CN114373941A - Modified anti-reversal catalyst and preparation method and application thereof - Google Patents
Modified anti-reversal catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 276
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
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- 239000006185 dispersion Substances 0.000 claims abstract description 44
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 40
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 37
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 239000002121 nanofiber Substances 0.000 claims abstract description 10
- 239000006256 anode slurry Substances 0.000 claims description 91
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 73
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 60
- 229910052697 platinum Inorganic materials 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 36
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 35
- 239000002002 slurry Substances 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
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- 239000000203 mixture Substances 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 229920000554 ionomer Polymers 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000010041 electrostatic spinning Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000446 fuel Substances 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 14
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 230000002441 reversible effect Effects 0.000 claims description 7
- 238000001523 electrospinning Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910001260 Pt alloy Inorganic materials 0.000 claims description 3
- 210000000170 cell membrane Anatomy 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 abstract description 11
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 31
- 235000019441 ethanol Nutrition 0.000 description 22
- 210000004027 cell Anatomy 0.000 description 17
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- 239000010410 layer Substances 0.000 description 14
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- 230000000694 effects Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
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- 230000009286 beneficial effect Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
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- 238000007731 hot pressing Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- 238000011068 loading method Methods 0.000 description 3
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- 238000006479 redox reaction Methods 0.000 description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 229920003937 Aquivion® Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- 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
- H01M4/8647—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
- H01M4/88—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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a modified antipole catalyst and a preparation method and application thereof. The modified anti-reverse catalyst comprises an anti-reverse catalyst and a surface coating, wherein the surface coating comprises polytetrafluoroethylene and/or a copolymer of polytetrafluoroethylene; the shape of the modified anti-reversal catalyst is in a nano-fiber shape. The modified anti-reversal catalyst obtained by coating the polytetrafluoroethylene or the copolymer thereof on the surface improves the dispersion stability of the anti-reversal catalyst, reduces the water decomposition potential, improves the catalyst efficiency and improves the water electrolysis performance of the anti-reversal catalyst.
Description
Technical Field
The invention belongs to the technical field of fuel cells, relates to a modified anti-reversal catalyst, and particularly relates to a modified anti-reversal catalyst, and a preparation method and application thereof.
Background
The hydrogen fuel cell directly converts chemical energy into electric energy by utilizing the reaction of hydrogen and oxygen. The proton exchange membrane fuel cell has the characteristics of low working temperature, quick start, high power density, mature application and the like, and is widely applied to automobiles. At present, the service life of the fuel cell of the commercial vehicle is 10000-15000h, and the service life requirement which is comparable to that of an internal combustion engine cannot be met, so that the service life is prolonged, and the service life is one of the most important problems in popularization and application of the fuel cell of the commercial vehicle.
However, the anode gas shortage caused by the air supply and exhaust faults, severe working conditions, misoperation, low-temperature cold start, flow field problems and the like in the actual running process of the fuel cell automobile is an important factor for accelerating the attenuation of the fuel cell, when the anode of the fuel cell is lack of hydrogen, the anode can not perform HOR reaction to provide protons and electrons, other single cells connected in series in the cell stack can provide energy to perform capacitive charging on the hydrogen-starved single cells, the anode potential is increased, the cathode potential is kept unchanged, the voltage of the single cells is reversed, and the voltage of the single cells is negative, namely, the reverse pole occurs. At this time, in order to maintain charge balance, hydrolysis occurs at a high anode potential to generate protons and electrons, and after a period of time, when the charge balance cannot be maintained by water electrolysis reaction, the anode potential continues to rise, and at this time, the carbon carrier in the membrane electrode catalytic layer and even the gas diffusion layer may undergo oxidation reaction to continue to provide protons and electrons, which seriously affects the performance and durability of the battery.
CN 111082078A provides a method for preparing a high-performance and voltage reversal resistant membrane electrode assembly, comprising the following steps: step one, sequentially adding a catalyst, an anti-reverse-pole electrolytic water catalysis material and a proper amount of nafion solution into a beaker, stirring for 10 minutes, adding a dispersing agent, and uniformly dispersing to obtain anode slurry; step two, spraying the anode slurry on the substrateAn anode side of the proton exchange membrane; adding a catalyst and a proper amount of nafion solution into a beaker, stirring for 10 minutes, adding a dispersing agent, and uniformly dispersing to obtain cathode slurry; step four, spraying the cathode slurry on the cathode side of the proton exchange membrane to obtain the required CCM; step five, applying 70kg/cm to the prepared CCM, the gas diffusion layer and the polyester frame through an oil press2Hot pressing to obtain MEA; and step six, assembling the prepared MEA into a single cell, and performing performance test and anti-reversal test.
CN 110534780A discloses a preparation method of a proton exchange membrane fuel cell membrane electrode, wherein, Pt/C catalyst layers are respectively coated on two surfaces of a proton membrane to prepare a CCM membrane semi-finished product, and anti-reversal slurry layers are respectively coated on the peripheral edges of the anode surface of the CCM membrane semi-finished product to achieve the purpose of anti-reversal.
CN 111900420a discloses an anode catalyst slurry, an anode catalyst layer, a membrane electrode and a fuel cell. The anode catalyst slurry includes a catalyst slurry body and an electrolyzed water catalyst. The catalyst slurry body contains a carbon-supported noble metal catalyst; the carbon-supported noble metal catalyst comprises a carbon support and a noble metal supported on the carbon support. The electrolyzed water catalyst is used for catalyzing the electrolyzed water reaction; the mass of the electrolyzed water catalyst is 20-100% of the mass of the noble metal. The anode catalyst layer is obtained by coating the anode catalyst slurry on a proton exchange membrane and drying.
In the technical scheme, the anti-reversal slurry and the anode slurry are blended to prepare the anode catalyst layer, although the anti-reversal performance of the battery can be improved, the anti-reversal catalyst is easy to shield reaction active sites of platinum, a shielding effect is generated on the platinum, the HOR reaction activity of the anode catalyst layer is seriously reduced, and the overall performance of the battery is further reduced; the anti-reverse slurry is separately prepared to the periphery of the anode catalyst layer, the HOR activity of the anode can be ensured, but the perforation phenomenon of the edge membrane can be improved, and the anti-reverse slurry cannot resist the reverse phenomenon generated in the central area of the membrane electrode.
How to improve the anti-reversal performance of the membrane electrode in the fuel cell and solve the problem of membrane electrode damage caused by voltage reversal due to insufficient supply of anode fuel is a technical problem which needs to be solved urgently.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a modified anti-reversal catalyst and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a modified anti-bipolar catalyst comprising an anti-bipolar catalyst and a surface coating comprising polytetrafluoroethylene and/or a copolymer of polytetrafluoroethylene;
the shape of the modified anti-reversal catalyst is in a nano-fiber shape.
The invention forms a coating layer with a loose structure by coating polytetrafluoroethylene or a copolymer thereof on the surface of the antipole catalyst. The existence of the coating layer can effectively reduce the shielding effect of the antipole catalyst on the platinum element, prevent the reduction of the catalytic activity of the anode catalyst in the catalytic oxidation reduction reaction and prevent the reduction of the HOR reaction activity of the anode catalyst layer. The hydrophobicity of the polytetrafluoroethylene or the copolymer thereof enables water to be gathered around and on the surface of the anti-reversal catalyst, and more water sources can be provided by electrolyzing the water, so that the anti-reversal time is prolonged. The modified anti-reversal catalyst obtained by coating polytetrafluoroethylene or a copolymer thereof on the surface improves the dispersion stability of the anti-reversal catalyst, reduces the overpotential and Tafel slope of the catalyst, and improves the water electrolysis performance of the anti-reversal catalyst.
Preferably, the antipole catalyst comprises any one of or a combination of at least two of elemental metal, metal oxide or carbon-supported metal, and typical but non-limiting combinations include a combination of elemental metal and metal oxide, a combination of metal oxide and carbon-supported metal, a combination of elemental metal and carbon-supported metal, or a combination of elemental metal, metal oxide and carbon-supported metal.
Preferably, the metal comprises iridium and/or ruthenium.
Preferably, the copolymer of polytetrafluoroethylene comprises polyperfluoroethylpropylene.
Preferably, the modified anti-antipole catalyst has a diameter of 10 to 25nm, which may be, for example, 10nm, 12nm, 15nm, 17nm, 18nm, 20nm, 22nm or 25nm, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the specific surface area of the surface of the modified anti-reversal catalyst is 240-500m2Per g, for example, may be 240m2/g、260m2/g、300m2/g、350m2/g、400m2/g、450m2G or 500m2The values/g are not limited to the values listed, and other values in the numerical range not listed are equally applicable.
In a second aspect, the present invention provides a method for preparing the modified anti-reversal catalyst of the first aspect, wherein the method comprises the following steps:
(1) mixing the surface coating, the spinning aid and the anti-reverse-pole catalyst dispersion liquid to obtain a precursor solution;
(2) performing electrostatic spinning on the precursor solution obtained in the step (1) to obtain precursor fibers;
(3) and (3) heating the precursor fiber obtained in the step (2) to obtain the modified anti-reversal catalyst.
According to the invention, the modified anti-reversal catalyst with the nanometer fiber shape is prepared by electrostatic spinning after the anti-reversal catalyst and the surface coating are fully mixed and dispersed, the surface coating forms a coating layer with a loose structure on the surface of the anti-reversal catalyst, so that the shielding effect of the anti-reversal catalyst on platinum elements is favorably reduced, the catalytic activity of the anode catalyst in catalytic oxidation-reduction reaction is prevented from being reduced due to the existence of the coating layer, and the HOR reaction activity of the anode catalyst layer is prevented from being reduced.
Preferably, the preparation method of the anti-bipolar catalyst dispersion liquid in the step (1) includes mixing the anti-bipolar catalyst and the solvent and then dispersing.
Preferably, the dispersing method comprises ultrasonic dispersion with power of 300-;
the power of the ultrasound is 300-1000W, such as 300W, 500W, 700W, 900W or 1000W, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
The ultrasonic dispersion time is 10-30min, for example 10min, 15min, 20min, 25min or 30min, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The rotation speed of the shear dispersion is 8000-30000rmp, and may be 8000rmp, 10000rmp, 15000rmp, 20000rmp or 30000rmp, for example, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
The shear dispersion time is 10-20min, for example 10min, 12min, 15min, 18min or 20min, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
The pressure of the high pressure micro jet circulation is 10000-30000 psi, such as 10000psi, 15000psi, 20000psi, 25000psi or 30000psi, but not limited to the values listed, and other values not listed in the range are also applicable.
The number of high-pressure microfluidics cycles is from 10 to 30, and may be, for example, 10, 15, 20, 25 or 30, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the solvent includes any one of water, chloroform, absolute ethanol, isopropanol, or N, N-dimethylformamide, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of water and chloroform, a combination of chloroform and absolute ethanol, a combination of absolute ethanol and isopropanol, a combination of isopropanol and N, N-dimethylformamide, a combination of water, chloroform and absolute ethanol, a combination of chloroform, absolute ethanol and isopropanol, a combination of absolute ethanol, isopropanol and N, N-dimethylformamide, or chloroform, absolute ethanol, isopropanol and N, N-dimethylformamide.
Preferably, the spinning aid in step (1) comprises any one of polyvinylpyrrolidone, polyacrylonitrile, polyacrylic acid or polyvinyl alcohol or a combination of at least two of them. Typical but non-limiting combinations include a combination of polyvinylpyrrolidone and polyacrylonitrile, a combination of polyacrylonitrile and polyacrylic acid, a combination of polyacrylic acid and polyvinyl alcohol, polyvinylpyrrolidone, a combination of polyacrylonitrile and polyacrylic acid, polyacrylonitrile, a combination of polyacrylic acid and polyvinyl alcohol, or a combination of polyvinylpyrrolidone, polyacrylonitrile, polyacrylic acid and polyvinyl alcohol.
Preferably, the mass ratio of the anti-reversal catalyst, the spinning assistant, the polytetrafluoroethylene and the solvent is 1 (12-24): (6-15): 136-168), and can be 1:12:6:136, 1:24:6:136, 1:12:15:136, 1:20:20:148 or 1:16:14:150, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the electrostatic spinning voltage in step (2) is 18-25kV, such as 18kV, 20kV, 22kV, 24kV or 25kV, but not limited to the recited values, and other values in the range are equally applicable.
Preferably, the electrospinning speed in step (2) is 0.3-1.2mL/h, and may be, for example, 0.3mL/h, 0.5mL/h, 0.8mL/h, 1mL/h or 1.2mL/h, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the heating temperature in step (3) is 350-400 ℃, for example, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃ or 400 ℃, but not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the heating time in step (3) is 10-30min, such as 10min, 15min, 20min, 25min or 30min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
In a third aspect, the present invention provides a reverse-resistant anode slurry comprising the modified reverse-resistant catalyst according to the first aspect.
In a fourth aspect, the present invention provides a method for preparing the anti-reverse-polarity anode slurry of the third aspect, wherein the method comprises the following steps:
(a) mixing the modified anti-bipolar catalyst and a dispersing agent, and dispersing to obtain modified anti-bipolar catalyst slurry;
(b) mixing a metal catalyst, an ionomer solution, a dispersant and the modified anti-bipolar catalyst slurry obtained in step (a) to obtain the anti-bipolar anode slurry.
Preferably, the dispersant in step (a) is a mixture of water and alcohol, the mass ratio of water and alcohol being 1 (1-8), and may be, for example, 1:1, 1:3, 1:4, 1:5, 1:7 or 1:8, but not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the alcohol comprises any one or a combination of at least two of methanol, ethanol, isopropanol, n-propanol or ethylene glycol. Typical but non-limiting combinations include a combination of methanol and ethanol, a combination of ethanol and isopropanol, a combination of isopropanol and n-propanol, a combination of n-propanol and ethylene glycol, a combination of methanol, ethanol and isopropanol, a combination of ethanol, isopropanol and n-propanol, a combination of isopropanol, n-propanol and ethylene glycol, a combination of methanol, ethanol, isopropanol and n-propanol, or a combination of ethanol, isopropanol, n-propanol and ethylene glycol.
Preferably, the mass ratio of the modified anti-reversal catalyst to the dispersant in the step (a) is 1 (100) -150, and for example, the mass ratio can be 1:100, 1:110, 1:120, 1:130, 1:140 or 1:150, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the dispersing method in the step (a) comprises ultrasonic dispersion with power of 300-. The power of the ultrasound is 300-1000W, such as 300W, 500W, 700W, 900W or 1000W, but not limited to the values listed, and other values not listed in the numerical range are also applicable. The ultrasonic dispersion time is 10-30min, for example 10min, 15min, 20min, 25min or 30min, but is not limited to the values listed, and other values not listed in the numerical range are also applicable. The shear rate is 8000-30000rmp, for example 8000rmp, 10000rmp, 15000rmp, 20000rmp or 30000rmp, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable. The shear dispersion time is 10-20min, for example 10min, 12min, 15min, 18min or 20min, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the metal catalyst of step (b) comprises a carbon-supported platinum catalyst and/or a platinum alloy catalyst.
The carbon-supported platinum catalyst and the platinum alloy catalyst of the present invention are conventional catalysts in the art, and the present invention does not limit the specific type of the metal catalyst of step (b).
Preferably, the EW value of the ionomer solution in step (b) is 720-820, which may be, for example, 720, 750, 780, 800 or 820, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the dispersant in step (b) is a mixture of water and alcohol, the mass ratio of water and alcohol being 1 (1-8), and may be, for example, 1:1, 1:3, 1:4, 1:5, 1:7 or 1:8, but not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the alcohol comprises any one or a combination of at least two of methanol, ethanol, isopropanol, n-propanol or ethylene glycol. Typical but non-limiting combinations include a combination of methanol and ethanol, a combination of ethanol and isopropanol, a combination of isopropanol and n-propanol, a combination of n-propanol and ethylene glycol, a combination of methanol, ethanol and isopropanol, a combination of ethanol, isopropanol and n-propanol, a combination of isopropanol, n-propanol and ethylene glycol, a combination of methanol, ethanol, isopropanol and n-propanol, or a combination of ethanol, isopropanol, n-propanol and ethylene glycol.
Preferably, the mixing method in step (b) comprises ultrasonic dispersion at power of 300-. The power of the ultrasound is 300-1000W, such as 300W, 500W, 700W, 900W or 1000W, but not limited to the values listed, and other values not listed in the numerical range are also applicable. The ultrasonic dispersion time is 10-30min, for example 10min, 15min, 20min, 25min or 30min, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the mass ratio of the carbon content, the ionomer solution and the dispersant in the anti-reverse anode slurry in the step (b) is 1 (0.8-2.2) to (30-400), and may be, for example, 1:0.8:30, 1:2.2:400, 1:0.8:400, 1:2.2:30, 1:1.2:200, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the mass ratio of the platinum element in the metal catalyst of step (b) to the anti-antipodal metal element in the modified anti-antipodal catalyst slurry is 1 (0.01-1), and may be, for example, 1:0.01, 1:0.1, 1:0.2, 1:0.5 or 1:1, but is not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
In a fifth aspect, the present invention provides a fuel cell membrane electrode comprising a reverse-polarity resistant anode slurry according to the third aspect.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the modified anti-reversal catalyst obtained by coating polytetrafluoroethylene or a copolymer thereof on the surface improves the dispersion stability of the anti-reversal catalyst, reduces the overpotential and Tafel slope of the catalyst, and improves the water electrolysis performance of the anti-reversal catalyst.
(2) According to the invention, the surface of the anti-reverse-pole catalyst is coated with polytetrafluoroethylene or a copolymer thereof to form a coating layer with a loose structure, and the existence of the coating layer can effectively reduce the shielding effect of the anti-reverse-pole catalyst on platinum element, prevent the catalytic activity of the anode catalyst in the catalytic oxidation-reduction reaction from being reduced, and prevent the HOR reaction activity of the anode catalyst layer from being reduced. The hydrophobicity of the polytetrafluoroethylene enables water to be gathered around and on the surface of the anti-reversal catalyst, and more water sources can be provided by electrolyzing the water, so that the anti-reversal time is prolonged.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a modified anti-reversal catalyst, which comprises iridium oxide and polytetrafluoroethylene as a surface coating, wherein the anti-reversal catalyst is in a shape of nano fiber, the diameter of the anti-reversal catalyst is 15nm, and the specific surface area of the surface of the anti-reversal catalyst is 350m2/g。
The preparation method of the modified catalyst comprises the following steps:
(1) mixing iridium oxide and N, N-dimethylformamide, performing ultrasonic dispersion at the power of 500W for 20min, performing shear dispersion at the rotation speed of 20000rmp for 15min, and performing high-pressure micro-jet circulation at the pressure of 20000psi for 20 times to obtain an anti-bipolar catalyst dispersion liquid, and mixing polytetrafluoroethylene, polyvinylpyrrolidone and the anti-bipolar catalyst dispersion liquid to obtain a precursor solution, wherein the mass ratio of the iridium oxide to the polyvinylpyrrolidone to the polytetrafluoroethylene to the N, N-dimethylformamide is 1:12:6: 136;
(2) performing electrostatic spinning on the precursor solution obtained in the step (1) at a voltage of 22kV, wherein the propelling speed is 0.8mL/h to obtain precursor fibers;
(3) and (3) heating the precursor fiber obtained in the step (2) at the temperature of 380 ℃ for 20min to obtain the modified anti-reversal catalyst.
Example 2
The embodiment provides a modified anti-reversal catalyst, which comprises anti-reversal catalyst ruthenium oxide and surface coating polytetrafluoroethylene, wherein the anti-reversal catalyst is in a shape of nano fiber, the diameter of the anti-reversal catalyst is 20nm, and the surface specific surface area of the anti-reversal catalyst is 400m2/g。
The preparation method of the modified catalyst comprises the following steps:
(1) mixing ruthenium oxide and water, performing ultrasonic dispersion at the power of 400W for 25min, performing shear dispersion at the rotation speed of 15000rmp for 18min, and performing high-pressure microjet circulation at the pressure of 15000psi for 25 times to obtain an anti-reverse-polarity catalyst dispersion liquid, and mixing polytetrafluoroethylene, polyacrylonitrile and the anti-reverse-polarity catalyst dispersion liquid to obtain a precursor solution, wherein the mass ratio of the ruthenium oxide to the water is 1:24:15: 168;
(2) performing electrostatic spinning on the precursor solution obtained in the step (1) at the voltage of 20kV, wherein the propelling speed is 1mL/h to obtain precursor fibers;
(3) and (3) heating the precursor fiber obtained in the step (2) at the temperature of 360 ℃ for 25min to obtain the modified anti-reversal catalyst.
Example 3
The embodiment provides a modified anti-reversal catalyst, which comprises an anti-reversal catalyst iridium black and a surface coating polytetrafluoroethylene, wherein the anti-reversal catalyst is in a shape of nano fiber, the diameter of the anti-reversal catalyst is 12nm, and the surface specific surface area of the anti-reversal catalyst is 450m2/g。
The preparation method of the modified catalyst comprises the following steps:
(1) mixing iridium black and chloroform, performing ultrasonic dispersion for 15min at the power of 800W, shear dispersion for 12min at the rotating speed of 25000rmp and high-pressure microjet circulation for 15 times at the pressure of 25000psi to obtain an anti-bipolar catalyst dispersion liquid, and mixing polytetrafluoroethylene, polyacrylic acid and the anti-bipolar catalyst dispersion liquid to obtain a precursor solution, wherein the mass ratio of the iridium black to the polyacrylic acid to the polytetrafluoroethylene to the chloroform is 1:12:15: 168;
(2) performing electrostatic spinning on the precursor solution obtained in the step (1) at a voltage of 24kV, wherein the propelling speed is 0.5mL/h to obtain precursor fibers;
(3) and (3) heating the precursor fiber obtained in the step (2) at the temperature of 380 ℃ for 15min to obtain the modified anti-reversal catalyst.
Example 4
This example provides a modified anti-bipolar catalyst comprising ruthenium anti-bipolar catalyst and a surface coatingThe shape of the anti-antipole catalyst is nano-fiber, the diameter is 10nm, and the surface specific surface area is 240m2/g。
The preparation method of the modified catalyst comprises the following steps:
(1) mixing ruthenium and absolute ethyl alcohol, performing ultrasonic dispersion for 30min at the power of 300W, performing shearing dispersion for 30min at the rotating speed of 8000rmp and performing high-pressure microjet circulation for 30 times at the pressure of 10000psi to obtain an anti-bipolar catalyst dispersion liquid, and mixing polytetrafluoroethylene, polyvinyl alcohol and the anti-bipolar catalyst dispersion liquid to obtain a precursor solution, wherein the mass ratio of the ruthenium to the polyvinyl alcohol to the polytetrafluoroethylene to the absolute ethyl alcohol is 1:24:6: 136;
(2) performing electrostatic spinning on the precursor solution obtained in the step (1) at the voltage of 18kV, wherein the propelling speed is 1.2mL/h to obtain precursor fibers;
(3) and (3) heating the precursor fiber obtained in the step (2) at the temperature of 350 ℃ for 30min to obtain the modified anti-reversal catalyst.
Example 5
The embodiment provides a modified anti-reversal catalyst, which comprises carbon-supported iridium as the anti-reversal catalyst and polytetrafluoroethylene as a surface coating, wherein the anti-reversal catalyst is in a shape of nano fiber, the diameter of the anti-reversal catalyst is 25nm, and the surface specific surface area of the anti-reversal catalyst is 500m2/g。
The preparation method of the modified catalyst comprises the following steps:
(1) mixing carbon-supported iridium and isopropanol, performing ultrasonic dispersion for 10min at the power of 1000W, performing shear dispersion for 10min at the rotating speed of 30000rmp and performing high-pressure microjet circulation for 10 times at the pressure of 30000psi to obtain an anti-bipolar catalyst dispersion liquid, and mixing polytetrafluoroethylene, polyvinylpyrrolidone and the anti-bipolar catalyst dispersion liquid to obtain a precursor solution, wherein the mass ratio of the carbon-supported iridium to the polyvinylpyrrolidone to the polytetrafluoroethylene to the isopropanol is 1:20:10: 145;
(2) performing electrostatic spinning on the precursor solution obtained in the step (1) at the voltage of 25kV, wherein the advancing speed is 0.3mL/h to obtain precursor fibers;
(3) and (3) heating the precursor fiber obtained in the step (2) at the temperature of 400 ℃ for 10min to obtain the modified anti-reversal catalyst.
Example 6
This example provides a modified anti-reverse catalyst prepared by the same method as in example 1, except that no ultrasonic dispersion was performed in step (1).
Example 7
This example provides a modified anti-stiction catalyst prepared by the same method as in example 1 except that no shear dispersion was performed in step (1).
Example 8
This example provides a modified anti-bipolar catalyst prepared by the same method as in example 1, except that no high pressure micro-jet cycling was performed in step (1).
Example 9
This example provides a modified anti-reverse catalyst, which is prepared by the same method as in example 1 except that the mass ratio of iridium oxide to polytetrafluoroethylene in step (1) is 1: 5.
Example 10
This example provides a modified anti-reverse catalyst, which is prepared by the same method as in example 1 except that the mass ratio of iridium oxide to polytetrafluoroethylene in step (1) is 1: 16.
Example 11
This example provides a modified anti-reverse catalyst, which was prepared in the same manner as in example 1, except that the voltage of the electrospinning in step (2) was 16 kV.
Example 12
This example provides a modified anti-reverse catalyst, which was prepared in the same manner as in example 1, except that the voltage of the electrospinning in step (2) was 28 kV.
Example 13
This example provides a modified anti-reverse catalyst prepared in the same manner as in example 1, except that the electrospinning speed in step (2) was 0.2 mL/h.
Example 14
This example provides a modified anti-reverse catalyst prepared in the same manner as in example 1 except that the electrospinning speed in step (2) was 1.4 mL/h.
Example 15
This example provides a modified anti-reverse catalyst prepared in the same manner as in example 1 except that the heating temperature in step (3) was 420 ℃.
Example 16
This example provides a modified antipole catalyst similar to that of example 1 except that the surface coating was replaced with equal mass of fluorinated ethylene propylene.
Example 17
This example provides a modified antipole catalyst similar to that of example 1 except that the surface coating was replaced with polytetrafluoroethylene and polyperfluoroethylene propylene in a 1:1 mass ratio.
Comparative example 1
This comparative example provides an anti-bipolar catalyst, which is iridium oxide, in the form of a nanofiber having a diameter of 15nm and a surface specific surface area of 350m2/g。
The preparation method of the anti-reversal catalyst comprises the following steps:
(1) mixing iridium oxide and N, N-dimethylformamide, performing ultrasonic dispersion at the power of 500W for 20min, performing shear dispersion at the rotation speed of 20000rmp for 15min, and performing high-pressure micro-jet circulation at the pressure of 20000psi for 20 times to obtain an anti-bipolar catalyst dispersion liquid, and mixing polyvinylpyrrolidone and the anti-bipolar catalyst dispersion liquid to obtain a precursor solution, wherein the mass ratio of the iridium oxide to the polyvinylpyrrolidone to the N, N-dimethylformamide is 1:12: 136;
(2) performing electrostatic spinning on the precursor solution obtained in the step (1) at a voltage of 22kV, wherein the propelling speed is 0.8mL/h to obtain precursor fibers;
(3) and (3) heating the precursor fiber obtained in the step (2) at the temperature of 380 ℃ for 20min to obtain the modified anti-reversal catalyst.
Comparative example 2
The comparative example provides a modified anti-reversal catalyst, which comprises iridium oxide and polyvinylidene fluoride as surface coatings, wherein the anti-reversal catalyst is in a nanofiber shape, the diameter of the anti-reversal catalyst is 15nm, and the specific surface area of the surface of the anti-reversal catalyst is 350m2/g。
The preparation method of the modified catalyst comprises the following steps:
(1) mixing iridium oxide and N, N-dimethylformamide, performing ultrasonic dispersion at the power of 500W for 20min, performing shear dispersion at the rotation speed of 20000rmp for 15min, and performing high-pressure micro-jet circulation at the pressure of 20000psi for 20 times to obtain an anti-bipolar catalyst dispersion liquid, and mixing polyvinylidene fluoride, polyvinylpyrrolidone and the anti-bipolar catalyst dispersion liquid to obtain a precursor solution, wherein the mass ratio of the iridium oxide to the polyvinylpyrrolidone to the polyvinylidene fluoride to the N, N-dimethylformamide is 1:12:6: 136;
(2) performing electrostatic spinning on the precursor solution obtained in the step (1) at a voltage of 22kV, wherein the propelling speed is 0.8mL/h to obtain precursor fibers;
(3) and (3) heating the precursor fiber obtained in the step (2) at the temperature of 380 ℃ for 20min to obtain the modified anti-reversal catalyst.
Application example 1
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 1;
the preparation method of the anti-reverse anode slurry comprises the following steps:
(a) mixing the modified anti-bipolar catalyst and the hydroalcoholic mixture in a mass ratio of 1:125, and dispersing to obtain modified anti-bipolar catalyst slurry; the water-alcohol mixture is water and methanol in a mass ratio of 1:5, and the dispersion method comprises ultrasonic dispersion with power of 500W for 20min and shear dispersion with rotation speed of 20000rmp for 15 min;
(b) mixing a carbon-supported platinum catalyst with the platinum loading of 60 wt%, an ionomer solution (Solvay, Aquivion D79-25BS) with the EW value of 790 and the mass fraction of 25%, a water-methanol mixture with the mass ratio of 1:5 and the modified anti-reverse-pole catalyst slurry obtained in the step (a), and performing ultrasonic dispersion with the power of 500W for 20min to obtain the anti-reverse-pole anode slurry, wherein the mass ratio of the carbon in the anti-reverse-pole anode slurry, the ionomer solution and the water-alcohol mixture is 1:2:200, and the mass ratio of the platinum element in the carbon-supported platinum catalyst to the anti-reverse-pole metal element in the modified anti-reverse-pole catalyst slurry is 1: 0.5.
Application example 2
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 2;
the preparation method of the anti-reverse anode slurry comprises the following steps:
(a) mixing the modified anti-bipolar catalyst and the hydroalcoholic mixture in a mass ratio of 1:110, and dispersing to obtain modified anti-bipolar catalyst slurry; the water-alcohol mixture comprises water and ethanol in a mass ratio of 1:3, and the dispersing method comprises ultrasonic dispersion with power of 400W for 25min and shear dispersion with rotation speed of 15000rmp for 18 min;
(b) mixing a platinum catalyst, an ionomer solution (FUMA, FSLNA-710) with the EW value of 750 and the mass fraction of 10%, a water-ethanol mixture with the mass ratio of 1:3 and the modified anti-reversal catalyst slurry obtained in the step (a), and carrying out ultrasonic dispersion with the power of 400W for 25min to obtain the anti-reversal anode slurry, wherein the mass ratio of carbon in the anti-reversal anode slurry, the ionomer solution and the water-ethanol mixture is 1:1:300, and the mass ratio of platinum elements in the platinum catalyst to anti-reversal metal elements in the modified anti-reversal catalyst slurry is 1: 0.1.
Application example 3
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 3;
the preparation method of the anti-reverse anode slurry comprises the following steps:
(a) mixing the modified anti-bipolar catalyst and the hydroalcoholic mixture in a mass ratio of 1:140, and dispersing to obtain modified anti-bipolar catalyst slurry; the water-alcohol mixture is water and isopropanol in a mass ratio of 1:6, and the dispersion method comprises ultrasonic dispersion at power of 800W for 15min and shear dispersion at rotation speed of 25000rmp for 12 min;
(b) mixing a platinum catalyst, an ionomer solution (DFPSA-2079) with the EW value of 800 and the mass fraction of 5%, a water and isopropanol mixture with the mass ratio of 1:6 and the modified anti-reverse-pole catalyst slurry obtained in the step (a), and carrying out ultrasonic dispersion with the power of 800W for 15min to obtain the anti-reverse-pole anode slurry, wherein the mass ratio of carbon in the anti-reverse-pole anode slurry, the ionomer solution and the water-alcohol mixture is 1:1.8:100, and the mass ratio of platinum element in the platinum catalyst to anti-reverse-pole metal element in the modified anti-reverse-pole catalyst slurry is 1: 0.8.
Application example 4
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 4;
the preparation method of the anti-reverse anode slurry comprises the following steps:
(a) mixing the modified anti-bipolar catalyst and the hydroalcoholic mixture in a mass ratio of 1:100, and dispersing to obtain modified anti-bipolar catalyst slurry; the water-alcohol mixture is water and n-propanol with the mass ratio of 1:1, and the dispersion method comprises ultrasonic dispersion with the power of 300W for 30min and shear dispersion with the rotating speed of 8000rmp for 20 min;
(b) mixing a platinum catalyst, an ionomer solution (Aquivion D79-25BS) with the EW value of 720 and the mass fraction of 25%, a water and n-propanol mixture with the mass ratio of 1:1 and the modified anti-reverse pole catalyst slurry obtained in the step (a), and performing ultrasonic dispersion with the power of 300W for 30min to obtain the anti-reverse pole anode slurry, wherein the mass ratio of carbon in the anti-reverse pole anode slurry, the ionomer solution and the water-alcohol mixture is 1:2.2:30, and the mass ratio of platinum element in the platinum catalyst to anti-reverse pole metal element in the modified anti-reverse pole catalyst slurry is 1: 0.01.
Application example 5
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 5;
the preparation method of the anti-reverse anode slurry comprises the following steps:
(a) mixing the modified anti-bipolar catalyst and the hydroalcoholic mixture in a mass ratio of 1:150, and dispersing to obtain modified anti-bipolar catalyst slurry; the water-alcohol mixture is water and glycol in a mass ratio of 1:8, and the dispersion method comprises ultrasonic dispersion with power of 1000W for 10min and shear dispersion with rotation speed of 30000rmp for 10 min;
(b) mixing a carbon-supported platinum catalyst with a loading of 60 wt%, an ionomer solution (3M, E21669A) with an EW value of 820 and a mass fraction of 5%, a water and ethylene glycol mixture with a mass ratio of 1:8, and the modified anti-reverse-polarity catalyst slurry obtained in the step (a), and performing ultrasonic dispersion with a power of 1000W for 10min to obtain the anti-reverse-polarity anode slurry, wherein the mass ratio of the carbon in the anti-reverse-polarity anode slurry, the ionomer solution and the water-alcohol mixture is 1:0.8:400, and the mass ratio of the platinum element in the carbon-supported platinum catalyst to the anti-reverse-polarity metal element in the modified anti-reverse-polarity catalyst slurry is 1:1.
Application example 5
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 5; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 6
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 6; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 7
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 7; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 8
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 8; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 9
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 9; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 10
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 10; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 11
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 11; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 12
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 12; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 13
The application example provides a reverse-polarity-resistant anode slurry, wherein the reverse-polarity-resistant anode slurry comprises the modified reverse-polarity-resistant catalyst in the embodiment 13; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 14
The application example provides a reverse-polarity-resistant anode slurry, wherein the reverse-polarity-resistant anode slurry comprises the modified reverse-polarity-resistant catalyst described in example 14; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 15
The application example provides a reverse-polarity-resistant anode slurry, wherein the reverse-polarity-resistant anode slurry comprises the modified reverse-polarity-resistant catalyst in the embodiment 15; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 16
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 1; in the preparation method of the anti-reversal electrode anode slurry, the other process steps are the same as the application example 1 except that the mass ratio of the platinum element in the carbon-supported platinum catalyst in the step (b) to the anti-reversal electrode metal element in the modified anti-reversal electrode catalyst slurry is 1: 0.008.
Application example 17
The application example provides anti-reverse anode slurry, wherein the anti-reverse anode slurry comprises the modified anti-reverse catalyst described in the embodiment 1; in the preparation method of the anti-reversal electrode anode slurry, the other process steps are the same as the application example 1 except that the mass ratio of the platinum element in the carbon-supported platinum catalyst in the step (b) to the anti-reversal electrode metal element in the modified anti-reversal electrode catalyst slurry is 1: 1.2.
Application example 18
The application example provides a reverse-polarity-resistant anode slurry, wherein the reverse-polarity-resistant anode slurry comprises the modified reverse-polarity-resistant catalyst described in example 16; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Application example 19
The application example provides a reverse-polarity-resistant anode slurry, wherein the reverse-polarity-resistant anode slurry comprises the modified reverse-polarity-resistant catalyst in the embodiment 17; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Comparative application example 1
The comparative application example provides an anti-reverse anode slurry, which comprises the modified anti-reverse catalyst described in comparative example 1; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
Comparative application example 2
The comparative application example provides an anti-reverse anode slurry, which comprises the modified anti-reverse catalyst described in comparative example 2; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
The modified anti-stiction catalysts obtained from examples 1-17 and comparative examples 1-2 were subjected to RDE testing. The test conditions were: in a 0.1M perchloric acid system, LSV scanning is carried out under the conditions of introducing oxygen for 30min and rotating speed of 1600rmp and under the voltage of 1.2-1.7V, and then overpotential and Tafel slope are calculated, and the results are shown in Table 1.
TABLE 1
The anti-reverse pole anode slurry provided in application examples 1-19 and comparative application examples 1-2 was sprayed on one side of a proton exchange membrane at 70 ℃ as the anode of a membrane electrode, and the prepared cathode slurry was sprayed on the other side as the cathode.
The preparation method of the cathode slurry comprises the following steps:
mixing a carbon-supported platinum catalyst with platinum loading of 60 wt%, an ionomer solution with an EW value of 780 and a mixture of water and isopropanol in a mass ratio of 1:5, and performing ultrasonic dispersion with power of 500W for 20min to obtain the cathode slurry, wherein the mass ratio of the carbon, the ionomer and the mixture of water and alcohol in the cathode slurry is 1:1: 60.
The platinum spraying amount of the cathode slurry is 0.3mg/cm2The platinum spraying amount of the anti-reverse anode slurry is 0.1mg/cm2(ii) a Drying for 8min at 70 ℃ after spraying under the vacuum adsorption condition, sealing the frame, wherein the thickness of the single side frame is 35 mu m, and then carrying out hot pressing for 15s at 105 ℃ under 0.5MPa to obtain a membrane electrode; and respectively arranging gas diffusion layers (CODEBO C24CX483) at two sides of the membrane electrode, and carrying out hot pressing for 10s at 80 ℃ under 0.5MPa to obtain the membrane electrode of the proton exchange membrane fuel cell.
The obtained area was 50cm2Counter-electrode resistance test of large and small membrane electrode. And (3) testing conditions are as follows: temperature 70 ℃, gas excess coefficient H2the/Air is 1.5/2.0, the humidity RH is 70%, and no back pressure is provided. The test results are shown in table 2.
TABLE 2
From the data in tables 1 and 2, the following conclusions can be drawn:
(1) from examples 1 to 5, 16 and 17 and application examples 1 to 5, 18 and 19, it can be seen that the modified anti-reversal catalyst with the surface coated with polytetrafluoroethylene or copolymer thereof provided by the invention has significantly lower overpotential and Tafel slope, and the prepared membrane electrode has high power density at 0.65 and 0.6V and long anti-reversal time. The modified anti-reversal catalyst provided by the invention improves the water electrolysis performance of the anti-reversal catalyst and improves the dispersion stability of the anti-reversal catalyst.
(2) As can be seen from comparison between examples 1 and 6 and between application examples 1 and 6, when the modified anti-reversal catalysts of examples 6 and 6 were prepared, ultrasonic dispersion was not performed in step (1), and the performance was degraded; as is clear from comparison between example 1 and example 7 and between application example 1 and application example 7, the modified anti-reversal catalysts in example 7 and application example 7 were prepared without shear dispersion in step (1), and their performance was reduced; as is clear from comparison between example 1 and example 8 and between application example 1 and application example 8, when the modified anti-reversal catalysts in example 8 and application example 8 were prepared, the performance was degraded because high-pressure microjet circulation was not performed in step (1); therefore, in the preparation process of the modified anti-reversal catalyst, the dispersibility can influence the anti-reversal performance of the modified anti-reversal catalyst, and the dispersion method provided by the invention is beneficial to preparing the modified anti-reversal catalyst with excellent anti-reversal performance.
(3) As can be seen from the comparison between examples 9 and 10 and example 1, and between application examples 9 and 10 and application example 1, when the mass ratio of the anti-reversal catalyst to polytetrafluoroethylene is not in the range of 1 (6-15), the overpotential and Tafel slope of the modified anti-reversal catalyst are high, which indicates that the water electrolysis performance of the anti-reversal catalyst is poor, the power density of the membrane electrode is small, and the anti-reversal time is short, which indicates that the mass ratio of the anti-reversal catalyst provided by the invention to polytetrafluoroethylene is favorable for preparing the modified anti-reversal catalyst with excellent anti-reversal performance.
(4) From the comparison between examples 11 to 12 and example 1, and between application examples 11 to 12 and application example 1, it can be seen that when the modified anti-reversal catalyst is prepared, and when the voltage of the electrostatic spinning in the step (2) is greater than 25kV or less than 18kV, the overpotential and Tafel slope of the modified anti-reversal catalyst are high, which indicates that the water electrolysis performance of the anti-reversal catalyst is poor, the power density of the membrane electrode is small, and the anti-reversal time is short, which indicates that the voltage of the electrostatic spinning in the step (2) when the modified anti-reversal catalyst is prepared according to the present invention is favorable for preparing the modified anti-reversal catalyst with excellent anti-reversal performance.
(5) As can be seen from the comparison between examples 13 to 14 and example 1, and between application examples 13 to 14 and application example 1, when the modified anti-reversal catalyst is prepared, and the speed of electrostatic spinning in the step (2) is greater than 1.2mL/h or less than 0.3mL/h, the overpotential and the Tafel slope of the modified anti-reversal catalyst are high, which indicates that the water electrolysis performance of the anti-reversal catalyst is poor, the power density of the membrane electrode is low, and the anti-reversal time is short, which indicates that the speed of electrostatic spinning in the step (2) when the modified anti-reversal catalyst is prepared according to the present invention is favorable for preparing the modified anti-reversal catalyst with excellent anti-reversal performance.
(6) From the comparison between example 15 and example 1, and between application example 15 and application example 1, it can be seen that when the modified anti-reversal catalyst is prepared, and the heating temperature in step (3) exceeds 400 ℃, the overpotential and Tafel slope of the modified anti-reversal catalyst are high, which indicates that the water electrolysis performance of the anti-reversal catalyst is poor, the power density of the membrane electrode is small, and the anti-reversal time is short, which indicates that the heating temperature in step (3) when the modified anti-reversal catalyst is prepared is favorable for preparing the modified anti-reversal catalyst with excellent anti-reversal performance.
(7) As can be seen from comparison between application examples 16 to 17 and application example 1, when the mass ratio of the platinum element in the anode catalyst to the anti-reversal metal element in the modified anti-reversal catalyst slurry is not in the range of 1 (0.01 to 1) in the preparation of the anti-reversal anode slurry, the power density of the membrane electrode is small and the anti-reversal time is short, which indicates that the mass ratio of the platinum element in the anode catalyst to the anti-reversal metal element in the modified anti-reversal catalyst slurry provided by the present invention is favorable for preparing the anti-reversal anode slurry and the membrane electrode having excellent anti-reversal performance.
(8) As can be seen from comparison of comparative example 1 with example 1 and comparison of application example 1 with application example 1, when the surface of the anti-reversal catalyst is not coated, the overpotential and Tafel slope of the anti-reversal catalyst are high, which indicates that the water electrolysis performance of the anti-reversal catalyst is poor, the power density of the membrane electrode is small, and the anti-reversal time is short, which indicates that the modified anti-reversal catalyst provided by the invention is beneficial to improving the anti-reversal performance and stability of the anti-reversal catalyst.
(9) As can be seen from comparison of comparative example 2 with example 1 and comparison of application example 2 with application example 1, when the coating is polyvinylidene fluoride and polytetrafluoroethylene is not coated, the overpotential and Tafel slope of the modified anti-bipolar catalyst are high, which indicates that the water electrolysis performance of the anti-bipolar catalyst is poor, the power density of the membrane electrode is low and the anti-bipolar time is short, which indicates that the modified anti-bipolar catalyst prepared by coating polytetrafluoroethylene provided by the invention is beneficial to improving the anti-bipolar performance and stability of the anti-bipolar catalyst.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A modified anti-stiction catalyst, comprising an anti-stiction catalyst and a surface coating, said surface coating comprising polytetrafluoroethylene and/or a copolymer of polytetrafluoroethylene;
the shape of the modified anti-reversal catalyst is in a nano-fiber shape.
2. The modified anti-reversal catalyst of claim 1, wherein the anti-reversal catalyst comprises any one of a simple metal, a metal oxide, or a carbon-supported metal, or a combination of at least two of the above;
preferably, the metal comprises iridium and/or ruthenium;
preferably, the copolymer of polytetrafluoroethylene comprises polyperfluoroethylpropylene.
3. The modified anti-bipolar catalyst of claim 1 or 2, wherein the modified anti-bipolar catalyst has a diameter of 10-25 nm;
preferably, the specific surface area of the surface of the modified anti-reversal catalyst is 240-500m2/g。
4. A method for preparing a modified anti-stiction catalyst according to any of claims 1-3, characterized in that it comprises the following steps:
(1) mixing the surface coating, the spinning aid and the anti-reverse-pole catalyst dispersion liquid to obtain a precursor solution;
(2) performing electrostatic spinning on the precursor solution obtained in the step (1) to obtain precursor fibers;
(3) and (3) heating the precursor fiber obtained in the step (2) to obtain the modified anti-reversal catalyst.
5. The method according to claim 4, wherein the anti-reverse catalyst dispersion of step (1) is prepared by mixing an anti-reverse catalyst with a solvent and dispersing;
preferably, the dispersing method comprises ultrasonic dispersion with power of 300-;
preferably, the solvent comprises any one of water, chloroform, absolute ethanol, isopropanol or N, N-dimethylformamide or a combination of at least two thereof;
preferably, the spinning aid in the step (1) comprises any one or a combination of at least two of polyvinylpyrrolidone, polyacrylonitrile, polyacrylic acid or polyvinyl alcohol;
preferably, the mass ratio of the anti-reverse-pole catalyst, the spinning assistant, the surface coating and the solvent is 1 (12-24) to (6-15) to (136-.
6. The production method according to claim 4 or 5, wherein the voltage of the electrospinning of step (2) is 18 to 25 kV;
preferably, the speed of electrostatic spinning in the step (2) is 0.3-1.2 mL/h;
preferably, the temperature of the heating in the step (3) is 350-400 ℃;
preferably, the heating time in the step (3) is 10-30 min.
7. A reverse-resistant anode slurry comprising the modified reverse-resistant catalyst according to any one of claims 1 to 3.
8. A method of preparing a counter-resistant anode slurry according to claim 7, comprising the steps of:
(a) mixing the modified anti-bipolar catalyst and a dispersing agent, and dispersing to obtain modified anti-bipolar catalyst slurry;
(b) mixing a metal catalyst, an ionomer solution, a dispersant and the modified anti-bipolar catalyst slurry obtained in step (a) to obtain the anti-bipolar anode slurry.
9. The preparation method according to claim 8, wherein the dispersant in the step (a) is a water-alcohol mixture, and the mass ratio of water to alcohol is 1 (1-8);
preferably, the alcohol comprises any one or a combination of at least two of methanol, ethanol, isopropanol, n-propanol or ethylene glycol;
preferably, the mass ratio of the modified anti-reversal catalyst to the dispersant in the step (a) is 1 (100-150);
preferably, the dispersing method in the step (a) comprises ultrasonic dispersing with power of 300-;
preferably, the metal catalyst of step (b) comprises a carbon-supported platinum catalyst and/or a platinum alloy catalyst;
preferably, the EW value of the ionomer solution in step (b) is 720-820;
preferably, the dispersant in the step (b) is a water-alcohol mixture, and the mass ratio of water to alcohol is 1 (1-8);
preferably, the alcohol comprises any one or a combination of at least two of methanol, ethanol, isopropanol, n-propanol or ethylene glycol;
preferably, the mixing method in step (b) comprises ultrasonic dispersion with power of 300-;
preferably, the mass ratio of the carbon content in the anti-reverse anode slurry in the step (b), the ionomer solution and the dispersant is 1 (0.8-2.2) to (30-400);
preferably, the mass ratio of the platinum element in the metal catalyst in the step (b) to the anti-reversal metal element in the modified anti-reversal catalyst slurry is 1 (0.01-1).
10. A fuel cell membrane electrode assembly comprising the reverse-resistant anode slurry of claim 7.
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