CN111286065A - Polytetrafluoroethylene diaphragm for preparing hydrogen for fuel cell and preparation method - Google Patents

Polytetrafluoroethylene diaphragm for preparing hydrogen for fuel cell and preparation method Download PDF

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CN111286065A
CN111286065A CN201810810444.XA CN201810810444A CN111286065A CN 111286065 A CN111286065 A CN 111286065A CN 201810810444 A CN201810810444 A CN 201810810444A CN 111286065 A CN111286065 A CN 111286065A
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polytetrafluoroethylene
membrane
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microporous membrane
hydrogen
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陈庆
廖健淞
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Chengdu New Keli Chemical Science Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention relates to the field of fuel cells, and discloses a polytetrafluoroethylene diaphragm for preparing hydrogen for a fuel cell and a preparation method thereof. The preparation method comprises the following preparation processes: (1) placing the polytetrafluoroethylene microporous membrane in a sodium naphthalene tetrahydrofuran solution, and reacting to obtain an activated polytetrafluoroethylene microporous membrane; (2) mixing polytetrafluoroethylene microporous membrane with methylvinyloxyethyltrimethyl ammonium chloride in an organic solvent, adding an auxiliary agent, and then using Co60And (4) irradiating, taking out the membrane material, washing and drying to obtain the polytetrafluoroethylene membrane for preparing hydrogen for the fuel cell.Compared with the common polytetrafluoroethylene diaphragm, the polytetrafluoroethylene diaphragm prepared by the invention has the advantages that the conductivity of the prepared polytetrafluoroethylene diaphragm is obviously improved by grafting the quaternary amine groups on the micropores and the surface of the PTFE, and the hydrophilic modification is realized by adding the sodium naphthalene tetrahydrofuran, and the polytetrafluoroethylene diaphragm has good mechanical properties.

Description

Polytetrafluoroethylene diaphragm for preparing hydrogen for fuel cell and preparation method
Technical Field
The invention relates to the field of fuel cells, and discloses a polytetrafluoroethylene diaphragm for preparing hydrogen for a fuel cell and a preparation method thereof.
Background
The energy is an important material basis for developing national economy and improving the quality of life of people, is an important restriction factor directly influencing economic development, and is also one of the bases of national strategic safety guarantee. In recent years, the demand of human society for energy is getting larger and larger, and the traditional energy structure and the consumption of a large amount of energy threaten the living environment of the human society, so that the development of a clean, efficient and sustainable new energy power technology becomes a very urgent task, and the hydrogen energy has been widely regarded as an efficient, clean and ideal secondary energy source all over the world.
The large-scale and low-cost hydrogen production is one of the important links for developing and utilizing hydrogen energy as a secondary energy source, the most abundant hydrogen-containing substance is water, and wives are various fossil fuels and various biomasses. Although the fossil fuel hydrogen production has low cost and wide application, the mineral reserves are limited, and the hydrogen production process can cause pollution to the environment. Therefore, in the long run, the preparation of hydrogen by using water as a raw material is the most promising method, the raw material is inexhaustible, and the method has no pollution to the environment.
In the method for preparing hydrogen by using water as a raw material, the operation of hydrogen preparation by water electrolysis is relatively simple, the technology is relatively mature, the purity of the prepared hydrogen is high, and the hydrogen preparation process is pollution-free, so that the method is an important means for realizing large-scale hydrogen production. The diaphragm material in the alkaline electrolytic cell is mainly formed by organizing the products of two poles of the electrolytic cell to be mixed with each other by physical or chemical means without obstructing the passing of current. At present, the non-asbestos diaphragm is mainly composed of asbestos and non-asbestos diaphragms, polyphenylene sulfide and polysulfone, and the asbestos diaphragm has the problems of high swelling rate, short service life and the like, so that the research and application of the non-asbestos diaphragm become hot spots.
Chinese patent application No. 201510264388.0 discloses an electrolytic separator comprising a fabric and a coating layer coated on the fabric; the fabric raw material comprises 30-100 parts by weight of polyphenylene sulfide sulfone short fibers and 0-70 parts by weight of polyphenylene sulfide short fibers; the coating is a resin coating containing polyphenylene sulfide sulfone or a resin coating containing polytetrafluoroethylene. The invention also provides a preparation method of the electrolytic diaphragm and application of the electrolytic diaphragm as a non-asbestos diaphragm in water electrolysis hydrogen production, water electrolysis oxygen production and chlor-alkali electrolytic tanks, and the diaphragm improves the heat resistance, is beneficial to prolonging the service life of the non-asbestos diaphragm and improves the efficiency.
Chinese patent application No. 200710144822.7 discloses an asbestos-free environment-friendly energy-saving diaphragm cloth and a weaving method thereof,polyphenylene sulfide fiber, or polyphenylene sulfide fiber and polyether ketone ether fiber, or polyphenylene sulfide fiber and polypropylene fiber are used as raw materials, and the following requirements are met: the unit weight is as follows: 0.5 to 1.5kg/m2(ii) a Cloth thickness range: 0.5-1.5 mm; and (3) warp and weft density: warp threads are 100-280 threads/10 cm, and weft threads are 56-150 threads/10 cm; alkali loss: not more than 2%; air tightness performance no air bubbles are allowed to generate within 2 minutes under the water column pressure of 300 mm, and the weaving can be carried out according to a wool spinning process and a cotton spinning process. The invention breaks through the trade barrier of developed countries, improves the overall level of hydrogen and oxygen production equipment by water electrolysis in China, and reduces the harm of asbestos dust to the environment and human bodies. Compared with the traditional asbestos diaphragm cloth, the thickness of the product can be reduced by 55-85%, and the energy is saved by more than 10%.
According to the above, in the diaphragm material for hydrogen production by water electrolysis in the existing scheme, asbestos has the problems of high swelling rate, short service life and the like, and non-asbestos mainly is a composite fiber of halogenated olefin polymer and inorganic matter, although the acid-base tolerance is good, the non-asbestos has the problems of poor hydrophilic property, low conductivity and the like, so that the application of the non-asbestos in industrial production is limited.
Disclosure of Invention
The invention provides a polytetrafluoroethylene diaphragm for preparing hydrogen for a fuel cell and a preparation method thereof, which can effectively solve the technical problems.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of a polytetrafluoroethylene diaphragm for preparing hydrogen for a fuel cell comprises the following specific steps:
(1) preparing a polytetrafluoroethylene microporous membrane by means of bidirectional melt stretching, then placing the polytetrafluoroethylene microporous membrane in a sodium naphthalene tetrahydrofuran solution, separating partial fluorine atoms on the surface of polytetrafluoroethylene by means of reaction to expose a carbon-based surface and polar groups, taking out a membrane material after black spots appear on the surface of the membrane material, washing the membrane material for 3-5 times by using deionized water, and drying to prepare an activated polytetrafluoroethylene microporous membrane;
(2) blending the activated polytetrafluoroethylene microporous membrane prepared in the step (1) with methylvinyloxyethyltrimethylammonium chloride in an organic solvent, adding an auxiliary agent, sealing, and using Co60And (3) irradiating to graft quaternary amine groups of the methyl vinyl acyloxy ethyl trimethyl ammonium chloride on micropores and surfaces of the polytetrafluoroethylene, taking out the membrane material, washing and drying to obtain the polytetrafluoroethylene membrane for preparing hydrogen for the fuel cell.
Preferably, the polytetrafluoroethylene microporous membrane in the step (1) has a stretching ratio of 3-3.5.
Preferably, the mass concentration of the sodium naphthalene tetrahydrofuran solution in the step (1) is 40-50%.
Preferably, the reaction temperature in the step (1) is 50-60 ℃ and the reaction time is 50-70 min.
Preferably, the organic solvent in step (2) is one of pyridine, phenol, diethyl ether, cyclohexanone and chlorobenzene.
Preferably, the auxiliary agent in step (2) is at least one of sodium stearate, potassium stearate, calcium stearate and magnesium stearate.
Preferably, said Co of step (2)60The irradiation intensity is 20-30 kGy, and the irradiation time is 15-20 min.
Preferably, in the step (2), the raw materials comprise, by weight, 12-15 parts of a polytetrafluoroethylene microporous membrane, 3-5 parts of methylvinyloxyethyltrimethylammonium chloride, 77-84 parts of an organic solvent and 1-3 parts of an auxiliary agent.
Preferably, the drying is infrared drying, the wavelength is 200-500 nm, and the drying time is 20-30 min.
The polytetrafluoroethylene diaphragm for preparing hydrogen for the fuel cell is prepared by the method, a Polytetrafluoroethylene (PTFE) microporous membrane prepared by a biaxial melt-draw method is used as a raw material, the raw material is placed in a sodium naphthalene tetrahydrofuran solution for reaction, the membrane material is taken out after black spots appear on the surface of the membrane material, is repeatedly washed and dried by deionized water, is then blended with methylvinyloxyethyltrimethyl ammonium chloride (DMC) in an organic solvent, is sealed after an auxiliary agent is added, and Co is used60And (4) irradiating, taking out the membrane material, washing and drying to obtain the modified polytetrafluoroethylene membrane. The fluorine atoms on the surface of the PTFE are torn off by the sodium naphthalene tetrahydrofuran to expose the carbon-based surface and the polar groups, and the irradiation treatment is carried out after the PTFE and the DMC are mixed, so that the DMC is grafted on the surface of the PTFE and in the micropores more easily.
The conductivity, contact angle and tensile strength of the polytetrafluoroethylene membrane prepared by the method are tested, and compared with the common polytetrafluoroethylene membrane, the method provided by the invention has obvious advantages, as shown in table 1.
Table 1:
Figure 854395DEST_PATH_IMAGE002
the invention provides a polytetrafluoroethylene diaphragm for preparing hydrogen for a fuel cell and a preparation method thereof, and compared with the prior art, the polytetrafluoroethylene diaphragm has the outstanding characteristics and excellent effects that:
1. a method for preparing a polytetrafluoroethylene membrane for hydrogen production for fuel cells by grafting DMC on the surface of PTFE and inside micropores is proposed.
2. By grafting quaternary amine groups on the micropores and the surface of the PTFE, the adsorption and permeation performance of the membrane material on hydroxide ions is improved, a good conductive channel is formed in the micropores, and the conductivity of the prepared polytetrafluoroethylene membrane is obviously improved.
3. By adding the sodium naphthalene tetrahydrofuran, partial fluorine atoms on the surface of the PTFE are separated, and a carbonization layer and polar groups are generated, so that the hydrophilicity of the surface of the membrane is improved, the PTFE and DMC are easier to compound, the hydrophilicity of the prepared polytetrafluoroethylene membrane is improved, and the prepared polytetrafluoroethylene membrane has good mechanical properties.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Preparing a polytetrafluoroethylene microporous membrane by means of bidirectional melt stretching, then placing the polytetrafluoroethylene microporous membrane in a sodium naphthalene tetrahydrofuran solution, separating partial fluorine atoms on the surface of polytetrafluoroethylene by means of reaction to expose a carbon-based surface and polar groups, taking out a membrane material after black spots appear on the surface of the membrane material, washing the membrane material for 3-5 times by using deionized water, and drying to prepare an activated polytetrafluoroethylene microporous membrane; the stretching multiple of the polytetrafluoroethylene microporous membrane is 3.5 times; the mass concentration of the sodium naphthalene tetrahydrofuran solution is 40 percent; the reaction temperature is 60 ℃ and the reaction time is 50 min;
(2) blending the activated polytetrafluoroethylene microporous membrane prepared in the step (1) with methylvinyloxyethyltrimethylammonium chloride in an organic solvent, adding an auxiliary agent, sealing, and using Co60Irradiating to graft quaternary amine groups of the methylvinyl acetoxy ethyl trimethyl ammonium chloride on micropores and surfaces of the polytetrafluoroethylene, taking out a membrane material, washing and drying to prepare the polytetrafluoroethylene membrane for preparing hydrogen for the fuel cell; the organic solvent is pyridine; the auxiliary agent is sodium stearate; co60The irradiation intensity is 30kGy, and the irradiation time is 15 min; wherein, 12 parts by weight of polytetrafluoroethylene microporous membrane, 5 parts by weight of methylvinyloxyethyltrimethyl ammonium chloride, 80 parts by weight of organic solvent and 3 parts by weight of auxiliary agent; the drying is infrared drying with wavelength of 500nm and drying time of 30 min.
The electric conductivity, contact angle and tensile strength of the polytetrafluoroethylene separator obtained in example 1 are shown in table 2.
Example 2
(1) Preparing a polytetrafluoroethylene microporous membrane by means of bidirectional melt stretching, then placing the polytetrafluoroethylene microporous membrane in a sodium naphthalene tetrahydrofuran solution, separating partial fluorine atoms on the surface of polytetrafluoroethylene by means of reaction to expose a carbon-based surface and polar groups, taking out a membrane material after black spots appear on the surface of the membrane material, washing the membrane material for 3-5 times by using deionized water, and drying to prepare an activated polytetrafluoroethylene microporous membrane; the stretching multiple of the polytetrafluoroethylene microporous membrane is 3 times; the mass concentration of the sodium naphthalene tetrahydrofuran solution is 50 percent; the reaction temperature is 50 ℃ and the reaction time is 70 min;
(2) blending the activated polytetrafluoroethylene microporous membrane prepared in the step (1) with methylvinyloxyethyltrimethylammonium chloride in an organic solvent, adding an auxiliary agent, sealing, and using Co60Irradiating to graft quaternary amine groups of the methylvinyl acetoxy ethyl trimethyl ammonium chloride on micropores and surfaces of the polytetrafluoroethylene, taking out a membrane material, washing and drying to prepare the polytetrafluoroethylene membrane for preparing hydrogen for the fuel cell; the organic solvent is chlorobenzene; the auxiliary agent is potassium stearate; co60The irradiation intensity is 28kGy, and the irradiation time is 18 min; wherein, 12 parts by weight of polytetrafluoroethylene microporous membrane, 5 parts by weight of methylvinyloxyethyltrimethyl ammonium chloride, 82 parts by weight of organic solvent and 1 part by weight of auxiliary agent; the drying is infrared drying with wavelength of 300nm and drying time of 23 min.
The electric conductivity, contact angle and tensile strength of the polytetrafluoroethylene separator obtained in example 2 are shown in table 2.
Example 3
(1) Preparing a polytetrafluoroethylene microporous membrane by means of bidirectional melt stretching, then placing the polytetrafluoroethylene microporous membrane in a sodium naphthalene tetrahydrofuran solution, separating partial fluorine atoms on the surface of polytetrafluoroethylene by means of reaction to expose a carbon-based surface and polar groups, taking out a membrane material after black spots appear on the surface of the membrane material, washing the membrane material for 3-5 times by using deionized water, and drying to prepare an activated polytetrafluoroethylene microporous membrane; the stretching multiple of the polytetrafluoroethylene microporous membrane is 3.5 times; the mass concentration of the sodium naphthalene tetrahydrofuran solution is 45 percent; the reaction temperature is 55 ℃ and the reaction time is 60 min;
(2) blending the activated polytetrafluoroethylene microporous membrane prepared in the step (1) with methylvinyloxyethyltrimethylammonium chloride in an organic solvent, adding an auxiliary agent, sealing, and using Co60Irradiating to graft quaternary amine groups of the methylvinyl acetoxy ethyl trimethyl ammonium chloride on micropores and surfaces of the polytetrafluoroethylene, taking out a membrane material, washing and drying to prepare the polytetrafluoroethylene membrane for preparing hydrogen for the fuel cell; the organic solvent is cyclohexanone; the auxiliary agent is calcium stearate; co60The irradiation intensity is 22kGy, and the irradiation time is 16 min; wherein, the polytetrafluoroethylene microporous membrane is 15 parts by weight5 parts of methyl vinyl acetoxy ethyl trimethyl ammonium chloride, 77 parts of organic solvent and 3 parts of auxiliary agent; the drying is infrared drying with wavelength of 400nm and drying time of 20 min.
The electric conductivity, contact angle and tensile strength of the polytetrafluoroethylene separator obtained in example 3 are shown in table 2.
Example 4
(1) Preparing a polytetrafluoroethylene microporous membrane by means of bidirectional melt stretching, then placing the polytetrafluoroethylene microporous membrane in a sodium naphthalene tetrahydrofuran solution, separating partial fluorine atoms on the surface of polytetrafluoroethylene by means of reaction to expose a carbon-based surface and polar groups, taking out a membrane material after black spots appear on the surface of the membrane material, washing the membrane material for 3-5 times by using deionized water, and drying to prepare an activated polytetrafluoroethylene microporous membrane; the stretching ratio of the polytetrafluoroethylene microporous membrane is 3 times. The mass concentration of the sodium naphthalene tetrahydrofuran solution is 46 percent; the reaction temperature is 52 ℃ and the reaction time is 55 min;
(2) blending the activated polytetrafluoroethylene microporous membrane prepared in the step (1) with methylvinyloxyethyltrimethylammonium chloride in an organic solvent, adding an auxiliary agent, sealing, and using Co60Irradiating to graft quaternary amine groups of the methylvinyl acetoxy ethyl trimethyl ammonium chloride on micropores and surfaces of the polytetrafluoroethylene, taking out a membrane material, washing and drying to prepare the polytetrafluoroethylene membrane for preparing hydrogen for the fuel cell; the organic solvent is diethyl ether; the auxiliary agent is magnesium stearate; co60The irradiation intensity is 30kGy, and the irradiation time is 15 min; wherein, 14 parts by weight of polytetrafluoroethylene microporous membrane, 4 parts by weight of methylvinyloxyethyltrimethyl ammonium chloride, 80 parts by weight of organic solvent and 2 parts by weight of auxiliary agent; the drying is infrared drying with wavelength of 500nm and drying time of 20 min.
The electric conductivity, contact angle and tensile strength of the polytetrafluoroethylene separator obtained in example 4 are shown in table 2.
Example 5
(1) Preparing a polytetrafluoroethylene microporous membrane by means of bidirectional melt stretching, then placing the polytetrafluoroethylene microporous membrane in a sodium naphthalene tetrahydrofuran solution, separating partial fluorine atoms on the surface of polytetrafluoroethylene by means of reaction to expose a carbon-based surface and polar groups, taking out a membrane material after black spots appear on the surface of the membrane material, washing the membrane material for 3-5 times by using deionized water, and drying to prepare an activated polytetrafluoroethylene microporous membrane; the stretching multiple of the polytetrafluoroethylene microporous membrane is 3.5 times; the mass concentration of the sodium naphthalene tetrahydrofuran solution is 40 percent; the reaction temperature is 60 ℃, and the reaction time is 60 min;
(2) blending the activated polytetrafluoroethylene microporous membrane prepared in the step (1) with methylvinyloxyethyltrimethylammonium chloride in an organic solvent, adding an auxiliary agent, sealing, and using Co60Irradiating to graft quaternary amine groups of the methylvinyl acetoxy ethyl trimethyl ammonium chloride on micropores and surfaces of the polytetrafluoroethylene, taking out a membrane material, washing and drying to prepare the polytetrafluoroethylene membrane for preparing hydrogen for the fuel cell; the organic solvent is phenol; the auxiliary agent is calcium stearate; co60The irradiation intensity is 25kGy, and the irradiation time is 18 min; wherein, 12 parts by weight of polytetrafluoroethylene microporous membrane, 3 parts by weight of methylvinyloxyethyltrimethyl ammonium chloride, 84 parts by weight of organic solvent and 1 part by weight of auxiliary agent; the drying is infrared drying with wavelength of 250nm and drying time of 27 min.
The electric conductivity, contact angle and tensile strength of the polytetrafluoroethylene separator obtained in example 5 are shown in table 2.
Example 6
(1) Preparing a polytetrafluoroethylene microporous membrane by means of bidirectional melt stretching, then placing the polytetrafluoroethylene microporous membrane in a sodium naphthalene tetrahydrofuran solution, separating partial fluorine atoms on the surface of polytetrafluoroethylene by means of reaction to expose a carbon-based surface and polar groups, taking out a membrane material after black spots appear on the surface of the membrane material, washing the membrane material for 3-5 times by using deionized water, and drying to prepare an activated polytetrafluoroethylene microporous membrane; the stretching multiple of the polytetrafluoroethylene microporous membrane is 3.5 times; the mass concentration of the sodium naphthalene tetrahydrofuran solution is 40 percent; the reaction temperature is 50 ℃ and the reaction time is 70 min;
(2) blending the activated polytetrafluoroethylene microporous membrane prepared in the step (1) with methylvinyloxyethyltrimethylammonium chloride in an organic solvent, adding an auxiliary agent, sealing, and using Co60Irradiating to obtain quaternary ammonium methyl vinyl oxyethyl trimethyl chlorideGrafting amine groups on micropores and surfaces of polytetrafluoroethylene, taking out a membrane material, washing and drying to prepare the polytetrafluoroethylene membrane for preparing hydrogen for the fuel cell; the organic solvent is chlorobenzene; the auxiliary agent is magnesium stearate; co60The irradiation intensity is 30kGy, and the irradiation time is 15 min; wherein, the polytetrafluoroethylene microporous membrane comprises 15 parts by weight of polytetrafluoroethylene microporous membrane, 5 parts by weight of methylvinyloxyethyltrimethyl ammonium chloride, 77 parts by weight of organic solvent and 3 parts by weight of auxiliary agent. The drying is infrared drying with wavelength of 200nm and drying time of 30 min.
The electric conductivity, contact angle and tensile strength of the polytetrafluoroethylene separator obtained in example 6 are shown in table 2.
Comparative example 1
Comparative example 1 a polytetrafluoroethylene membrane was prepared in the same manner as in example 1 without partially removing fluorine atoms from the surface of the polytetrafluoroethylene by using a sodium naphthalene tetrahydrofuran solution, and the electrical conductivity, contact angle and tensile strength thereof are shown in table 2.
The performance index testing method comprises the following steps:
conductivity: the polytetrafluoroethylene diaphragm prepared by the invention is prepared into a sample with the length of 6cm and the width of 2cm, the relative humidity is 55 percent, and the current density is 15mA/cm2Measuring the conductivity of the diaphragm by adopting an FT-333 four-probe resistivity tester at the liquid temperature of 60 ℃;
contact angle: the polytetrafluoroethylene membrane produced according to the invention was prepared into a sample of 80 mm × 80 mm, the water contact angle of the sample was measured by a liquid drop method using a contact angle meter, the brightness of the goniometer and the light beam was controlled by a computer, and the result was displayed as an image on a computer screen, and the image was photographed by a digital camera. To mitigate the effects of gravity, the volume of each droplet was adjusted from a fine level to 0.1 mL. The measurements were carried out at 18 ℃ and 42% Relative Humidity (RH).
Tensile strength: the polytetrafluoroethylene diaphragm prepared by the invention is prepared into a sample with the length of 6cm and the width of 2cm, an MTS810 material testing machine is adopted to carry out tensile test at room temperature, the stress is 50N, the testing speed is 10mm/min, and the tensile strength of the diaphragm is measured.
Table 2:
Figure 284239DEST_PATH_IMAGE004

Claims (10)

1. a preparation method of a polytetrafluoroethylene diaphragm for preparing hydrogen for a fuel cell is characterized by comprising the following specific preparation processes:
(1) preparing a polytetrafluoroethylene microporous membrane by means of bidirectional melt stretching, then placing the polytetrafluoroethylene microporous membrane in a sodium naphthalene tetrahydrofuran solution, separating partial fluorine atoms on the surface of polytetrafluoroethylene by means of reaction to expose a carbon-based surface and polar groups, taking out a membrane material after black spots appear on the surface of the membrane material, washing the membrane material for 3-5 times by using deionized water, and drying to prepare an activated polytetrafluoroethylene microporous membrane;
(2) blending the activated polytetrafluoroethylene microporous membrane prepared in the step (1) with methylvinyloxyethyltrimethylammonium chloride in an organic solvent, adding an auxiliary agent, sealing, and using Co60And (3) irradiating to graft quaternary amine groups of the methyl vinyl acyloxy ethyl trimethyl ammonium chloride on micropores and surfaces of the polytetrafluoroethylene, taking out the membrane material, washing and drying to obtain the polytetrafluoroethylene membrane for preparing hydrogen for the fuel cell.
2. The method for producing a polytetrafluoroethylene membrane for producing hydrogen for fuel cells according to claim 1, characterized in that: and (2) the polytetrafluoroethylene microporous membrane in the step (1) has a stretching multiple of 3-3.5 times.
3. The method for producing a polytetrafluoroethylene membrane for producing hydrogen for fuel cells according to claim 1, characterized in that: the mass concentration of the sodium naphthalene tetrahydrofuran solution in the step (1) is 40-50%.
4. The method for producing a polytetrafluoroethylene membrane for producing hydrogen for fuel cells according to claim 1, characterized in that: the reaction temperature in the step (1) is 50-60 ℃, and the reaction time is 50-70 min.
5. The method for producing a polytetrafluoroethylene membrane for producing hydrogen for fuel cells according to claim 1, characterized in that: and (3) the organic solvent in the step (2) is one of pyridine, phenol, ether, cyclohexanone and chlorobenzene.
6. The method for producing a polytetrafluoroethylene membrane for producing hydrogen for fuel cells according to claim 1, characterized in that: and (3) the auxiliary agent in the step (2) is at least one of sodium stearate, potassium stearate, calcium stearate and magnesium stearate.
7. The method for producing a polytetrafluoroethylene membrane for producing hydrogen for fuel cells according to claim 1, characterized in that: co described in step (2)60The irradiation intensity is 20-30 kGy, and the irradiation time is 15-20 min.
8. The method for producing a polytetrafluoroethylene membrane for producing hydrogen for fuel cells according to claim 1, characterized in that: in the step (2), the raw materials comprise, by weight, 12-15 parts of a polytetrafluoroethylene microporous membrane, 3-5 parts of methylvinyloxyethyltrimethylammonium chloride, 77-84 parts of an organic solvent and 1-3 parts of an auxiliary agent.
9. The method for producing a polytetrafluoroethylene membrane for producing hydrogen for fuel cells according to claim 1, characterized in that: the drying is infrared drying, the wavelength is 200-500 nm, and the drying time is 20-30 min.
10. A polytetrafluoroethylene membrane prepared by the method of any one of claims 1 to 9 for use in the production of hydrogen for fuel cells.
CN201810810444.XA 2018-07-23 2018-07-23 Polytetrafluoroethylene diaphragm for preparing hydrogen for fuel cell and preparation method Withdrawn CN111286065A (en)

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