CN108365241A - A kind of special amino modified perfluoro sulfonic acid membrane of fuel cell and preparation method - Google Patents

A kind of special amino modified perfluoro sulfonic acid membrane of fuel cell and preparation method Download PDF

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CN108365241A
CN108365241A CN201810121808.3A CN201810121808A CN108365241A CN 108365241 A CN108365241 A CN 108365241A CN 201810121808 A CN201810121808 A CN 201810121808A CN 108365241 A CN108365241 A CN 108365241A
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fuel cell
sulfonic acid
perfluoro sulfonic
amino modified
acid membrane
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陈庆
廖健淞
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Chengdu New Keli Chemical Science Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F114/00—Homopolymers 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
    • C08F114/18—Monomers containing fluorine
    • C08F114/185—Monomers containing fluorine not covered by the groups C08F114/20 - C08F114/28
    • 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
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • 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
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • 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
    • H01M8/1088—Chemical modification, e.g. sulfonation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Organic Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

The present invention relates to a kind of special amino modified perfluoro sulfonic acid membrane of fuel cell and preparation methods, belong to fuel cell barrier film technical field.The technical problem to be solved by the present invention is to provide a kind of preparation methods of the special amino modified perfluoro sulfonic acid membrane of fuel cell.This method includes the sulfonation of tetrafluoroethene, fluorination, condensation reaction, polycondensation reaction and the acidification of 3 amino propylene, double short sulfonic group branches are combined by N atoms, it is graft-polymerized onto main chain, improve sulfonic group content and its structural symmetry, keep its membrane material structure in swelling process more stable, ion cluster is more readily formed inside membrane material, to improve its proton adsorption and transfer ability.This method is simple for process, and feasibility is high.Thus the amino modified perfluoro sulfonic acid membrane being prepared, structural symmetry is high, and regularity is good, is easy crystallization, and the mechanical strength of membrane material is preferable, and proton conductivity is high, suitable for being used in the environment of high temperature low humidity.

Description

A kind of special amino modified perfluoro sulfonic acid membrane of fuel cell and preparation method
Technical field
The present invention relates to a kind of special amino modified perfluoro sulfonic acid membrane of fuel cell and preparation method, belong to fuel cell every Technical field of membrane.
Background technology
Fuel cell is a kind of hair that the chemical energy of fuel and oxidant is directly changed into electric energy by electrochemical reaction Electric installation.Mainly it is made of anode, cathode, electrolyte and ancillary equipment.Since fuel cell has, efficient, startup is fast, dirty Contaminate the advantages that small, it is considered to be it is hopeful largely to provide the 4th kind of generation technology of electric energy after wind-force, waterpower and solar energy, It is a kind of green energy resource technology, " energy shortage " and " environmental pollution " this two hang-up that the current world faces can be effectively relieved, Realize the diversification of the energy.Proton Exchange Membrane Fuel Cells（PEMFC）Other than the general characteristic for having fuel cell, also have Have and starts that fast, electroless liquid stream is lost, corrosion-free, energy transformation ratio is high, long lifespan, light-weight, small, pollution-free and infrared spoke The features such as penetrating is with a wide range of applications in traffic power source, portable power supplies and stationary electric power plant field of power supplies.
In fuel battery inside, proton exchange membrane provides channel for the migration and conveying of proton so that proton by film from Anode reaches cathode, constitutes circuit with the electronics transfer of external circuit, outwardly provides electric current, therefore the performance pair of proton exchange membrane The performance of fuel cell plays very important effect, its quality directly affects the service life of battery.By far the most commonly used Proton exchange membrane（PEMFC）It is still the Nafion membrane of DuPont Corporation, is a kind of perfluoro sulfonic acid membrane, the film is to temperature and contains Water requires height, and the optimum working temperature of Nafion series membranes is 70~90 DEG C, its water content can be made drastically to drop more than this temperature Low, electric conductivity declines rapidly, hinders and improves electrode reaction rate by properly increasing operating temperature and overcome in catalyst The problem of poison.Therefore, it is necessary to be improved to existing proton exchange membrane.
Application No. is 201710824018.7 patents of invention to disclose a kind of cross-linking fluorine-containing sulfonated polyether compound And preparation method thereof.First with decafluorobiphenyl, prepared by the polycondensation reaction of 2,2'- diallyl bisphenols and bisphenol-A for the invention Then cross-linking fluorinated poly arylene ether compound is reacted with a certain amount of 4- sodium hydroxybenzenesulfonate, to draw in the polymer Enter sulfonic group, cross-linking fluorine-containing sulfonated polyether compound is finally made.The cross-linking fluorine-containing sulfonated polyether compound can be with It is formed a film with solution-cast.Gained proton exchange membrane have preparation process is simple, thermal stability is good, oxidation stability is good, proton pass The features such as conductance is high, mechanical property is good.By the way that radical initiator is added, crosslinking proton exchange membrane can be prepared, is improved resistance to molten Agent ability.
Application No. is 201710618439.4 patents of invention to disclose a kind of side chain type sulfonated polyamides Asia of sulfuryl bridge joint The method of its preparation proton exchange membrane of amine and preparation method thereof and application, wherein the side chain type sulfonated polyamides of sulfuryl bridge joint is sub- The structure feature of amine is used as bridge joint group by sulfuryl for the side chain with sulfonic acid group and is connected on polyimides main chain, with sulfone Base ensure that the acidity of side chain flexibility and sulfonic acid group as bridge joint group, and obtained polymer has higher Molecular weight and good hydrolytic stability；The present invention is simple, and reaction condition is easy to operate and control, and is suitable for work Industry metaplasia is produced.The proton exchange membrane prepared using the side chain type sulfonated polyimides of invention sulfuryl bridge joint has higher proton Conductivity has potential application prospect.
Application No. is 201710017584.7 patents of invention to disclose a kind of sulfonate polybenzimidazole cross linking membrane and its system Preparation Method.The invention synthesizes the sulfonate polybenzimidazole for having crosslinkable groups amino group on side chain first, is configured to film Liquid is added graphene oxide crosslinking agent, is reacted with amino group, hands over sulfonate polybenzimidazole polymer in film forming procedure Connection.Assign the good mechanical property of cross linking membrane and with higher proton conductivity, hydrolytic stability, antioxidative stabilizer.It should Its preparation process controllability of the described method of invention is good, and more traditional sulfonate polybenzimidazole film is compared, and mechanical strength is high, resists Hydrolysis and oxidability are strong, good stability of the dimension, and proton conductivity is high, have in polymer dielectric film fuel cell wide Application prospect.
Foregoing invention patent is the improvement to fuel battery proton exchange film, but longer due to its branch, leads to it It is larger for the content control dependence of outside moisture, while limiting its use at high temperature.It was found by the inventors of the present invention that The chain structure symmetry higher of short-chain branch film, regularity are more preferable, it is easier to crystallize, the mechanical strength of membrane material also higher is preferably It is used in the environment of high temperature low humidity.Therefore there is highly important practical meaning for the study on the modification of short-chain branch proton exchange membrane Justice.
Invention content
For disadvantages described above, it is special amino modified that first technical problem that the present invention solves is to provide a kind of fuel cell The preparation method of perfluoro sulfonic acid membrane.
The preparation method of the special amino modified perfluoro sulfonic acid membrane of fuel cell of the present invention, includes the following steps：
A, the sulfonation of tetrafluoroethene：Sulfuric acid is added in closed container, vacuumizes, make its pressure be 10Pa hereinafter, then passing to Tetrafluoroethene, and heat and reacted, reaction temperature is 600~800 DEG C, and pressure is that 3~6MPa is obtained after reacting 10~20h COFCF2SO2F；
B, the fluorination of 3- amino propylene：Under conditions of starvation, 3- amino propylene is fluorinated, is obtained CF2CFCF2NF2；Fluorination fluorination reagent used is fluoro-gas, in the fluoro-gas fluorine gas percent by volume be 50% with On；
C, condensation reaction：By the COFCF of a steps2SO2The CF of F and b step2CFCF2NF2It is placed in closed container, in high temperature height Pressure carries out 10~15h of reaction, so that two sulfonic branched carbon atoms is grafted on backbone nitrogen atom, obtains modified monomer； The temperature of the high temperature and pressure is 400~600 DEG C, and pressure is 1~3MPa；
D, polycondensation reaction：Initiator is added in the modified monomer of step c, polycondensation reaction is carried out at 200~400 DEG C, is formed High molecular polymer；Wherein, the addition of initiator is the 0.5~2% of modified monomer weight；
E, it is acidified：The high molecular polymer of Step d is placed in acid, after impregnating 5~10h under room temperature, is taken out, dry, film forming obtains To the special amino modified perfluoro sulfonic acid membrane of fuel cell.
The present invention combines double short sulfonic group branches by N atoms, is graft-polymerized onto main chain, improves sulfonic group content and its Structural symmetry keeps its membrane material structure in swelling process more stable, makes that ion cluster is more readily formed inside membrane material, to carry Its high proton adsorption and transfer ability.
Wherein, a steps are the sulfonation of tetrafluoroethene, and used sulfonated reagent is sulfuric acid, at high temperature under high pressure, tetrafluoro second Alkene is reacted with sulfuric acid, obtains the tetrafluoroethene after sulfonation, i.e. COFCF2SO2F。
Tetrafluoroethene, also known as perfluoroethylene, the product after being replaced by whole fluorine atoms for the hydrogen in ethylene molecule.Under room temperature For the gas of no color or smell, -76.3 DEG C of boiling point；Can be pressurized liquefied, 33.3 DEG C of critical-temperature, critical pressure 3.92MPa.The present invention It uses tetrafluoroethene for raw material, by high temperature and pressure sulfonating reaction, obtains containing sulfonic product COFCF2SO2F。
In the reaction, reaction temperature and pressure and reaction time are crucial, and inventor has found, temperature be 600~ 800 DEG C, pressure is 3~6MPa, and the reaction time can be by the complete sulfonation of tetrafluoroethene when being 10~20h.In order to improve sulfonation effect Fruit and sulfonation efficiency, it is preferred that reaction temperature is 700 DEG C, pressure 5MPa, reaction time 18h.
B step is the fluorination of 3- amino propylene.It uses fluoro-gas to be fluorinated for fluorination reagent, obtains the 3- of perfluoro Amino propylene, i.e. CF2CFCF2NF2.Fluorinated method is the state of the art, and this will not be repeated here.
3- amino propylene is a kind of chemical name, and allyl amine content 99% is limpid light yellow liquid, the product In oxygen, easily burn.It is toxic, there is corrosivity.Therefore, for the safety for being smoothed out and reacting of reaction, fluorine Change reaction to need to carry out under conditions of starvation.
Theoretically, as long as the gas containing fluorine gas can be used as fluorination reagent to carry out fluorination reaction, such as pure fluorine gas, Mixed gas, fluorine gas and the neon of the mixed gas of fluorine gas and carbon dioxide, the mixed gas of fluorine gas and nitrogen, fluorine gas and argon gas Mixed gas etc., in order to cost-effective, it is preferred that fluorination reagent is the mixed gas of fluorine gas and nitrogen.
The volume ratio of fluorine gas and nitrogen will influence fluorinated effect to fluorination.In mixed gas, fluorine gas is very few, and reaction is not It completely, can not accomplish perfluorinated, and fluorine gas is excessive, it will causes the waste of raw material, while can also influence fluorine to a certain extent Change effect.Therefore, in order to reach good fluorination effect, it is preferred that the volume ratio of fluorine gas and nitrogen is 1~4:1.As preferred The volume ratio of scheme, fluorine gas and nitrogen is 2:1.
The proportioning of 3- amino propylene and fluorine gas will generate fluorination reaction certain influence, it is preferred that the 3- amino The molar ratio of propylene and fluorine gas is 1：5~10；The molar ratio of more preferable 3- amino propylene and fluorine gas is 1：7.
In the present invention, a steps and b step do not have time sequencing, can first carry out a steps, obtain the tetrafluoro after sulfonation Ethylene, then b step is carried out, obtain the 3- amino propylene of perfluoro；B step can also be first carried out, the 3- amino of perfluoro is obtained Propylene, then a steps are carried out, obtain the tetrafluoroethene after sulfonation；It can be carried out at the same time with a, b step.
Step c is condensation reaction, by the COFCF of a steps2SO2The CF of F and b step2CFCF2NF2It is placed in closed container, Reaction 10~15h, two COFCF are carried out at high temperature under high pressure2SO2Sulfonic branched carbon atoms in F are grafted to CF2CFCF2NF2Nitrogen-atoms on, obtain modified monomer.
Reaction in step c, temperature and pressure are main influence factor.Preferably, the high temperature and pressure is 500 DEG C of temperature, pressure 2MPa.
Initiator is mainly added in Step d, causes monomer and carries out polymerisation, obtains high molecular polymer.
Wherein, initiator is the key that polymerisation occurs, initiator, also known as radical initiator, for it is a kind of be easy by It is thermally decomposed into free radical（That is primary group of free radicals）Compound, can be used for cause alkenes, double vinyl monomers free radical polymerization and Copolymerization, it can also be used to which the crosslinking curing and high molecular crosslink of unsaturated polyester (UP) react.The present invention is drawn using initiator It sends out vinyl monomer and carries out polycondensation reaction, common initiator is suitable for the present invention.For example, benzoyl peroxide, the peroxidating moon The acyls class peroxide such as osmanthus acyl, the dialkyl peroxides such as di-t-butyl peroxide, cumyl peroxide, peroxidating first and second The esters mistakes such as the ketones such as ketone, cyclohexanone peroxide peroxide, peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid tertiary butyl ester The azo-initiators such as oxide, azodiisobutyronitrile, azobisisoheptonitrile.Preferably, the initiator is benzoyl peroxide first Acyl or azobisisoheptonitrile.
The addition of initiator has a certain impact to polymerisation.Preferably, the addition of initiator is modified monomer The 0.5~2% of weight.The addition of initiator is very few, and polymerisation is incomplete, it will leads to the molecular weight of high molecular polymer It is not high, it could even be possible to cause reaction incomplete, also remaining a large amount of modified monomer after reaction.And addition is excessive, having can Reaction early period can be caused violent, to generate security risk.The present inventor show that initiator adds by a large number of experiments It is 0.5~2% being advisable for modified monomer weight to enter amount.
Step e is the process of acidification, and the high molecular polymer of Step d is placed in acid, is impregnated under room temperature i.e. acidificable.This I.e. under room temperature, without heating or freezing, temperature can be with Changes in weather, it is only necessary to ensure that temperature is for the invention room temperature 5~35 DEG C.
Step e, which needs polymer being immersed in acid, to be acidified, and is not required particularly acid used, in order to save Cost, preferably common inorganic acid or organic acid.Preferably, the acid is sulfuric acid, hydrochloric acid or acetic acid.
Preferably, the time of immersion is 8h.
It is taken out after immersion, conventional method may be used and be dried, such as the drying of direct normal-temperature vacuum.It is dry Afterwards, existing method film forming, such as fusion drawn or the tape casting film forming may be used.
Second technical problem that the present invention solves is to provide a kind of amino modified perfluoro sulfonic acid membrane.
Amino modified perfluoro sulfonic acid membrane of the present invention, using the above-mentioned special amino modified perfluorinated sulfonic acid of fuel cell The preparation method of film is prepared.The amino modified perfluoro sulfonic acid membrane is short-chain branch proton exchange membrane, and chain structure symmetry is high, rule Whole property is good, is easy crystallization, and the mechanical strength of membrane material is preferable, suitable for being used in the environment of high temperature low humidity.
Compared with prior art, the present invention has the advantages that：
The preparation method of the special amino modified perfluoro sulfonic acid membrane of fuel cell of the present invention combines double short sulfonic groups by N atoms Branch is graft-polymerized onto main chain, improves sulfonic group content and its structural symmetry, make its membrane material knot in swelling process Structure is more stable, and ion cluster is more readily formed inside membrane material, to improve its proton adsorption and transfer ability.This method technique letter Single, feasibility is high.Thus the amino modified perfluoro sulfonic acid membrane being prepared, structural symmetry is high, and regularity is good, is easy crystallization, The mechanical strength of membrane material is preferable, and proton conductivity is high, suitable for being used in the environment of high temperature low humidity.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The special amino modified perfluoro sulfonic acid membrane of fuel cell is prepared with the following method：
A, the sulfonation of tetrafluoroethene：Sulfuric acid is added in closed container, vacuumizes, make its pressure be 10Pa hereinafter, then passing to Tetrafluoroethene, and heat and reacted, reaction temperature is 600 DEG C, pressure 3MPa, after reacting 20h, obtains COFCF2SO2F；
B, the fluorination of 3- amino propylene：Under conditions of starvation, 3- amino propylene is fluorinated, is obtained CF2CFCF2NF2；Fluorination fluorination reagent used is the mixed gas of fluorine gas and nitrogen, fluorine gas volume hundred in the mixed gas Divide than being 30% or more；And the molar ratio of 3- amino propylene and fluorine gas is 1：10；
C, condensation reaction：By the COFCF of a steps2SO2The CF of F and b step2CFCF2NF2It is placed in closed container, in high temperature height Pressure carries out reaction 10h, obtains modified monomer；The high temperature and pressure is 600 DEG C of temperature, pressure 3MPa；
D, polycondensation reaction：Initiator benzoyl peroxide is added in the modified monomer of step c, it is anti-that polycondensation is carried out at 400 DEG C It answers, forms high molecular polymer；Wherein, the addition of initiator benzoyl peroxide is the 0.5% of modified monomer weight；
E, it is acidified：The high molecular polymer of Step d is placed in acetic acid, after impregnating 5h under room temperature, is taken out, dry, film forming obtains The special amino modified perfluoro sulfonic acid membrane of fuel cell.
In humidity 100%, temperature is respectively to detect the fuel cell special ammonia under conditions of 25 DEG C, 40 DEG C, 60 DEG C, 80 DEG C Base is modified the proton conductivity of perfluoro sulfonic acid membrane.It is examined under the conditions of dry state, temperature are respectively 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C Survey the proton conductivity of the special amino modified perfluoro sulfonic acid membrane of the fuel cell.Testing result is as shown in table 1.Specific assay method It is as follows：It is measured using CHI650 type electrochemical workstations.Test condition：Using two-probe method, range of scanned frequencies 1Hz To 100kHz；Amplitude is 10mV.The conductivity of film is calculated by the following formula to obtain：
σ=l/ (RA)
σ is the conductivity of film in formula（S/cm）, l is the thickness of film（cm）, R is the impedance value measured（Ω）, A is the significant surface of film Product（cm2）, its value is 0.2826cm in the present embodiment2。
Embodiment 2
The special amino modified perfluoro sulfonic acid membrane of fuel cell is prepared with the following method：
A, the sulfonation of tetrafluoroethene：Sulfuric acid is added in closed container, vacuumizes, make its pressure be 10Pa hereinafter, then passing to Tetrafluoroethene, and heat and reacted, reaction temperature is 800 DEG C, pressure 6MPa, after reacting 10h, obtains COFCF2SO2F；
B, the fluorination of 3- amino propylene：Under conditions of starvation, 3- amino propylene is fluorinated, is obtained CF2CFCF2NF2；Fluorination fluorination reagent used is the mixed gas of fluorine gas and nitrogen, fluorine gas and nitrogen in the mixed gas Volume ratio be 1:1；And the molar ratio of 3- amino propylene and fluorine gas is 1：5；
C, condensation reaction：By the COFCF of a steps2SO2The CF of F and b step2CFCF2NF2It is placed in closed container, in high temperature height Pressure carries out reaction 15h, obtains modified monomer；The high temperature and pressure is 400 DEG C of temperature, pressure 1MPa；
D, polycondensation reaction：Initiator benzoyl peroxide is added in the modified monomer of step c, it is anti-that polycondensation is carried out at 200 DEG C It answers, forms high molecular polymer；Wherein, the addition of initiator benzoyl peroxide is the 2% of modified monomer weight；
E, it is acidified：The high molecular polymer of Step d is placed in acetic acid, after impregnating 10h under room temperature, is taken out, dry, film forming obtains To the special amino modified perfluoro sulfonic acid membrane of fuel cell.
In humidity 100%, temperature is respectively to detect the fuel cell special ammonia under conditions of 25 DEG C, 40 DEG C, 60 DEG C, 80 DEG C Base is modified the proton conductivity of perfluoro sulfonic acid membrane.It is examined under the conditions of dry state, temperature are respectively 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C Survey the proton conductivity of the special amino modified perfluoro sulfonic acid membrane of the fuel cell.Testing result is as shown in table 1.Specific assay method With reference to embodiment 1.
Embodiment 3
The special amino modified perfluoro sulfonic acid membrane of fuel cell is prepared with the following method：
A, the sulfonation of tetrafluoroethene：Sulfuric acid is added in closed container, vacuumizes, make its pressure be 10Pa hereinafter, then passing to Tetrafluoroethene, and heat and reacted, reaction temperature is 700 DEG C, pressure 4MPa, after reacting 12h, obtains COFCF2SO2F；
B, the fluorination of 3- amino propylene：Under conditions of starvation, 3- amino propylene is fluorinated, is obtained CF2CFCF2NF2；Fluorination fluorination reagent used is the mixed gas of fluorine gas and nitrogen, fluorine gas and nitrogen in the mixed gas Volume ratio be 2.5:1；And the molar ratio of 3- amino propylene and fluorine gas is 1：9；
C, condensation reaction：By the COFCF of a steps2SO2The CF of F and b step2CFCF2NF2It is placed in closed container, in high temperature height Pressure carries out reaction 12h, obtains modified monomer；The high temperature and pressure is 450 DEG C of temperature, pressure 2MPa；
D, polycondensation reaction：Initiator benzoyl peroxide is added in the modified monomer of step c, it is anti-that polycondensation is carried out at 280 DEG C It answers, forms high molecular polymer；Wherein, the addition of initiator benzoyl peroxide is the 1.5% of modified monomer weight；
E, it is acidified：The high molecular polymer of Step d is placed in acetic acid, after impregnating 9h under room temperature, is taken out, dry, film forming obtains The special amino modified perfluoro sulfonic acid membrane of fuel cell.
In humidity 100%, temperature is respectively to detect the fuel cell special ammonia under conditions of 25 DEG C, 40 DEG C, 60 DEG C, 80 DEG C Base is modified the proton conductivity of perfluoro sulfonic acid membrane.It is examined under the conditions of dry state, temperature are respectively 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C Survey the proton conductivity of the special amino modified perfluoro sulfonic acid membrane of the fuel cell.Testing result is as shown in table 1.Specific assay method With reference to embodiment 1.
Embodiment 4
The special amino modified perfluoro sulfonic acid membrane of fuel cell is prepared with the following method：
A, the sulfonation of tetrafluoroethene：Sulfuric acid is added in closed container, vacuumizes, make its pressure be 10Pa hereinafter, then passing to Tetrafluoroethene, and heat and reacted, reaction temperature is 680 DEG C, pressure 5MPa, after reacting 15h, obtains COFCF2SO2F；
B, the fluorination of 3- amino propylene：Under conditions of starvation, 3- amino propylene is fluorinated, is obtained CF2CFCF2NF2；Fluorination fluorination reagent used is the mixed gas of fluorine gas and nitrogen, fluorine gas and nitrogen in the mixed gas Volume ratio be 2:1；And the molar ratio of 3- amino propylene and fluorine gas is 1：8；
C, condensation reaction：By the COFCF of a steps2SO2The CF of F and b step2CFCF2NF2It is placed in closed container, in high temperature height Pressure carries out reaction 13h, obtains modified monomer；The high temperature and pressure is 550 DEG C of temperature, pressure 2.5MPa；
D, polycondensation reaction：Initiator azobisisoheptonitrile is added in the modified monomer of step c, it is anti-that polycondensation is carried out at 350 DEG C It answers, forms high molecular polymer；Wherein, the addition of initiator azobisisoheptonitrile is the 1% of modified monomer weight；
E, it is acidified：The high molecular polymer of Step d is placed in acetic acid, after impregnating 7h under room temperature, is taken out, dry, film forming obtains The special amino modified perfluoro sulfonic acid membrane of fuel cell.
In humidity 100%, temperature is respectively to detect the fuel cell special ammonia under conditions of 25 DEG C, 40 DEG C, 60 DEG C, 80 DEG C Base is modified the proton conductivity of perfluoro sulfonic acid membrane.It is examined under the conditions of dry state, temperature are respectively 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C Survey the proton conductivity of the special amino modified perfluoro sulfonic acid membrane of the fuel cell.Testing result is as shown in table 1.Specific assay method With reference to embodiment 1.
Embodiment 5
The special amino modified perfluoro sulfonic acid membrane of fuel cell is prepared with the following method：
A, the sulfonation of tetrafluoroethene：Sulfuric acid is added in closed container, vacuumizes, make its pressure be 10Pa hereinafter, then passing to Tetrafluoroethene, and heat and reacted, reaction temperature is 730 DEG C, pressure 5MPa, after reacting 14h, obtains COFCF2SO2F；
B, the fluorination of 3- amino propylene：Under conditions of starvation, 3- amino propylene is fluorinated, is obtained CF2CFCF2NF2；Fluorination fluorination reagent used is the mixed gas of fluorine gas and nitrogen, fluorine gas and nitrogen in the mixed gas Volume ratio be 3:1；And the molar ratio of 3- amino propylene and fluorine gas is 1：6；
C, condensation reaction：By the COFCF of a steps2SO2The CF of F and b step2CFCF2NF2It is placed in closed container, in high temperature height Pressure carries out reaction 11h, obtains modified monomer；The high temperature and pressure is 500 DEG C of temperature, pressure 1.5MPa；
D, polycondensation reaction：Initiator azobisisoheptonitrile is added in the modified monomer of step c, it is anti-that polycondensation is carried out at 250 DEG C It answers, forms high molecular polymer；Wherein, the addition of initiator azobisisoheptonitrile is the 1.5% of modified monomer weight；
E, it is acidified：The high molecular polymer of Step d is placed in acetic acid, after impregnating 6h under room temperature, is taken out, dry, film forming obtains The special amino modified perfluoro sulfonic acid membrane of fuel cell.
In humidity 100%, temperature is respectively to detect the fuel cell special ammonia under conditions of 25 DEG C, 40 DEG C, 60 DEG C, 80 DEG C Base is modified the proton conductivity of perfluoro sulfonic acid membrane.It is examined under the conditions of dry state, temperature are respectively 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C Survey the proton conductivity of the special amino modified perfluoro sulfonic acid membrane of the fuel cell.Testing result is as shown in table 1.Specific assay method With reference to embodiment 1.
Embodiment 6
The special amino modified perfluoro sulfonic acid membrane of fuel cell is prepared with the following method：
A, the sulfonation of tetrafluoroethene：Sulfuric acid is added in closed container, vacuumizes, make its pressure be 10Pa hereinafter, then passing to Tetrafluoroethene, and heat and reacted, reaction temperature is 700 DEG C, pressure 5MPa, after reacting 18h, obtains COFCF2SO2F；
B, the fluorination of 3- amino propylene：Under conditions of starvation, 3- amino propylene is fluorinated, is obtained CF2CFCF2NF2；Fluorination fluorination reagent used is the mixed gas of fluorine gas and nitrogen, fluorine gas and nitrogen in the mixed gas Volume ratio be 2:1；And the molar ratio of 3- amino propylene and fluorine gas is 1：7；
C, condensation reaction：By the COFCF of a steps2SO2The CF of F and b step2CFCF2NF2It is placed in closed container, in high temperature height Pressure carries out reaction 14h, obtains modified monomer；The high temperature and pressure is 500 DEG C of temperature, pressure 2MPa；
D, polycondensation reaction：Initiator azobisisoheptonitrile is added in the modified monomer of step c, it is anti-that polycondensation is carried out at 300 DEG C It answers, forms high molecular polymer；Wherein, the addition of initiator azobisisoheptonitrile is the 1% of modified monomer weight；
E, it is acidified：The high molecular polymer of Step d is placed in acetic acid, after impregnating 8h under room temperature, is taken out, dry, film forming obtains The special amino modified perfluoro sulfonic acid membrane of fuel cell.
In humidity 100%, temperature is respectively to detect the fuel cell special ammonia under conditions of 25 DEG C, 40 DEG C, 60 DEG C, 80 DEG C Base is modified the proton conductivity of perfluoro sulfonic acid membrane.It is examined under the conditions of dry state, temperature are respectively 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C Survey the proton conductivity of the special amino modified perfluoro sulfonic acid membrane of the fuel cell.Testing result is as shown in table 1.Specific assay method With reference to embodiment 1.
Comparative example 1
Using commercially available Nafion membrane, in humidity 100%, temperature is respectively to detect under conditions of 25 DEG C, 40 DEG C, 60 DEG C, 80 DEG C The proton conductivity of the film.The proton of the film is detected under the conditions of dry state, temperature are respectively 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C Conductivity.Testing result is as shown in table 1.Specific assay method is with reference to embodiment 1.
Table 1

Claims (10)

1. a kind of preparation method of the special amino modified perfluoro sulfonic acid membrane of fuel cell, which is characterized in that include the following steps：
A, the sulfonation of tetrafluoroethene：Sulfuric acid is added in closed container, vacuumizes, make its pressure be 10Pa hereinafter, then passing to Tetrafluoroethene, and heat and reacted, reaction temperature is 600~800 DEG C, and pressure is that 3~6MPa is obtained after reacting 10~20h COFCF2SO2F；
B, the fluorination of 3- amino propylene：Under conditions of starvation, 3- amino propylene is fluorinated, is obtained CF2CFCF2NF2；Fluorination fluorination reagent used is fluoro-gas, in the fluoro-gas fluorine gas percent by volume be 30% with On；
C, condensation reaction：By the COFCF of a steps2SO2The CF of F and b step2CFCF2NF2It is placed in closed container, in high temperature and pressure Under carry out 10~15h of reaction, obtain modified monomer；The temperature of the high temperature and pressure is 400~600 DEG C, and pressure is 1~3MPa；
D, polycondensation reaction：Initiator is added in the modified monomer of step c, polycondensation reaction is carried out at 200~400 DEG C, is formed High molecular polymer；Wherein, the addition of initiator is the 0.5~2% of modified monomer weight；
E, it is acidified：The high molecular polymer of Step d is placed in acid, after impregnating 5~10h under room temperature, is taken out, dry, film forming obtains To the special amino modified perfluoro sulfonic acid membrane of fuel cell.
2. the preparation method of the special amino modified perfluoro sulfonic acid membrane of fuel cell according to claim 1, it is characterised in that： In a steps, reaction temperature is 700 DEG C, pressure 5MPa, reaction time 18h.
3. the preparation method of the special amino modified perfluoro sulfonic acid membrane of fuel cell according to claim 1, it is characterised in that： In b step, fluorination reagent is the mixed gas of fluorine gas and nitrogen.
4. the preparation method of the special amino modified perfluoro sulfonic acid membrane of fuel cell according to claim 3, it is characterised in that： In b step, the volume ratio of fluorine gas and nitrogen is 1~4:1.
5. the preparation method of the special amino modified perfluoro sulfonic acid membrane of fuel cell according to claim 1, it is characterised in that： In b step, the molar ratio of 3- amino propylene and fluorine gas is 1：5~10.
6. the preparation method of the special amino modified perfluoro sulfonic acid membrane of fuel cell according to claim 1, it is characterised in that： In step c, the high temperature and pressure is 500 DEG C of temperature, pressure 2MPa.
7. the preparation method of the special amino modified perfluoro sulfonic acid membrane of fuel cell according to claim 1, it is characterised in that： In Step d, the initiator is benzoyl peroxide or azobisisoheptonitrile.
8. the preparation method of the special amino modified perfluoro sulfonic acid membrane of fuel cell according to claim 1, it is characterised in that： In step e, the acid is sulfuric acid, hydrochloric acid or acetic acid.
9. the preparation method of the special amino modified perfluoro sulfonic acid membrane of fuel cell according to claim 1, it is characterised in that： In step e, the time of immersion is 8h.
10. the preparation method of the special amino modified perfluoro sulfonic acid membrane of claim 1~9 any one of them fuel cell is prepared into The amino modified perfluoro sulfonic acid membrane arrived.
CN201810121808.3A 2018-02-07 2018-02-07 A kind of special amino modified perfluoro sulfonic acid membrane of fuel cell and preparation method Withdrawn CN108365241A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110336052A (en) * 2019-06-25 2019-10-15 大连理工大学 A kind of mixed-matrix type cation-exchange membrane and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110336052A (en) * 2019-06-25 2019-10-15 大连理工大学 A kind of mixed-matrix type cation-exchange membrane and preparation method thereof
CN110336052B (en) * 2019-06-25 2022-04-12 大连理工大学 Mixed matrix type cation exchange membrane and preparation method thereof

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