CN116387580A - Self-humidifying fuel cell membrane electrode and preparation method thereof - Google Patents
Self-humidifying fuel cell membrane electrode and preparation method thereof Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims abstract description 41
- 210000000170 cell membrane Anatomy 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 98
- 239000003054 catalyst Substances 0.000 claims abstract description 88
- 239000002002 slurry Substances 0.000 claims abstract description 59
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000005507 spraying Methods 0.000 claims abstract description 27
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
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- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 10
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 49
- 239000010408 film Substances 0.000 claims description 44
- 229910052697 platinum Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- 238000011068 loading method Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 10
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- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- CAXLRMXJZKJFTG-UHFFFAOYSA-N N-methylmethanamine silane Chemical compound [SiH4].CNC.CNC.CNC.CNC CAXLRMXJZKJFTG-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 210000004027 cell Anatomy 0.000 abstract description 21
- 150000003460 sulfonic acids Chemical class 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 4
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- 238000000231 atomic layer deposition Methods 0.000 description 6
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- 230000008569 process Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QYERSNHTHORBCJ-UHFFFAOYSA-N trimethylalumane;hydrate Chemical compound O.C[Al](C)C QYERSNHTHORBCJ-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- 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
- H01M4/8807—Gas diffusion layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a self-humidifying fuel cell membrane electrode and a preparation method thereof, which belong to the technical field of fuel cells, and the preparation method comprises the following steps: s1, mixing a platinum-carbon catalyst, distilled water and isopropanol, stirring and dispersing, and adding a perfluorosulfonic acid resin solution to obtain slurry; s2, placing the proton exchange membrane on a heating plate, pouring the slurry into a spray gun, and slowly spraying the slurry on the proton exchange membrane to obtain an anode surface catalyst membrane, and spraying the slurry on the other surface of the proton exchange membrane to obtain a cathode surface catalyst membrane; s3, depositing a hydrophilic oxide film on the anode surface of the catalyst film by a reaction source to obtain the anode hydrophilic catalyst film; s4, placing the gas diffusion layers on two sides of the catalyst film, and hot-press forming. The hydrophilic oxide is uniformly doped in the catalyst and the perfluorinated sulfonic acid resin, so that the hydrophilicity of the anode surface of the membrane electrode is improved, the hydrophilic substances are uniformly dispersed, and the problem of production consistency is solved.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a self-humidifying fuel cell membrane electrode and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) directly convert chemical energy into electric energy without a fuel combustion process, have high energy conversion efficiency and zero emission, can be started quickly at low temperature, and have wide application prospects. Membrane Electrodes (MEA) are the core components of proton exchange membrane fuel cells, directly determining the performance of the fuel cell. The membrane electrode consists of a proton exchange membrane, a cathode/anode catalytic layer and a cathode/anode gas diffusion layer, and all parts of the membrane electrode have great influence on the membrane electrode. The membrane electrode generally needs to humidify the reaction gas, the moisture wets the proton exchange membrane to ensure the transmission of protons, and when the proton exchange membrane is dry, the proton conductivity is poor, the impedance of the membrane electrode is greatly increased, and the performance of the membrane electrode is reduced.
In order to solve the above problems, a gas humidification module is generally added to a fuel cell system to humidify a reaction gas, increase wettability of a proton exchange membrane, and improve proton conductivity. However, the humidification assembly is an additional load to the fuel cell that not only increases the complexity of the system, but also increases the volume and cost of the system. Therefore, the preparation of the self-humidifying fuel cell membrane electrode has great significance for simplifying the system and the process and reducing the cost.
Publication No. CN107482228A discloses a humidifying-free membrane electrode constructed by an anode catalyst and a preparation method thereof, and a novel Pt/RuO is designed 2 -SiO 2 The composite catalyst is used as anode catalyst to construct membrane electrode, and the prepared membrane electrode has excellent hydrophilic capacity and electrochemical performance. Publication number CN101702439a discloses a fuel cell catalyst coated membrane electrode with self-humidifying function and a preparation method thereof, and the self-humidifying performance of the membrane electrode is improved by designing a double-layer structure of an inner catalyst layer and an outer catalyst layer and by self-humidifying agents (such as titanium dioxide, silicon dioxide, zirconium dioxide and the like) in the inner catalyst layer. Publication No. CN104716351A provides a self-humidifying membrane electrode of a proton exchange membrane fuel cell and a preparation method thereof, wherein platinum-carbon catalysis is adoptedThe catalyst, inorganic hydrophilic metal oxide nano particles, perfluorinated sulfonic acid polymer and low boiling point solvent are mixed to be used as an anode catalytic layer, and hydrophilic oxide is used as a self-humidifying substance.
The patent mostly improves the self-humidification performance of the membrane electrode by adding hydrophilic oxides (silicon oxide, aluminum oxide and the like) into the catalyst slurry of the membrane electrode, however, the hydrophilic oxides have poor conductivity, the performance of the membrane electrode is seriously affected by excessive addition, and the uniformity of membrane electrode products in the amplifying production process is affected by uneven dispersion of trace hydrophilic oxides in the slurry system due to the excessive addition.
Disclosure of Invention
The invention aims to provide a self-humidifying fuel cell membrane electrode and a preparation method thereof, which are used for solving the problem of poor product consistency after hydrophilic oxide is added into catalyst slurry of the membrane electrode.
The aim of the invention can be achieved by the following technical scheme:
a method for preparing a self-humidifying fuel cell membrane electrode, comprising the steps of:
s1, mixing a platinum-carbon catalyst, distilled water and isopropanol, stirring and dispersing, adding a perfluorosulfonic acid resin solution, and uniformly stirring to obtain slurry;
s2, placing the proton exchange membrane on a heating plate, pouring the slurry into a spray gun, and slowly spraying the slurry on the proton exchange membrane to obtain an anode surface catalyst membrane, and spraying the slurry on the other surface of the proton exchange membrane to obtain a cathode surface catalyst membrane; placing the volatilized redundant solution after spraying;
s3, depositing a hydrophilic oxide film on the anode surface of the catalyst film by a reaction source to obtain the anode hydrophilic catalyst film;
s4, placing the gas diffusion layers on two sides of the catalyst membrane, and putting the catalyst membrane into a mould for hot press molding to obtain the self-humidifying fuel cell membrane electrode.
Further, the platinum carbon catalyst comprises 50% of platinum by mass, 20% of solid content of perfluorosulfonic acid resin solution by weight, and the volume ratio of distilled water to isopropanol is 0.5-1.5:8.5-9.5; the mass ratio of the dry weight of the perfluorosulfonic acid resin to the carbon carrier in the catalyst is 0.7-0.8:1, the solid content in the slurry is 1-2%.
Further, the total platinum loading on both sides of the proton exchange membrane was 0.5mg/cm 2 The platinum loading ratio of the anode face to the cathode face was 1:4.
further, the reaction source is one of an aqueous solution of trimethylaluminum, an aqueous solution of tetra (dimethylamide) silane and an aqueous solution of titanium tetraisopropoxide; the mass fraction of the reaction source is 1%.
Further, the deposition temperature is 200 ℃, and the working pressure of the reaction cavity is kept
Further, the hydrophilic oxide film includes Al 2 O 3 Film, siO 2 Film and TiO 2 One of the films.
Further, the number of layers of the hydrophilic oxide film is 2 to 6.
Further, the conditions of the hot press molding are: the temperature is 140 ℃, the pressure is 3MPa, and the hot pressing is 2min.
The self-humidifying fuel cell membrane electrode is prepared by the preparation method.
The invention has the beneficial effects that:
in the invention, the catalyst and the perfluorinated sulfonic acid resin are firstly loaded on the proton exchange membrane by a spraying process to form a catalyst membrane, and then hydrophilic oxide is uniformly dispersed on the anode surface of the catalyst membrane by an atomic layer deposition mode to finish the manufacture of the membrane electrode anode. Compared with other self-humidifying membrane electrode production methods, the method has the remarkable advantages that: the hydrophilic oxide can be uniformly doped in the catalyst and the perfluorinated sulfonic acid resin, so that the hydrophilicity of the anode surface of the membrane electrode is improved, the hydrophilic substances are kept uniformly dispersed, and the problem of production consistency is solved; and the hydrophilic oxide film with proper thickness covers the catalyst film layer, which is more beneficial to improving the electrochemical performance of the fuel cell.
Drawings
The invention is further described below with reference to the accompanying drawings.
Fig. 1 is a voltage-current curve of a measured battery of the samples prepared in example 1 and comparative examples 1-3 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a self-humidifying fuel cell membrane electrode, which comprises the following steps:
s1, weighing 0.5g of platinum-carbon catalyst (the mass percent of platinum is 50%), adding 3.375mL of distilled water and 64.125mL of isopropanol, stirring for 30min at 500rpm in a 30W ultrasonic cleaner, adding 0.875g of perfluorosulfonic acid resin solution (the solid content is 20 wt%) and stirring for 30min at 10000rpm at normal temperature to form uniformly dispersed ink-like slurry. The volume ratio of water/isopropanol in the slurry was 0.5:9.5, the mass ratio of the dry weight of the perfluorinated sulfonic acid resin to the carbon carrier in the catalyst is 0.7, and the total solid content in the slurry is 1%.
S2, placing the proton exchange membrane with the thickness of 12 mu m on a heating plate with the temperature of 90 ℃, pouring the slurry into a spray gun, slowly spraying the slurry on the proton exchange membrane, placing the slurry at the temperature of 40 ℃ for 1h, and volatilizing the redundant solution to obtain the anode surface catalyst membrane. And then spraying slurry on the other surface of the proton exchange membrane in the same manner to obtain the cathode surface catalyst membrane. The total platinum loading on both sides of the proton exchange membrane is controlled to be 0.5mg/cm by controlling the spraying thickness 2 The platinum loading ratio of the anode face to the cathode face was 1:4.
s3, atomic layer deposition of hydrophilic oxide: the method is characterized in that 1% trimethyl aluminum water solution is used as a reaction source, the deposition temperature is set at 200 ℃, the working pressure of a reaction cavity is kept at 0.3 ∈3, and K9 glass with the thickness of 2mm is adopted as a substrate. Under such conditions, depositing a catalyst film on the anode side of the catalyst film2 layers of Al 2 O 3 Thin film, to give anode hydrophilic catalyst film.
S4, placing 220 mu m gas diffusion layers on two sides of the catalyst film, placing the catalyst film into a die of a hot press, and hot-press molding the catalyst film at the temperature of 140 ℃ and the pressure of 3MPa for 2min to obtain the self-humidifying fuel cell film electrode.
Example 2
S1, weighing 0.5g of platinum-carbon catalyst (the mass percent of platinum is 50%), adding 4.58mL of distilled water and 41.25mL of isopropanol, stirring for 30min at 500rpm in a 30W ultrasonic cleaner, adding 0.9375g of perfluorosulfonic acid resin solution (the solid content is 20 wt%) and stirring for 30min at 10000rpm at normal temperature to form uniformly dispersed ink-shaped slurry. The volume ratio of water/isopropanol in the slurry is 1:9, the mass ratio of the dry weight of the perfluorinated sulfonic acid resin to the carbon carrier in the catalyst is 0.75, and the total solid content in the slurry is 1.5%.
S2, placing the proton exchange membrane with the thickness of 12 mu m on a heating plate with the temperature of 90 ℃, pouring the slurry into a spray gun, slowly spraying the slurry on the proton exchange membrane, placing the slurry at the temperature of 40 ℃ for 1h, and volatilizing the redundant solution to obtain the anode surface catalyst membrane. And then spraying slurry on the other surface of the proton exchange membrane in the same manner to obtain the cathode surface catalyst membrane. The total platinum loading on both sides of the proton exchange membrane is controlled to be 0.5mg/cm by controlling the spraying thickness 2 The platinum loading ratio of the anode face to the cathode face was 1:4.
s3, atomic layer deposition of hydrophilic oxide: the method comprises the steps of taking 1% of tetra (dimethylamide) silane aqueous solution as a reaction source, setting the deposition temperature at 200 ℃, and keeping the working pressure of a reaction cavity
The substrate was made of K9 glass having a thickness of 2 mm. Under the condition, 4 layers of SiO are deposited on the anode surface of the catalyst film 2 Thin film, to give anode hydrophilic catalyst film.
S4, placing 220 mu m gas diffusion layers on two sides of the catalyst film, placing the catalyst film into a die of a hot press, and hot-press molding for 2min at the temperature of 140 ℃ and the pressure of 3MPa to obtain the self-humidifying fuel cell film electrode.
Example 3
S1, weighing 0.5g of platinum-carbon catalyst (the mass percent of platinum is 50%), adding 5.25mL of distilled water and 29.75mL of isopropanol, stirring for 30min at 500rpm in a 30W ultrasonic cleaner, adding 1.0g of perfluorosulfonic acid resin solution (the solid content is 20 wt%) and stirring for 30min at 10000rpm at normal temperature to form uniformly dispersed ink-shaped slurry. The volume ratio of water/isopropanol in the slurry is 1.5:8.5, the mass ratio of the dry weight of the perfluorinated sulfonic acid resin to the carbon carrier in the catalyst is 0.8, and the total solid content in the slurry is 2%.
S2, placing the proton exchange membrane with the thickness of 12 mu m on a heating plate with the temperature of 90 ℃, pouring the slurry into a spray gun, slowly spraying the slurry on the proton exchange membrane, placing the slurry at the temperature of 40 ℃ for 1h, and volatilizing the redundant solution to obtain the anode surface catalyst membrane. And then spraying slurry on the other surface of the proton exchange membrane in the same manner to obtain the cathode surface catalyst membrane. The total platinum loading on both sides of the proton exchange membrane is controlled to be 0.5mg/cm by controlling the spraying thickness 2 The platinum loading ratio of the anode face to the cathode face was 1:4.
s3, atomic layer deposition of hydrophilic oxide: titanium tetraisopropoxide aqueous solution with 1% content is taken as a reaction source, the deposition temperature is set at 200 ℃, and the working pressure of a reaction cavity is kept
The substrate was made of K9 glass having a thickness of 2 mm. Under the condition, 6 layers of TiO are deposited on the anode surface of the catalyst film 2 Thin film, to give anode hydrophilic catalyst film.
S4, placing 220 mu m gas diffusion layers on two sides of the catalyst film, placing the catalyst film into a die of a hot press, and hot-press molding for 2min at the temperature of 140 ℃ and the pressure of 3MPa to obtain the self-humidifying fuel cell film electrode.
Comparative example 1
S1, weighing 0.5g of platinum-carbon catalyst (the mass percent of platinum is 50%) and 25mg of hydrophilic alumina, adding 3.375mL of distilled water and 64.125mL of isopropanol, stirring at 500rpm for 30min in a 30W ultrasonic cleaner, adding 0.875g of perfluorosulfonic acid resin solution (the solid content is 20 wt%), and stirring at 10000rpm for 30min at normal temperature to form uniformly dispersed ink-like slurry. The volume ratio of water/isopropanol in the slurry was 0.5:9.5, the mass ratio of the dry weight of the perfluorinated sulfonic acid resin to the carbon carrier in the catalyst is 0.7, and the total solid content in the slurry is 1%.
S2, placing the proton exchange membrane with the thickness of 12 mu m on a heating plate with the temperature of 90 ℃, pouring the slurry into a spray gun, slowly spraying the slurry on the proton exchange membrane, placing the slurry at the temperature of 40 ℃ for 1h, and volatilizing the redundant solution to obtain the anode surface catalyst membrane. And then spraying slurry on the other surface of the proton exchange membrane in the same manner to obtain the cathode surface catalyst membrane. The total platinum loading on both sides of the proton exchange membrane is controlled to be 0.5mg/cm by controlling the spraying thickness 2 The platinum loading ratio of the anode face to the cathode face was 1:4.
s3, placing 220 mu m gas diffusion layers on two sides of the catalyst film, placing the catalyst film into a die of a hot press, and hot-press molding for 2min at a certain temperature of 140 ℃ and a pressure of 3MPa to obtain the self-humidifying fuel cell membrane electrode.
Comparative example 2
S1, weighing 0.5g of platinum-carbon catalyst (the mass percent of platinum is 50%), adding 3.375mL of distilled water and 64.125mL of isopropanol, stirring for 30min at 500rpm in a 30W ultrasonic cleaner, adding 0.875g of perfluorosulfonic acid resin solution (the solid content is 20 wt%) and stirring for 30min at 10000rpm at normal temperature to form uniformly dispersed ink-shaped slurry. The volume ratio of water/isopropanol in the slurry was 0.5:9.5, the mass ratio of the dry weight of the perfluorinated sulfonic acid resin to the carbon carrier in the catalyst is 0.7, and the total solid content in the slurry is 1%.
S2, placing the proton exchange membrane with the thickness of 12 mu m on a heating plate with the temperature of 90 ℃, pouring the slurry into a spray gun, slowly spraying the slurry on the proton exchange membrane, placing the slurry at the temperature of 40 ℃ for 1h, and volatilizing the redundant solution to obtain the anode surface catalyst membrane. And then spraying slurry on the other surface of the proton exchange membrane in the same manner to obtain the cathode surface catalyst membrane. The total platinum loading on both sides of the proton exchange membrane is controlled to be 0.5mg/cm by controlling the spraying thickness 2 The platinum loading ratio of the anode face to the cathode face was 1:4.
s3, atomic layer deposition of hydrophilic oxides: taking 1% trimethyl aluminum aqueous solution as a reaction source, setting the deposition temperature at 200 ℃, and keeping the working pressure of a reaction cavity
The substrate was made of K9 glass having a thickness of 2 mm. Under such conditions, 12 layers of Al are deposited on the anode surface of the catalyst film 2 O 3 Thin film, to give anode hydrophilic catalyst film.
S4, placing 220 mu m gas diffusion layers on two sides of the catalyst film, placing the catalyst film into a die of a hot press, and hot-press molding for 2min at a certain temperature of 140 ℃ and a pressure of 3MPa to obtain the self-humidifying fuel cell membrane electrode.
Comparative example 3
S1, weighing 0.5g of platinum-carbon catalyst (the mass percent of platinum is 50%), adding 3.375mL of distilled water and 64.125mL of isopropanol, stirring for 30min at 500rpm in a 30W ultrasonic cleaner, adding 0.875g of perfluorosulfonic acid resin solution (the solid content is 20 wt%) and stirring for 30min at 10000rpm at normal temperature to form uniformly dispersed ink-like slurry. The volume ratio of water/isopropanol in the slurry was 0.5:9.5, the mass ratio of the dry weight of the perfluorinated sulfonic acid resin to the carbon carrier in the catalyst is 0.7, and the total solid content in the slurry is 1%.
S2, placing the proton exchange membrane with the thickness of 12 mu m on a heating plate with the temperature of 90 ℃, pouring the slurry into a spray gun, slowly spraying the slurry on the proton exchange membrane, placing the slurry at the temperature of 40 ℃ for 1h, and volatilizing the redundant solution to obtain the anode surface catalyst membrane. And then spraying slurry on the other surface of the proton exchange membrane in the same manner to obtain the cathode surface catalyst membrane. The total platinum loading on both sides of the proton exchange membrane is controlled to be 0.5mg/cm by controlling the spraying thickness 2 The platinum loading ratio of the anode face to the cathode face was 1:4.
s3, placing 220 mu m gas diffusion layers on two sides of the catalyst film, placing the catalyst film into a die of a hot press, and hot-press molding the catalyst film at the temperature of 140 ℃ and the pressure of 3MPa for 2min to obtain the fuel cell film electrode.
Performance tests were performed on example 1 and comparative examples 1-3:
the testing method comprises the following steps: electric property of membrane electrodeThe fuel cell test system is used for testing, reactants used by the system are compressed air and high-purity hydrogen, and the system is provided with an external humidifying system, so that different gas humidifying effects are obtained by controlling the temperature of a humidifier. Before testing, the MEA was activated for the purpose of having the Nafion resin contained in the proton exchange membrane and catalytic layer contain sufficient water to ensure adequate conductivity. And after the working conditions are stable, controlling different discharging currents or voltages of the battery, and after the test is finished, deriving experimental data. The unit cell of the fuel cell consists of a membrane electrode, a polar plate, a sealing gasket, an end plate and the like. The polar plate adopts an impermeable hard graphite plate with the size of 50 multiplied by 3mm, and the inner side is designed into a parallel snake-shaped three-flow passage; the sealing gasket adopts a common plastic gasket; stainless steel plates were used as end plates. The components are tightly assembled to reduce the internal resistance of the battery. The effective area of the membrane electrode in the self-made single battery is 25cm 2 . The effective area of the electrode is 25cm 2 After the membrane electrode of the battery is arranged in the single cell experimental battery, the performance test of the single cell is carried out on a test bench. The electrochemical performance test conditions of the membrane electrode are divided into hydrogen and oxygen without humidification, the operation under the condition of no humidification means that the heating device of the hydrogen and the oxygen is in a closed state, the temperature is room temperature, the hydrogen pressure and the oxygen pressure are respectively regulated to 0.28MPa and 0.30MPa, the single battery is connected with an external constant-current constant-voltage power supply, the temperature of the battery is increased to 50 ℃, and the voltage-current curve of the battery is measured, and is shown in the figure 1.
From comparison of the polarization curve data of example 1 and comparative example 1, it is clear from the examination of the hydrophilic oxide and doping method in the above examples and comparative example that the in-situ doping of comparative example 1 has limited dispersion effect on the hydrophilic oxide, as the current density is lower, the performance of the membrane electrode obtained by the method is comparable to that of the membrane electrode obtained in example 1, however, as the current density is increased, the voltage loss is larger. From comparison of the polarization data of example 1 and comparative example 2, atomic layer deposition of 12 layers of hydrophilic oxide was performed in comparative example 2, and the overall performance was lower than that of example 1 throughout the entire current density interval, indicating that too thick a hydrophilic oxide film resulted in partial coverage of the catalytic layer, affecting the electrical performance of the fuel cell catalyst. From the polarization data of example 1 and comparative example 3, the performance of comparative example 3 without the hydrophilic oxide added is far lower than that of example 1, comparative example 1 and comparative example 2, indicating that the membrane electrode with hydrophilic oxide added can improve the electrochemical performance of the fuel cell under the condition of no humidification.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A method for preparing a self-humidifying fuel cell membrane electrode, comprising the steps of: s1, mixing a platinum-carbon catalyst, distilled water and isopropanol, stirring and dispersing, adding a perfluorosulfonic acid resin solution, and uniformly stirring to obtain slurry;
s2, placing the proton exchange membrane on a heating plate, pouring the slurry into a spray gun, and slowly spraying the slurry on the proton exchange membrane to obtain an anode surface catalyst membrane, and spraying the slurry on the other surface of the proton exchange membrane to obtain a cathode surface catalyst membrane; placing the volatilized redundant solution after spraying;
s3, depositing a hydrophilic oxide film on the anode surface of the catalyst film by a reaction source to obtain the anode hydrophilic catalyst film;
s4, placing the gas diffusion layers on two sides of the catalyst membrane, and placing the catalyst membrane into a mould for hot press molding to obtain the self-humidifying fuel cell membrane electrode.
2. The method for preparing a self-humidifying fuel cell membrane electrode according to claim 1 wherein the mass percentage of platinum in the platinum-carbon catalyst is 50%, the solid content of the perfluorosulfonic acid resin solution is 20% by weight, and the volume ratio of distilled water to isopropyl alcohol is 0.5-1.5:8.5-9.5; the mass ratio of the dry weight of the perfluorosulfonic acid resin to the carbon carrier in the catalyst is 0.7-0.8:1, the solid content in the slurry is 1-2%.
3. The method for preparing a self-humidifying fuel cell membrane electrode according to claim 1 wherein the total platinum loading on both sides of the proton exchange membrane is 0.5mg/cm 2 The platinum loading ratio of the anode face to the cathode face was 1:4.
4. the method for preparing a self-humidifying fuel cell membrane electrode according to claim 1 wherein the reaction source is one of an aqueous trimethylaluminum solution, an aqueous tetra (dimethylamide) silane solution and an aqueous titanium tetraisopropoxide solution; the mass fraction of the reaction source is 1%.
5. The method of preparing a self-humidifying fuel cell membrane electrode according to claim 1 wherein the deposition temperature is 200 ℃ and the reaction chamber operating pressure is maintained at 0.3 τ.
6. The method for producing a self-humidifying fuel cell membrane electrode according to claim 1 wherein the hydrophilic oxide film comprises Al 2 O 3 Film, siO 2 Film and TiO 2 One of the films.
7. The method for producing a self-humidifying fuel cell membrane electrode according to claim 1 wherein the number of hydrophilic oxide thin films is 2 to 6.
8. The method for preparing a self-humidifying fuel cell membrane electrode according to claim 1 wherein the hot press molding conditions are: the temperature is 140 ℃, the pressure is 3MPa, and the hot pressing is carried out for 2min.
9. A self-humidifying fuel cell membrane electrode prepared by the method of any one of claims 1-8.
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| CN117577906B (en) * | 2023-12-16 | 2024-05-03 | 杭州质子动力有限公司 | Self-humidifying membrane electrode of air-cooled fuel cell and preparation method thereof |
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