CN111146482A - Self-humidifying proton exchange membrane and preparation method and application thereof - Google Patents
Self-humidifying proton exchange membrane and preparation method and application thereof Download PDFInfo
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- CN111146482A CN111146482A CN201911258947.1A CN201911258947A CN111146482A CN 111146482 A CN111146482 A CN 111146482A CN 201911258947 A CN201911258947 A CN 201911258947A CN 111146482 A CN111146482 A CN 111146482A
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
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- H—ELECTRICITY
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- 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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
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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
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a self-humidifying proton exchange membrane and a preparation method and application thereof, wherein the self-humidifying proton exchange membrane comprises a first perfluorosulfonic acid resin layer, a second perfluorosulfonic acid resin layer and an intermediate layer positioned between the first perfluorosulfonic acid resin layer and the second perfluorosulfonic acid resin layer, wherein the intermediate layer contains perfluorosulfonic acid resin, a platinum-based catalyst and a humectant; the platinum-based catalyst includes an active center including platinum and a support including a nano metal oxide. The self-humidifying proton exchange membrane provided by the invention is non-conductive, the catalyst and the carrier are not easy to agglomerate, the self-humidifying effect is good, the electrochemical performance is good, and the self-humidifying proton exchange membrane is suitable for hydrogen dye batteries.
Description
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to a self-humidifying proton exchange membrane and a preparation method and application thereof.
Background
The hydrogen fuel cell automobile has the typical characteristics of zero emission, long driving range and quick fuel filling, and is one of important trends of the development of the automobile industry in the future. Meanwhile, the development of a hydrogen fuel cell automobile has very significant significance for improving the energy structure and developing low-carbon traffic.
Proton Exchange Membrane Fuel Cells (PEMFCs) are one of the more widely used types of hydrogen fuel cells today.
In the actual use process of the currently used proton exchange membrane fuel cell, certain moisture is needed for proton conduction, and the proton conduction and the whole chemical reaction are completed by combining with water to synthesize hydrated ions. In the absence of water, the proton conductivity decreases dramatically, leading to reduced membrane electrode and cell performance. To address the problem of water content in proton exchange membranes, a humidification system is typically added to the system, typically by humidifying the inlet air to introduce moisture. However, the humidification system not only complicates the fuel cell system and increases the external size, but also increases the cost. Therefore, it is highly desirable to develop a fuel cell with humidification-free or self-humidification, so as to reduce the cost of the fuel cell and increase the specific power of the fuel cell.
The self-humidifying fuel cell can realize self-humidifying by adopting a membrane electrode with self-humidifying function and adopting a uniquely designed bipolar plate structure. The membrane electrode is the core component of the PEMFC, and generally consists of a proton exchange membrane, an anode and cathode catalyst, and anode and cathode gas diffusion layers. Thus, the self-humidifying membrane electrode can be respectively self-humidifying proton exchange membrane, self-humidifying gas diffusion layer and self-humidifying catalyst layer. Recently, the development of a film having a self-humidifying function has received much attention.
The existing self-humidifying proton exchange membrane is mainly divided into the following types: one is to use the microporous structure of PTFE to achieve self-humidification. The other method is to introduce platinum catalyst into the membrane to realize the catalysis of the oxygen and air entering the interface of the membrane, and the water generated by the catalysis is stored and released under different operating conditions, so that the proton conductivity of the membrane is ensured to the maximum extent, and the working performance of the battery is improved.
The incorporation of platinum requires a support, such as carbon black or silica. The conventional carrier is difficult to uniformly disperse, and agglomeration is easy to occur in use after dispersion. Agglomeration can potentially create a pathway for electrons, which is quite dangerous.
CN101170183A discloses a self-humidifying composite proton exchange membrane based on carbon nanotube reinforcement for fuel cell and its preparation method. The method comprises the following steps: the carbon nano tube reinforced perfluorinated sulfonic acid resin membrane is prepared by a solution casting method, and then Pt is introduced into the membrane to be used as a self-humidifying catalyst. Wherein Pt can be directly supported on the carbon nano tube or supported on the nano SiO2The thickness of the prepared film on the particles is 10-100 mu m. In the invention, carbon nano tube or SiO is used2The particles are used as a carrier of the platinum catalyst, and have the problems of easy agglomeration and short circuit risk.
CN108598534A discloses a self-humidifying water-controlling proton exchange membrane for a fuel cell and a preparation method thereof, wherein hollow fibers are immersed in a hot-melt polyethylene glycol phase-change material, and are woven after polyethylene glycol is adsorbed to obtain a woven layer; dispersing gelatin in silicon dioxide aerogel, uniformly dispersing to ensure that the gelatin is uniformly adsorbed in micropores of the silicon dioxide aerogel, and condensing and dispersing to obtain gelatin-loaded particles; grinding and loading metal platinum and graphene to obtain metal platinum loaded particles; adding metal platinum loaded particles into a perfluorinated sulfonic acid resin solution for dispersion, then immersing a polytetrafluoroethylene microporous membrane, drying to obtain a perfluorinated sulfonic acid polymer composite membrane taking the polytetrafluoroethylene microporous membrane as a network framework, then spraying gelatin particles on the surface of the membrane close to the anode, and attaching a textile layer. The proton exchange membrane of the invention has the advantages that the components such as polyethylene glycol, silicon dioxide aerogel and the like in the membrane micro-regulate the water balance in the membrane, and the proton exchange membrane has good self-humidifying water control characteristics, thereby realizing good self-humidifying and humidifying management. However, the carrier graphene of the platinum catalyst is easy to agglomerate, so that a road is formed.
CN103078122A discloses a self-humidifying membrane electrode for proton exchange membrane fuel cell and its preparation method. The preparation process of the membrane electrode comprises the following steps: 1) pretreating the proton exchange membrane; 2) mixing a carbon-supported platinum catalyst or a platinum-ruthenium catalyst, a perfluorinated sulfonic acid resin solution, a hydrophilic organic high polymer and an inorganic oxide in water or a low-boiling-point solvent, and ultrasonically forming a catalyst slurry, and spraying the catalyst slurry on one side of a proton exchange membrane by adopting an illumination direct coating technology to prepare an anode catalyst layer; 3) spraying slurry which does not contain hydrophilic organic high molecular polymer and inorganic oxide on the other side of the proton exchange membrane to obtain a cathode catalyst layer; 4) and pressing the proton exchange membrane with the catalyst coated on both sides and the gas diffusion layer to obtain the self-humidifying membrane electrode. Because the anode catalyst layer contains the hydrophilic organic high molecular polymer and the inorganic oxide, the prepared self-humidifying membrane electrode shows excellent self-humidifying performance at high cell temperature and low humidity. However, the carrier in the carbon-supported platinum catalyst is carbon, and also belongs to an easily-agglomerated material.
Therefore, the development of a novel self-humidifying proton exchange membrane is urgently needed in the field, the problem of agglomeration caused by the conventional carrier is solved, and the self-humidifying effect is good.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a self-humidifying proton exchange membrane which is non-conductive, not easy to agglomerate a catalyst and a carrier, good in self-humidifying effect and electrochemical performance and suitable for a hydrogen dye battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a self-humidifying proton exchange membrane which comprises a first perfluorosulfonic acid resin layer, a second perfluorosulfonic acid resin layer and an intermediate layer positioned between the first perfluorosulfonic acid resin layer and the second perfluorosulfonic acid resin layer, wherein the intermediate layer contains perfluorosulfonic acid resin, a platinum-based catalyst and a humectant;
the platinum-based catalyst includes an active center including platinum and a support including a nano metal oxide.
The invention provides a novel self-humidifying proton exchange membrane, which takes nano metal oxide as a carrier of a platinum-based catalyst, has more stable load structure, is not easy to agglomerate, avoids the potential safety hazard of short circuit, and has excellent catalytic performance, and simultaneously, a humectant is introduced into an intermediate layer to absorb and store water generated by catalysis, thereby finally obtaining the proton exchange membrane with excellent self-humidifying effect.
The self-humidifying proton exchange membrane provided by the invention has a structure shown in figure 1, and comprises a first perfluorosulfonic acid resin layer 1, a second perfluorosulfonic acid resin layer 3 and an intermediate layer 2.
Preferably, the nano metal oxide comprises any one or at least two combinations of aluminum oxide, iron oxide, zinc oxide, magnesium oxide and copper oxide, preferably any one or at least two combinations of aluminum oxide, iron oxide and zinc oxide.
The invention preferably uses the specific nano metal oxides as carriers, and the carriers can increase the area of the platinum catalyst so as to further improve the catalytic performance, wherein the effects of the aluminum oxide, the iron oxide and the zinc oxide are optimal.
Preferably, the particle size of the platinum-based catalyst is 2 to 10nm, such as 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm, 5nm, 5.5nm, 6nm, 6.5nm, 7nm, 7.5nm, 8nm, 8.5nm, 9nm, 9.5nm, and the like.
According to the invention, the platinum-based catalyst preferably has the specific particle size, and has better catalytic performance within the particle size range, so that the self-humidifying performance is improved, the process cannot be realized due to the excessively small particle size, and the catalytic efficiency is reduced due to the excessively large particle size.
Preferably, the content of the platinum-based catalyst in the intermediate layer is 0.3 to 10%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc.
According to the invention, the specific content of the platinum-based catalyst in the intermediate layer is preferably selected, and within the content range, the catalyst has better catalytic performance, so that the self-humidifying performance is improved, the catalyst agglomeration and even short circuit can be caused by excessive content, and the incomplete reaction of permeated hydrogen and oxygen can be caused by insufficient content.
Preferably, the humectant comprises an oxide humectant, preferably any one or a combination of at least two of silicon dioxide, titanium dioxide and zirconium dioxide.
The present invention uses an oxide such as silica as a humectant, and can sufficiently bind with the generated water to play a role in retaining water.
Preferably, the particle size of the humectant is 1 to 50nm, such as 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm and the like.
The preferable humectant has the specific particle size, and within the particle size range, the proton exchange membrane has better self-humidifying performance, the process cannot be realized due to the excessively small particle size, and the integral performance is influenced due to the nonuniform dispersion due to the excessively large particle size.
Preferably, the moisture retention agent content in the intermediate layer is 1-10%, such as 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc.
The content of the humectant is preferably 1-10%, and the proton exchange membrane can have better self-humidifying performance in the range, the water-retaining effect is reduced due to too low content of the humectant, the humectant content is too high, and the humectant is easy to agglomerate.
Preferably, the thickness of the intermediate layer is 5 to 50 μm, such as 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, and the like.
Preferably, the first perfluorosulfonic acid resin layer and the second perfluorosulfonic acid resin layer independently have a thickness of 10 to 100 μm, for example, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or the like. The above thickness refers to the thickness of one layer of the perfluorosulfonic acid resin.
Preferably, the thickness of the self-humidifying proton exchange membrane is 10-150 μm, such as 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, and the like.
The second purpose of the present invention is to provide a method for preparing a self-humidifying proton exchange membrane, which comprises the following steps:
(1) mixing a platinum-based catalyst, a humectant and a perfluorinated sulfonic acid resin solution to obtain an intermediate layer solution;
the platinum-based catalyst comprises an active center and a carrier, wherein the active center comprises platinum, and the carrier comprises nano metal oxide;
(2) casting the intermediate layer solution on a substrate, and drying to obtain an intermediate layer;
(3) and respectively forming a first perfluorosulfonic acid resin layer and a second perfluorosulfonic acid resin layer on two sides of the middle layer by spraying or dipping a perfluorosulfonic acid resin solution, and drying to obtain the self-humidifying proton exchange membrane.
Preferably, the preparation method of the perfluorosulfonic acid resin solution comprises the following steps:
(a) mixing a perfluorosulfonic acid resin film, an organic solvent having a boiling point of 45 to 120 ℃ (e.g., 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃ and the like) and water, and performing ultrasonic treatment to obtain a first perfluorosulfonic acid resin solution;
(b) mixing an organic solvent having a boiling point of 300 to 350 ℃ (for example, 305 ℃, 310 ℃, 315 ℃, 320 ℃, 325 ℃, 330 ℃, 335 ℃, 340 ℃, 345 ℃ and the like) with the first perfluorosulfonic acid resin solution, and performing ultrasonic treatment to obtain a second perfluorosulfonic acid resin solution.
The perfluorosulfonic acid resin film is treated by adopting the low-boiling-point organic solvent and the high-boiling-point organic solvent, the low-boiling-point organic solvent mainly plays a role in swelling, and the high-boiling-point organic solvent is mainly used for completely dissolving the perfluorosulfonic acid film, so that a better dissolving effect can be achieved, and the use of toxic and harmful substances is reduced.
Preferably, the first perfluorosulfonic acid resin solution has a solid content of 1 to 15%, such as 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, etc. The solid content refers to the mass ratio of the perfluorosulfonic acid resin in the perfluorosulfonic acid resin solution.
Preferably, in the step (a), the time of the ultrasonic treatment is 0.5-3 h, such as 0.8h, 1h, 1.2h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h and the like.
Preferably, in the step (a), the organic solvent with a boiling point of 45-120 ℃ comprises any one or at least two of methanol, ethanol, isopropanol and n-butanol.
Preferably, in the step (b), the volume ratio of the organic solvent with the boiling point of 300-350 ℃ to the first perfluorosulfonic acid resin solution is 1 (5-50), such as 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, etc.
Preferably, in the step (b), the time of the ultrasonic treatment is 1 to 5 hours, such as 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours and the like.
Preferably, in the step (b), the organic solvent with a boiling point of 300-350 ℃ comprises any one or a combination of at least two of N, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and polyvinylpyrrolidone.
Preferably, the preparation method of the perfluorosulfonic acid resin solution comprises the following steps:
(a) mixing a perfluorinated sulfonic acid resin film, an organic solvent with a boiling point of 45-120 ℃ and water, and carrying out ultrasonic treatment for 0.5-3 h to obtain a first perfluorinated sulfonic acid resin solution with a solid content of 1-15%;
(b) mixing an organic solvent with a boiling point of 300-350 ℃ with the first perfluorosulfonic acid resin solution according to a volume ratio of 1 (5-50), and carrying out ultrasonic treatment for 1-5 h to obtain a second perfluorosulfonic acid resin solution.
Preferably, step (1) comprises: and mixing the platinum-based catalyst, the humectant and the perfluorinated sulfonic acid resin solution, and performing ultrasonic treatment to obtain an intermediate layer solution.
Preferably, in the step (1), the time of the ultrasonic treatment is 1-10 h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h and the like.
Preferably, in step (2), the substrate comprises a glass plate.
Preferably, in the step (2), the drying temperature is 50-150 ℃, such as 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and the like.
Preferably, in the step (2), the drying time is 1-5 h, such as 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, and the like.
Preferably, in the step (2), the drying is performed in a vacuum oven.
Preferably, in the step (2), the interlayer solution is naturally leveled on the substrate.
Preferably, the thickness of the intermediate layer obtained in the step (2) is 5-50 μm. The thickness refers to the thickness after the drying in the step (2), the same as below.
Preferably, the thicknesses of the first perfluorosulfonic acid resin layer and the second perfluorosulfonic acid resin layer obtained in step (3) are independently 2 to 50 μm.
Preferably, in the step (3), the drying temperature is 150 to 250 ℃, such as 155 ℃, 160 ℃, 165 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 245 ℃ and the like.
Preferably, in the step (3), the drying time is 1-15 h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, and the like.
Preferably, in the step (3), the drying is performed in a vacuum oven.
Preferably, the preparation method comprises the following steps:
(1) mixing a platinum-based catalyst, a humectant and a perfluorinated sulfonic acid resin solution, and carrying out ultrasonic treatment for 1-10 h to obtain an intermediate layer solution;
(2) casting the intermediate layer solution on a glass plate, naturally leveling, and drying in a vacuum oven at 50-150 ℃ for 1-5 h to obtain an intermediate layer with the thickness of 5-50 mu m;
(3) and respectively forming a first perfluorosulfonic acid resin layer and a second perfluorosulfonic acid resin layer with the thickness of 2-50 mu m on two sides of the middle layer by spraying or dipping a perfluorosulfonic acid resin solution, and then drying in a vacuum oven at 150-250 ℃ for 1-15 h to obtain the self-humidifying proton exchange membrane.
It is a further object of the present invention to provide a hydrogen fuel cell comprising the self-humidifying proton exchange membrane according to one of the objects.
The hydrogen fuel cell comprising the self-humidifying proton exchange membrane provided by the invention has excellent electrochemical performance and higher current efficiency under a certain voltage condition.
Preferably, the hydrogen fuel cell is a proton exchange membrane fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel self-humidifying proton exchange membrane, which takes nano metal oxide as a carrier of a platinum-based catalyst, has more stable load structure, is not easy to agglomerate, avoids the potential safety hazard of short circuit, and has excellent catalytic performance, and simultaneously, a humectant is introduced into an intermediate layer to absorb and store water generated by catalysis, thereby finally obtaining the proton exchange membrane with excellent self-humidifying effect.
Drawings
FIG. 1 is a schematic structural view of a self-humidifying proton exchange membrane provided by the present invention;
wherein, the resin layer comprises 1-a first perfluorosulfonic acid resin layer, 2-an intermediate layer and 3-a second perfluorosulfonic acid resin layer.
FIG. 2 is a polarization curve measured under non-humidified conditions for each of the membrane electrodes of examples 1 to 4 and comparative example 1.
FIG. 3 is a polarization curve measured under humidified conditions for each of the membrane electrodes composed of examples 1 to 4 and comparative example 1.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The perfluorosulfonic acid resin films used in the following examples and comparative examples were purchased from the east Yue group under the trade designation DF 980; the platinum catalyst loaded by alumina is purchased from Beijing German island gold science and technology Limited and has the commercial number of 7440-06-4; the iron oxide supported platinum catalyst is purchased from Beijing Deke island gold science and technology Co., Ltd, and has a commercial product number of 7440-06-4; the platinum catalyst loaded with zinc oxide is purchased from Beijing German island gold science and technology Limited and has the commercial product number of 7440-06-4; the magnesium oxide supported platinum catalyst is purchased from Beijing Deke island gold science and technology Co., Ltd, and has a commercial product number of 7440-06-4; organic solvents such as isopropyl alcohol, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc. are all available from chemical reagents of national drug group, Inc.; humectants such as silicon dioxide, titanium dioxide, and zirconium dioxide are available from Shanghai Michelin Biochemical technologies, Inc.
Example 1
The embodiment provides a self-humidifying proton exchange membrane, which is prepared by the following steps:
(1) cutting 0.1g of perfluorosulfonic acid resin film into pieces, pouring the pieces into a small beaker, adding 10mL of isopropanol and 1mL of water, and carrying out ultrasonic treatment for 0.5h to obtain a perfluorosulfonic acid resin solution with the solid content of 1%;
(2) 50mL of DMF is poured into the solution in the step (1), and the solution is ultrasonically treated for 1h to be uniformly stirred;
(3) adding 2g of alumina-supported platinum catalyst and 4g of silicon dioxide into the solution in the step (3), and ultrasonically dispersing for 2 hours to make the solution uniform;
(4) and (3) casting the perfluorinated sulfonic acid solution prepared in the step (3) on a horizontally placed glass plate, naturally leveling, and drying in a vacuum oven at 100 ℃ for 2 hours to form an intermediate layer with the thickness of 5 microns.
(5) And (3) taking out the membrane prepared in the step (4), spraying a mixed solution of 0.5g of 10% perfluorosulfonic acid resin solution (10% represents solid content) and 20mL of isopropanol on two sides, naturally airing, and respectively forming 3 mu m pure perfluorosulfonic acid resin layers on two sides of the membrane.
(6) And (3) putting the composite membrane prepared in the step (5) into a vacuum oven at 150 ℃, drying for 2h, and cooling to obtain the three-layer self-humidifying proton exchange membrane with the thickness of 10 microns and taking the platinum-containing self-humidifying catalyst as the middle layer.
Example 2
The embodiment provides a self-humidifying proton exchange membrane, which is prepared by the following steps:
(1) cutting 0.3g of perfluorosulfonic acid resin membrane into pieces, pouring the pieces into a small beaker, adding 2mL of methanol, 3mL of isopropanol and 1mL of water, and carrying out ultrasonic treatment for 2 hours to obtain a perfluorosulfonic acid resin solution with the solid content of 4.8%;
(2) pouring 30mL of DMSO and 60mL of DMF into the solution in the step (1), and carrying out ultrasonic treatment for 3h to uniformly stir the solution;
(3) adding a mixture of 15g of iron oxide-supported platinum catalyst and alumina-supported platinum catalyst (mass ratio of 1:1) and 8g of a mixture of titanium dioxide and zirconium dioxide (mass ratio of 1:1) to the solution in (3), and ultrasonically dispersing for 2h to homogenize;
(4) and (4) casting the perfluorinated sulfonic acid solution prepared in the step (3) on a horizontally placed glass plate, naturally leveling, and drying in a vacuum oven at 110 ℃ for 18h to form an intermediate layer with the thickness of 15 microns.
(5) And (4) taking out the membrane prepared in the step (4), spraying a mixed solution of 1g of 10% perfluorosulfonic acid resin solution and 30mL of isopropanol on two sides, and naturally airing to form 20 mu m pure perfluorosulfonic acid resin layers on two sides of the membrane respectively.
(6) And (3) putting the composite membrane prepared in the step (5) into a vacuum oven at 200 ℃, drying for 10h, and cooling to obtain the three-layer self-humidifying proton exchange membrane with the thickness of 40 microns and taking the platinum-containing self-humidifying catalyst as the middle layer.
Example 3
The embodiment provides a self-humidifying proton exchange membrane, which is prepared by the following steps:
(1) cutting 0.5g of perfluorosulfonic acid resin membrane into pieces, pouring the pieces into a small beaker, adding 1mL of ethanol, 3mL of isopropanol and 1.5mL of water, and carrying out ultrasonic treatment for 2h to obtain a perfluorosulfonic acid resin solution with the solid content of 8.3%;
(2) pouring 60mL of DMSO and 60mL of polyvinylpyrrolidone (PVP) into the solution in the step (1), and performing ultrasonic treatment for 4 hours to uniformly stir the solution;
(3) adding 10g of a mixture of an iron oxide-supported platinum catalyst and an aluminum oxide-supported platinum catalyst (mass ratio of 3:1) and 10g of a mixture of titanium dioxide and zirconium dioxide (mass ratio of 1:3) to the solution in (3), and ultrasonically dispersing for 3 hours to make the mixture uniform;
(4) and (4) casting the perfluorinated sulfonic acid solution prepared in the step (3) on a horizontally placed glass plate, naturally leveling, and drying in a vacuum oven at 130 ℃ for 10 hours to form an intermediate layer with the thickness of 25 microns.
(5) And (4) taking out the membrane prepared in the step (4), spraying a mixed solution of 3g of 10% perfluorosulfonic acid resin solution and 50mL of isopropanol on two sides, and naturally airing to form pure perfluorosulfonic acid resin layers of 30 microns on two sides of the membrane respectively.
(6) And (3) putting the composite membrane prepared in the step (5) into a vacuum oven at 220 ℃, drying for 15h, and cooling to obtain the three-layer proton exchange membrane with the thickness of 80 microns and taking the platinum-containing self-humidifying catalyst as the middle layer.
Example 4
The embodiment provides a self-humidifying proton exchange membrane, which is prepared by the following steps:
(1) cutting 0.1g of perfluorosulfonic acid resin membrane into pieces, pouring the pieces into a small beaker, adding 2mL of methanol, 4mL of n-butanol and 1mL of water, and carrying out ultrasonic treatment for 3h to obtain a perfluorosulfonic acid resin solution with the solid content of 1.4%;
(2) 150mL of DMF and 200mL of N-methylpyrrolidone (NMP) are poured into the solution in the step (1), and the solution is stirred uniformly by ultrasonic treatment for 5 hours;
(3) adding a mixture of 42g of iron oxide-supported platinum catalyst and zinc oxide-supported platinum catalyst (mass ratio of 4:3) and a mixture of 18g of titanium dioxide and zirconium dioxide (mass ratio of 1:2) to the solution in (3), and ultrasonically dispersing for 2h to homogenize;
(4) and (4) casting the perfluorinated sulfonic acid solution prepared in the step (3) on a horizontally placed glass plate, naturally leveling, and drying in a vacuum oven at 150 ℃ for 5 hours to form an intermediate layer with the thickness of 50 microns.
(5) And (4) taking out the membrane prepared in the step (4), spraying 5g of a mixed solution of 10% perfluorosulfonic acid resin solution and 200mL of isopropanol on two sides, and naturally airing to form 60-micron pure perfluorosulfonic acid resin layers on two sides of the membrane respectively.
(6) And (3) putting the composite membrane prepared in the step (5) into a vacuum oven at 250 ℃, drying for 10h, and cooling to obtain the 150-micron-thick three-layer self-humidifying proton exchange membrane taking the platinum-containing self-humidifying catalyst as the middle layer.
Example 5
The embodiment provides a self-humidifying proton exchange membrane, which is prepared by the following steps:
(1) cutting 2.2g of perfluorosulfonic acid resin film into pieces, pouring the pieces into a small beaker, adding 10mL of isopropanol and 1mL of water, and carrying out ultrasonic treatment for 0.5h to obtain a perfluorosulfonic acid resin solution with the solid content of 15%;
(2) 50mL of DMF is poured into the solution in the step (1), and the solution is ultrasonically treated for 1h to be uniformly stirred;
(3) adding 2g of magnesium oxide supported platinum catalyst and 4g of cerium dioxide into the solution in the step (3), and ultrasonically dispersing for 1h to make the solution uniform;
(4) and (4) casting the perfluorinated sulfonic acid solution prepared in the step (3) on a horizontally placed glass plate, naturally leveling, and drying in a vacuum oven at 50 ℃ for 1h to form an intermediate layer with the thickness of 7 microns.
(5) And (3) taking out the membrane prepared in the step (4), spraying a mixed solution of 0.5g of 10% perfluorosulfonic acid resin solution (10% represents solid content) and 20mL of isopropanol on two sides, naturally airing, and forming 2 mu m pure perfluorosulfonic acid resin layers on two sides of the membrane respectively.
(6) And (3) putting the composite membrane prepared in the step (5) into a vacuum oven at 150 ℃, drying for 1h, and cooling to obtain the three-layer self-humidifying proton exchange membrane with the thickness of 10 microns and taking the platinum-containing self-humidifying catalyst as the middle layer.
Example 6
The embodiment provides a self-humidifying proton exchange membrane, which is prepared by the following steps:
(1) cutting 0.1g of perfluorosulfonic acid resin film into pieces, pouring the pieces into a small beaker, adding 10mL of isopropanol and 1mL of water, and carrying out ultrasonic treatment for 0.5h to obtain a perfluorosulfonic acid resin solution with the solid content of 1%;
(2) 50mL of DMF is poured into the solution in the step (1), and the solution is ultrasonically treated for 1h to be uniformly stirred;
(3) adding 2g of alumina-supported platinum catalyst and 4g of silicon dioxide into the solution in the step (3), and performing ultrasonic dispersion for 10 hours to ensure that the solution is uniform;
(4) and (3) casting the perfluorinated sulfonic acid solution prepared in the step (3) on a horizontally placed glass plate, naturally leveling, and drying in a vacuum oven at 100 ℃ for 2 hours to form an intermediate layer with the thickness of 5 microns.
(5) And (3) taking out the membrane prepared in the step (4), spraying a mixed solution of 9g of 10% perfluorosulfonic acid resin solution (10% represents solid content) and 300mL of isopropanol on two sides, and naturally airing to form 50-micron pure perfluorosulfonic acid resin layers on two sides of the membrane respectively.
(6) And (3) putting the composite membrane prepared in the step (5) into a vacuum oven at 150 ℃, drying for 2h, and cooling to obtain the three-layer self-humidifying proton exchange membrane with the thickness of 10 microns and taking the platinum-containing self-humidifying catalyst as the middle layer.
Comparative example 1
Dupont 211 proton exchange membrane, 25 μm thick.
Comparative example 2
The difference from example 1 is that the alumina-supported platinum catalyst was replaced with an equivalent mass of silica-supported platinum catalyst (available from Shanghai QianlingChemicals Co., Ltd., commercial name: 60676-86-0).
Comparative example 3
The difference from example 1 is that no silica is added in step (3).
Performance testing
Cutting the self-humidifying proton exchange membranes of the examples and the comparative examples with the size of 5 multiplied by 5cm respectively, and placing the self-humidifying proton exchange membranes in 3 percent hydrogen peroxide water at the temperature of 80 ℃ for boiling for 1 hour; taking out and washing with deionized water for 3 times; then placed in 0.5M H at 80 deg.C2SO4Acidifying the solution for 1h, washing with deionized water for 2 times, and placing into deionized water for later use.
(1) Water absorption test
GB/T20042.3-2009 proton exchange membrane fuel cell part 3: proton exchange membrane test methods;
(2) conductivity test
GB/T20042.3-2009 proton exchange membrane fuel cell part 3: proton exchange membrane test methods;
(3) tensile Strength test
GB/T20042.3-2009 proton exchange membrane fuel cell part 3: proton exchange membrane test methods;
the results of the performance tests (1) to (3) are shown in table 1.
TABLE 1
| Thickness/mum | Water absorption/%) | conductivity/S/cm | Tensile strength/MPa | |
| Example 1 | 10 | 30 | 0.211 | 250 |
| Example 2 | 40 | 40 | 0.163 | 450 |
| Example 3 | 80 | 60 | 0.114 | 600 |
| Example 4 | 150 | 87 | 0.079 | 850 |
| Example 5 | 10 | 30 | 0.215 | 240 |
| Example 6 | 10 | 38 | 0.223 | 260 |
| Comparative example 1 | 25 | 50 | 0.081 | 280 |
| Comparative example 2 | 10 | 35 | 0.235 | 260 |
| Comparative example 3 | 10 | 40 | 0.248 | 240 |
As can be seen from Table 1, the self-humidifying proton exchange membrane provided by the invention has proper water absorption performance, conductivity and mechanical properties, wherein the water absorption rate is 30-87%, the conductivity is 0.079-0.223S/cm, and the tensile strength is 200-850 MPa.
(4) Humidification polarization curve testing
Preparing a porous gas diffusion electrode on carbon paper by using a perfluorinated sulfonic acid resin solution, a polytetrafluoroethylene solution, XC-72 carbon powder and a 30% platinum-carbon catalyst, wherein the loading capacity of an anode catalyst is 0.2g/cm, and the loading capacity of a cathode catalyst is 0.4g/cm2. The prepared gas diffusion electrodes were placed on both sides of the self-humidifying proton exchange membranes of the treated examples and comparative examples, respectively, and hot-pressed at 160 ℃ under 1.2MPa for 3min to form membrane electrodes. And (4) forming a single cell by the prepared membrane electrode, the snakelike flow field graphite plate, the current collector and the end plate.
The battery operating conditions were: the temperature is 75 ℃, the air inlet pressure is 50KPa, the hydrogen inlet pressure is 50KPa, the air excess coefficient is 2.5, and the hydrogen excess coefficient is 1.5. And the polarization curve test comprises a humidifying part and a non-humidifying part, wherein the humidifying test is that air and hydrogen enter the cell after passing through a humidifier at 75 ℃.
Fig. 2 is a polarization curve measured under a non-humidified condition in examples 1 to 4 and comparative example 1, fig. 3 is a polarization curve measured under a humidified condition in examples 1 to 4 and comparative example 1, and fig. 2 and fig. 3 show that the current density of the cell including the membrane of examples 1 to 4 is higher than that of comparative example 1 under the same voltage condition regardless of non-humidified or humidified conditions, thereby proving that the cell has excellent electrochemical performance because the catalyst carrier in the self-humidifying proton exchange membrane of the present invention is not easily agglomerated, thereby exhibiting excellent self-humidifying performance and further improving the electrochemical performance of the cell.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The self-humidifying proton exchange membrane is characterized by comprising a first perfluorosulfonic acid resin layer, a second perfluorosulfonic acid resin layer and an intermediate layer positioned between the first perfluorosulfonic acid resin layer and the second perfluorosulfonic acid resin layer, wherein the intermediate layer contains perfluorosulfonic acid resin, a platinum-based catalyst and a humectant;
the platinum-based catalyst includes an active center including platinum and a support including a nano metal oxide.
2. The self-humidifying proton exchange membrane according to claim 1, wherein the nano metal oxide comprises any one or at least two combinations of aluminum oxide, iron oxide, zinc oxide, magnesium oxide and copper oxide, preferably any one or at least two combinations of aluminum oxide, iron oxide and zinc oxide;
preferably, the particle size of the platinum-based catalyst is 2-10 nm.
3. The self-humidifying proton exchange membrane according to claim 1 or 2, wherein the content of the platinum-based catalyst in the intermediate layer is 0.3-10%.
4. The self-humidifying proton exchange membrane according to any one of claims 1 to 3, wherein the humectant comprises an oxide humectant, preferably any one or a combination of at least two of silicon dioxide, titanium dioxide and zirconium dioxide;
preferably, the particle size of the humectant is 1-50 nm;
preferably, the content of the moisture retention agent in the middle layer is 1-10%.
5. The self-humidifying proton exchange membrane according to any one of claims 1 to 4, wherein the thickness of the intermediate layer is 5 to 50 μm;
preferably, the thicknesses of the first perfluorosulfonic acid resin layer and the second perfluorosulfonic acid resin layer are independently 10 to 100 μm;
preferably, the thickness of the self-humidifying proton exchange membrane is 10-150 μm.
6. A method of preparing a self-humidifying proton exchange membrane according to any one of claims 1-5, comprising the steps of:
(1) mixing a platinum-based catalyst, a humectant and a perfluorinated sulfonic acid resin solution to obtain an intermediate layer solution;
the platinum-based catalyst comprises an active center and a carrier, wherein the active center comprises platinum, and the carrier comprises nano metal oxide;
(2) casting the intermediate layer solution on a substrate, and drying to obtain an intermediate layer;
(3) and respectively forming a first perfluorosulfonic acid resin layer and a second perfluorosulfonic acid resin layer on two sides of the middle layer by spraying or dipping a perfluorosulfonic acid resin solution, and drying to obtain the self-humidifying proton exchange membrane.
7. The method according to claim 6, wherein the method for preparing the perfluorosulfonic acid resin solution comprises the steps of:
(a) mixing a perfluorinated sulfonic acid resin film, an organic solvent with a boiling point of 45-120 ℃ and water, and performing ultrasonic treatment to obtain a first perfluorinated sulfonic acid resin solution;
(b) mixing an organic solvent with a boiling point of 300-350 ℃ with the first perfluorosulfonic acid resin solution, and performing ultrasonic treatment to obtain a second perfluorosulfonic acid resin solution;
preferably, the solid content of the first perfluorosulfonic acid resin solution is 1-15%;
preferably, in the step (a), the ultrasonic time is 0.5-3 h;
preferably, in the step (a), the organic solvent with the boiling point of 45-120 ℃ comprises any one or at least two of methanol, ethanol, isopropanol and n-butanol;
preferably, in the step (b), the volume ratio of the organic solvent with the boiling point of 300-350 ℃ to the first perfluorosulfonic acid resin solution is 1 (5-50);
preferably, in the step (b), the time of the ultrasonic treatment is 1-5 h;
preferably, in the step (b), the organic solvent with a boiling point of 300-350 ℃ comprises any one or a combination of at least two of N, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and polyvinylpyrrolidone;
preferably, the preparation method of the perfluorosulfonic acid resin solution comprises the following steps:
(a) mixing a perfluorinated sulfonic acid resin film, an organic solvent with a boiling point of 45-120 ℃ and water, and carrying out ultrasonic treatment for 0.5-3 h to obtain a first perfluorinated sulfonic acid resin solution with a solid content of 1-15%;
(b) mixing an organic solvent with a boiling point of 300-350 ℃ with the first perfluorosulfonic acid resin solution according to a volume ratio of 1 (5-50), and carrying out ultrasonic treatment for 1-5 h to obtain a second perfluorosulfonic acid resin solution.
8. The production method according to claim 6 or 7, wherein the step (1) comprises: mixing a platinum-based catalyst, a humectant and a perfluorinated sulfonic acid resin solution, and performing ultrasonic treatment to obtain an intermediate layer solution;
preferably, in the step (1), the ultrasonic time is 1-10 h;
preferably, in step (2), the substrate comprises a glass plate;
preferably, in the step (2), the drying temperature is 50-150 ℃;
preferably, in the step (2), the drying time is 1-5 h;
preferably, in the step (2), the drying is performed in a vacuum oven;
preferably, in the step (2), the interlayer solution naturally levels on the substrate;
preferably, the thickness of the intermediate layer obtained in the step (2) is 5-50 μm;
preferably, the thicknesses of the first perfluorosulfonic acid resin layer and the second perfluorosulfonic acid resin layer obtained in the step (3) are independently 2 to 50 μm;
preferably, in the step (3), the drying temperature is 150-250 ℃;
preferably, in the step (3), the drying time is 1-15 h;
preferably, in the step (3), the drying is performed in a vacuum oven.
9. The method according to any one of claims 6 to 8, characterized by comprising the steps of:
(1) mixing a platinum-based catalyst, a humectant and a perfluorinated sulfonic acid resin solution, and carrying out ultrasonic treatment for 1-10 h to obtain an intermediate layer solution;
(2) casting the intermediate layer solution on a glass plate, naturally leveling, and drying in a vacuum oven at 50-150 ℃ for 1-5 h to obtain an intermediate layer with the thickness of 5-50 mu m;
(3) and respectively forming a first perfluorosulfonic acid resin layer and a second perfluorosulfonic acid resin layer with the thickness of 2-50 mu m on two sides of the middle layer by spraying or dipping a perfluorosulfonic acid resin solution, and then drying in a vacuum oven at 150-250 ℃ for 1-15 h to obtain the self-humidifying proton exchange membrane.
10. A hydrogen fuel cell comprising the self-humidifying proton exchange membrane according to any one of claims 1 to 5;
preferably, the hydrogen fuel cell is a proton exchange membrane fuel cell.
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