CN114373941B - Modified anti-reverse electrode catalyst and preparation method and application thereof - Google Patents
Modified anti-reverse electrode catalyst and preparation method and application thereof Download PDFInfo
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- CN114373941B CN114373941B CN202210060414.8A CN202210060414A CN114373941B CN 114373941 B CN114373941 B CN 114373941B CN 202210060414 A CN202210060414 A CN 202210060414A CN 114373941 B CN114373941 B CN 114373941B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 274
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000006185 dispersion Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 39
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 37
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 37
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 73
- 239000006256 anode slurry Substances 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 71
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 41
- 239000002243 precursor Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 229910052697 platinum Inorganic materials 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 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 30
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 229920000554 ionomer Polymers 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000446 fuel Substances 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 238000010041 electrostatic spinning Methods 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 238000001523 electrospinning Methods 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000002904 solvent Substances 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
- 238000009987 spinning Methods 0.000 claims description 5
- 229910001260 Pt alloy Inorganic materials 0.000 claims description 3
- 210000000170 cell membrane Anatomy 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- IDOWTHOLJBTAFI-UHFFFAOYSA-N phenmedipham Chemical compound COC(=O)NC1=CC=CC(OC(=O)NC=2C=C(C)C=CC=2)=C1 IDOWTHOLJBTAFI-UHFFFAOYSA-N 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 abstract description 11
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- 238000010008 shearing Methods 0.000 description 12
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 11
- 229910000457 iridium oxide Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000006257 cathode slurry Substances 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 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
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XIUFWXXRTPHHDQ-UHFFFAOYSA-N prop-1-ene;1,1,2,2-tetrafluoroethene Chemical group CC=C.FC(F)=C(F)F XIUFWXXRTPHHDQ-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-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
- 239000000463 material Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
Abstract
The invention provides a modified anti-counter electrode catalyst, and a preparation method and application thereof. The modified anti-counter electrode catalyst comprises an anti-counter electrode catalyst and a surface coating, wherein the surface coating comprises polytetrafluoroethylene and/or a copolymer of polytetrafluoroethylene; the modified anti-reverse electrode catalyst is in a nanofiber shape. The modified anti-reverse electrode catalyst obtained by coating polytetrafluoroethylene or a copolymer thereof on the surface of the catalyst improves the dispersion stability of the anti-reverse electrode catalyst, reduces the water decomposition potential, improves the catalyst efficiency and improves the water electrolysis performance of the anti-reverse electrode catalyst.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and relates to a modified anti-reverse electrode catalyst, in particular to a modified anti-reverse electrode catalyst, a preparation method and application thereof.
Background
Hydrogen fuel cells utilize hydrogen and oxygen to react and directly convert chemical energy into electrical energy. 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. The service life of the fuel cell of the commercial vehicle is 10000-15000h at present, and the service life requirement which is comparable with that of an internal combustion engine is not met, so that the service life is improved, and the service life is one of the most important problems in popularization and application of the fuel cell of the commercial vehicle.
However, under-gassing of the anode caused by 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 lacks hydrogen, the anode cannot perform HOR reaction to provide protons and electrons, other single cells connected in series in the electric pile can provide energy to capacitively charge 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 so-called reverse polarity occurs. In order to maintain charge balance, hydrolysis is performed under the high potential of the anode to generate protons and electrons, and after a period of time, when the water electrolysis reaction cannot maintain charge balance, 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 can perform oxidation reaction to continuously provide protons and electrons, so that the performance and durability of the battery are seriously affected.
CN 111082078A provides a preparation method of a high-performance and voltage reversal resistant membrane electrode assembly, which comprises the following steps: sequentially adding a catalyst, an anti-reverse electrode electrolyzed water catalytic 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, anode slurry is sprayed on protons An anode side of the exchange membrane; step three, 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; spraying cathode slurry on the cathode side of the proton exchange membrane to obtain a required CCM; step five, applying 70kg/cm to the prepared CCM and the gas diffusion layer and polyester frame through an oil press 2 Is subjected to force hot pressing to obtain MEA; and step six, assembling the prepared MEA into a single cell, and performing performance test and anti-counter electrode test.
CN 110534780a discloses a preparation method of membrane electrode of proton exchange membrane fuel cell, which comprises coating Pt/C catalytic layers on two sides of proton membrane to obtain semi-finished CCM membrane, and coating anti-counter electrode slurry layers on peripheral edges of anode surface of semi-finished CCM membrane to achieve the purpose of counter electrode resistance.
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 includes 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.
According to the technical scheme, the anti-counter electrode slurry and the anode slurry are mixed to prepare the anode catalytic layer, so that the anti-counter electrode performance of the battery can be improved, but the anti-counter electrode catalyst easily shields the reactive active sites of platinum, a shielding effect is generated on the platinum, the HOR (organic oxygen-rich reactor) reactive activity of the anode catalytic layer is seriously reduced, and the overall performance of the battery is further reduced; the anti-counter electrode slurry is independently prepared around the anode catalytic layer, and the anode HOR activity can be ensured, but only the edge membrane perforation phenomenon can be improved, and the anti-electrode phenomenon generated in the central area of the membrane electrode can not be resisted.
How to improve the anti-reverse performance of the membrane electrode in the fuel cell and solve the problem of membrane electrode damage caused by voltage reverse due to insufficient anode fuel supply is a technical problem to be solved in the hydrogen fuel cell.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a modified anti-reverse electrode catalyst, a preparation method and application thereof, and the polytetrafluoroethylene is coated on the surface, so that the shielding effect of the anti-reverse electrode catalyst on an anode catalyst is reduced, the reduction of the catalytic activity of the anode catalyst for catalyzing the oxygen reduction reaction is effectively prevented, and the power density of a membrane electrode is enhanced.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a modified anti-reverse catalyst comprising an anti-reverse catalyst and a surface coating comprising polytetrafluoroethylene and/or a copolymer of polytetrafluoroethylene;
the modified anti-reverse electrode catalyst is in a nanofiber shape.
According to the invention, polytetrafluoroethylene or a copolymer thereof is coated on the surface of the anti-counter electrode catalyst, so that a coating layer with loose structure is formed. The existence of the coating layer can effectively reduce the shielding effect of the anti-counter electrode catalyst on the platinum element, prevent the catalytic activity of the anode catalyst for catalyzing the oxidation-reduction reaction from being reduced, and prevent the activity of the anode catalyst layer HOR from being reduced. The hydrophobicity of polytetrafluoroethylene or its copolymer causes water to accumulate around and on the surface of the anti-counter electrode catalyst, and can electrolyze water to provide more water source, thereby prolonging the anti-counter electrode time. According to the modified anti-reverse-polarity catalyst obtained by coating polytetrafluoroethylene or a copolymer thereof on the surface, the dispersion stability of the anti-reverse-polarity catalyst is improved, the overpotential and Tafel slope of the catalyst are reduced, and the water electrolysis performance of the anti-reverse-polarity catalyst is improved.
Preferably, the anti-counter electrode catalyst comprises any one or a combination of at least two of a simple metal, a metal oxide or a carbon supported metal, typically but not limited to a combination of a simple metal and a metal oxide, a combination of a metal oxide and a carbon supported metal, a combination of a simple metal and a carbon supported metal, or a combination of a simple metal, a metal oxide and a carbon supported metal.
Preferably, the metal comprises iridium and/or ruthenium.
Preferably, the copolymer of polytetrafluoroethylene comprises a perfluoroethylene propylene.
Preferably, the diameter of the modified anti-counter electrode catalyst is 10-25nm, which may be, for example, 10nm, 12nm, 15nm, 17nm, 18nm, 20nm, 22nm or 25nm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the specific surface area of the surface of the modified anti-reverse electrode catalyst is 240-500m 2 /g, for example, may be 240m 2 /g、260m 2 /g、300m 2 /g、350m 2 /g、400m 2 /g、450m 2 /g or 500m 2 The values of/g are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
In a second aspect, the present invention provides a method for preparing the modified anti-counter electrode catalyst according to the first aspect, the method comprising the steps of:
(1) Mixing the surface coating, the spinning aid and the anti-counter electrode catalyst dispersion to obtain a precursor solution;
(2) Carrying out 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-counter electrode catalyst.
According to the invention, the nanofiber modified anti-counter electrode catalyst is prepared by fully mixing and dispersing the anti-counter electrode catalyst and the surface coating, and then electrostatic spinning is carried out, so that the surface coating forms a loose-structure coating layer on the surface of the anti-counter electrode catalyst, which is beneficial to reducing the shielding effect of the anti-counter electrode catalyst on platinum element, the existence of the coating layer prevents the catalytic activity of the catalytic oxidation reduction reaction of the anode catalyst from being reduced, and the activity of the anode catalytic layer HOR reaction from being reduced.
Preferably, the preparation method of the anti-reverse electrode catalyst dispersion liquid in the step (1) comprises mixing the anti-reverse electrode catalyst with a solvent and then dispersing.
Preferably, the dispersing method comprises ultrasonic dispersing for 10-30min with power of 300-1000W, shearing dispersing for 10-20min with rotation speed of 8000-30000rmp and high-pressure micro-jet circulation for 10-30 times with pressure of 10000-30000 psi;
the power of the ultrasound is 300-1000W, for example, 300W, 500W, 700W, 900W or 1000W, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The ultrasonic dispersion time is 10-30min, for example, 10min, 15min, 20min, 25min or 30min, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The shear dispersion speed is 8000-30000rmp, for example 8000rmp, 10000rmp, 15000rmp, 20000rmp or 30000rmp, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
The shear dispersion time is 10-20min, for example, 10min, 12min, 15min, 18min or 20min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The pressure of the high pressure microfluidic cycle is 10000-30000 psi, such as 10000psi, 15000psi, 20000psi, 25000psi or 30000psi, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The number of high pressure microfluidic cycles is 10-30, for example 10, 15, 20, 25 or 30, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the solvent comprises any one or a combination of at least two of water, chloroform, absolute ethanol, isopropanol or N, N-dimethylformamide. Typical, but non-limiting, combinations include combinations of water and chloroform, combinations of chloroform and absolute ethanol, combinations of absolute ethanol and isopropanol, combinations of isopropanol and N, N-dimethylformamide, combinations of water, chloroform and absolute ethanol, combinations of chloroform, absolute ethanol and isopropanol, or combinations of chloroform, absolute ethanol, isopropanol and N, N-dimethylformamide.
Preferably, the spinning aid in step (1) comprises any one or a combination of at least two of polyvinylpyrrolidone, polyacrylonitrile, polyacrylic acid or polyvinyl alcohol. Typical, but non-limiting, combinations include combinations of polyvinylpyrrolidone and polyacrylonitrile, combinations of polyacrylonitrile and polyacrylic acid, combinations of polyacrylic acid and polyvinyl alcohol, combinations of polyvinylpyrrolidone, polyacrylonitrile and polyacrylic acid, combinations of polyacrylonitrile, polyacrylic acid and polyvinyl alcohol, or combinations of polyvinylpyrrolidone, polyacrylonitrile, polyacrylic acid and polyvinyl alcohol.
Preferably, the mass ratio of the anti-counter electrode catalyst, the spinning aid, the polytetrafluoroethylene and the solvent is 1 (12-24): (6-15): (136-168), and for example, may 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 recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the voltage of the electrospinning in the step (2) is 18-25kV, for example, 18kV, 20kV, 22kV, 24kV or 25kV, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the speed of the electrospinning in the step (2) is 0.3-1.2mL/h, for example, 0.3mL/h, 0.5mL/h, 0.8mL/h, 1mL/h or 1.2mL/h, but not limited to the recited values, and other non-recited values in the range of values are equally 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 non-recited values in the range of values are equally applicable.
Preferably, the heating time in the step (3) is 10-30min, for example, 10min, 15min, 20min, 25min or 30min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In a third aspect, the present invention provides a counter-anode slurry comprising a modified counter-anode catalyst as described in the first aspect.
In a fourth aspect, the present invention provides a method for preparing the anti-counter anode slurry according to the third aspect, the method comprising the steps of:
(a) Mixing the modified anti-reverse electrode catalyst and a dispersing agent, and dispersing to obtain modified anti-reverse electrode catalyst slurry;
(b) Mixing a metal catalyst, an ionomer solution, a dispersant and the modified anti-counter electrode catalyst slurry obtained in step (a) to obtain the anti-counter electrode anode slurry.
Preferably, the dispersant in step (a) is a water-alcohol mixture, the mass ratio of water to alcohol is 1 (1-8), for example, it may be 1:1, 1:3, 1:4, 1:5, 1:7 or 1:8, but not limited to the recited values, and other non-recited values in 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 combinations of methanol and ethanol, combinations of ethanol and isopropanol, combinations of isopropanol and n-propanol, combinations of n-propanol and ethylene glycol, combinations of methanol, ethanol and isopropanol, combinations of ethanol, isopropanol and n-propanol, combinations of isopropanol, n-propanol and ethylene glycol, combinations of methanol, ethanol, isopropanol and n-propanol, or combinations of ethanol, isopropanol, n-propanol and ethylene glycol.
Preferably, the mass ratio of the modified anti-counter electrode catalyst to the dispersant in step (a) is 1 (100-150), and may be, for example, 1:100, 1:110, 1:120, 1:130, 1:140 or 1:150, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the dispersion method in step (a) comprises ultrasonic dispersion at a power of 300-1000W for 10-30min and shear dispersion at a rotational speed of 8000-30000rmp for 10-20min. The power of the ultrasound is 300-1000W, for example, 300W, 500W, 700W, 900W or 1000W, but not limited to the recited values, and other non-recited values in the range of values are equally applicable. The ultrasonic dispersion time is 10-30min, for example, 10min, 15min, 20min, 25min or 30min, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable. The shearing speed is 8000-30000rmp, for example 8000rmp, 10000rmp, 15000rmp, 20000rmp or 30000rmp, but not limited to the values listed, and other values not listed in the range of values are equally applicable. The shear dispersion time is 10-20min, for example, 10min, 12min, 15min, 18min or 20min, but not limited to the recited values, and other non-recited values in the range of values 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 is not limited to the specific type of the metal catalyst of step (b).
Preferably, the ionomer solution of step (b) has an EW value of 720 to 820, which may be, for example, 720, 750, 780, 800 or 820, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the dispersant in step (b) is a water-alcohol mixture, the mass ratio of water to alcohol is 1 (1-8), for example, it may be 1:1, 1:3, 1:4, 1:5, 1:7 or 1:8, but not limited to the recited values, and other non-recited values in 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 combinations of methanol and ethanol, combinations of ethanol and isopropanol, combinations of isopropanol and n-propanol, combinations of n-propanol and ethylene glycol, combinations of methanol, ethanol and isopropanol, combinations of ethanol, isopropanol and n-propanol, combinations of isopropanol, n-propanol and ethylene glycol, combinations of methanol, ethanol, isopropanol and n-propanol, or combinations of ethanol, isopropanol, n-propanol and ethylene glycol.
Preferably, the method of mixing in step (b) comprises ultrasonic dispersion at a power of 300-1000W for 10-30min. The power of the ultrasound is 300-1000W, for example, 300W, 500W, 700W, 900W or 1000W, but not limited to the recited values, and other non-recited values in the range of values are equally applicable. The ultrasonic dispersion time is 10-30min, for example, 10min, 15min, 20min, 25min or 30min, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the mass ratio of carbon content, ionomer solution and dispersant in the anti-counter anode slurry of step (b) is 1 (0.8-2.2): (30-400), which 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 recited values, other non-recited values within the range of values are equally applicable.
Preferably, the mass ratio of the platinum element in the metal catalyst of step (b) to the anti-counter metal element in the modified anti-counter 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 non-recited values within the range of values are equally applicable.
In a fifth aspect, the present invention provides a fuel cell membrane electrode comprising a counter anode slurry according to the third aspect.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the modified anti-reverse-polarity catalyst obtained by coating polytetrafluoroethylene or a copolymer thereof on the surface, the dispersion stability of the anti-reverse-polarity catalyst is improved, the overpotential and Tafel slope of the catalyst are reduced, and the water electrolysis performance of the anti-reverse-polarity catalyst is improved.
(2) According to the invention, polytetrafluoroethylene or a copolymer thereof is coated on the surface of the anti-counter electrode catalyst 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-counter electrode catalyst on platinum element, prevent the catalytic activity of the anode catalyst for catalyzing oxidation-reduction reaction from being reduced, and prevent the activity of the anode catalyst layer HOR from being reduced. The hydrophobicity of polytetrafluoroethylene enables water to accumulate around and on the surface of the anti-counter electrode catalyst, and can electrolyze water to provide more water source, thereby prolonging the anti-counter electrode time.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
Example 1
The embodiment provides a modified anti-counter electrode catalyst, which comprises anti-counter electrode catalyst iridium oxide and surface coating polytetrafluoroethylene, wherein the anti-counter electrode catalyst is in a nanofiber shape, the diameter is 15nm, and the specific surface area of the surface is 350m 2 /g。
The preparation method of the modified catalyst comprises the following steps:
(1) Mixing iridium oxide and N, N-dimethylformamide, performing ultrasonic dispersion for 20min at the power of 500W, performing shearing dispersion for 15min at the rotating speed of 20000rmp and performing high-pressure microjet circulation for 20 times at the pressure of 20000psi to obtain anti-counter electrode catalyst dispersion liquid, and mixing polytetrafluoroethylene, polyvinylpyrrolidone and the anti-counter electrode catalyst dispersion liquid to obtain precursor solution, wherein the mass ratio of iridium oxide to polyvinylpyrrolidone to polytetrafluoroethylene to N, N-dimethylformamide is 1:12:6:136;
(2) Carrying out electrostatic spinning on the precursor solution obtained in the step (1) under 22kV voltage, wherein the advancing speed is 0.8mL/h to obtain precursor fibers;
(3) And (3) heating the precursor fiber obtained in the step (2) at 380 ℃ for 20min to obtain the modified anti-counter electrode catalyst.
Example 2
The embodiment provides a modified anti-counter electrode catalyst, which comprises ruthenium oxide of the anti-counter electrode catalyst and polytetrafluoroethylene of a surface coating, wherein the anti-counter electrode catalyst is in a nanofiber shape, has the diameter of 20nm and the specific surface area of 400m 2 /g。
The preparation method of the modified catalyst comprises the following steps:
(1) Mixing ruthenium oxide and water, performing ultrasonic dispersion for 25min at 400W, performing shearing dispersion for 18min at the rotating speed of 15000rmp and performing high-pressure microjet circulation for 25 times at the pressure of 15000psi to obtain anti-reverse-polarity catalyst dispersion liquid, and mixing polytetrafluoroethylene, polyacrylonitrile and the anti-reverse-polarity catalyst dispersion liquid to obtain precursor solution, wherein the mass ratio of ruthenium oxide to polyacrylonitrile to polytetrafluoroethylene to water is 1:24:15:168;
(2) Carrying out electrostatic spinning on the precursor solution obtained in the step (1) under 20kV voltage, wherein the advancing speed is 1mL/h to obtain precursor fibers;
(3) And (3) heating the precursor fiber obtained in the step (2) at a temperature of 360 ℃ for 25min to obtain the modified anti-counter electrode catalyst.
Example 3
The embodiment provides a modified anti-counter electrode catalyst, which comprises an anti-counter electrode catalyst iridium black and a surface coating polytetrafluoroethylene, wherein the anti-counter electrode catalyst is in a nanofiber shape, has a diameter of 12nm and a surface specific surface area of 450m 2 /g。
The preparation method of the modified catalyst comprises the following steps:
(1) Mixing iridium black and chloroform, performing ultrasonic dispersion for 15min at 800W, performing shearing dispersion for 12min at the rotating speed of 25000rmp, performing high-pressure micro-jet circulation for 15 times at the pressure of 25000psi to obtain anti-reverse-polarity catalyst dispersion liquid, and mixing polytetrafluoroethylene, polyacrylic acid and the anti-reverse-polarity catalyst dispersion liquid to obtain precursor solution, wherein the mass ratio of iridium black to polyacrylic acid to polytetrafluoroethylene to chloroform is 1:12:15:168;
(2) Carrying out electrostatic spinning on the precursor solution obtained in the step (1) under 24kV voltage, wherein the advancing speed is 0.5mL/h to obtain precursor fibers;
(3) And (3) heating the precursor fiber obtained in the step (2) at 380 ℃ for 15min to obtain the modified anti-counter electrode catalyst.
Example 4
The embodiment provides a modified anti-counter electrode catalyst, which comprises ruthenium which is an anti-counter electrode catalyst and surface coatingThe shape of the anti-counter electrode catalyst is nanofiber, the diameter is 10nm, and the specific surface area is 240m 2 /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, performing high-pressure micro-jet circulation for 30 times at the pressure of 10000psi to obtain anti-counter electrode catalyst dispersion liquid, and mixing polytetrafluoroethylene, polyvinyl alcohol and the anti-counter electrode catalyst dispersion liquid to obtain precursor solution, wherein the mass ratio of ruthenium to polyvinyl alcohol to polytetrafluoroethylene to absolute ethyl alcohol is 1:24:6:136;
(2) Carrying out electrostatic spinning on the precursor solution obtained in the step (1) under 18kV voltage, wherein the advancing 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-counter electrode catalyst.
Example 5
The embodiment provides a modified anti-counter electrode catalyst, which comprises carbon-supported iridium of the anti-counter electrode catalyst and polytetrafluoroethylene of a surface coating, wherein the anti-counter electrode catalyst is in a nanofiber shape, has a diameter of 25nm and a specific surface area of 500m 2 /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 a power of 1000W, performing shearing dispersion for 10min at a rotating speed of 30000rmp, and performing high-pressure microjet circulation for 10 times at a pressure of 30000psi to obtain an anti-reverse-polarity catalyst dispersion liquid, and mixing polytetrafluoroethylene, polyvinylpyrrolidone and the anti-reverse-polarity 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) Carrying out electrostatic spinning on the precursor solution obtained in the step (1) under 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 400 ℃ for 10min to obtain the modified anti-counter electrode catalyst.
Example 6
This example provides a modified anti-counter electrode catalyst prepared in the same manner as in example 1 except that no ultrasonic dispersion was performed in step (1).
Example 7
This example provides a modified anti-counter electrode catalyst prepared in the same manner as in example 1 except that no shear dispersion was performed in step (1).
Example 8
This example provides a modified anti-counter electrode catalyst prepared in the same manner as in example 1 except that the high pressure microfluidic cycle was not performed in step (1).
Example 9
The present example provides a modified anti-reverse electrode catalyst, and the preparation method of the modified anti-reverse electrode catalyst is the same as that of example 1 except that the mass ratio of iridium oxide to polytetrafluoroethylene in step (1) is 1:5.
Example 10
The present example provides a modified anti-reverse electrode catalyst, and the preparation method of the modified anti-reverse electrode catalyst is the same as that of example 1 except that the mass ratio of iridium oxide to polytetrafluoroethylene in step (1) is 1:16.
Example 11
The present example provides a modified anti-reverse electrode catalyst, and the preparation method of the modified anti-reverse electrode catalyst is the same as that of example 1 except that the voltage of the electrostatic spinning in the step (2) is 16 kV.
Example 12
The present example provides a modified anti-reverse electrode catalyst, and the preparation method of the modified anti-reverse electrode catalyst is the same as that of example 1 except that the voltage of the electrostatic spinning in the step (2) is 28 kV.
Example 13
This example provides a modified anti-reverse catalyst, which was prepared in the same manner as in example 1, except that the electrospinning speed in step (2) was 0.2 mL/h.
Example 14
The present example provides a modified anti-reverse catalyst, which was 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-counter electrode catalyst prepared in the same manner as in example 1 except that the temperature of heating in step (3) was 420 ℃.
Example 16
This example provides a modified anti-reverse catalyst, the remainder being the same as example 1 except that the surface coating was replaced with equal mass of polyperfluoroethylene propylene.
Example 17
This example provides a modified anti-reverse catalyst, the remainder being the same as example 1 except that the surface coating was replaced with polytetrafluoroethylene and perfluoroethylene propylene in a mass ratio of 1:1.
Comparative example 1
The comparative example provides an anti-counter electrode catalyst which is iridium oxide, is in the shape of nanofiber, has a diameter of 15nm and a specific surface area of 350m 2 /g。
The preparation method of the anti-counter electrode catalyst comprises the following steps:
(1) Mixing iridium oxide and N, N-dimethylformamide, performing ultrasonic dispersion for 20min at the power of 500W, performing shearing dispersion for 15min at the rotating speed of 20000rmp and performing high-pressure microjet circulation for 20 times at the pressure of 20000psi to obtain anti-counter electrode catalyst dispersion liquid, and mixing polyvinylpyrrolidone and the anti-counter electrode catalyst dispersion liquid to obtain precursor solution, wherein the mass ratio of iridium oxide to polyvinylpyrrolidone to N, N-dimethylformamide is 1:12:136;
(2) Carrying out electrostatic spinning on the precursor solution obtained in the step (1) under 22kV voltage, wherein the advancing speed is 0.8mL/h to obtain precursor fibers;
(3) And (3) heating the precursor fiber obtained in the step (2) at 380 ℃ for 20min to obtain the modified anti-counter electrode catalyst.
Comparative example 2
The comparative example provides a modified anti-counter electrode catalyst comprising anti-counter electrode catalyst iridium oxide and surface-coated polyvinylidene fluoride, the anti-counter electrode catalyst being in the form of nanofibers with a diameter of 15nm and a specific surface area of 350m 2 /g。
The preparation method of the modified catalyst comprises the following steps:
(1) Mixing iridium oxide and N, N-dimethylformamide, performing ultrasonic dispersion for 20min at the power of 500W, performing shearing dispersion for 15min at the rotating speed of 20000rmp and performing high-pressure microjet circulation for 20 times at the pressure of 20000psi to obtain an anti-reverse catalyst dispersion liquid, and mixing polyvinylidene fluoride, polyvinylpyrrolidone and the anti-reverse catalyst dispersion liquid to obtain a precursor solution, wherein the mass ratio of iridium oxide to polyvinylpyrrolidone to polyvinylidene fluoride to N, N-dimethylformamide is 1:12:6:136;
(2) Carrying out electrostatic spinning on the precursor solution obtained in the step (1) under 22kV voltage, wherein the advancing speed is 0.8mL/h to obtain precursor fibers;
(3) And (3) heating the precursor fiber obtained in the step (2) at 380 ℃ for 20min to obtain the modified anti-counter electrode catalyst.
Application example 1
The application example provides a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst in the embodiment 1;
The preparation method of the anti-counter anode slurry comprises the following steps:
(a) Mixing a modified anti-counter electrode catalyst and a hydroalcoholic mixture with a mass ratio of 1:125, and dispersing to obtain modified anti-counter electrode catalyst slurry; the water-alcohol mixture is water and methanol with the mass ratio of 1:5, and the dispersion method is ultrasonic dispersion with the power of 500W for 20min and shearing dispersion with the rotating speed of 20000rmp for 15min;
(b) Mixing a carbon-supported platinum catalyst with a platinum loading amount of 60wt%, an ionomer solution with an EW value of 790 and a mass fraction of 25% (Soervion D79-25 BS), a water and methanol mixture with a mass ratio of 1:5, and the modified anti-counter electrode catalyst slurry obtained in the step (a), and performing ultrasonic dispersion with a power of 500W for 20min to obtain the anti-counter electrode anode slurry, wherein the mass ratio of carbon in the anti-counter electrode anode slurry, the ionomer solution and the water-alcohol mixture is 1:2:200, and the mass ratio of platinum element in the carbon-supported platinum catalyst to anti-counter electrode metal element in the modified anti-counter electrode catalyst slurry is 1:0.5.
Application example 2
The application example provides a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst in the embodiment 2;
The preparation method of the anti-counter anode slurry comprises the following steps:
(a) Mixing a modified anti-counter electrode catalyst and a hydroalcoholic mixture with a mass ratio of 1:110, and dispersing to obtain modified anti-counter electrode catalyst slurry; the water-alcohol mixture is water and ethanol with the mass ratio of 1:3, and the dispersion method is ultrasonic dispersion with the power of 400W for 25min and shearing dispersion with the rotating speed of 15000rmp for 18min;
(b) Mixing a platinum catalyst, an ionomer solution (FUMA, FSLNA-710) with an EW value of 750 and a mass fraction of 10%, a mixture of water and ethanol with a mass ratio of 1:3, and the modified anti-counter electrode catalyst slurry obtained in the step (a), and performing ultrasonic dispersion with a power of 400W for 25min to obtain the anti-counter electrode anode slurry, wherein the mass ratio of carbon in the anti-counter electrode anode slurry, the ionomer solution and the water-alcohol mixture is 1:1:300, and the mass ratio of platinum element in the platinum catalyst to anti-counter electrode metal element in the modified anti-counter electrode catalyst slurry is 1:0.1.
Application example 3
The application example provides a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst in the embodiment 3;
the preparation method of the anti-counter anode slurry comprises the following steps:
(a) Mixing a modified anti-counter electrode catalyst and a water-alcohol mixture in a mass ratio of 1:140, and dispersing to obtain modified anti-counter electrode catalyst slurry; the water-alcohol mixture is water and isopropanol with the mass ratio of 1:6, and the dispersing method is that ultrasonic dispersion with the power of 800W is carried out for 15min and shearing dispersion with the rotating speed of 25000rmp is carried out for 12min;
(b) Mixing a platinum catalyst, an ionomer solution (Ai Mengte, DFPSA-2079) with an EW value of 800 and a mass fraction of 5%, a mixture of water and isopropanol with a mass ratio of 1:6, and the modified anti-counter electrode catalyst slurry obtained in the step (a), and performing ultrasonic dispersion with a power of 800W for 15min to obtain the anti-counter electrode anode slurry, wherein the mass ratio of carbon in the anti-counter electrode anode slurry, the ionomer solution and the hydroalcoholic mixture is 1:1.8:100, and the mass ratio of platinum element in the platinum catalyst to anti-counter electrode metal element in the modified anti-counter electrode catalyst slurry is 1:0.8.
Application example 4
The application example provides a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst in the embodiment 4;
the preparation method of the anti-counter anode slurry comprises the following steps:
(a) Mixing a modified anti-counter electrode catalyst and a hydroalcoholic mixture in a mass ratio of 1:100, and dispersing to obtain modified anti-counter electrode catalyst slurry; the water-alcohol mixture is water and n-propanol with the mass ratio of 1:1, and the dispersion method is ultrasonic dispersion with the power of 300W for 30min and shear dispersion with the rotating speed of 8000rmp for 20min;
(b) Mixing a platinum catalyst, an ionomer solution (Solvin D79-25 BS) with an EW value of 720 and a mass fraction of 25%, a mixture of water and n-propanol with a mass ratio of 1:1, and the modified anti-counter electrode catalyst slurry obtained in the step (a), and performing ultrasonic dispersion with a power of 300W for 30min to obtain the anti-counter electrode anode slurry, wherein the mass ratio of carbon in the anti-counter electrode 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 the anti-counter electrode metal element in the modified anti-counter electrode catalyst slurry is 1:0.01.
Application example 5
The application example provides a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst in the embodiment 5;
the preparation method of the anti-counter anode slurry comprises the following steps:
(a) Mixing a modified anti-counter electrode catalyst and a water-alcohol mixture in a mass ratio of 1:150, and dispersing to obtain modified anti-counter electrode catalyst slurry; the water-alcohol mixture is water and glycol with the mass ratio of 1:8, and the dispersion method is ultrasonic dispersion with the power of 1000W for 10min and shear dispersion with the rotating speed of 30000rmp for 10min;
(b) Mixing a carbon-supported platinum catalyst with a loading capacity of 60wt%, an ionomer solution (3M, E21669A) with an EW value of 820 and a mass fraction of 5%, a mixture of water and glycol with a mass ratio of 1:8, and the modified anti-counter electrode catalyst slurry obtained in the step (a), and performing ultrasonic dispersion with a power of 1000W for 10min to obtain the anti-counter electrode anode slurry, wherein the mass ratio of carbon in the anti-counter electrode anode slurry, the ionomer solution and the water-alcohol mixture is 1:0.8:400, and the mass ratio of platinum element in the carbon-supported platinum catalyst to anti-counter electrode metal element in the modified anti-counter electrode catalyst slurry is 1:1.
Application example 5
The application example provides a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst 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 a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst 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 a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst 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 a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst 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 a counter-electrode anode slurry, wherein the counter-electrode anode slurry comprises the modified counter-electrode catalyst 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 a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst 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 a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst of 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 a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst of 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 counter-electrode anode slurry, which comprises the modified counter-electrode catalyst of 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 counter-electrode anode slurry, which comprises the modified counter-electrode catalyst of the embodiment 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 counter-electrode anode slurry, which comprises the modified counter-electrode catalyst of 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 a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst in the embodiment 1; in the preparation method of the anti-reverse anode slurry, the rest process steps are the same as in 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-reverse metal element in the modified anti-reverse catalyst slurry is 1:0.008.
Application example 17
The application example provides a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst in the embodiment 1; in the preparation method of the anti-reverse anode slurry, the rest process steps are the same as in 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-reverse metal element in the modified anti-reverse catalyst slurry is 1:1.2.
Application example 18
The application example provides a counter-electrode anode slurry, which comprises the modified counter-electrode catalyst of the embodiment 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 counter-electrode anode slurry, which comprises the modified counter-electrode catalyst of 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 a counter-electrode anode slurry comprising the modified counter-electrode catalyst of 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 a counter-electrode anode slurry comprising the modified counter-electrode catalyst of comparative example 2; the preparation method of the anti-reverse anode slurry is the same as that of application example 1.
RDE tests were performed on the modified anti-counter electrode catalysts obtained in examples 1-17 and comparative examples 1-2. The test conditions were: in a 0.1M perchloric acid system, oxygen was introduced for 30min, LSV scanning was performed at a rotational speed of 1600rmp under a voltage of 1.2-1.7V, and then overpotential and Tafel slopes were calculated, and the results are shown in Table 1.
TABLE 1
The anti-counter anode slurries provided in application examples 1-19 and comparative application examples 1-2 were sprayed at 70 ℃ onto one side of a proton exchange membrane as the anode of the membrane electrode and the cathode slurry prepared by spraying on the other side was used as the cathode.
The preparation method of the cathode slurry comprises the following steps:
mixing a carbon-supported platinum catalyst with a platinum loading amount of 60wt%, an ionomer solution with an EW value of 780 and a mixture of water and isopropanol with a mass ratio of 1:5, and performing ultrasonic dispersion with a power of 500W for 20min to obtain the cathode slurry, wherein the mass ratio of carbon, ionomer and water-alcohol mixture in the cathode slurry is 1:1:60.
The platinum spraying amount of the cathode slurry is 0.3mg/cm 2 The platinum spraying amount of the anti-counter anode slurry was 0.1mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying for 8min at 70 ℃ under vacuum adsorption condition after spraying, sealing the frame, wherein the thickness of the single side frame is 35 mu m, and then hot-pressing for 15s at 105 ℃ under 0.5MPa to obtain a membrane electrode; gas diffusion layers (Kedbao C24CX 483) are respectively arranged at two sides of the membrane electrode, and the membrane electrode of the proton exchange membrane fuel cell is obtained by hot-pressing for 10s at the temperature of 80 ℃ under the pressure of 0.5 MPa.
The area obtained was 50cm 2 Anti-counter electrode test for large and small membrane electrode. Test conditions: temperature 70 ℃, gas excess coefficient H 2 Air=1.5/2.0, humidity RH 70%, no back pressure. The test results are shown in Table 2.
TABLE 2
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From the data in tables 1 and 2, the following conclusions can be drawn:
(1) As can be seen from examples 1 to 5, 16 and 17 and application examples 1 to 5, 18 and 19, the modified anti-counter electrode catalyst of the surface-coated polytetrafluoroethylene or the copolymer thereof provided by the invention has the advantages of obviously lower overpotential and Tafel slope, large power density of the prepared membrane electrode under 0.65V and 0.6V and long anti-counter electrode time. The modified anti-reverse electrode catalyst provided by the invention improves the water electrolysis performance of the anti-reverse electrode catalyst and improves the dispersion stability of the anti-reverse electrode catalyst.
(2) As is clear from the comparison of example 1 and example 6, application example 1 and application example 6, the modified anti-reverse electrode catalyst in example 6 and application example 6 was prepared without ultrasonic dispersion in step (1), and the performance was lowered; as is clear from the comparison of example 1 and example 7, application example 1 and application example 7, when the modified anti-reverse electrode catalyst in example 7 and application example 7 was prepared, no shear dispersion was performed in step (1), and the performance was degraded; as is clear from the comparison of example 1 and example 8, application example 1 and application example 8, when the modified anti-reverse electrode catalyst in example 8 and application example 8 was prepared, the high-pressure micro-jet cycle was not performed in step (1), and the performance was degraded; therefore, in the preparation process of the modified anti-counter electrode catalyst, the dispersibility can influence the anti-counter electrode performance of the modified anti-counter electrode catalyst.
(3) As can be seen from the comparison of examples 9 and 10 with example 1 and the comparison of application examples 9 and 10 with application example 1, when the mass ratio of the anti-counter electrode catalyst to polytetrafluoroethylene is not within the range of (6-15), the overpotential and Tafel slope of the modified anti-counter electrode catalyst are high, which indicates that the anti-counter electrode catalyst has poor water electrolysis performance, the power density of the membrane electrode is small and the anti-counter electrode time is short, which indicates that the mass ratio of the anti-counter electrode catalyst to polytetrafluoroethylene provided by the invention is favorable for preparing the modified anti-counter electrode catalyst with excellent anti-counter electrode performance.
(4) As can be seen from the comparison of examples 11-12 with example 1 and application examples 11-12 with application example 1, when the voltage of the electrospinning in the step (2) is greater than 25kV or less than 18kV, the overpotential and Tafel slope of the modified anti-counter electrode catalyst are high, which indicates that the anti-counter electrode catalyst has poor water electrolysis performance, and the membrane electrode has low power density and short anti-counter electrode time, which indicates that the voltage of the electrospinning in the step (2) is favorable for preparing the modified anti-counter electrode catalyst with excellent anti-counter electrode performance when the modified anti-counter electrode catalyst is prepared.
(5) As can be seen from the comparison of examples 13-14 with example 1 and application examples 13-14 with application example 1, when the speed of electrospinning in the step (2) is greater than 1.2mL/h or less than 0.3mL/h, the overpotential and Tafel slope of the modified anti-counter electrode catalyst are high, which indicates that the anti-counter electrode catalyst has poor water electrolysis performance, and the membrane electrode has small power density and short anti-counter electrode time, which indicates that the speed of electrospinning in the step (2) is favorable for preparing the modified anti-counter electrode catalyst with excellent anti-counter electrode performance when the modified anti-counter electrode catalyst is prepared.
(6) As can be seen from comparison of example 15 and example 1, application example 15 and application example 1, when the heating temperature in the step (3) exceeds 400 ℃, the overpotential and Tafel slope of the modified anti-counter electrode catalyst are high, which indicates that the anti-counter electrode catalyst has poor water electrolysis performance, and the membrane electrode has small power density and short anti-counter electrode time, which indicates that the heating temperature in the step (3) is favorable for preparing the modified anti-counter electrode catalyst with excellent anti-counter electrode performance when the modified anti-counter electrode catalyst is prepared.
(7) As can be seen from comparison of application examples 16-17 with application example 1, when the anti-counter electrode anode slurry is prepared, the mass ratio of the platinum element in the anode catalyst to the anti-counter electrode metal element in the modified anti-counter electrode catalyst slurry is not within the range of (0.01-1), and the power density of the membrane electrode is small and the anti-counter electrode time is short, which indicates that the mass ratio of the platinum element in the anode catalyst to the anti-counter electrode metal element in the modified anti-counter electrode catalyst slurry provided by the invention is favorable for preparing the anti-counter electrode anode slurry and the membrane electrode with excellent anti-counter electrode performance.
(8) As can be seen from comparison of comparative example 1 with example 1 and comparative application example 1 with application example 1, when the surface of the anti-counter electrode catalyst is not coated, the overpotential and Tafel slope of the anti-counter electrode catalyst are high, which indicates that the anti-counter electrode catalyst has poor water electrolysis performance, and the membrane electrode has small power density and short anti-counter electrode time, which indicates that the modified anti-counter electrode catalyst provided by the invention is beneficial to improving the anti-counter electrode performance and stability of the anti-counter electrode catalyst.
(9) As can be seen from comparison of comparative example 2 with example 1 and comparative 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 antipode catalyst are high, which indicates that the antipode catalyst has poor water electrolysis performance, and the membrane electrode has small power density and short antipole time, which indicates that the modified antipode catalyst prepared by coating polytetrafluoroethylene provided by the invention is beneficial to improving the antipole performance and stability of the antipole catalyst.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (30)
1. A modified anti-reverse catalyst, characterized in that the modified anti-reverse catalyst comprises an anti-reverse catalyst and a surface coating comprising polytetrafluoroethylene and/or a copolymer of tetrafluoroethylene;
The shape of the modified anti-counter electrode catalyst is nanofiber-shaped;
the modified anti-counter electrode catalyst is prepared by the following method, and the preparation method comprises the following steps:
(1) Mixing the surface coating, the spinning aid and the anti-counter electrode catalyst dispersion to obtain a precursor solution;
(2) Carrying out 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-counter electrode catalyst.
2. The modified counter electrode catalyst of claim 1, wherein the counter electrode catalyst comprises any one or a combination of at least two of elemental metal, metal oxide, or carbon supported metal.
3. The modified counter electrode catalyst of claim 2 wherein the metal comprises iridium and/or ruthenium.
4. The modified counter electrode catalyst of claim 1 wherein the copolymer of tetrafluoroethylene comprises a polyperfluoroethylene propylene.
5. The modified counter electrode catalyst of claim 1, wherein the diameter of the modified counter electrode catalyst is from 10 to 25nm.
6. The modified counter electrode catalyst according to claim 1, wherein the specific surface area of the modified counter electrode catalyst surface is 240-500m 2 /g。
7. A process for the preparation of a modified counter electrode catalyst according to any one of claims 1 to 6, characterized in that it comprises the steps of:
(1) Mixing the surface coating, the spinning aid and the anti-counter electrode catalyst dispersion to obtain a precursor solution;
(2) Carrying out 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-counter electrode catalyst.
8. The method of claim 7, wherein the step (1) of preparing the anti-reverse catalyst dispersion comprises mixing the anti-reverse catalyst with a solvent and then dispersing.
9. The method of claim 8, wherein the dispersing method comprises ultrasonic dispersion at a power of 300-1000W for 10-30min, shear dispersion at a rotational speed of 8000-30000rmp for 10-20min, and high pressure micro-jet circulation at a pressure of 10000-30000 psi for 10-30 times.
10. The method of claim 8, wherein the solvent comprises any one or a combination of at least two of water, chloroform, absolute ethanol, isopropanol, or N, N-dimethylformamide.
11. The method of claim 7, wherein the spin aid of step (1) comprises any one or a combination of at least two of polyvinylpyrrolidone, polyacrylonitrile, polyacrylic acid, or polyvinyl alcohol.
12. The method of claim 8, wherein the mass ratio of the anti-counter electrode catalyst, the co-spin agent, the surface coating and the solvent in step (1) is 1 (12-24): 6-15): 136-168.
13. The method according to claim 7, wherein the voltage of the electrospinning in the step (2) is 18 to 25kV.
14. The method according to claim 7, wherein the electrospinning speed in step (2) is 0.3 to 1.2mL/h.
15. The method of claim 7, wherein the heating in step (3) is performed at a temperature of 350-400 ℃.
16. The method according to claim 7, wherein the heating in step (3) is performed for a period of 10 to 30 minutes.
17. A counter-anode slurry comprising the modified counter-anode catalyst of any one of claims 1-6.
18. A method of preparing an anti-counter anode slurry according to claim 17, comprising the steps of:
(a) Mixing the modified anti-reverse electrode catalyst and a dispersing agent, and dispersing to obtain modified anti-reverse electrode catalyst slurry;
(b) Mixing a metal catalyst, an ionomer solution, a dispersant and the modified anti-counter electrode catalyst slurry obtained in step (a) to obtain the anti-counter electrode anode slurry.
19. The method of claim 18, wherein the dispersant in step (a) is a water-alcohol mixture, and the mass ratio of water to alcohol is 1 (1-8).
20. The method of claim 19, wherein the alcohol of step (a) comprises any one or a combination of at least two of methanol, ethanol, isopropanol, n-propanol, or ethylene glycol.
21. The method of claim 18, wherein the mass ratio of modified anti-counter electrode catalyst to dispersant in step (a) is 1 (100-150).
22. The method of claim 18, wherein the dispersing in step (a) comprises ultrasonic dispersion at a power of 300-1000W for 10-30min and shear dispersion at a rotational speed of 8000-30000rmp for 10-20min.
23. The method of claim 18, wherein the metal catalyst of step (b) comprises a carbon supported platinum catalyst and/or a platinum alloy catalyst.
24. The method of claim 18 wherein the ionomer solution of step (b) has an EW value of 720 to 820.
25. The method of claim 18, wherein the dispersant in step (b) is a water-alcohol mixture, and the mass ratio of water to alcohol is 1 (1-8).
26. The method of claim 25, wherein the alcohol of step (b) comprises any one or a combination of at least two of methanol, ethanol, isopropanol, n-propanol, or ethylene glycol.
27. The method of claim 18, wherein the method of mixing in step (b) comprises ultrasonic dispersion at a power of 300-1000W for 10-30min.
28. The method of claim 23 wherein the carbon content, ionomer solution and dispersant in the anti-counter anode slurry of step (b) is 1 (0.8-2.2) by mass (30-400).
29. The method according to claim 18, wherein the mass ratio of the platinum element in the metal catalyst in the step (b) to the anti-counter metal element in the modified anti-counter catalyst slurry is 1 (0.01-1).
30. A fuel cell membrane electrode comprising the anti-counter anode slurry according to claim 17.
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