CN108123154A - A kind of fuel cell pyridines compound proton exchange membrane and preparation method - Google Patents
A kind of fuel cell pyridines compound proton exchange membrane and preparation method Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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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
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- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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Abstract
The invention belongs to field of fuel cell technology, fuel cell of the present invention is by anhydrous pyridine, halogenated alkane, in ice-water bath with pyridines compound proton exchange membrane, add in sulfonated reagent, by complex reaction, sulfonation pyridine is generated, is process afterwards with proton exchange membrane basal lamina material by rolling process.Fuel cell prepared by the present invention is high with the chemical stability of pyridines compound proton exchange membrane, it can work in 100 DEG C or more of environment, proton exchange membrane rate of ageing is slow so that battery is to appoint so to have good proton conductivity and water conservation rate working at high temperature；Fuel cell pyridines compound proton exchange membrane of the present invention is by making pyridines sulfonating polymers polycondensation, using nitrogen heterocycle perssad proton transport medium is served as instead of hydrone, not only increase the operating temperature of proton exchange membrane, anti-aging property under its high temperature can also be improved simultaneously, it is compound eventually by being carried out with proton exchange membrane basement membranes such as polyethylene, it prevents proton exchange basement membrane from hydrolyzing, adds the mechanical property of basement membrane, improve the service life of proton exchange membrane.
Description
Technical field
The invention belongs to field of fuel cell technology, and in particular to a kind of preparation method of compound proton exchange membrane, especially
It is to be related to a kind of fuel cell pyridines compound proton exchange membrane and preparation method.
Background technology
Proton exchange membrane (Proton Exchange Membrane Fuel, PEM) is the core component of PEMFC, PEM with
The membrane used in general electrochmical power source is had any different.Proton Exchange Membrane Fuel Cells has become gasoline engine power and has most competed
The clean substitution power source of power.Material as PEM should meet the following conditions：Good proton conductivity, hydrone are in film
In electro-osmotic effects it is small, permeability that gas is in film is as small as possible, electrochemical stability is good, dry and wet conversion performance is good, tool
Have that certain mechanical strength, machinability are good, price is appropriate.
Proton Exchange Membrane Fuel Cells has operating temperature is low, startup is fast, specific power is high, simple in structure, easy to operate etc.
Advantage is acknowledged as the preferred energy at electric vehicle, stationary power generation station etc..In fuel battery inside, proton exchange membrane is proton
Migration and conveying passage is provided so that proton reaches cathode by film from anode, and circuit is formed with the transfer of the electronics of external circuit,
Electric current is outwardly provided, therefore the performance of proton exchange membrane plays very important effect to the performance of fuel cell, it good
The bad service life for directly affecting battery.
The operating temperature of fuel cell is generally below 80 DEG C at present, and the operating temperature for improving fuel cell is to simplify electricity
One of effective measures of water heat management system and solution catalyst poisoning；Battery negative and positive the two poles of the earth can also be improved simultaneously, especially
It is the dynamics of the redox reactions of cathode, and then improves the work efficiency of battery.
But temperature is when raising, in film the evaporation of moisture can cause the drastically decline of nephew's conductive performance, it is and easy under high temperature
Recurring structure changes and chemical degradation, the mechanical performance of film also decrease.
Chinese invention patent application number 201310432731.9 discloses a kind of nano yttrium oxide and pyridine ion liquid two
First doping vario-property Sulfonated Polyphenylene Sulfide proton exchange membrane and preparation method thereof.The present invention relates to a kind of nano yttrium oxide and pyridines
Binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of ionic liquid and preparation method thereof.The composition and matter of the proton exchange membrane
Measuring percentage is：Sulfonation degree is 57%~90% Sulfonated Polyphenylene Sulfide：80%~99%；Nano yttrium oxide and pyridine ion liquid group
Into binary doped phase:1%~20%, wherein nano yttrium oxide and pyridine ion liquid molar ratio are 1:(1~4).The present invention uses
The SPPS of medium sulfonation degree is as basis material, to overcome highly sulfonated SPPS excessively high there are water absorption rate, compound membrane stability
The shortcomings that poor, and ensure that composite membrane has certain water absorption rate；Pass through nano-scale rare earth metal oxide yttrium and pyridine
The binary doped mode of ionic liquid makes SPPS matrixes that soda acid use directly occur with the dopant material, to improve composite membrane
Comprehensive performance.
Chinese invention patent application number 201110185147.9 discloses a kind of silsesquioxane hydridization sulfonated polyimide
Sulfonated diamine monomer and non-sulfonated diamine monomer are added in dianhydride and catalyst form reactant by the preparation method of proton exchange membrane
System obtains the sulfonated polyimide solution of the anhydride group containing end；By the sulfonated polyimide solution precipitating into solvent, washing is simultaneously
Drying obtains the sulfonated polyimide of the anhydride group containing end；By the sulfonated polyimide of anhydride group containing end, silsesquioxane and
Catalyst dissolves together, cast, and removing organic solvent obtains the proton exchange membrane of silsesquioxane hydridization.Matter provided by the invention
Proton exchange has larger IEC values, and splendid dimensional stability and water resistance are of low cost, are provided for fuel cell field
A kind of proton exchange membrane for having industrial applicibility.
Chinese invention patent application number 201110340228.1 discloses a kind of poly- pyrrole throat/sulfonated polymer composite proton and hands over
Change membrane material and preparation method and application, disclose a kind of poly- pyrrole throat/sulfonated polymer composite proton exchange membrane material and its
Preparation method.The composite proton exchange membrane material is prepared by method as steps described below：1) under inert atmosphere protection, make
Tetramines aromatic monomer, aromatic dianhydride monomer and catalyst carry out home position polymerization reaction in sulfonate polymer solution, are contained
There is the preparation liquid of poly- pyrrole throat prepolymer；2) preparation liquid is coated on carrier and carries out heat treatment film, film terminates postcooling and takes off
Film makes the transition gained film through acid solution wash, obtains the poly- pyrrole throat/sulfonated polymer composite proton exchange membrane material.This hair
Bright method have the characteristics that each component disperse evenly, operation it is simpler.Prepared composite membrane has good machinery by force
Degree and conductivity, compared to the sulfonated polymer without changing surname, dimensional stability, alcohol-rejecting ability greatly improve, and can be applied to matter
The fields such as proton exchange membrane, ion exchange resin, UF membrane, the sensor of proton exchange film fuel cell.
It can be seen that the existing method being modified to proton exchange membrane is the conductivity for improving proton exchange membrane mostly
With mechanical performance etc., and traditional proton exchange membrane operating temperature is 60~80 DEG C, when operating temperature is excessively high, film wetting
Property reduce, the excessive evaporation of water in film, proton transfer rate decreases, easy aging, and seriously affect fuel cell uses the longevity
Life, in addition also there are the problems such as environmental pollution is serious, film is of high cost and preparation process is complicated for existing perfluoro sulfonic acid membrane.Therefore dropping
Low material cost, so that proton exchange membrane at more than 80 DEG C or more or even 100 DEG C still with higher proton conductivity and good
Good water conservation rate and the durability of 10 years or more anticipate to the development of Proton Exchange Membrane Fuel Cells with important reality
Justice.
The content of the invention
In view of the deficiencies of the prior art, the present invention proposes a kind of at low cost that service life is long, has high temperature resistant, high proton
The fuel cell of electrical conductivity and high-moisture-retention performance pyridines compound proton exchange membrane.
To solve the above problems, the present invention uses following technical scheme：
A kind of fuel cell pyridines compound proton exchange membrane, the fuel cell with pyridines compound proton exchange membrane be by
Anhydrous pyridine, halogenated alkane in ice-water bath, add in sulfonated reagent, by complex reaction, generate sulfonation pyridine, afterwards and matter
Proton exchange basal lamina material is process by rolling process；Wherein, anhydrous pyridine, halogenated alkane, sulfonated reagent and proton exchange
The mass ratio of film basement membrane is：1~10:0.5~3:15~30:100.
Further, above-mentioned a kind of fuel cell pyridines compound proton exchange membrane, wherein the halogenated alkane can be with
Make pyridine that polycondensation reaction occur, it is convenient to carry out complex reaction with proton exchange membrane basement membrane.
Further, above-mentioned a kind of fuel cell pyridines compound proton exchange membrane, wherein the halogenated alkane is bromine
For at least one of alkane, alkane iodide, chloralkane.
Further, above-mentioned a kind of fuel cell pyridines compound proton exchange membrane, wherein the halogenated alkane is excellent
Elect at least one of dichloromethane, carbon tetrachloride as.
Further, a kind of above-mentioned fuel cell pyridines compound proton exchange membrane, which is characterized in that the sulfonation examination
Agent is at least one of sulfur trioxide vapor, oleum, chlorosulfonic acid, chlorosulfuric acid, sulfamic acid.Wherein oleum refers to
There is excessive sulfur trioxide to be present in sulfuric acid, when it is in the air, the SO that evaporates3With the vapor in air
It forms the tiny dew drop of sulfuric acid and smolders, so referred to as oleum.
Technical solution more preferably, fuel cell of the present invention in pyridines compound proton exchange membrane preparation process,
In order to improve reaction efficiency and reactivity, the generation of side reaction is reduced, is steamed wherein the sulfonated reagent is preferably sulfur trioxide
Vapour.
Further, above-mentioned a kind of fuel cell pyridines compound proton exchange membrane, wherein the anhydrous pyridine, halogenated
The mass ratio of alkane, sulfonated reagent and proton exchange membrane basement membrane is 5:2:20:100, chemical reaction rate and reactant yield
It is best.
Further, above-mentioned a kind of fuel cell pyridines compound proton exchange membrane, when adding in sulfonated reagent, also
Add in the mercury of anhydrous pyridine quality 0.5~1%；Correlative study is shown, in pyridine sulfonation process, adds in a small amount of catalyst mercury,
The yield of sulfonation pyridine can be made to improve 20~30%, while accelerate reaction rate.But mercury has severe toxicity, in use
It especially notes that safety, takes corresponding safeguard procedures, recycled in time after use, it is securely held.
Further, above-mentioned a kind of fuel cell pyridines compound proton exchange membrane, wherein the proton exchange membrane base
Film is at least one of copolymer of polyethylene, vinylidene, cross-linked polytetrafluoroethylthrough, ethylene-tetrafluoroethylene；It is preferably poly-
Vinyl film.
The present invention also provides a kind of preparation methods of above-mentioned fuel cell pyridines compound proton exchange membrane.
A kind of above-mentioned fuel cell preparation method of pyridines compound proton exchange membrane, comprises the following steps：
A, the preparation of sulfonation pyridine：Anhydrous pyridine is taken, adds halogenated alkane, in ice-water bath, adds sulfonated reagent, and adds in catalyst
Complex reaction occurs at 40~45 DEG C for mercury, recycles halogenated alkane and catalyst, dry, and sulfonation pyridine is prepared；
B, the sulfonation pyridine for obtaining a steps and proton exchange membrane basement membrane, heat 10~30min, in vacuum at 30~60 DEG C
In drying box be dried in vacuo 2~5h, finally at 130~150 DEG C 5~15min of hot pressing to get.
Fuel cell is a kind of the chemical energy of fuel and oxidant to be directly changed into electric energy by electrochemical reaction mode
Efficient electric installation, energy conversion rate is high, is a kind of environmental-friendly novel energy.
Fuel cell prepared by the present invention is high with the chemical stability of pyridines compound proton exchange membrane, can be in operating temperature
It is worked normally in environment more than 80 DEG C, it might even be possible to it works in 100 DEG C or more of environment, proton exchange membrane rate of ageing
Slowly, will not even aging, fundamentally solve that the aging under 80 DEG C or more working environments of traditional proton exchange membrane is serious etc. to ask
Topic substantially increases the service life of battery so that battery is to appoint so there is good proton conductivity and water to protect working at high temperature
Holdup；Fuel cell pyridines compound proton exchange membrane of the present invention utilizes azepine by making pyridines sulfonating polymers polycondensation
Cyclic group serves as proton transport medium instead of hydrone, not only increases the operating temperature of proton exchange membrane, while can also carry
Anti-aging property under its high high temperature, it is compound eventually by being carried out with proton exchange membrane basement membranes such as polyethylene, prevent proton exchange base
Film water solution substantially increases the efficiency of battery, adds the mechanical property of basement membrane, improves the service life of proton exchange membrane.
Specific embodiment
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
Scope be only limitted to following example.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
Fuel cell prepared by the present invention is as follows with pyridines compound proton exchange membrane step：
Mass ratio according to anhydrous pyridine, dichloromethane, sulfonated reagent and proton exchange membrane basement membrane is：5:2:20:100；
A, the preparation of sulfonation pyridine：Anhydrous pyridine is taken, is added methylene chloride, in ice-water bath, adds sulfonated reagent, and adds in catalyst
Complex reaction occurs at 40 DEG C for mercury, recycles dichloromethane and catalyst, dry, and sulfonation pyridine is prepared；Wherein, it is described
Sulfonated reagent is sulfur trioxide vapor；The addition of catalyst mercury is anhydrous pyridine quality 0.5%, after the completion of reaction, in time by mercury
It recycles and securely held, is adding in reaction process, carrying out security protection；
B, the sulfonation pyridine for obtaining a steps and proton exchange membrane basement membrane, heat 20min, in vacuum drying chamber at 50 DEG C
Be dried in vacuo 3h, finally at 140 DEG C hot pressing 10min to get.Wherein proton exchange membrane basement membrane is polyethylene film.
The thickness of above-mentioned fuel cell pyridines compound proton exchange membrane is 10~30 μm；Highest under normal work is resistance to
It is shown in Table 1 by temperature, moisture content, tensile strength, water resistant swellbility, electrical conductivity test result.
Wherein, water absorption rate test：A block film piece is sheared, record weight is m1, is then immersed in 48h in distilled water, is taken out
After dry surface moisture, be weighed as m2, obtain water absorption rate=（m2-m1）/m1；
Water resistant swelling test：A block film piece is sheared, is immersed in 60h in 60 DEG C of water, dries surface moisture, weight in wet base m3 is weighed, will try
Drying to constant weight at 90 DEG C for sample, weigh dry weight for m4. calculate sample swellbility=（m3-m4）/m4×100%；
Electrical conductivity（σ）It measures：Proton conductivity（σ）It is using four probe electrochemical impedance instrument, frequency 100Hz to 100KHz's
Under the conditions of measure, an ionic membrane and two pairs of black coating platinum electrodes are mounted in polytetrafluoroethylene (PTFE) battery, battery is in cocurrent mode
Lower carry out dry gas（From humidification）Electrical conductivity is tested.Electrical conductivity can be calculated by following formula：σ=D/（LBR）.Wherein, D is
The distance between two electrodes, L and B are respectively the thickness and width of proton exchange membrane, and R is the impedance value measured.At 40 DEG C
High purity water in test when, it is necessary to be calculated using the size of the film under abundant water suction state.
Embodiment 2
Fuel cell prepared by the present invention is as follows with pyridines compound proton exchange membrane step：
Mass ratio according to anhydrous pyridine, dichloromethane, sulfonated reagent and proton exchange membrane basement membrane is：10:1:15:100；
A, the preparation of sulfonation pyridine：Anhydrous pyridine is taken, is added methylene chloride, in ice-water bath, adds sulfonated reagent, and adds in catalyst
Complex reaction occurs at 45 DEG C for mercury, recycles dichloromethane and catalyst, dry, and sulfonation pyridine is prepared；The sulfonation examination
Agent is sulfur trioxide vapor；The addition of catalyst mercury is anhydrous pyridine quality 0.8%, after the completion of reaction, in time by mercury recycling simultaneously
It is securely held, it is adding in reaction process, is carrying out security protection；
B, the sulfonation pyridine for obtaining a steps and proton exchange membrane basement membrane, heat 10min, in vacuum drying chamber at 60 DEG C
Be dried in vacuo 5h, finally at 130 DEG C hot pressing 15min to get.Wherein proton exchange membrane basement membrane is polyethylene.
The thickness of above-mentioned fuel cell pyridines compound proton exchange membrane is 10~30 μm；Highest under normal work is resistance to
It is shown in Table 1 by temperature, moisture content, tensile strength, water resistant swellbility, electrical conductivity test result.
Wherein, water absorption rate test, water resistant swelling test and electrical conductivity（σ）It measures with embodiment 1.
Embodiment 3
Fuel cell prepared by the present invention is as follows with pyridines compound proton exchange membrane step：
Mass ratio according to anhydrous pyridine, diiodomethane, sulfonated reagent and proton exchange membrane basement membrane is：1:3:20:100；
A, the preparation of sulfonation pyridine：Anhydrous pyridine is taken, adds diiodomethane, in ice-water bath, adds sulfonated reagent, and adds in catalyst
Complex reaction occurs at 45 DEG C for mercury, recycles diiodomethane and catalyst, dry, and sulfonation pyridine is prepared；The sulfonation examination
Agent is oleum；The addition of catalyst mercury be anhydrous pyridine quality 0.8%, after the completion of reaction, in time by mercury recycle and it is safe
It preserves, is adding in reaction process, carrying out security protection；
B, the sulfonation pyridine for obtaining a steps and proton exchange membrane basement membrane, heat 20min, in vacuum drying chamber at 60 DEG C
Be dried in vacuo 4h, finally at 150 DEG C hot pressing 5min to get.Wherein proton exchange membrane basement membrane is vinylidene.
The thickness of above-mentioned fuel cell pyridines compound proton exchange membrane is 10~30 μm；Highest under normal work is resistance to
It is shown in Table 1 by temperature, moisture content, tensile strength, water resistant swellbility, electrical conductivity test result.
Wherein, water absorption rate test, water resistant swelling test and electrical conductivity（σ）It measures with embodiment 1.
Embodiment 4
Fuel cell prepared by the present invention is as follows with pyridines compound proton exchange membrane step：
Mass ratio according to anhydrous pyridine, carbon tetrachloride, sulfonated reagent and proton exchange membrane basement membrane is：5:2.5:20:100；
A, the preparation of sulfonation pyridine：Anhydrous pyridine is taken, adds carbon tetrachloride, in ice-water bath, adds sulfonated reagent, and adds in catalyst
Complex reaction occurs at 42 DEG C for mercury, recycles carbon tetrachloride and catalyst, dry, and sulfonation pyridine is prepared；The sulfonation examination
Agent is sulfur trioxide vapor；The addition of catalyst mercury is anhydrous pyridine quality 1%, after the completion of reaction, mercury is recycled and pacified in time
All risk insurance is deposited, and is being added in reaction process, is being carried out security protection；
B, the sulfonation pyridine for obtaining a steps and proton exchange membrane basement membrane, heat 15min, in vacuum drying chamber at 50 DEG C
Be dried in vacuo 4h, finally at 140 DEG C hot pressing 15min to get.Wherein proton exchange membrane basement membrane is cross-linked polytetrafluoroethylthrough.
The thickness of above-mentioned fuel cell pyridines compound proton exchange membrane is 10~30 μm；Highest under normal work is resistance to
It is shown in Table 1 by temperature, moisture content, tensile strength, water resistant swellbility, electrical conductivity test result.
Wherein, water absorption rate test, water resistant swelling test and electrical conductivity（σ）It measures with embodiment 1.
Embodiment 5
Fuel cell prepared by the present invention is as follows with pyridines compound proton exchange membrane step：
Mass ratio according to anhydrous pyridine, methylene bromide, sulfonated reagent and proton exchange membrane basement membrane is：6:2:25:100；
A, the preparation of sulfonation pyridine：Anhydrous pyridine is taken, adds methylene bromide, in ice-water bath, adds sulfonated reagent, and adds in catalyst
Complex reaction occurs at 45 DEG C for mercury, recycles methylene bromide and catalyst, dry, and sulfonation pyridine is prepared；The sulfonation examination
Agent is sulfur trioxide vapor；The addition of catalyst mercury is anhydrous pyridine quality 0.6%, after the completion of reaction, in time by mercury recycling simultaneously
It is securely held, it is adding in reaction process, is carrying out security protection；
B, the sulfonation pyridine for obtaining a steps and proton exchange membrane basement membrane, heat 20min, in vacuum drying chamber at 40 DEG C
Be dried in vacuo 3h, finally at 130 DEG C hot pressing 8min to get.Wherein proton exchange membrane basement membrane is the copolymerization of ethylene-tetrafluoroethylene
Object.
The thickness of above-mentioned fuel cell pyridines compound proton exchange membrane is 10~30 μm；Highest under normal work is resistance to
It is shown in Table 1 by temperature, moisture content, tensile strength, water resistant swellbility, electrical conductivity test result.
Wherein, water absorption rate test, water resistant swelling test and electrical conductivity（σ）It measures with embodiment 1.
Comparative example 1
It is as follows to prepare fuel cell pyridines compound proton exchange membrane step：
By anhydrous pyridine and proton exchange membrane basement membrane, 20min is heated at 40 DEG C, 5h is dried in vacuo in vacuum drying chamber, most
Afterwards at 140 DEG C hot pressing 10min to get.Wherein, the mass ratio of anhydrous pyridine and proton exchange membrane basement membrane is：10:100；Wherein
Proton exchange membrane basement membrane is polyethylene film.
The thickness of above-mentioned fuel cell pyridines compound proton exchange membrane is 1~20 μm；Highest under normal work is resistance to
It is shown in Table 1 by temperature, moisture content, tensile strength, water resistant swellbility, electrical conductivity test result.
Wherein, water absorption rate test, water resistant swelling test and electrical conductivity（σ）It measures with embodiment 1.
Comparative example 2
Fuel cell prepared by the present invention is as follows with pyridines compound proton exchange membrane step：
A, the preparation of sulfonation pyridine：Anhydrous pyridine is taken, is added methylene chloride, in ice-water bath, adds sulfonated reagent, is occurred at 45 DEG C
Dichloromethane and catalyst are recycled in complex reaction, dry, and sulfonation pyridine is prepared；The sulfonated reagent steams for sulfur trioxide
Vapour；
B, the sulfonation pyridine for obtaining a steps and proton exchange membrane basement membrane, heat 20min, in vacuum drying chamber at 40 DEG C
Be dried in vacuo 3h, finally at 140 DEG C hot pressing 10min to get.Wherein, anhydrous pyridine, dichloromethane, sulfonated reagent and proton
The mass ratio of exchange membrane basement membrane is：15:5:10:100；Wherein proton exchange membrane basement membrane is polyethylene.
The thickness of above-mentioned fuel battery proton exchange film is 10~20 μm；Highest tolerable temperature, aqueous under normal work
The test results such as rate, tensile strength, water resistant swellbility, electrical conductivity are shown in Table 1；Wherein because the catalysis for lacking catalyst mercury is made
Slower with reaction rate during, reaction, the reaction time is longer, and the productivity ratio embodiment 1 of the product sulfonation pyridine finally obtained obtains
Sulfonation yield lacked 28%, thus, it could be seen that during pyridine is sulfonated reagent sulfonation, the effect of catalyst be compared with
Important.
Wherein, water absorption rate test, water resistant swelling test and electrical conductivity（σ）It measures with embodiment 1.
Comparative example 3
Commercially available Nafion117 films are carried out to work normally lower highest tolerable temperature, water absorption rate test, water resistant swelling test and electricity
Conductance（σ）Etc. being tested, test mode is shown in Table 1 with embodiment 1, test result.
The performance test for the product that 1 Examples 1 to 5 of table and comparative example 1~3 obtain
In addition, fuel cell pyridines compound proton exchange membrane prepared by the embodiment of the present invention 1~5 can operate item in dry gas
Regular picture under part illustrates that its film has good moisture retention.
Claims (9)
1. a kind of fuel cell pyridines compound proton exchange membrane, which is characterized in that the fuel cell pyridines are compound
Proton exchange membrane is by anhydrous pyridine, halogenated alkane, in ice-water bath, adds in sulfonated reagent, by complex reaction, generates sulfonation
Pyridine is process afterwards with proton exchange membrane basal lamina material by rolling process；Wherein, anhydrous pyridine, halogenated alkane, sulfonation examination
Agent and the mass ratio of proton exchange membrane basement membrane are：1~10:0.5~3:15~30:100.
2. a kind of fuel cell pyridines compound proton exchange membrane according to claim 1, which is characterized in that described anhydrous
Pyridine, halogenated alkane, the mass ratio of sulfonated reagent and proton exchange membrane basement membrane are：5:2:20:100.
3. a kind of fuel cell pyridines compound proton exchange membrane according to claim 1, which is characterized in that described halogenated
Alkane is at least one of brominated alkanes, alkane iodide, chloralkane.
4. a kind of fuel cell pyridines compound proton exchange membrane according to claim 3, which is characterized in that described halogenated
Alkane is at least one of dichloromethane, carbon tetrachloride.
A kind of 5. fuel cell pyridines compound proton exchange membrane according to claim 1, which is characterized in that the sulfonation
Reagent is at least one of sulfur trioxide vapor, oleum, chlorosulfonic acid, chlorosulfuric acid, sulfamic acid.
A kind of 6. fuel cell pyridines compound proton exchange membrane according to claim 5, which is characterized in that the sulfonation
Reagent is sulfur trioxide vapor.
7. a kind of fuel cell pyridines compound proton exchange membrane according to claim 1, which is characterized in that adding in sulphur
When changing reagent, the mercury of anhydrous pyridine quality 0.5~1% is additionally added.
A kind of 8. fuel cell pyridines compound proton exchange membrane according to claim 1, which is characterized in that the proton
Exchange membrane basement membrane is at least one of copolymer of polyethylene, vinylidene, cross-linked polytetrafluoroethylthrough, ethylene-tetrafluoroethylene.
9. a kind of preparation method of any one of claim 1~8 fuel cell pyridines compound proton exchange membrane, special
Sign is, comprises the following steps：
A, the preparation of sulfonation pyridine：Anhydrous pyridine is taken, adds halogenated alkane, in ice-water bath, adds sulfonated reagent, and adds in catalyst
Complex reaction occurs at 40~45 DEG C for mercury, recycles halogenated alkane and catalyst, dry, and sulfonation pyridine is prepared；
B, the sulfonation pyridine for obtaining a steps and proton exchange membrane basement membrane, heat 10~30min, in vacuum at 30~60 DEG C
In drying box be dried in vacuo 2~5h, finally at 130~150 DEG C 5~15min of hot pressing to get.
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| CN113782797A (en) * | 2021-08-19 | 2021-12-10 | 深圳氢时代新能源科技有限公司 | MOF material and preparation method thereof, proton exchange membrane and preparation method thereof, and fuel cell |
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| JP2005097136A (en) * | 2003-09-22 | 2005-04-14 | Fuji Photo Film Co Ltd | Method for producing pyridine derivative containing sulfo group |
| CN101252178A (en) * | 2008-04-07 | 2008-08-27 | 深圳市富易达电子科技有限公司 | Method for preparing sulphonation battery exchanging film |
| CN103288767A (en) * | 2012-03-05 | 2013-09-11 | 南京航空航天大学 | Tetrazole proton transfer agent and preparation method of proton exchange membrane of high-temperature fuel cell thereof |
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| JP2005097136A (en) * | 2003-09-22 | 2005-04-14 | Fuji Photo Film Co Ltd | Method for producing pyridine derivative containing sulfo group |
| CN101252178A (en) * | 2008-04-07 | 2008-08-27 | 深圳市富易达电子科技有限公司 | Method for preparing sulphonation battery exchanging film |
| CN103288767A (en) * | 2012-03-05 | 2013-09-11 | 南京航空航天大学 | Tetrazole proton transfer agent and preparation method of proton exchange membrane of high-temperature fuel cell thereof |
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| 姚映钦主编: "《有机化学 第3版》", 31 August 2011 * |
| 广东工学院精细化工教研室编: "《精细化工基本生产技术及其应用》", 31 August 1995 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113782797A (en) * | 2021-08-19 | 2021-12-10 | 深圳氢时代新能源科技有限公司 | MOF material and preparation method thereof, proton exchange membrane and preparation method thereof, and fuel cell |
| CN113782797B (en) * | 2021-08-19 | 2022-10-21 | 深圳氢时代新能源科技有限公司 | MOF material and preparation method thereof, proton exchange membrane and preparation method thereof, and fuel cell |
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