CN114899464A - Microporous membrane and preparation method and application thereof - Google Patents
Microporous membrane and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 35
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Images
Classifications
-
- 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
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- 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
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
-
- 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
-
- 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 discloses a microporous membrane and a preparation method and application thereof, wherein the microporous membrane comprises a polytetrafluoroethylene fiber membrane body and platinum group metal-loaded nano-oxide particles; the nanometer oxide particles loaded with platinum group metal are uniformly distributed in the pores of the polytetrafluoroethylene fiber membrane body. The microporous membrane has good wetting performance and self-humidifying performance, and can reduce the hydrogen permeation performance of a proton exchange membrane, improve the electrochemical degradation resistance and further prolong the service life of the proton exchange membrane when being used for the proton exchange membrane.
Description
Technical Field
The invention belongs to the technical field of proton exchange membranes, and particularly relates to a microporous membrane and a preparation method and application thereof.
Background
The environmental pollution and energy problems are more prominent, and hydrogen-oxygen fuel cells and PEM water electrolysis hydrogen production are considered to be one of the important methods for solving the environmental pollution and energy problems. Proton exchange membranes are important components in fuel cells and PEM water electrolysis hydrogen production technologies. The proton exchange membrane has high requirements on the proton exchange membrane, and has the functions of proton conduction, reaction gas barrier and the like, such as high proton conduction capability, low reaction gas permeability, certain mechanical strength, good chemical and electrochemical stability and the like, so that the proton exchange membrane becomes a research hotspot of a hydrogen energy source technology and a membrane preparation technology.
Although the traditional Nafion membrane of Dupont company shows excellent electrochemical performance and mechanical performance at low temperature, the perfluorinated sulfonic acid resin is large in dosage, thick in membrane, expensive, and performance attenuation phenomenon occurs at high temperature. Particularly, when the battery operation temperature reaches a high temperature of more than 80 ℃, the conductivity of the proton exchange membrane and the output performance of the battery are attenuated to a certain degree under the influence of the environment. The main reason for this phenomenon may be that with the rise of temperature, the water in the proton exchange membrane evaporates, the Nafion gradually dehydrates, and the structure of the hydrophilic phase in the membrane is damaged to a certain extent, so that the proton transmission in the membrane is directly affected, and the proton conductivity of the membrane is reduced. In addition, because the glass transition temperature of the traditional Nafion series perfluorosulfonic acid proton exchange membrane is low, the application of the membrane under the high-temperature condition is limited due to the structural damage at the high temperature. With the development of hydrogen energy technology, the quality of perfluorosulfonic acid resin and the improvement of a Membrane preparation process, a proton exchange Membrane is also continuously optimized and developed, and a Composite proton exchange Membrane is prepared by firstly immersing Nafion solution into an expanded polytetrafluoroethylene (ePTFE, hereinafter ePTFE is referred to as expanded polytetrafluoroethylene) microporous Membrane material from Penner R M and Matrin CR (Ion-transporting Composite Membrane, Nafion-impregnated Gore-tex), wherein the application of the ePTFE microporous Membrane greatly improves the performance of the Composite proton exchange Membrane. The ePTFE microporous membrane has good mechanical property and hydrophobicity, can well keep the size of the proton exchange membrane, greatly reduces the swelling deformation of the proton exchange membrane, reduces the thickness and the resistance of the proton exchange membrane, and greatly improves the durability and the practical performance of the proton exchange membrane of the fuel cell. However, the impregnation performance of the ePTFE microporous membrane is deviated, which is not beneficial to the impregnation of the perfluorosulfonic acid resin solution, so that the entering amount of the perfluorosulfonic acid resin among the ePTFE micropores is slightly small, the conductivity of the proton exchange membrane is difficult to improve, and the durability is poor. In addition, because the soakage performance of the ePTFE microporous membrane is deviated, and the strict requirement of the fuel cell on the membrane material causes higher requirements on the porosity, the mechanical property and the soakage performance composite processing performance of the expanded polytetrafluoroethylene membrane material.
At present, a great deal of research on electrochemical degradation resistance of a proton exchange membrane is to directly add an antioxidant into a homogeneous membrane, and partially add the antioxidant into a Nafion solution to prepare a composite proton exchange membrane by compounding an ePTFE (expanded polytetrafluoroethylene) microporous membrane. With the above two modification methods, it is still difficult to change the wetting property of the perfluorosulfonic acid resin solution, and it is difficult to achieve uniform dispersion of the antioxidant.
Therefore, the problems of poor hydrophilicity and poor wetting performance of the ePTFE microporous membrane in the process of preparing the composite reinforced proton exchange membrane are very necessary.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a microporous membrane, wherein the platinum group metal-loaded nano oxide is a hard chemically inert material, has the advantages of small particle size, large specific surface area, good hydrophilic property, strong surface adsorption force, high surface energy, good mechanical property, high wear resistance, stable size, etc., is a good carrier-reinforced material, and can improve the wettability and self-humidification performance of the microporous membrane by compounding the microporous membrane with a polytetrafluoroethylene fiber membrane; meanwhile, the platinum group metal loaded with the platinum group metal nano oxide is a good free radical quencher, can quench free radicals in the use process of the composite proton exchange membrane, is beneficial to the adhesion of perfluorinated sulfonic acid resin and the electrochemical degradation resistance, reduces the hydrogen transmittance of the proton exchange membrane, and prolongs the service life of the whole proton exchange membrane.
Another object of the present invention is to provide a method for preparing a microporous membrane.
It is yet another object of the present invention to provide a proton exchange membrane.
Still another object of the present invention is to provide a method for preparing a proton exchange membrane.
In order to achieve the above object, a first embodiment of the present invention provides a microporous membrane, comprising a ptfe membrane body and platinum group metal-loaded nano-oxide particles; the nanometer oxide particles loaded with platinum group metals are uniformly distributed in the pores of the polytetrafluoroethylene fiber membrane body.
According to the microporous membrane disclosed by the embodiment of the invention, the platinum group metal-loaded nano oxide is a hard chemical inert material, has the advantages of small particle size, large specific surface area, good hydrophilic property, strong surface adsorption force, high surface energy, good mechanical property, high wear resistance, stable size and the like, is a good carrier reinforcing material, and can improve the wettability and self-humidifying property of the microporous membrane by compounding the microporous membrane with a polytetrafluoroethylene fiber membrane; meanwhile, the platinum group metal loaded with the platinum group metal nano oxide is a good free radical quencher, can quench free radicals in the use process of the composite proton exchange membrane, is beneficial to the adhesion of perfluorinated sulfonic acid resin and the electrochemical degradation resistance, reduces the hydrogen transmittance of the proton exchange membrane, and prolongs the service life of the whole proton exchange membrane.
In some embodiments of the invention, the polytetrafluoroethylene fibers have a diameter of 50-500nm and an average pore size of 100-400 nm; the particle diameter of the platinum group metal-loaded nano-oxide particles is less than 100 nm.
In some embodiments of the invention, the platinum group metal-loaded nano-oxide particles are hydrophilic particles; the nano oxide is one or more than two of nano silicon dioxide, nano titanium dioxide and nano zirconium dioxide.
In some embodiments of the invention, the platinum group metal loading in the platinum group metal-loaded nano-oxide particles is from 1 to 50 wt%; the mass ratio of the polytetrafluoroethylene fiber membrane body to the platinum group metal-loaded nano-oxide particles is 100: 1-20.
In order to achieve the above object, an embodiment of the second aspect of the present invention provides a method for preparing a microporous membrane, including
Mixing the precursor solution of the platinum group metal with nano oxide powder for reaction, and then carrying out centrifugal separation and calcination to obtain the platinum group metal-loaded nano oxide particles;
uniformly mixing polytetrafluoroethylene resin powder and the platinum group metal-loaded nano oxide particles, curing, and extruding under the action of a lubricant to form a raw material blank;
rolling the raw material blank to form a first rolled film, and drying the first rolled film to obtain a second rolled film;
and sequentially carrying out longitudinal stretching and transverse stretching on the second rolled film, and then sintering and shaping to obtain the microporous film.
The preparation method of the microporous membrane provided by the embodiment of the invention has the beneficial effects that: the hydrophilic performance and the wetting performance of the microporous membrane are improved; the chemical degradation resistance of the microporous membrane is improved, and the binding performance of the microporous membrane and the perfluorosulfonic acid resin is improved.
In some embodiments of the invention, the nano-oxide particles are prepared by a sol-gel process; the conditions for mixing and reacting the precursor solution of the platinum group metal and the nano oxide powder are as follows: the temperature is 70-90 ℃, the pH is 6.5-7.5, and the reaction time is 0.5-1.5 h; the calcining temperature is 150-250 ℃, and the calcining time is 0.5-1.5 h.
In some embodiments of the invention, the method of curing is: and standing the uniformly mixed polytetrafluoroethylene resin powder and the platinum group metal-loaded nano oxide particle material at 25-40 ℃ for 24-72 h.
In some embodiments of the invention, the lubricant is one or more of petroleum ether, white oil, silicone oil, alcohols, aromatic hydrocarbons; the addition amount of the lubricant is 15-30% of the mass of the polytetrafluoroethylene resin powder; the extrusion pressure is 3-10 MPa; the temperature of the longitudinal stretching is 300-350 ℃, and the stretching ratio of the longitudinal stretching is 600-1000%; the temperature of the transverse stretching is 200-220 ℃, and the stretching ratio of the transverse stretching is 1000-2500%; the temperature for sintering and shaping is 350-400 ℃.
In order to achieve the above object, an embodiment of the third aspect of the present invention provides a proton exchange membrane comprising the microporous membrane as described above.
The proton exchange membrane of the embodiment of the invention has substantially the same beneficial effects as the microporous membrane of the embodiment of the invention, and is not described herein again.
In order to achieve the above object, an embodiment of a fourth aspect of the present invention provides a method for preparing a proton exchange membrane, including adding a surfactant to a perfluorosulfonic acid resin solution to obtain a sulfonic acid resin solution;
spreading and soaking the microporous membrane in the sulfonic acid resin solution to form an impregnated membrane;
and drying the impregnated membrane to obtain the proton exchange membrane.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic diagram of a simple structure of a microporous membrane according to one embodiment of the present invention.
Fig. 2 is a schematic view showing a state in which polytetrafluoroethylene resin particles and platinum group metal-loaded nano-oxide particles are uniformly mixed during the preparation of a microporous membrane according to an embodiment of the present invention.
Fig. 3 is a schematic diagram of a proton exchange membrane according to an embodiment of the present invention.
Reference numerals:
1-a polytetrafluoroethylene fiber membrane body; 101-polytetrafluoroethylene fibers; 102-polytetrafluoroethylene fiber nodes; 2-platinum group metal-loaded nano-oxide particles; 3-polytetrafluoroethylene resin microparticles; 100-microporous membrane; a 200-perfluorosulfonic acid resin layer.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The microporous membrane, the method for producing the microporous membrane, and the proton exchange membrane according to the embodiments of the present invention will be described below with reference to the accompanying drawings.
Fig. 1 is a schematic diagram of a simple structure of a microporous membrane according to one embodiment of the present invention.
As shown in fig. 1, a microporous membrane according to an embodiment of the present invention includes a polytetrafluoroethylene membrane body 1 and platinum group metal-loaded nano-oxide fine particles 2; the nanometer oxide particles 2 loaded with platinum group metal are evenly distributed in the pores of the polytetrafluoroethylene fiber membrane body 1.
The polytetrafluoroethylene fibers in the present example are expanded polytetrafluoroethylene (ePTFE), which is known in its structure, including polytetrafluoroethylene fiber membrane fibers and polytetrafluoroethylene fiber nodes (as shown in fig. 1), and are not the focus of the present invention.
According to the microporous membrane disclosed by the embodiment of the invention, the platinum group metal-loaded nano oxide is a hard chemical inert material, has the advantages of small particle size, large specific surface area, good hydrophilic property, strong surface adsorption force, high surface energy, good mechanical property, high wear resistance, stable size and the like, is a good carrier reinforcing material, and can improve the wettability and self-humidifying property of the microporous membrane by compounding the microporous membrane with a polytetrafluoroethylene fiber membrane; meanwhile, the platinum group metal loaded with the platinum group metal nano oxide is a good free radical quencher, can quench free radicals in the use process of the composite proton exchange membrane, is beneficial to the adhesion of perfluorinated sulfonic acid resin and the electrochemical degradation resistance, reduces the hydrogen transmittance of the proton exchange membrane, and prolongs the service life of the whole proton exchange membrane.
Optionally, the diameter of the polytetrafluoroethylene fiber is 50-500nm, and the average pore diameter is 100-400 nm; the particle diameter of the platinum group metal-supporting nano-oxide particles is 100nm or less.
Optionally, the platinum group metal-loaded nano-oxide particles are hydrophilic particles, wherein the platinum group metal is preferably platinum; the nano oxide is one or more than two of nano silicon dioxide, nano titanium dioxide and nano zirconium dioxide, and preferably, the nano silicon dioxide. The nanometer oxide loaded with platinum group metal is a hard chemical inert material, has the advantages of small particle size, large specific surface area, good hydrophilic property, strong surface adsorption force, high surface energy, good mechanical property, high wear resistance, stable size and the like, and is a good carrier reinforcing material. Wherein the density of the nano silicon dioxide is 2.2g/cm 3 About the same as the density of polytetrafluoroethylene resin (2.1-2.3 g/cm) 3 ) The polytetrafluoroethylene membrane material is a good polytetrafluoroethylene membrane material reinforcing material, can play a certain reinforcing role in the expanded polytetrafluoroethylene membrane material, and can improve the infiltration performance and the self-wetting performance of ePTFE (expanded polytetrafluoroethylene). The addition of the nano platinum group metal can reduce the hydrogen transmission rate of the proton exchange membrane containing the microporous membrane.
The nano oxide can be prepared by itself or commercial reagents can be purchased on platforms such as Mecline, Chinese medicine reagent nets and the like.
The self-preparation of the nano oxide can adopt a sol-gel method, wherein:
the preparation method of the nano silicon dioxide comprises the following steps: tetrabutyl silicate, ethanol and deionized water are subjected to hydrolysis reaction under an alkaline condition, and then the nano silicon dioxide is prepared by stirring, centrifugal separation, freeze drying and calcination. Wherein: the hydrolysis reaction equation is
SiO 4 (C 4 H 8 ) 4 +NH 3 H 2 O－SiO 2 +4C 4 H 8 OH+H 2 O；
In the preparation process of the nano silicon dioxide: the volume ratio of tetrabutyl silicate to ethanol to deionized water is 1:1.5: 2; the conditions of the hydrolysis reaction are as follows: the temperature is 50 ℃, the pH value is 5-6, and the reaction time is 30 min; the freeze drying temperature is-50 ℃, the freeze drying time is 24h, the calcining temperature is 600 ℃, and the calcining time is 1 h.
The preparation method of the nano titanium dioxide comprises the following steps: tetrabutyl titanate and ethanol are mixed according to the volume ratio of 1: 3.5 preparing a clear first solution, and stirring for 10min at the temperature of 50 ℃; preparing acetic acid, distilled water and ethanol in a volume ratio of 1: 5: 16 and a small amount of hydrochloric acid is added to adjust the pH to 3. Mixing the first solution and the second solution according to a volume ratio of 1:1 stirring and mixing, heating in water bath for 1h at 40 ℃, carrying out centrifugal separation, washing with distilled water for three times, carrying out freeze drying for 24h at-50 ℃, and calcining for 1h at 600 ℃ to obtain the nano titanium dioxide.
The preparation method of the nano zirconium dioxide can be carried out according to the preparation method of the nano silicon dioxide and the preparation method of the nano titanium dioxide.
Optionally, the platinum group metal loading in the platinum group metal-loaded nano-oxide particles is 1-50 wt%; the mass ratio of the polytetrafluoroethylene fiber membrane body to the platinum group metal-loaded nano-oxide particles is 100: 1-20.
The preparation method of the microporous membrane comprises the following steps:
a: mixing and stirring a precursor solution of platinum group metal and the nano oxide powder, adding a certain amount of ammonia water, carrying out mixing reaction under the stirring condition, and then carrying out centrifugal separation and calcination to obtain the platinum group metal-loaded nano oxide particles. The conditions for mixing and reacting the precursor solution of the platinum group metal and the nano oxide powder are as follows: the temperature is 70-90 ℃, the pH is 6.5-7.5, and the reaction time is 0.5-1.5 h; the calcination temperature is 150-250 ℃, and the calcination time is 0.5-1.5 h.
B: selecting polytetrafluoroethylene resin powder with the grain diameter of about 3-5 mu m, wherein the crystallinity of the polytetrafluoroethylene resin is required to be not less than 98 percent so as to ensure the strength and the tensile effect of the ePTFE microporous membrane.
C: the amount of the added polytetrafluoroethylene resin was taken as 100 parts by mass, 1-20 parts by mass of platinum group metal-loaded nano-oxide fine particles were weighed, and the polytetrafluoroethylene resin and the platinum group metal-loaded nano-oxide fine particles were put into a mixer and mixed for 12 hours (the mixed state is shown in fig. 2).
D: curing treatment: standing the uniformly mixed raw materials at 25-40 deg.C for aging for not less than 24 hr (preferably 24-72 hr).
E: adding 15-30 parts by mass of lubricant into the cured mixture, and fully mixing for later use (the lubricant mainly comprises mixed organic solvents such as petroleum ether, white oil, silicone oil, alcohols, aromatic hydrocarbon and the like).
F: and extruding the mixed material added with the lubricant under the pressure of 3-10MPa to form a raw material blank.
G: and (3) rolling the blank raw material at the temperature of 50-80 ℃ to form a first rolled film, wherein the thickness of the first rolled film is about 1 mm.
H: and (3) drying treatment: and (3) heating and drying the first rolled film at the temperature of 200-300 ℃ to remove the lubricant in the first rolled film to obtain a second rolled film, wherein the lubricant can be recycled.
I: longitudinal stretching: the second calendered film was subjected to 600-.
J: and (3) transverse stretching: the second calendered film, pressed longitudinally stretched, was subjected to transverse stretching of 1000-.
K: the PTFE membrane (i.e., the second calendered membrane) after longitudinal stretching and transverse stretching is sintered and shaped at the temperature of 350-. Wherein, the sintering temperature adopts gradient temperature rise, which can ensure the aperture uniformity and the shaping strength.
The microporous membrane prepared by the preparation method can produce the following effects:
1. the platinum group metal-loaded nano-oxide particles can be uniformly distributed among pores of the ePTFE microporous membrane.
2. The platinum group metal-loaded nano-oxide particles have a large specific surface area and can provide certain hydrophilicity to the ePTFE.
3. The platinum group metal on the surface of the platinum group metal-loaded nano oxide particle is a good free radical quencher, can quench free radicals in the use process of the composite proton exchange membrane, and is beneficial to the adhesion and the electrochemical degradation resistance of the perfluorosulfonic acid resin.
4. The platinum group metal-loaded nano-oxide particles have large specific surface area and adsorption effect, and can provide a certain degree of enhancement for PTFE fiber interaction. As shown in fig. 3, the proton exchange membrane of the embodiment of the present invention includes a microporous membrane 100 of the embodiment of the present invention.
Preferably, the proton exchange membrane further comprises a perfluorosulfonic acid resin layer 200, and the perfluorosulfonic acid resin layer is wrapped on the outer surface of the microporous membrane.
More preferably, the perfluorosulfonic acid resin layer of the proton exchange membrane is disposed on opposite sides of the microporous membrane (as shown in FIG. 3), and the perfluorosulfonic acid resin layer preferably covers the entire microporous membrane side on which it is disposed.
The preparation method of the proton exchange membrane comprises the following steps:
(1) adding a surfactant into the perfluorinated sulfonic acid resin solution to obtain a sulfonic acid resin solution;
(2) spreading and soaking the microporous membrane in a sulfonic acid resin solution to form a soaking membrane;
(3) and drying the impregnated membrane to obtain the proton exchange membrane.
Optionally, in the step (1), the solid content of the perfluorosulfonic acid resin solution is 10-30 wt%, preferably 20 wt%; the addition amount of the surface additive is 0.5-1.5 percent of the mass of the perfluorinated sulfonic acid resin solution, and is preferably 1 percent; the surfactant can be selected from Triton X100, Triton X114, etc.
Optionally, in the step (2), the soaking time of the microporous membrane in the sulfonic acid resin solution is 3-8min, preferably 5 min.
Optionally, in the step (3), the temperature of the drying treatment is 80-100 ℃, and the time of the drying treatment is 10 min.
The microporous membrane and the preparation method thereof, and the proton exchange membrane and the preparation method thereof according to the present invention will be described below with reference to specific examples and comparative examples.
Raw material reagents and equipment related in the embodiments of the present invention are commercially available raw materials and equipment unless otherwise specified; the methods mentioned in the examples of the present invention are conventional methods unless otherwise specified.
First, examples and comparative examples
Example 1
(1) Preparation of microporous membranes
A: preparing nano silicon dioxide: tetrabutyl silicate, ethanol and deionized water in a volume ratio of 1:1.5:2 preparing a clear solution, stirring (magnetic stirring) for 30min at 50 ℃, dropwise adding an ammonia water solution while stirring until the pH value is 5-6, then carrying out centrifugal separation, freeze-drying the silica gel obtained by centrifugal separation at-50 ℃ for 24h, and calcining at 600 ℃ for 1h to obtain the nano-silica.
B: mixing chloroplatinic acid: nano silicon dioxide: deionized water according to the proportion of 1: 10: 500, dropwise adding ammonia water to a pH value of 7 under the condition of stirring (magnetic stirring) at 80 ℃, continuously stirring for 1h, then carrying out centrifugal separation, washing Pt-loaded particles obtained by centrifugal separation with deionized water for three times, and calcining for 1h under the condition of nitrogen at 200 ℃ to obtain the Pt-loaded nano-silica particles, wherein the loading capacity of Pt is 3%.
C: selecting polytetrafluoroethylene resin powder with the grain diameter of about 3-5 mu m, wherein the crystallinity of the polytetrafluoroethylene resin is 98.5%.
D: weighing 7 parts by weight of Pt-loaded nano silicon dioxide particles by taking 100 parts by weight of polytetrafluoroethylene resin as an additive, and uniformly mixing polytetrafluoroethylene and the Pt-loaded nano silicon dioxide particles in a mixer for 12 hours.
E: curing treatment: standing and curing the uniformly mixed raw materials at 30 ℃ for 36 h.
F: and adding 20 parts by mass of lubricant petroleum ether into the cured mixture, and fully mixing for later use.
G: and extruding the mixed material added with the lubricant into a raw material blank under the pressure of 5 MPa.
H: the raw stock material was calendered at a temperature of 65 ℃ to form a first calendered film having a thickness of 1 mm.
I: and (3) drying treatment: and (3) heating and drying the first rolled film at 250 ℃, removing the lubricant in the first rolled film to obtain a second rolled film, and recycling the lubricant.
J: longitudinal stretching: the second calendered film was subjected to 1000% machine direction stretching at a temperature of 300 ℃.
K: and (3) transverse stretching: the second calendered film, pressed longitudinally stretched, was subjected to 2000% transverse stretching at a temperature of 200 ℃.
L: the PTFE membrane stretched longitudinally and transversely (i.e., the second rolled membrane) was set at a temperature of 350 ℃ for 15min to obtain an ePTFE microporous membrane of the present example.
(2) Preparation of proton exchange membranes
Adding 1g of surfactant Triton X100 into 100mL of perfluorinated sulfonic acid resin solution with the solid content of 20 wt% to obtain sulfonic acid resin solution; spreading and soaking the ePTFE microporous membrane prepared in the embodiment in a sulfonic acid resin solution for 5min to ensure that the upper surface and the lower surface of the ePTFE microporous membrane are both soaked in the sulfonic acid resin solution to form a soaked membrane; the impregnated membrane was dried at 90 ℃ for 10min to obtain a proton exchange membrane of this example.
Example 2
(1) Preparation of microporous membranes
A: preparing nano silicon dioxide: tetrabutyl silicate, ethanol and deionized water in a volume ratio of 1:1.5:2 preparing a clear solution, stirring (magnetic stirring) for 30min at 50 ℃, dropwise adding an ammonia water solution while stirring until the pH value is 5-6, then carrying out centrifugal separation, freeze-drying the silica gel obtained by centrifugal separation at-50 ℃ for 24h, and calcining at 600 ℃ for 1h to obtain the nano-silica.
B: mixing chloroplatinic acid: nano silicon dioxide: deionized water according to the proportion of 1: 10: 500, dropwise adding ammonia water to a pH value of 7 under the condition of stirring (magnetic stirring) at 80 ℃, continuously stirring for 1h, then carrying out centrifugal separation, washing Pt-loaded particles obtained by centrifugal separation with deionized water for three times, and calcining for 1h under the condition of nitrogen at 200 ℃ to obtain the Pt-loaded nano-silica particles, wherein the loading capacity of Pt is 3%.
C: selecting polytetrafluoroethylene resin powder with the grain diameter of about 3-5 mu m.
D: weighing 5 parts by weight of Pt-loaded nano silicon dioxide particles by taking 100 parts by weight of polytetrafluoroethylene resin as an additive, and uniformly mixing polytetrafluoroethylene and the Pt-loaded nano silicon dioxide particles in a mixer for 12 hours.
E: curing treatment: standing and curing the uniformly mixed raw materials at 25 ℃ for 48 h.
F: and adding 20 parts by mass of lubricant polydimethylsiloxane into the cured mixture, and fully mixing for later use.
G: and extruding the mixed material added with the lubricant into a raw material blank under the pressure of 5 MPa.
H: the raw stock material was calendered at a temperature of 50 ℃ to form a first calendered film having a thickness of 1.2 mm.
I: and (3) drying treatment: and (3) heating and drying the first rolled film at 250 ℃, removing the lubricant in the first rolled film to obtain a second rolled film, and recycling the lubricant.
J: longitudinal stretching: the second calendered film was subjected to 800% machine direction stretching at a temperature of 350 ℃.
K: and (3) transverse stretching: the second calendered film, pressed longitudinally stretched, was subjected to 1200% transverse stretching at a temperature of 200 ℃.
L: the PTFE membrane stretched longitudinally and transversely (i.e., the second calendered membrane) was set at 380 ℃ for 15min to obtain the ePTFE microporous membrane of this example.
(2) Preparation of proton exchange membranes
Adding 1g of surfactant Triton X100 into 100mL of perfluorinated sulfonic acid resin solution with the solid content of 15 wt% to obtain sulfonic acid resin solution; spreading and soaking the ePTFE microporous membrane prepared in the embodiment in a sulfonic acid resin solution for 3min, so that the upper surface and the lower surface of the ePTFE microporous membrane are both soaked in the sulfonic acid resin solution to form a soaked membrane; the impregnated membrane was dried at 80 ℃ for 10min to obtain a proton exchange membrane of this example.
Example 3
(1) Preparation of microporous membranes
A: preparing nano silicon dioxide: tetrabutyl silicate, ethanol and deionized water in a volume ratio of 1:1.5:2 preparing a clear solution, stirring (magnetic stirring) for 30min at 50 ℃, dropwise adding an ammonia water solution while stirring until the pH value is 5-6, then carrying out centrifugal separation, freeze-drying the silica gel obtained by centrifugal separation at-50 ℃ for 24h, and calcining at 600 ℃ for 1h to obtain the nano-silica.
B: mixing chloroplatinic acid: nano silicon dioxide: deionized water according to the proportion of 1: 3: 500, dropwise adding ammonia water to a pH value of 7 under the condition of stirring (magnetic stirring) at 80 ℃, continuously stirring for 1h, then carrying out centrifugal separation, washing Pt-loaded particles obtained by centrifugal separation with deionized water for three times, and calcining for 1h under the condition of nitrogen at 200 ℃ to obtain the Pt-loaded nano-silica particles, wherein the loading capacity of Pt is 11%.
C: selecting polytetrafluoroethylene resin powder with the grain diameter of about 3-5 mu m.
D: weighing 7 parts by weight of Pt-loaded nano silicon dioxide particles by taking 100 parts by weight of polytetrafluoroethylene resin as an additive, and uniformly mixing polytetrafluoroethylene and the Pt-loaded nano silicon dioxide particles in a mixer for 12 hours.
E: curing treatment: standing and curing the uniformly mixed raw materials at 30 ℃ for 30 h.
F: adding 20 parts by mass of lubricant n-heptanol into the cured mixture, and fully mixing for later use.
G: and extruding the mixed material added with the lubricant into a raw material blank under the pressure of 5 MPa.
H: the raw stock material was calendered at a temperature of 80 c to form a first calendered film having a thickness of 0.9 mm.
I: and (3) drying treatment: and (3) heating and drying the first rolled film at 250 ℃, removing the lubricant in the first rolled film to obtain a second rolled film, and recycling the lubricant.
J: longitudinal stretching: the second calendered film was subjected to 1000% machine direction stretching at a temperature of 330 ℃.
K: and (3) transverse stretching: the second calendered film, pressed, longitudinally stretched, was subjected to a transverse stretching of 2000% at a temperature of 210 ℃.
L: the PTFE membrane stretched longitudinally and transversely (i.e., the second calendered membrane) was set at 350 ℃ for 15min to obtain the ePTFE microporous membrane of this example.
(2) Preparation of proton exchange membranes
Adding 1g of surfactant Triton X100 into 100L of perfluorinated sulfonic acid resin solution with the solid content of 20 wt% to obtain sulfonic acid resin solution; spreading and soaking the ePTFE microporous membrane prepared in the embodiment in a sulfonic acid resin solution for 5min to ensure that the upper surface and the lower surface of the ePTFE microporous membrane are both soaked in the sulfonic acid resin solution to form a soaked membrane; the impregnated membrane was dried at 90 ℃ for 10min to obtain a proton exchange membrane of this example.
Example 4
(1) Preparation of microporous membranes
A: preparing nano silicon dioxide: tetrabutyl silicate, ethanol and deionized water in a volume ratio of 1:1.5:2 preparing clear solution, stirring (magnetic stirring) for 30min at 50 ℃, dropwise adding ammonia water solution while stirring until the pH value is 5-6, then carrying out centrifugal separation, carrying out freeze drying on the silicon dioxide gel obtained by centrifugal separation for 24h at-50 ℃, and calcining for 1h at 600 ℃ to obtain the nano silicon dioxide.
B: mixing chloroplatinic acid: nano silicon dioxide: deionized water according to the proportion of 1: 1: 500, dropwise adding ammonia water to a pH value of 7 under the condition of stirring (magnetic stirring) at 80 ℃, continuously stirring for 1h, then carrying out centrifugal separation, washing Pt-loaded particles obtained by centrifugal separation with deionized water for three times, and calcining for 1h under the condition of nitrogen at 200 ℃ to obtain the Pt-loaded nano-silica particles, wherein the loading capacity of Pt is 27%.
C: selecting polytetrafluoroethylene resin powder with the grain diameter of about 3-5 mu m.
D: weighing 1 part of Pt-loaded nano silicon dioxide particles by taking 100 parts of polytetrafluoroethylene resin as an added mass, and uniformly mixing polytetrafluoroethylene and the Pt-loaded nano silicon dioxide particles in a mixer for 12 hours.
E: curing treatment: standing and curing the uniformly mixed raw materials at 30 ℃ for 80 h.
F: 20 parts by mass of a lubricant (10 parts by mass of petroleum ether and 10 parts by mass of polydimethylsiloxane) was added to the cured mixture, and the mixture was thoroughly mixed for use.
G: and extruding the mixed material added with the lubricant into a raw material blank under the pressure of 5 MPa.
H: the raw stock material was calendered at a temperature of 65 ℃ to form a first calendered film having a thickness of 1 mm.
I: and (3) drying treatment: and (3) heating and drying the first rolled film at 250 ℃, removing the lubricant in the first rolled film to obtain a second rolled film, and recycling the lubricant.
J: longitudinal stretching: the second calendered film was subjected to 1000% machine direction stretching at a temperature of 340 ℃.
K: and (3) transverse stretching: the second calendered film, pressed, longitudinally stretched, was subjected to a transverse stretching of 2000% at a temperature of 210 ℃.
L: the PTFE membrane stretched longitudinally and transversely (i.e., the second calendered membrane) was set at 350 ℃ for 15min to obtain the ePTFE microporous membrane of this example.
(2) Preparation of proton exchange membranes
Adding 1g of surfactant Triton X114 into 100mL of perfluorinated sulfonic acid resin solution with the solid content of 25 wt% to obtain sulfonic acid resin solution; spreading and soaking the ePTFE microporous membrane prepared in the embodiment in a sulfonic acid resin solution for 8min to ensure that the upper surface and the lower surface of the ePTFE microporous membrane are both soaked in the sulfonic acid resin solution to form a soaked membrane; the impregnated membrane was dried at 100 ℃ for 10min to obtain a proton exchange membrane of this example.
Example 5
(1) Preparation of microporous membranes
A: preparing nano titanium dioxide: tetrabutyl titanate and ethanol are mixed according to the volume ratio of 1: 3.5 preparing a clear first solution, and stirring for 10min at the temperature of 50 ℃; preparing acetic acid, distilled water and ethanol in a volume ratio of 1: 5: 16 and a small amount of hydrochloric acid is added to adjust the pH to 3. Mixing the first solution and the second solution according to a volume ratio of 1:1 stirring and mixing, heating in water bath for 1h at 40 ℃, carrying out centrifugal separation, washing the titanium dioxide gel obtained by centrifugal separation with distilled water for three times, freeze-drying for 24h at-50 ℃, and calcining for 1h at 600 ℃ to obtain the nano titanium dioxide.
B: mixing chloroplatinic acid: nano titanium dioxide: deionized water according to the proportion of 1: 5: 500, dropwise adding ammonia water to a pH value of 7 under the condition of stirring (magnetic stirring) at 80 ℃, continuously stirring for 1h, then carrying out centrifugal separation, washing Pt-loaded particles obtained by centrifugal separation with deionized water for three times, and calcining for 1h under the condition of nitrogen at 200 ℃ to obtain the Pt-loaded nano-silica particles, wherein the loading capacity of Pt is 6%.
C: selecting polytetrafluoroethylene resin powder with the grain diameter of about 3-5 mu m.
D: weighing 3 parts by weight of Pt-loaded nano titanium dioxide particles by taking 100 parts by weight of polytetrafluoroethylene resin as an additive, and uniformly mixing polytetrafluoroethylene and the Pt-loaded nano titanium dioxide particles in a mixer for 12 hours.
E: curing treatment: standing and curing the uniformly mixed raw materials at 30 ℃ for 72 h.
F: and adding 20 parts by mass of lubricant petroleum ether into the cured mixture, and fully mixing for later use.
G: and extruding the mixed material added with the lubricant into a raw material blank under the pressure of 5 MPa.
H: the raw stock material was calendered at a temperature of 65 ℃ to form a first calendered film having a thickness of 1 mm.
I: and (3) drying treatment: and (3) heating and drying the first rolled film at 250 ℃, removing the lubricant in the first rolled film to obtain a second rolled film, and recycling the lubricant.
J: longitudinal stretching: the second calendered film was subjected to 1000% machine direction stretching at a temperature of 320 ℃.
K: and (3) transverse stretching: the second calendered film, pressed, longitudinally stretched, was subjected to 2000% transverse stretching at a temperature of 220 ℃.
L: the PTFE membrane stretched longitudinally and transversely (i.e., the second calendered membrane) was set at 350 ℃ for 15min to obtain the ePTFE microporous membrane of this example.
(2) Preparation of proton exchange membranes
Adding 1g of surfactant Triton X114 into 100mL of perfluorinated sulfonic acid resin solution with the solid content of 20 wt% to obtain sulfonic acid resin solution; spreading and soaking the ePTFE microporous membrane prepared in the embodiment in a sulfonic acid resin solution for 5min to ensure that the upper surface and the lower surface of the ePTFE microporous membrane are both soaked in the sulfonic acid resin solution to form a soaked membrane; the impregnated membrane was dried at 90 ℃ for 10min to obtain a proton exchange membrane of this example.
Example 6
This example is substantially the same as example 1 except that the stretching ratio in the machine direction was 600% and the stretching ratio in the transverse direction was 1750% in the microporous membrane production process.
Example 7
This example is substantially the same as example 1 except that the stretching ratio in the machine direction was 900% and the stretching ratio in the transverse direction was 2500% in the microporous film production process.
Example 8
This embodiment is substantially the same as embodiment 1 except that: in the preparation process of the microporous membrane, the platinum group metal in the platinum group metal-loaded nano oxide particles is palladium, and chloroplatinic acid in the step B is replaced by chloroplatinic acid.
Example 9
This embodiment is substantially the same as embodiment 1 except that: in the preparation process of the microporous membrane, the weight of the added polytetrafluoroethylene resin is 100 parts, and the Pt-loaded nano silicon dioxide particles are weighed by 10 parts.
Example 10
This embodiment is substantially the same as embodiment 1 except that: in the preparation process of the microporous membrane, the weight of the added polytetrafluoroethylene resin is 100 parts, and the Pt-loaded nano silicon dioxide particles are weighed by 19 parts.
Example 11
This embodiment is substantially the same as embodiment 1 except that: in the preparation process of the microporous membrane, chloroplatinic acid: nano silicon dioxide: deionized water according to the proportion of 5: 2: mixing at a mass ratio of 500; pt-loaded nano-silica fine particles in which the loading amount of Pt was 48%.
Comparative example
The microporous membrane of the comparative example is a certain market-sold ePTFE, the proton exchange membrane is prepared by adopting the market-sold ePTFE, and the preparation method of the proton exchange membrane is the same as that of the example 1.
Second, performance detection
The microporous films of examples 1 to 7 and comparative example were examined for thickness, tensile strength, elongation at break, water contact angle, porosity, and pore diameter, and the results are shown in table 1.
The proton exchange membranes of examples 1-7 and comparative example were tested for fluoride ion loss and the results are shown in Table 1. The method for testing the loss rate of the fluorine ions comprises the following steps: weigh 5cm by 5cm proton exchange membranes and soak in 1500mL Fenton reagent (15% H) 2 O 2 ；20ppm Fe 3+ ) In 24h, taking out the proton exchange membrane, and testing F of the Fenton reagent - Ion concentration, measuring F - Ion content, comparing the mass of the proton exchange membrane to obtain F - Ion loss rate. By F - The ion concentration and content characterize the electrochemical degradation degree of the proton exchange membrane caused by the attack of free radicals in the Fenton reagent, wherein F is - The higher the ion content, F - The higher the ion loss rate, the poorer the degradation resistance of the proton exchange membrane.
Table 1 performance test results of microporous membranes and proton exchange membranes of examples 1 to 7 and comparative example
As can be seen from Table 1, the tensile strength and the elongation at break of the microporous membrane of the embodiment of the invention are improved compared with those of the microporous membrane of the comparative example, and the hydrophilic property is improved; the loss rate of the fluorine ions of the proton exchange membrane in the embodiment of the invention is only 31.8% -54.5% of that of the comparative example, and the degradation resistance of the proton exchange membrane in the embodiment of the invention is greatly improved.
In conclusion, the microporous membrane of the embodiment of the invention can improve the wetting property and the self-humidifying property of the microporous membrane by adding the nano oxide loaded with platinum group metals such as Pt and the like to quench free radicals, has excellent mechanical property, good membrane material surface property and high porosity, can be widely applied to the field of proton exchange membrane materials of fuel cells, reduces the hydrogen permeation property of the ePTFE composite enhanced proton exchange membrane, improves the electrochemical degradation resistance, further prolongs the service life of the proton exchange membrane, and improves the overall application performance of the proton exchange membrane.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
In the present invention, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A microporous membrane, comprising a polytetrafluoroethylene membrane body and platinum group metal-loaded nano-oxide particles;
the nanometer oxide particles loaded with platinum group metals are uniformly distributed in the pores of the polytetrafluoroethylene fiber membrane body.
2. The microporous membrane of claim 1, wherein the polytetrafluoroethylene fibers have a diameter of 50-500nm and an average pore size of 100-400 nm; the particle diameter of the platinum group metal-loaded nano-oxide particles is less than 100 nm.
3. The microporous membrane of claim 1, wherein the platinum group metal-loaded nano-oxide particles are hydrophilic particles; the nano oxide is one or more than two of nano silicon dioxide, nano titanium dioxide and nano zirconium dioxide.
4. The microporous membrane of claim 1, wherein the platinum group metal loading in the platinum group metal-loaded nano-oxide particles is from 1 to 50 wt%; the mass ratio of the polytetrafluoroethylene fiber membrane body to the platinum group metal-loaded nano-oxide particles is 100: 1-20.
5. A method of making the microporous membrane of any of claims 1 to 4, comprising
Mixing the precursor solution of the platinum group metal with nano oxide powder for reaction, and then carrying out centrifugal separation and calcination to obtain the platinum group metal-loaded nano oxide particles;
uniformly mixing polytetrafluoroethylene resin powder and the platinum group metal-loaded nano oxide particles, curing, and extruding under the action of a lubricant to form a raw material blank;
rolling the raw material blank to form a first rolled film, and drying the first rolled film to obtain a second rolled film;
and sequentially carrying out longitudinal stretching and transverse stretching on the second rolled film, and then sintering and shaping to obtain the microporous film.
6. The method of producing a microporous membrane according to claim 5, wherein the nano-oxide fine particles are produced by a sol-gel method; the conditions for mixing and reacting the precursor solution of the platinum group metal and the nano oxide powder are as follows: the temperature is 70-90 ℃, the pH is 6.5-7.5, and the reaction time is 0.5-1.5 h; the calcining temperature is 150-250 ℃, and the calcining time is 0.5-1.5 h.
7. The method of claim 5, wherein the aging is performed by: and standing the uniformly mixed polytetrafluoroethylene resin powder and the platinum group metal-loaded nano oxide particle material at 25-40 ℃ for 24-72 h.
8. The method for preparing a microporous membrane according to claim 5, wherein the lubricant is one or more of petroleum ether, white oil, silicone oil, alcohols, and aromatic hydrocarbons; the addition amount of the lubricant is 15-30% of the mass of the polytetrafluoroethylene resin powder; the extrusion pressure is 3-10 MPa; the temperature of the longitudinal stretching is 300-350 ℃, and the stretching ratio of the longitudinal stretching is 600-1000%; the temperature of the transverse stretching is 200-220 ℃, and the stretching ratio of the transverse stretching is 1000-2500%; the temperature for sintering and shaping is 350-400 ℃.
9. A proton exchange membrane comprising the microporous membrane of any one of claims 1 to 5.
10. A method of preparing a proton exchange membrane according to claim 9 comprising
Adding a surfactant into the perfluorinated sulfonic acid resin solution to obtain a sulfonic acid resin solution;
spreading and soaking the microporous membrane in the sulfonic acid resin solution to form an impregnated membrane;
and drying the impregnated membrane to obtain the proton exchange membrane.
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