is reduced. The invention aims at the catalyst surface ultrathin ionomer film (5-10nm) to carry out pore forming, converts the traditional multi-step mass transfer of 'adsorption-diffusion-re-adsorption' into surface mass transfer, and simultaneously increases the free volume in the ionic resin and reduces the local oxygen mass transfer resistance.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses polyvinyl alcohol to carry out microscopic adjustment on the internal structure and the distribution state of the ionic resin in the catalyst layer, on one hand, the multi-step mass transfer of 'adsorption-diffusion-reabsorption' is converted into surface mass transfer, on the other hand, the free volume in 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 invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a graph showing the performance test of the membrane electrode prepared in example 1;
FIG. 2 is a graph showing the performance test of the membrane electrode prepared in example 2;
FIG. 3 is a graph showing the performance test of the membrane electrode prepared in comparative example 1;
fig. 4 is a performance test chart of the membrane electrode 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 invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment provides a membrane electrode preparation method for accelerating local oxygen mass transfer, which comprises the following steps:
1. adding a commercial Pt/C catalyst, deionized water, a Nafion solution and isopropanol in sequence, ultrasonically stirring for 20 minutes, then carrying out ball milling and dispersing for 5 hours, and preparing 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;
2. preparing an aqueous solution with the mass fraction of a polyvinyl alcohol solution being 5%, sequentially adding a commercial Pt/C catalyst, deionized water, Nafion resin, a polyvinyl alcohol solution and isopropanol, and mixing to prepare 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; after mixing, both were ultrasonically stirred for 20 minutes and then dispersed for 5 hours using a ball mill.
3. Spraying cathode and anode catalyst slurry on the surface of the proton exchange membrane by using an electrostatic spraying instrument, and controlling the platinum loading of the cathode catalyst layer to be 0.1mgPt/cm2。
4. The membrane electrode was digested in water at 95 ℃ for 2h, repeated 10 times.
5. Drying the membrane electrode in the air.
The performance test conditions of the prepared membrane electrode are as follows: and respectively introducing hydrogen/air into the anode/cathode, wherein the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100%. The test results are shown in fig. 1.
Example 2
The embodiment provides a membrane electrode preparation method for accelerating local oxygen mass transfer, which comprises the following steps:
1. adding a commercial Pt/C catalyst, deionized water, a Nafion solution and isopropanol in sequence, ultrasonically stirring for 25 minutes, then performing 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 a polyvinyl alcohol solution being 5%, 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 cathode catalyst slurry; after mixing, the mixture was ultrasonically stirred for 20 minutes and then dispersed for 5 hours using a ball mill.
3. Spraying cathode and anode catalyst slurry on the surface of the proton exchange membrane by using an electrostatic spraying instrument, and controlling the platinum loading of the cathode catalyst layer to be 0.1mgPt/cm2。
4. The membrane electrode was boiled in 99 ℃ water for 2h and repeated 10 times.
5. Drying the membrane electrode in the air.
The performance test conditions of the prepared membrane electrode are as follows: and respectively introducing hydrogen/air into the anode/cathode, wherein the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100%. The test results are shown in fig. 2.
Comparative example 1
The comparative example provides a membrane electrode preparation method for accelerating local oxygen mass transfer, which is basically similar to that of example 1, and is different only in that: polyvinyl alcohol was not prepared as a solution, and added in equal amounts and mixed.
The prepared membrane electrode test conditions are as follows: and respectively introducing hydrogen/air into the anode/cathode, wherein the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100%. 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: no digestion treatment was performed.
The prepared membrane electrode test conditions are as follows: and respectively introducing hydrogen/air into the anode/cathode, wherein the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100%. The test results are shown in fig. 4.
Comparative example 3
The comparative example provides a membrane electrode preparation method for accelerating local oxygen mass transfer, which is basically similar to the example, and is different only in that: the temperature of the hot water for the digestion was 120 ℃. The polyvinyl alcohol partially remains after embrittlement.
The prepared membrane electrode test conditions are as follows: and respectively introducing hydrogen/air into the anode/cathode, wherein the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100%.
Comparative example 4
The comparative example provides a membrane electrode preparation method for accelerating local oxygen mass transfer, which is basically similar to the example and differs only in that: the mass fraction of the polyvinyl alcohol solution is 1 percent.
The prepared membrane electrode test conditions are as follows: and respectively introducing hydrogen/air into the anode/cathode, wherein the working temperature is 80 ℃, the working pressure is 150kPa, and the relative humidity is 100%.
Comparative example 5
The comparative example provides a membrane electrode preparation method for accelerating local oxygen mass transfer, which is basically similar to the example, and is different only in that: the membrane electrode was not subjected to the immersion treatment, but was heated at 200 ℃ for 10min and then placed in 1M sulfuric acid for 20 min.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. A membrane electrode preparation method for accelerating local oxygen mass transfer is characterized by comprising the following steps:
s1, mixing the catalyst, the ionic resin and the dispersing solvent, stirring, and then performing ball milling dispersion 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 performing ball milling dispersion to obtain cathode catalyst slurry;
s4, spraying the cathode and anode catalyst slurry obtained in the step S1 and the step S3 on two sides of the proton exchange membrane;
and S5, soaking and boiling the paper exchange membrane obtained in the step S4 in hot water, and drying to obtain the membrane electrode.
2. A membrane electrode production method according to claim 1, wherein the catalyst in step S1 is a Pt/C catalyst; the ionic resin is Nafion resin; the dispersing solvent comprises one or more of deionized water, isopropanol and ethanol.
3. A membrane electrode preparation method according to claim 1, wherein the stirring in step S1 is ultrasonic stirring for 10 to 30 minutes.
4. The membrane electrode preparation method according to claim 1, wherein the time of the ball milling in step S1 is 4 to 6 hours.
5. The membrane electrode preparation method according to claim 1, wherein the mass fraction of the polyvinyl alcohol solution in step S2 is 5% to 10%.
6. A membrane electrode production method according to claim 1, wherein the catalyst in step S3 is a Pt/C catalyst; the ionic resin is Nafion resin; the dispersing solvent comprises one or more of deionized water, isopropanol and ethanol.
7. A membrane electrode preparation method according to claim 1, wherein the stirring in step S3 is ultrasonic stirring for 15 to 25 minutes.
8. The membrane electrode preparation method according to claim 1, wherein the time of the ball milling in step S3 is 4 to 6 hours.
9. The membrane electrode preparation method according to claim 1, wherein the slurry spraying in step S4 is to spray the cathode and anode catalyst slurry on the surface of the proton exchange membrane by using an electrostatic sprayer.
10. The membrane electrode preparation method according to claim 1, wherein the hot water temperature in step S5 is 95 to 99 ℃, and the soak time is 2 to 3 hours.
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1776942A (en) * | 2004-11-03 | 2006-05-24 | 三星Sdi株式会社 | Electrode for fuel cell, and membrane-electrode assembly and fuel cell system comprising the same |
| CN1964111A (en) * | 2005-11-10 | 2007-05-16 | 中国科学院大连化学物理研究所 | Electrode and membrane electrode of proton exchange membrane fuel cell, and making method and application |
| 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 |
| US20090042091A1 (en) * | 2007-08-09 | 2009-02-12 | Matsushita Electric Industrial Co., Ltd. | Supported catalyst layers for direct oxidation fuel cells |
| CN101540405A (en) * | 2008-01-25 | 2009-09-23 | 汉能科技有限公司 | Fuel cell leveling layer composition and preparation method thereof as well as gas diffusion layer |
| CN101652887A (en) * | 2007-02-07 | 2010-02-17 | 株式会社可乐丽 | Catalyst layer, method for producing the same, membrane-electrode assembly using the catalyst layer, and solid polymer fuel cell |
| CN103078122A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Self-humidification membrane electrode for proton exchange membrane fuel cell and preparation method thereof |
| CN105261765A (en) * | 2014-07-17 | 2016-01-20 | 中国科学院大连化学物理研究所 | Method for preparing LSM-YSZ nanocomposite electrode through high temperature phase separation |
| CN105358740A (en) * | 2013-03-28 | 2016-02-24 | Cuf-化学工业股份有限公司 | Electrodes/electrolyte assembly, reactor and method for direct am i nation of hydrocarbons |
| JP2018060714A (en) * | 2016-10-06 | 2018-04-12 | 凸版印刷株式会社 | Method for manufacturing electrode catalyst layer for fuel cell, method for manufacturing catalyst ink, catalyst ink, and electrode catalyst layer for fuel cell |
| CN109713321A (en) * | 2018-12-29 | 2019-05-03 | 上海交通大学 | A kind of adjustable membrane electrode of pore structure and preparation method thereof |
| CN109904469A (en) * | 2019-02-26 | 2019-06-18 | 武汉理工大学 | A kind of method for preparing membrane electrode optimizing cathode catalysis layer structure |
| CN110890550A (en) * | 2019-11-29 | 2020-03-17 | 蔚蓝(广东)新能源科技有限公司 | Air electrode and preparation method and application thereof |
| CN113991127A (en) * | 2021-10-28 | 2022-01-28 | 无锡威孚高科技集团股份有限公司 | Gas diffusion layer of proton exchange membrane fuel cell and preparation method thereof |
| CN114079059A (en) * | 2020-08-20 | 2022-02-22 | 王益成 | Oxygen reduction electrode structure and manufacturing method thereof |
| CN114210532A (en) * | 2021-12-15 | 2022-03-22 | 中国科学院大连化学物理研究所 | CCM continuous coating process for membrane electrode of fuel cell |
-
2022
- 2022-03-29 CN CN202210320223.0A patent/CN114725457B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1776942A (en) * | 2004-11-03 | 2006-05-24 | 三星Sdi株式会社 | Electrode for fuel cell, and membrane-electrode assembly and fuel cell system comprising the same |
| CN1964111A (en) * | 2005-11-10 | 2007-05-16 | 中国科学院大连化学物理研究所 | Electrode and membrane electrode of proton exchange membrane fuel cell, and making method and application |
| 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 |
| CN101652887A (en) * | 2007-02-07 | 2010-02-17 | 株式会社可乐丽 | Catalyst layer, method for producing the same, membrane-electrode assembly using the catalyst layer, and solid polymer fuel cell |
| US20090042091A1 (en) * | 2007-08-09 | 2009-02-12 | Matsushita Electric Industrial Co., Ltd. | Supported catalyst layers for direct oxidation fuel cells |
| CN101540405A (en) * | 2008-01-25 | 2009-09-23 | 汉能科技有限公司 | Fuel cell leveling layer composition and preparation method thereof as well as gas diffusion layer |
| CN103078122A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Self-humidification membrane electrode for proton exchange membrane fuel cell and preparation method thereof |
| CN105358740A (en) * | 2013-03-28 | 2016-02-24 | Cuf-化学工业股份有限公司 | Electrodes/electrolyte assembly, reactor and method for direct am i nation of hydrocarbons |
| CN105261765A (en) * | 2014-07-17 | 2016-01-20 | 中国科学院大连化学物理研究所 | Method for preparing LSM-YSZ nanocomposite electrode through high temperature phase separation |
| JP2018060714A (en) * | 2016-10-06 | 2018-04-12 | 凸版印刷株式会社 | Method for manufacturing electrode catalyst layer for fuel cell, method for manufacturing catalyst ink, catalyst ink, and electrode catalyst layer for fuel cell |
| CN109713321A (en) * | 2018-12-29 | 2019-05-03 | 上海交通大学 | A kind of adjustable membrane electrode of pore structure and preparation method thereof |
| CN109904469A (en) * | 2019-02-26 | 2019-06-18 | 武汉理工大学 | A kind of method for preparing membrane electrode optimizing cathode catalysis layer structure |
| CN110890550A (en) * | 2019-11-29 | 2020-03-17 | 蔚蓝(广东)新能源科技有限公司 | Air electrode and preparation method and application thereof |
| CN114079059A (en) * | 2020-08-20 | 2022-02-22 | 王益成 | Oxygen reduction electrode structure and manufacturing method thereof |
| CN113991127A (en) * | 2021-10-28 | 2022-01-28 | 无锡威孚高科技集团股份有限公司 | Gas diffusion layer of proton exchange membrane fuel cell and preparation method thereof |
| CN114210532A (en) * | 2021-12-15 | 2022-03-22 | 中国科学院大连化学物理研究所 | CCM continuous coating process for membrane electrode of fuel cell |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117525448A (en) * | 2024-01-08 | 2024-02-06 | 未势能源科技有限公司 | Preparation method of catalyst ink for preparing membrane electrode and membrane electrode |
| CN117525448B (en) * | 2024-01-08 | 2024-04-26 | 未势能源科技有限公司 | Preparation method of catalyst ink for preparing membrane electrode and membrane electrode |
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