CN117691124A - Proton exchange membrane fuel cell low platinum membrane electrode and preparation method thereof - Google Patents
Proton exchange membrane fuel cell low platinum membrane electrode and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 134
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 92
- 239000000446 fuel Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 239000002002 slurry Substances 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000010023 transfer printing Methods 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000000956 alloy Substances 0.000 claims abstract description 19
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- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 150000003460 sulfonic acids Chemical class 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 8
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- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 5
- 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
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- 239000007788 liquid Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- 229940123457 Free radical scavenger Drugs 0.000 description 3
- 229910002844 PtNi Inorganic materials 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 230000001147 anti-toxic effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
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- 238000006276 transfer reaction Methods 0.000 description 1
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Classifications
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to a low-platinum membrane electrode of a proton exchange membrane fuel cell and a preparation method thereof, wherein the preparation method comprises the following steps: s1: preparing a catalytic layer slurry; s2: preparing buffer layer slurry; s3: coating the catalytic layer slurry and the buffer layer slurry: coating the catalytic layer slurry on a transfer printing substrate film, air-drying, coating the buffer layer slurry on the catalytic layer slurry, and drying to obtain a transfer printing substrate film containing the catalytic layer and the buffer layer; s4: and (3) hot pressing transfer printing: and placing two transfer substrate films containing the catalytic layer and the buffer layer on two sides of the proton exchange film for hot-press transfer printing to obtain the three-in-one low-platinum membrane electrode. Compared with the prior art, the invention reduces the utilization rate of Pt and simultaneously realizes the optimization of the battery performance. The buffer layer can improve the output power of the low-platinum membrane electrode by using the alloy catalyst with high electrochemical activity area, and simultaneously ensures the service life of the low-platinum membrane electrode, and the preparation method is simple and easy to implement.
Description
Technical Field
The invention relates to the field of proton exchange membrane fuel cells, in particular to a low-platinum membrane electrode of a proton exchange membrane fuel cell and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of high energy conversion rate, environmental friendliness, silence, high reliability and the like, and are considered to be one of the most potential clean energy technologies. Under the background of the global energy structure toward clean and low-carbonization transformation, the government in China highly pays attention to the industrial development of hydrogen energy fuel cells, and the government and related departments sequentially release a plurality of top-level plans to encourage and guide the technical research of PEMFC. Promote the development of PEMFC technology chain and hydrogen fuel cell automobile industry chain.
Proton exchange membrane fuel cells are devices that use electrochemical reactions to generate electricity. The hydrogen and oxygen reach the anode and cathode of the cell through the gas channels on the bipolar plate, respectively, and reach the catalytic layer through the diffusion layer on the low platinum membrane electrode assembly. On the anode side of the membrane, hydrogen dissociates into hydrated protons and electrons on the anode catalyst surface, the former being transported through the sulfonic acid groups on the proton exchange membrane to the cathode, and electrons flow through the load to the cathode through an external circuit, where oxygen molecules combine with the hydrated protons and electrons transported from the anode to produce water molecules. Therefore, the low-platinum membrane electrode is a final place where the electrochemical reaction occurs, is a core component of the PEMFC, and the difference of the preparation technology thereof directly affects the internal microstructure of the low-platinum membrane electrode, thereby greatly affecting the performance, the service life and the cost of the PEMFC. Currently, the catalysts used for preparing the low-platinum membrane electrode are Pt-containing catalysts, and the cost thereof is about 30% of the total cost of the PEMFC, which seriously hinders the commercialization process of the PEMFC. Therefore, the method has the advantages of designing a good low-platinum membrane electrode structure, developing a new preparation technology with strong adaptability to improve the utilization rate of the Pt catalyst, reducing the loading of noble metal Pt in the catalyst, and being particularly important for reducing the cost of the low-platinum membrane electrode and even the fuel cell. The performance and life of the low platinum membrane electrode are the core technology of proton exchange membrane fuel cells, wherein mass transfer and electrochemical reaction in the three-phase reaction zone of the catalytic layer are key points of PEMFC research. The use of the PtM/C catalyst with high specific activity can reduce the content of platinum in the low-platinum membrane electrode and ensure the catalytic activity of the low-platinum membrane electrode. However, the metal cations in the PtM/C catalyst are easy to dissolve out to destroy the proton exchange membrane, so that irreversible performance is degraded, and the service life of the low-platinum membrane electrode cannot meet the commercial requirement.
Aiming at the problems, china patent 201611177018.4 proposes a preparation scheme of a proton exchange membrane fuel cell low-platinum membrane electrode with a buffer layer structure. According to the scheme, the thickness of a catalytic layer is reduced by reducing the thickness of a proton exchange membrane, a catalyst with high Pt loading is used for reducing the thickness of the catalytic layer, and carbon nanotubes or carbon fibers are introduced into a cathode catalytic layer and a gas diffusion layer to improve the mass transfer effect of a gas-liquid two-phase flow in a low-platinum membrane electrode, so that the performance of the low-platinum membrane electrode is improved. According to the scheme, the thickness of the low-platinum membrane electrode is reduced, and the mass transfer resistance of the low-platinum membrane electrode can be truly reduced by using the carbon nano tube as an additive, so that the power generation of the low-platinum membrane electrode is improved. However, the Pt in the catalyst layer with high Pt loading is easy to migrate, run away, agglomerate, etc. under long-time working conditions, so that the catalytic performance is fast degraded. In addition, the dissolved Pt atoms are easy to deposit on the surface and inside of the thinner proton exchange membrane, so that the low-platinum membrane electrode is irreversibly damaged, and the durability of the battery is drastically reduced.
Chinese patent 202011555669.9 proposes a high performance proton exchange membrane fuel cell low platinum membrane electrode structure for improving durability and a preparation method thereof, wherein the low platinum membrane electrode is prepared by fixing the quality of cathode and anode catalysis and ionomer, and adding different types and quality of free radical scavengers into the cathode and anode catalysis layer. The free radical scavenger added in the catalyst layer involves a plurality of metal ions, wherein a plurality of metal cations can be dissociated into ionic polymers (proton exchange membrane and proton conductive agent) under the long-term working environment of the fuel cell to destroy the sulfonic acid functional groups of the full-service sulfonic acid resin, so that the sulfonic acid functional groups lose proton conductivity, and therefore, along with the increase of the free radical scavenger, the catalyst activity of the catalyst is prevented from being destroyed by the free radicals while the running time of the fuel cell is prolonged, but the dissolution poisoning of the metal cations suffered by the proton exchange membrane still cannot be effectively relieved, so that the service life of the low-platinum membrane electrode still cannot be guaranteed. Furthermore, the prior patent suggests that the addition of an appropriate amount of radical scavenger to the catalytic layer tends to cause significant battery performance losses.
Although the low platinum membrane electrode preparation method proposed by the above report has different degrees of contribution in improving the power and life of the low platinum membrane electrode. But at present, further technical innovation is needed for proton exchange membrane fuel cells in the transportation field in order to enhance the competitiveness of fuel cell cost, performance and life. Therefore, the low-platinum membrane electrode structure with good design and the development of a new preparation technology with strong adaptability are particularly important for the commercial application of proton exchange membrane fuel to improve the output power and durability of the low-platinum membrane electrode. The prior proton exchange membrane fuel cell for the traffic transportation field still cannot solve the technical problem of irreversible performance degradation caused by the fact that metal cations in PtM/C catalysts are easy to dissolve out and destroy a proton exchange membrane, and cannot guarantee the service life and the performance of the cell and reduce the cost.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a low-platinum membrane electrode of a proton exchange membrane fuel cell and a preparation method thereof. The buffer layer can improve the output power of the low-platinum membrane electrode by using the alloy catalyst with high electrochemical activity area, and simultaneously ensures the service life of the low-platinum membrane electrode, and the preparation method is simple and easy to implement.
The aim of the invention can be achieved by the following technical scheme:
the invention provides a low-platinum membrane electrode of a proton exchange membrane fuel cell and a preparation method thereof, wherein an alloy catalyst with high electrochemical activity is used, and meanwhile, a buffer layer with an antitoxic effect is added between a catalytic layer and a proton exchange membrane, so that the prepared low-platinum membrane electrode can ensure the service life of the high-performance low-platinum membrane electrode while the catalytic activity of the high-performance catalyst is allowed to be exerted. The scheme starts from the structural design of the low-platinum membrane electrode, and the problem that the performance and the service life of a plurality of high-activity alloy catalysts in the application of the low-platinum membrane electrode cannot be balanced can be solved by only adding a simple coating process on the basis of the existing preparation process of the low-platinum membrane electrode. The preparation method of the low-platinum membrane electrode can realize comprehensive improvement of performance and service life.
The aim of the invention is achieved by the following technical scheme:
the invention provides a preparation method of a low-platinum membrane electrode of a proton exchange membrane fuel cell, which comprises the following steps:
s1: preparing a catalytic layer slurry: adding deionized water into a platinum carbon catalyst or a platinum-based alloy catalyst, uniformly stirring, adding a perfluorinated sulfonic acid polymer solution and a volatile solvent, and dispersing to obtain a catalyst layer slurry;
s2: preparing buffer layer slurry: adding deionized water into the high-conductivity corrosion-resistant carbon material, uniformly stirring, adding a perfluorinated sulfonic acid polymer solution and a volatile solvent, and dispersing to obtain buffer layer slurry;
s3: coating the catalytic layer slurry and the buffer layer slurry: coating the catalytic layer slurry on a transfer printing substrate film, air-drying, coating the buffer layer slurry on the catalytic layer slurry, and drying to obtain a transfer printing substrate film containing the catalytic layer and the buffer layer;
s4: and (3) hot pressing transfer printing: and placing two transfer substrate films containing the catalytic layer and the buffer layer on two sides of the proton exchange film for hot-press transfer printing to obtain the three-in-one low-platinum membrane electrode. The hot pressing transfer printing process specifically comprises the following steps: and (3) respectively adhering one sides of two transfer printing substrate films respectively containing the catalytic layer and the buffer layer to two sides of one proton exchange film, completing hot pressing through a hot press, removing the transfer printing substrate films, and then hot pressing the transfer printing substrate films and the two gas diffusion layers together to obtain the low-platinum membrane electrode.
Further, in S1, the mass ratio of the platinum carbon catalyst or the platinum-based alloy catalyst, the perfluorosulfonic acid polymer solution, and the volatile solvent is 1:0.1 to 10: 1-20, preferably, a platinum carbon catalyst or a platinum-based alloy catalyst, a perfluorosulfonic acid polymer solution and a volatile solvent are mixed according to the mass ratio of 1:9.5:12.
further, in S2, the mass ratio of the high-conductivity corrosion-resistant carbon material, the perfluorinated sulfonic acid polymer solution and the volatile solvent is 1:0.1 to 10: 1-20, preferably, the mass ratio of the high-conductivity corrosion-resistant carbon material, the perfluorosulfonic acid polymer solution and the volatile solvent is 1:9.5:12.
further, in S1, the mass ratio of Pt in the platinum-based alloy catalyst is 20% -60%, the mass ratio of alloy elements is 1% -20%, and the types of the alloy elements are one or more of Co, mn, ni, ir, rb, ru.
In the S1 and the S2, the perfluorinated sulfonic acid polymer solution is one or more of D520, D521, D1020 and D2020 with the mass ratio of the perfluorinated sulfonic acid resin Nafion of 1-20%.
In the step S1 and S2, the volatile solvent is one or more of deionized water, ethanol, isopropanol, and n-propanol.
Further, in S2, the high-conductivity corrosion-resistant carbon material is one or more of superconducting carbon black XC-72, ketjen black EC300J, highly graphitized carbon EA, carbon nano-tube and graphene oxide.
In the step S1 and the step S2, the dispersing method is one or more of ultrasonic dispersing, ball milling, grinding and mechanical stirring.
Further, in S3, the transfer substrate film is one or more of polytetrafluoroethylene film, polyimide film, polyvinylidene fluoride film and polyfluorinated ethylene propylene film, and the thickness of the transfer substrate film is 20-200um; the thickness of the buffer layer is controlled between 0.1um and 10um or the carbon loading is controlled at 0.1ug/cm 2 -1mg/cm 2 Between them.
The invention also provides a proton exchange membrane fuel cell low-platinum membrane electrode, which is prepared by the preparation method of the proton exchange membrane fuel cell low-platinum membrane electrode, and comprises a proton exchange membrane, buffer layers arranged on two sides of the proton exchange membrane and catalytic layers arranged on two sides of the buffer layers.
Compared with the prior art, the invention has the following advantages:
(1) The alloy catalyst with high electrochemical activity selected by the invention can effectively improve the electrochemical reaction activity in the low-platinum membrane electrode, reduce the utilization rate of Pt and realize the optimization of the battery performance. Meanwhile, a buffer layer is added in the catalytic layer and the proton exchange membrane to help relieve the poisoning effect of metal cations on the proton exchange membrane, which is caused by dissolution in the catalytic layer, so that the service life of the low-platinum membrane electrode under the long-term working condition is greatly prolonged.
(2) The high power density performance of the low platinum membrane electrode prepared by the invention is as follows: for a plurality of alloy catalysts which show excellent redox activity in half batteries at present, the battery performance is fast attenuated due to the dissolution of metal elements in the endurance test of the low-platinum membrane electrode, so that the high-performance catalyst of the practical application is affected, and the buffer layer antitoxic strategy can ensure the service life of the low-platinum membrane electrode while improving the output power of the low-platinum membrane electrode by using the alloy catalyst with high electrochemical activity area.
(3) The preparation method of the double-sublayer structure low-platinum membrane electrode is simple and easy to implement, and the preparation of the novel low-platinum membrane electrode can be completed by adding a coating or spraying process on the production line for the current batch production of the low-platinum membrane electrode, so that the preparation method has stronger applicability with the current technology.
(4) The single cell assembled by the low-platinum membrane electrode has good performance, the performance requirements under different potentials can be controlled by selecting different types of catalysts, and the durability can achieve the expected aim by controlling the types, thickness and the like of the buffer layer material.
Drawings
Fig. 1 is a schematic structural diagram of a low platinum membrane electrode of a proton exchange membrane fuel cell with a buffer layer structure.
Fig. 2 is a comparison of current density and power density after various accelerated endurance test turns for comparative example 1.
FIG. 3 is a comparison of current density and power density after various accelerated endurance test turns for example 1.
Fig. 4 is a comparison of current density and power density after various accelerated endurance test turns for example 2.
Reference numerals: 1-a catalytic layer; 2-a buffer layer; 3-proton exchange membrane.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. Features such as a part model, a material name, a connection structure, a control method, an algorithm and the like which are not explicitly described in the technical scheme are all regarded as common technical features disclosed in the prior art.
Comparative example 1
A1: preparing a catalytic layer 1 slurry: firstly, weighing PtNi/C (Pt-30% and Ni-10%) catalyst with the mass of 0.2g, putting the catalyst into a ball milling tank, then weighing 1.2ml of deionized water by a liquid transferring gun, dripping the deionized water into the ball milling tank for wetting the catalyst, and mechanically stirring and matching with ultrasonic dispersion for 2 minutes after water is added to ensure that the catalyst is completely wetted; subsequently 1.2g of isopropanol and 1.9g of 5% Nafion solution were added dropwise to the wet catalyst, and finally 4g of ZrO were added 2 Ball milling; after sealing the ball milling tank, putting the ball milling tank into a planetary ball mill for ball milling for 2 hours, and setting the rotating speed to 300r/min to obtain the prepared slurry of the catalytic layer 1.
A2: catalytic layer 1 slurry coating: taking out the ball milling tank, dripping the slurry of the catalytic layer 1 onto a clean transfer printing substrate film, selecting a wire rod with a proper size, and uniformly coating the slurry of the catalytic layer 1 on the surface of the transfer printing substrate film by an automatic coating machine; after the coating was completed, the transfer substrate film was transferred to a forced air drying oven at a temperature of 80℃for a drying period of 20 minutes, and dried to obtain a transfer substrate film containing the catalytic layer 1.
A3: and (3) hot pressing transfer printing: cutting the transfer substrate film containing the catalytic layer 1 into a size of 5cm×5cm, and controlling the Pt loading to 0.2mg/cm 2 Two pieces of the catalyst are respectively used as the cathode and anode catalyst layers 1, and are placed on two sides of the proton exchange membrane 3 for hot-press transfer printing, so that the three-in-one low-platinum membrane electrode is obtained.
A4: and (3) fixing the three-in-one low-platinum membrane electrode obtained in the step A3 between two gas diffusion layers, then placing the three-in-one low-platinum membrane electrode between metal serpentine flow fields, and performing electrochemical performance test by setting the clamping force to be 0.9MPa through cylinder clamping. Under the condition of polarization curve of single cell, the temperature of the cell is controlled at 80 ℃, the metering ratio of air and hydrogen respectively introduced into the cathode and anode is set to 2.0/1.5, the gas humidification is set to 100%, and the back pressure is 1.5bar/1.5bar. The temperature of the battery is controlled to be 80 ℃ under the condition of low platinum membrane electrode durability test, nitrogen and hydrogen are respectively introduced into the cathode and anode, the gas flow is set to be 200/400sccm, the gas humidification is set to be 100%, the back pressure is 1.5bar/1.5bar, a square wave acceleration durability test signal is provided through an electrochemical platform, and square wave parameters are respectively 3s at 0.6V and 3s at 0.95V. The polarization curve test was performed every 10000 turns, and the test results are shown in fig. 2.
Example 1
A1: preparing a catalytic layer 1 slurry: firstly, weighing PtNi/C (Pt-30% and Ni-10%) catalyst with the mass of 0.2g, putting the catalyst into a ball milling tank, then weighing 1.2ml of deionized water by a liquid transferring gun, dripping the deionized water into the ball milling tank for wetting the catalyst, and mechanically stirring and matching with ultrasonic dispersion for 2 minutes after water is added to ensure that the catalyst is completely wetted; subsequently 1.2g of isopropanol and 1.9g of 5% Nafion solution were added dropwise to the wet catalyst, and finally 4g of ZrO were added 2 Ball milling; after sealing the ball milling tank, putting the ball milling tank into a planetary ball mill for ball milling for 2 hours, and setting the rotating speed to 300r/min to obtain the prepared slurry of the catalytic layer 1.
A2: preparing buffer layer 2 slurry: firstly, weighing XC-72 with the mass of 0.2g, putting the XC-72 into a ball milling tank, and then weighing 1.2ml of deionized water by a liquid transferring gun and dripping the deionized water into the ball milling tank; subsequently, 1.2g of isopropanol and 3.2g of 5% Nafion solution were added dropwise, and finally 4g of ZrO were added 2 Ball milling. After sealing the ball milling tank, putting the ball milling tank into a planetary ball mill for ball milling for 2 hours, and setting the rotating speed to 300r/min to obtain the prepared slurry of the buffer layer 2.
A3: coating the slurry of the catalytic layer 1 and the slurry of the buffer layer 2: taking out the ball milling tank, dripping the slurry of the catalytic layer 1 onto a clean transfer printing substrate film, selecting a wire rod with a proper size, uniformly coating the slurry of the catalytic layer 1 on the surface of the transfer printing substrate film by an automatic coating machine, naturally airing for 30min, then coating the slurry of the buffer layer 2 on the surface of the catalytic layer 1 by the same steps, and realizing the control of the thickness of the buffer layer 2 by selecting the wire rods with different sizes; after the coating was completed, the transfer substrate film was transferred to a forced air drying oven at a temperature of 80 ℃ for a drying period of 20 minutes, and dried to obtain a transfer substrate film containing the catalytic layer 1 and the buffer layer 2.
A4: and (3) hot pressing transfer printing: cutting the transfer substrate film containing the catalytic layer 1 and the buffer layer 2 into a size of 5cm×5cm, and controlling the Pt loading amount to be 0.2mg/cm 2 Selecting two pieces of partsAnd the three-in-one low-platinum membrane electrode is obtained by placing the three-in-one low-platinum membrane electrode on two sides of the proton exchange membrane 3 for hot-pressing transfer printing respectively serving as the cathode and anode catalytic layers 1.
A5: and (3) fixing the three-in-one low-platinum membrane electrode obtained in the step A4 between two gas diffusion layers, then placing the three-in-one low-platinum membrane electrode between metal serpentine flow fields, and performing electrochemical performance test by setting the clamping force to be 0.9MPa through cylinder clamping. Under the condition of polarization curve of single cell, the temperature of the cell is controlled at 80 ℃, the metering ratio of air and hydrogen respectively introduced into the cathode and anode is set to 2.0/1.5, the gas humidification is set to 100%, and the back pressure is 1.5bar/1.5bar. The temperature of the battery is controlled to be 80 ℃ under the condition of low platinum membrane electrode durability test, nitrogen and hydrogen are respectively introduced into the cathode and anode, the gas flow is set to be 200/400sccm, the gas humidification is set to be 100%, the back pressure is 1.5bar/1.5bar, a square wave acceleration durability test signal is provided through an electrochemical platform, and square wave parameters are respectively 3s at 0.6V and 3s at 0.95V. The polarization curve test was performed every 10000 turns, and the test results are shown in fig. 3.
Example 2
A1: preparing a catalytic layer 1 slurry: firstly, weighing PtNi/C (Pt-30% and Ni-10%) catalyst with the mass of 0.2g, putting the catalyst into a ball milling tank, then weighing 1.2ml of deionized water by a liquid transferring gun, dripping the deionized water into the ball milling tank for wetting the catalyst, and mechanically stirring and matching with ultrasonic dispersion for 2 minutes after water is added to ensure that the catalyst is completely wetted. Subsequently 1.2g of isopropanol and 1.9g of 5% Nafion solution were added dropwise to the wet catalyst, and finally 4g of ZrO were added 2 Ball milling. After sealing the ball milling tank, putting the ball milling tank into a planetary ball mill for ball milling for 2 hours, and setting the rotating speed to 300r/min. The prepared slurry of the catalytic layer 1 is obtained.
A2: preparing buffer layer 2 slurry: firstly, weighing carbon nano tubes with the mass of 0.2g, putting the carbon nano tubes into a ball milling tank, and then weighing 1.2ml of deionized water by a liquid transferring gun and dripping the deionized water into the ball milling tank. Subsequently, 1.2g of isopropanol and 3.2g of 5% Nafion solution were added dropwise, and finally 4g of ZrO were added 2 Ball milling. After sealing the ball milling tank, putting the ball milling tank into a planetary ball mill for ball milling for 2 hours, and setting the rotating speed of 300r/min to obtain the prepared slurry of the buffer layer 2.
A3: coating the slurry of the catalytic layer 1 and the slurry of the buffer layer 2: taking out the ball milling tank, dripping the slurry of the catalytic layer 1 onto a clean transfer printing substrate film, selecting a wire rod with a proper size, uniformly coating the slurry of the catalytic layer 1 on the surface of the transfer printing substrate film by an automatic coating machine, and naturally airing for 30min. The slurry of the buffer layer 2 is coated on the surface of the catalytic layer 1 through the same steps, and the thickness of the buffer layer 2 is controlled through selecting wire rods with different sizes. After the coating was completed, the transfer substrate film was transferred to a forced air drying oven at a temperature of 80 ℃ for a drying period of 20 minutes, and dried to obtain a transfer substrate film containing the catalytic layer 1 and the buffer layer 2.
A4: and (3) hot pressing transfer printing: cutting the transfer substrate film containing the catalytic layer 1 and the buffer layer 2 into a size of 5cm×5cm, and controlling the Pt loading amount to be 0.2mg/cm 2 Two pieces of the catalyst are respectively used as the cathode and anode catalyst layers 1, and are placed on two sides of the proton exchange membrane 3 for hot-press transfer printing, so that the three-in-one low-platinum membrane electrode is obtained.
A5: and (3) fixing the three-in-one low-platinum membrane electrode obtained in the step A4 between two gas diffusion layers, then placing the three-in-one low-platinum membrane electrode between metal serpentine flow fields, and performing electrochemical performance test by setting the clamping force to be 0.9MPa through cylinder clamping. Under the condition of polarization curve of single cell, the temperature of the cell is controlled at 80 ℃, the metering ratio of air and hydrogen respectively introduced into the cathode and anode is set to 2.0/1.5, the gas humidification is set to 100%, and the back pressure is 1.5bar/1.5bar. The temperature of the battery is controlled to be 80 ℃ under the condition of low platinum membrane electrode durability test, nitrogen and hydrogen are respectively introduced into the cathode and anode, the gas flow is set to be 200/400sccm, the gas humidification is set to be 100%, the back pressure is 1.5bar/1.5bar, a square wave acceleration durability test signal is provided through an electrochemical platform, and square wave parameters are respectively 3s at 0.6V and 3s at 0.95V. The polarization curve test was performed every 10000 turns, and the test results are shown in fig. 4.
According to fig. 2, 3 and 4, the cell polarization curves of comparative example 1, example 1 and example 2 can be compared, and it can be obtained that adding a buffer layer 2 in the catalytic layer 1 and the proton exchange membrane 3 helps to alleviate the poisoning effect of metal cations dissolved in the catalytic layer 1 on the proton exchange membrane 3, and the buffer layer 2 can ensure the service life of the low platinum membrane electrode while improving the output power of the low platinum membrane electrode by using the alloy catalyst with high electrochemical activity area.
Unless specifically indicated otherwise, the reagents, methods, apparatus and devices employed in the present invention are those conventional in the art. Unless otherwise indicated, reagents and materials used in the following examples were all commercially available, analytical grade.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the low-platinum membrane electrode of the proton exchange membrane fuel cell is characterized by comprising the following steps:
s1: preparing slurry of a catalytic layer (1): adding deionized water into a platinum carbon catalyst or a platinum-based alloy catalyst, uniformly stirring, adding a perfluorinated sulfonic acid polymer solution and a volatile solvent, and dispersing to obtain a catalyst layer (1) slurry;
s2: preparing slurry of a buffer layer (2): adding deionized water into the high-conductivity corrosion-resistant carbon material, uniformly stirring, adding a perfluorinated sulfonic acid polymer solution and a volatile solvent, and dispersing to obtain a slurry of the buffer layer (2);
s3: coating the slurry of the catalytic layer (1) and the slurry of the buffer layer (2): coating the slurry of the catalytic layer (1) on a transfer printing substrate film, air-drying, coating the slurry of the buffer layer (2) on the slurry of the catalytic layer (1), and drying to obtain the transfer printing substrate film containing the catalytic layer (1) and the buffer layer (2);
s4: and (3) hot pressing transfer printing: and placing two transfer substrate films containing the catalytic layer (1) and the buffer layer (2) on two sides of the proton exchange film (3) for hot-press transfer printing to obtain the three-in-one low-platinum film electrode.
2. The preparation method of the low-platinum membrane electrode of the proton exchange membrane fuel cell according to claim 1, wherein in the S1, the mass ratio of the platinum carbon catalyst or the platinum-based alloy catalyst, the perfluorinated sulfonic acid polymer solution and the volatile solvent is 1:0.1 to 10:1 to 20.
3. The preparation method of the low-platinum membrane electrode of the proton exchange membrane fuel cell according to claim 1, wherein in the S2, the mass ratio of the high-conductivity corrosion-resistant carbon material to the perfluorosulfonic acid polymer solution to the volatile solvent is 1:0.1 to 10:1 to 20.
4. The method for preparing a low-platinum membrane electrode for a proton exchange membrane fuel cell according to claim 1, wherein in S1, the mass ratio of Pt in the platinum-based alloy catalyst is 20% -60%, the mass ratio of alloy elements is 1% -20%, and the alloy element type is one or more of Co, mn, ni, ir, rb, ru.
5. The method for preparing a low-platinum membrane electrode of a proton exchange membrane fuel cell according to claim 1, wherein in S1 and S2, the perfluorinated sulfonic acid polymer solution is one or more of D520, D521, D1020 and D2020 with a perfluorinated sulfonic acid resin Nafion mass ratio of 1% -20%.
6. The method for preparing a low-platinum membrane electrode for a proton exchange membrane fuel cell according to claim 1, wherein in S1 and S2, the volatile solvent is one or more of deionized water, ethanol, isopropanol and n-propanol.
7. The method for preparing a low-platinum membrane electrode for a proton exchange membrane fuel cell according to claim 1, wherein in S2, the high-conductivity corrosion-resistant carbon material is one or more of superconducting carbon black XC-72, ketjen black EC300J, highly graphitized carbon EA, carbon nanotubes and graphene oxide.
8. The method for preparing a low-platinum membrane electrode of a proton exchange membrane fuel cell according to claim 1, wherein in S1 and S2, the dispersing method is one or more of ultrasonic dispersing, ball milling, grinding and mechanical stirring.
9. The method for preparing a low platinum membrane electrode for a proton exchange membrane fuel cell according to claim 1, wherein in S3, the transfer substrate film is one or more of polytetrafluoroethylene film, polyimide film, polyvinylidene fluoride film and polyfluorinated ethylene propylene film, and the thickness of the transfer substrate film is 20-200um; the thickness of the buffer layer (2) is controlled between 0.1um and 10um or the carbon loading is controlled at 0.1ug/cm 2 -1mg/cm 2 Between them.
10. The low-platinum membrane electrode for the proton exchange membrane fuel cell is characterized by being prepared by a preparation method of the low-platinum membrane electrode for the proton exchange membrane fuel cell according to any one of claims 1 to 9 and comprising a proton exchange membrane (3), buffer layers (2) arranged on two sides of the proton exchange membrane (3) and catalytic layers (1) arranged on two sides of the buffer layers (2).
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