CN113745612A - Membrane electrode with high-efficiency proton transmission network and preparation method thereof - Google Patents
Membrane electrode with high-efficiency proton transmission network and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 38
- 230000005540 biological transmission Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 83
- 239000011347 resin Substances 0.000 claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 53
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 52
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000007590 electrostatic spraying Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 9
- 239000002121 nanofiber Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 229910052697 platinum Inorganic materials 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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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
- H01M4/90—Selection of catalytic material
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a membrane electrode with a high-efficiency proton transmission network, which comprises an anode catalyst layer, a proton exchange membrane and a cathode catalyst layer; and the cathode catalyst layer is provided with sulfonated carbon nanofibers, wherein the mass ratio of the sulfonated carbon nanofibers to the platinum carbon catalyst is 0.1-0.4:1, and protons are transported in the sulfonated carbon nanofibers. The carbon nanofiber is subjected to sulfonic group modification, so that the carbon nanofiber has a proton conduction function; the modified nano-fiber has hydrophilicity and is easy to adsorb ion resin, so that the ion resin is distributed along the fiber, the order of the ion resin is enhanced, and the proton mass transfer efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a membrane electrode with a high-efficiency proton transmission network and a preparation method thereof.
Background
The membrane electrode composed of cathode, anode and proton exchange membrane is an important component of proton exchange membrane fuel cell. The cathode catalyst layer is composed of ionic resin and catalyst, and hydrogen forms protons at the anode, is transmitted to the cathode through the proton membrane, and is transmitted to the platinum surface in the ionic resin at the cathode to react. Therefore, the transmission efficiency of protons in the cathode catalyst layer is improved, the dosage of the ionic resin can be reduced, the battery performance is improved, and the production cost is reduced. Currently, the preparation of the catalyst layer of the proton exchange membrane fuel cell generally uses a mode of mechanically mixing ionic resin and a catalyst, and the ionic resin is adsorbed on the surface of the catalyst to form a proton transmission network. Firstly, the ionic resin is randomly adsorbed on the surface of the catalyst in a disorderly manner, and the proton conduction efficiency has no adjustability; secondly, the ion resin is heavily accumulated in part of the active centers, which affects oxygen transmission.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a membrane electrode with a high-efficiency proton transmission network and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the first aspect of the present invention provides a membrane electrode with a high-efficiency proton transmission network, comprising an anode catalyst layer, a proton exchange membrane and a cathode catalyst layer; and the cathode catalyst layer is provided with sulfonated carbon nanofibers, wherein the mass ratio of the sulfonated carbon nanofibers to the platinum carbon catalyst is 0.1-0.4:1, and protons are transported in the sulfonated carbon nanofibers.
Furthermore, the sulfonated carbon nanofiber is prepared by modifying sulfonic groups and other hydrophilic groups on the surface of carbon after the carbon nanofiber reacts with concentrated sulfuric acid and concentrated nitric acid.
The second aspect of the present invention provides a method for preparing the membrane electrode with ordered proton transmission channels, which comprises the following steps:
s1, preparing sulfonated carbon nanofiber: reacting the carbon nanofiber with concentrated sulfuric acid and concentrated nitric acid, and modifying sulfonic groups on the surface of carbon to prepare sulfonated carbon nanofiber with proton transmission capability;
s2, adding the ionic resin solution and a platinum-carbon catalyst into a solvent, adding the sulfonated carbon nanofiber obtained in the step S1, and stirring for 24 hours to obtain cathode catalyst layer slurry;
s3, adding the ionic resin solution and a platinum-carbon catalyst into a solvent, and stirring to obtain anode catalyst layer slurry;
and S4, spraying the cathode catalyst layer slurry obtained in the step S2 on one surface of the proton exchange membrane by adopting an electrostatic spraying method, spraying the anode catalyst layer slurry obtained in the step S3 on the other surface of the proton exchange membrane, and drying to obtain the membrane electrode assembly with the ordered proton transmission channel. Preferably, the proton exchange membrane is a Nafion proton membrane.
Further, in step S1, the mass fraction of the carbon nanofibers is 10-20%, the mass fraction of the concentrated sulfuric acid is 40-60%, and the balance is concentrated nitric acid, preferably, the mass ratio of the carbon nanofibers, the concentrated sulfuric acid, and the concentrated nitric acid is 1:3: 3.
Further, in step S1, the reaction temperature is 70-90 ℃ and the reaction time is 24-48 h.
Further, in step S2, the mass ratio of the sulfonated carbon nanofibers to the platinum carbon catalyst is 0.1-0.4: 1; in the obtained cathode catalyst layer slurry, in step S2, the mass ratio of the ionic resin to the platinum-carbon catalyst is 0.2-0.3: 1. Specifically, a certain proportion of perfluorosulfonic acid resin dispersion (20% by weight) and a platinum-carbon catalyst are added into a solvent, and the mass ratio of the ionic resin and the platinum-carbon catalyst in the solvent after the addition is 0.2-0.3: 1. And because the gain effect of adding too little sulfonated carbon fiber is not obvious, and the catalyst layer is thickened and the bulk mass transfer resistance is increased if adding too much sulfonated carbon fiber, the mass ratio of the mass of the added sulfonated carbon fiber to the mass of the negative charge modified platinum carbon catalyst is between 0.1 and 0.4.
Further, in step S2, the ionic resin solution is a perfluorosulfonic acid resin dispersion liquid with a mass percentage of 20%.
Further, in step S2 and step S3, the solvent is a mixed solvent of isopropanol and water, and in step S3, the mass ratio of the ionic resin to the platinum-carbon catalyst is 0.2-0.3: 1.
Further, in step S2, the Pt loading of the cathode catalyst layer is 0.05-0.1mg/cm2。
Further, in step S3, the Pt loading of the anode catalyst layer is 0.05-0.1mg/cm2。
The invention realizes the ordering of the catalytic layer proton transmission channel by combining materials with different properties. The invention focuses on the construction mode of the catalyst layer, realizes the improvement of proton transmission performance, but does not adopt measures for improving the activity of the catalyst, but improves the proton transmission efficiency in the catalyst layer by introducing the proton network based on the carbon nano fiber, which is attributed to the construction method of the catalyst layer.
Compared with the prior art, the invention has the following beneficial effects:
1. the carbon nanofiber is subjected to sulfonic group modification, so that the carbon nanofiber has a proton conduction function; the modified nanofiber has hydrophilicity and is easy to adsorb ion resin, so that the ion resin is distributed along the fiber, the order of the ion resin is enhanced, and the proton mass transfer efficiency is improved;
2. according to the invention, the carbon nanofibers with modified sulfonic groups are doped in the cathode catalyst layer, so that the distribution of the ion resin can be guided, the excessive accumulation of the ion resin on the platinum surface can be prevented, and the oxygen mass transfer efficiency of the catalyst layer can be 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 of the air performance of cells with different levels of sulfonated nanofibers;
FIG. 2 is a graph showing the effect of sulfonated nanofibers on cyclic voltammetry tests at consistent ionic resin loading;
fig. 3 is a graph of the effect of sulfonated nanofiber characteristics on battery air performance.
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.
In the membrane electrode, the sulfonic group of the sulfonated carbon nanofiber has certain proton transmission capability, and meanwhile, a continuous proton transmission network is formed based on a one-dimensional structure of the sulfonated carbon nanofiber, so that the proton transmission efficiency is improved, the dosage of ionic resin in a catalyst layer can be reduced, and the cost is reduced; in a word, the carbon nano-fiber capable of conducting protons is doped, so that the proton conductivity in the electrode is optimized, and the performance of the battery is improved.
In the following examples, commercial ionic resin solutions are available from Dombent, Asahi Kasei, Asahi glass and other trades or selected from Dupont ionic resin Nafion solutions.
Example 1
A method for preparing a membrane electrode having ordered proton transfer channels, said method comprising the steps of:
s1, mixing the carbon nanofiber with concentrated sulfuric acid and concentrated nitric acid (the mass ratio is 1:3:3), and reacting for 48 hours at 90 ℃ to obtain the sulfonated carbon nanofiber modified by sulfonic acid groups and having proton transmission capability;
s2, adding 0.1g of commercial ionic resin solution (20% by weight, namely perfluorinated sulfonic acid resin dispersion liquid) and 0.1g of platinum-carbon catalyst (platinum loading 50%) into 15ml of mixed solvent of isopropanol and water (volume ratio is 3:1), adding 0.01g of sulfonated carbon nanofiber obtained in the step S1, and stirring the mixed slurry for 24 hours to obtain cathode catalyst layer slurry; wherein the mass ratio of the sulfonated carbon nanofiber to the platinum carbon catalyst is 0.1: 1; in the obtained cathode catalyst layer slurry, the mass ratio of the ionic resin to the platinum-carbon catalyst is 0.2: 1.
S3, adding 0.1g of commercial ionic resin solution (20% by weight, namely perfluorinated sulfonic acid resin dispersion liquid) and 0.1g of platinum-carbon catalyst (platinum loading 50%) into 15ml of mixed solvent (volume ratio is 3:1) of isopropanol and water, and stirring for 24h to obtain anode catalyst layer slurry.
And S4, spraying the cathode catalyst layer slurry obtained in the step S2 on one surface of the Nafion proton membrane by adopting an electrostatic spraying method, spraying the anode catalyst layer slurry obtained in the step S3 on the other surface of the Nafion proton membrane, and drying to obtain the membrane electrode assembly with the ordered proton transmission channel. The Pt loading amounts of the anode and cathode catalyst layers are controlled to be 0.1mg/cm by adjusting the spraying times of the spraying machine2。
Example 2
This example is the same as the method of example 1 except that in step S2, the mass ratio of sulfonated carbon nanofibers to negatively charged modified platinum carbon catalyst (catalyst platinum loading about 50%) is 0.2: 1.
Example 3
This example is the same as the method of example 1 except that in step S2, the mass ratio of sulfonated carbon nanofibers to negatively charged modified platinum carbon catalyst (catalyst platinum loading about 50%) is 0.4: 1.
Example 4
This example is the same as example 2 except that in step S2, 0.15g of a commercial ionic resin solution (20% by weight, i.e., perfluorosulfonic acid resin dispersion) and 0.1g of platinum carbon catalyst (platinum loading 50%) were added to give an ionic resin to platinum carbon catalyst mass ratio of 0.3:1 and in step S3, the ionic resin to platinum carbon catalyst mass ratio was 0.3: 1.
Comparative example 1
The comparative example was the same as the preparation method of example 4, in which the mass ratio of the ionic resin to the platinum-carbon catalyst in the catalytic layer was 0.3:1, and different from example 4, the cathode catalytic layer slurry did not contain carbon nanofibers subjected to sulfonation treatment.
Comparative example 2
The comparative example is the same as the preparation method of example 2, the mass ratio of the ionic resin to the platinum-carbon catalyst in the catalytic layer is 0.2:1, and the difference from example 2 is that the cathode catalytic layer slurry does not contain carbon nanofibers subjected to sulfonation treatment.
Comparative example 3
The comparative example is the same as the preparation method of example 2, the mass ratio of the ionic resin to the platinum-carbon catalyst in the catalyst layer is 0.2:1, and the difference from example 2 is that carbon nanofibers which are not subjected to sulfonation treatment are doped in the cathode catalyst layer slurry. The mass ratio of the carbon nano-fiber to the platinum-carbon catalyst is 0.2: 1.
The membrane electrodes obtained in the above examples and comparative examples were subjected to the following performance tests:
the test temperature of cyclic voltammetry was 80 ℃ and the humidity was 67%. The test gas amount is 160cc/min of hydrogen, 20cc/min of nitrogen, and the test back pressure is 100 KPaabs.
The temperature and humidity for testing the battery performance are 80 ℃ and 100 percent respectively. The test backpressure was 150 KPaabs. The flow channel selected by the cell is a 5-channel serpentine flow field with 5cm by 5cm, and the metering ratio of the test gas is H2:Air=2:2。
As can be seen from comparison of the battery performances of examples 1 to 3 of fig. 1, under the condition that the mass ratio of the ionic resin to the platinum-carbon catalyst is 0.2:1, when the mass ratio of the sulfonated carbon nanofibers to the negatively charged modified platinum-carbon catalyst is 0.2:1, the battery performance is optimal. This is because too little doping does not significantly improve the proton transport ability of the catalytic layer, while too much doping increases the thickness and mass transfer resistance of the catalytic layer.
Because the doped sulfonated carbon nanofiber has a proton conduction function, more three-phase interfaces can be established in the catalyst layer, and the platinum active area is increased. From the cyclic voltammetry test result of fig. 2, it can be found that in the membrane electrode in which the mass ratio of the ionic resin to the platinum carbon catalyst is 0.2:1 (example 2 and comparative example 2), the platinum active area of the catalytic layer is significantly increased after the sulfonated carbon nanofibers are added. The increase in platinum active area (area of Pt available) increases the efficiency of the electrochemical reaction, making example 2 significantly better performing than comparative example 2 (fig. 3). As can be seen from the performances of example 2 and comparative example 1, even if the mass ratio of the ionic resin to the platinum-carbon catalyst of the catalytic layer is reduced from 0.3:1 (comparative example 1) to 0.2:1 (example 2), no significant reduction in the performance of the cell occurs by constructing a highly efficient proton transport network. By comparing the large current zones, it can be found that the slope of the performance curve of example 2 is significantly greater than that of comparative example 1, indicating that the mass transfer conditions of example 2 are significantly better than that of comparative example 1 because the ionic resin is partially distributed on the carbon fibers, reducing the mass transfer resistance of the platinum surface. Comparing the performance of example 2 with that of comparative example 3, it can be seen that there is no gain in cell performance if the carbon fibers are not treated, i.e., the carbon fibers do not have a proton transport function.
Example 4 and comparative example 1 both increased the level of ionic resin, which is about the minimum level of known ionic resin. The gain effect of example 4 over comparative example 1 is limited relative to example 2 and comparative example 2, mainly because the ionic resin content is high and sufficient proton transport channels have been established in the catalytic layer, reducing the marginal effect of proton transport efficiency. From the results, it can be seen that the carbon nanofibers subjected to sulfonation treatment can significantly improve proton transfer efficiency, and further reduce the amount of the ionic resin used while maintaining the battery performance.
The foregoing description of specific embodiments of the present invention has been presented. 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 with a high-efficiency proton transmission network comprises an anode catalyst layer, a proton exchange membrane and a cathode catalyst layer; the catalyst is characterized in that sulfonated carbon nanofibers are arranged in the cathode catalyst layer, wherein the mass ratio of the sulfonated carbon nanofibers to the platinum carbon catalyst is 0.1-0.4:1, and protons are transported in the sulfonated carbon nanofibers.
2. The membrane electrode assembly with a high-efficiency proton transmission network as claimed in claim 1, wherein the sulfonated carbon nanofibers are prepared by modifying sulfonic acid groups on the carbon surface after the carbon nanofibers are reacted with concentrated sulfuric acid and concentrated nitric acid.
3. A method for preparing a membrane electrode with a high efficiency proton transport network according to claim 1, wherein the method comprises the following steps:
s1, preparing sulfonated carbon nanofiber: reacting the carbon nanofiber with concentrated sulfuric acid and concentrated nitric acid, and modifying sulfonic groups on the surface of carbon to prepare sulfonated carbon nanofiber with proton transmission capability;
s2, adding the ionic resin solution and a platinum-carbon catalyst into a solvent, adding the sulfonated carbon nanofiber obtained in the step S1, and stirring to obtain cathode catalyst layer slurry;
s3, adding the ionic resin solution and a platinum-carbon catalyst into a solvent, and stirring to obtain anode catalyst layer slurry;
and S4, spraying the cathode catalyst layer slurry obtained in the step S2 on one surface of the proton exchange membrane by adopting an electrostatic spraying method, spraying the anode catalyst layer slurry obtained in the step S3 on the other surface of the proton exchange membrane, and drying to obtain the membrane electrode with the ordered proton transmission channel.
4. The method for preparing a membrane electrode with a high-efficiency proton transmission network according to claim 3, wherein in step S1, the mass fraction of the carbon nanofibers is 10-20%, the mass fraction of the concentrated sulfuric acid is 40-60%, and the balance is concentrated nitric acid.
5. The method for preparing a membrane electrode assembly having a high efficiency proton transport network according to claim 3, wherein the reaction temperature is 70-90 ℃ and the reaction time is 24-48h in step S1.
6. The method for preparing a membrane electrode with a high efficiency proton transport network according to claim 3, wherein in step S2, the mass ratio of the sulfonated carbon nanofibers to the platinum carbon catalyst is 0.1-0.4: 1; in the obtained cathode catalyst layer slurry, the mass ratio of the ionic resin to the platinum-carbon catalyst is 0.2-0.3: 1.
7. The method of claim 3, wherein in step S2, the ionic resin solution is 20% by mass of perfluorosulfonic acid resin dispersion.
8. The method for preparing a membrane electrode with a high efficiency proton transport network according to claim 3, wherein the solvent is a mixed solvent of isopropanol and water in step S2 and in step S3, and the mass ratio of the ionic resin to the platinum-carbon catalyst in step S3 is 0.2-0.3: 1.
9. The method for preparing a membrane electrode with a high efficiency proton transport network according to claim 3, wherein in step S2, the Pt loading of the cathode catalyst layer is 0.05-0.1mg/cm2。
10. The method of claim 3, wherein in step S3, the Pt loading of the anode catalyst layer is 0.05-0.1mg/cm2。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114497582A (en) * | 2021-12-23 | 2022-05-13 | 上海唐锋能源科技有限公司 | Preparation method of membrane electrode catalyst layer |
CN114737211A (en) * | 2022-05-26 | 2022-07-12 | 中自环保科技股份有限公司 | Proton exchange composite reinforced membrane, preparation method, water electrolysis membrane electrode and application |
CN114976049A (en) * | 2022-05-13 | 2022-08-30 | 一汽解放汽车有限公司 | Cathode catalyst and preparation method and application thereof |
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