CN108336385A - A kind of inorganic-organic selfreparing fuel battery proton exchange film and preparation method - Google Patents
A kind of inorganic-organic selfreparing fuel battery proton exchange film 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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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Abstract
The present invention relates to inorganic organic selfreparing fuel battery proton exchange film and preparation methods, belong to Proton Exchange Membrane Fuel Cells technical field.The present invention proposes the inorganic organic selfreparing fuel battery proton exchange film of one kind and preparation method.Inorganic organic selfreparing fuel battery proton exchange film, is prepared by the raw material including following parts by weight：10~30 parts of alum, 1~20 part of dodecyl ethyoxyl sulfobetaines, 2~15 parts of triethanolamine, 5~15 parts of sodium methyl silicate, 5~20 parts of aerosil, 3~18 parts of calcium sulfate, 30~50 parts of sulfonated polyether-ether-ketone.The present invention selects inorganic base of the specified raw material composition with selfreparing, can overcome swelling at high temperature, extend the service life of film, improves hot operation stability.In addition, specific constituent and content so that sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) channel broadens, and proton conductivity increases, and the performance of fuel cell is more preferable.
Description
Technical field
The present invention relates to inorganic-organic selfreparing fuel battery proton exchange film and preparation methods, belong to proton exchange membrane
Field of fuel cell technology.
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 (Proton Exchange Membrane Fuel Cell,
PEMFC) belong to low-temperature fuel cell, in addition to have fuel cell it is general it is specific other than, also have operating temperature it is low, start
Soon, electroless liquid stream is lost, corrosion-free, energy transformation ratio is high, long lifespan, it is light-weight, small the features such as, be portable power,
The ideal substitute electric power of distributed power station, the following electric vehicle.
Proton exchange membrane (PEM) is the critical component of Proton Exchange Membrane Fuel Cells, directly affects battery performance and longevity
Life.Currently, common proton exchange membrane is perfluoro sulfonic acid membrane, but it is affected by temperature larger, when high temperature can reduce the energy of battery
Measure transformation efficiency.In order to overcome these disadvantages, various countries researcher to have been devoted to research and development new polymers proton exchange
Film.Polyether-ether-ketone is a kind of heat-resisting material haveing excellent performance, and sulfonated polyether-ether-ketone has preferable alcohol-rejecting ability, thermal stability
With chemical stability, and proton conductivity is higher, has obtained preferable development, but easily cause membrane swelling in hot operation,
The defects of embrittlement, influences service life.Therefore, the scientific research personnel of this field has been devoted to the study on the modification of polyether-ether-ketone.
Application No. is 201310700094.9 patent of invention disclose a kind of inorganic/organic composite proton exchange membrane and its
Preparation method；By sol-gel process, perfluorinated sulfonic acid polymer is introduced and is fixed on SiO2In skeleton, obtain containing perfluor
The proton conducting glass of sulfonic acid polymer, it is then that it is compound with inexpensive sulfonation polycyclic aromatic hydrocarbon polymer, thus to obtain it is inorganic/
Organic composite proton exchange membrane.Compared with perfluorinated sulfonic acid polymer proton exchange membrane (such as Nafion membrane), which exchanges
Film only contains a small amount of high cost perfluorinated sulfonic acid polymer, therefore overall cost is greatly lowered；With sulfonation polycyclic aromatic hydrocarbon polymer
(such as sulfonated polyether-ether-ketone) is compared, and SiO is fixed on2The introducing of a small amount of perfluorinated sulfonic acid polymer in glass skeleton improves multiple
The proton conductivity of film is closed, and improves the durability of composite membrane.The compound proton exchange membrane that the invention is prepared, both reduced
Cost, and have high-quality electron conductivity and a good durability.But the invention uses perfluorinated sulfonic acid polymer for organic matrix,
It since perfluorinated sulfonic acid polymer cost is higher, and is affected by temperature larger, causes its conductivity not high, from the number of embodiment
According to can be seen that the conductivity of the composite proton exchange membrane material 10-2 S·cm-1, need further to improve.
Application No. is 201610893595.7 patents of invention to disclose a kind of sulfonated phosphazene/ether ether ketone proton exchange membrane
Material and preparation method thereof, the proton exchange membrane material using the sulfonated polyether-ether-ketone of medium sulfonation degree as basis material, with
Overcame water absorption rate existing for highly sulfonated SPEEK excessively high, the poor disadvantage of compound membrane stability, and ensure that composite membrane has
There are certain mechanical strength and good alcohol-rejecting ability.The introducing of phosphonitrile three-membered ring structures improves sulfonated polyether-ether-ketone membrane material
Thermal stability and antioxygenic property；Fragrant amino phenyl ring further improves alcohol-rejecting ability and drop as the introducing of hydrophobic grouping
The low swelling action of water；A large amount of sulfonic acid groups improve the proton conductivity of proton exchange membrane by the introducing of chemical bond mode,
It avoids the physics of sulfonic acid group from being lost in, improves the service life of film.The present invention is with manufacturing cost is low, conductivity is high, alcohol-resistant performance
It can good and heat-resist feature.But for its method, the preparation method of the material is complicated, the difficulty of industrial applications
Proton exchange membrane material that is larger, and obtaining, the conductivity at 20 DEG C~90 DEG C are 2 .00 × 10-3~5 .20 × 10- 1S·cm-1, need further to improve.
Invention content
Proton exchange membrane is used under high temperature operating conditions easily by swelling breakage for existing sulfonated polyether-ether-ketone, leads to electricity
The not high defect of conductance, a kind of inorganic-organic selfreparing fuel battery proton exchange film of present invention proposition and preparation method.
First technical problem that the present invention solves is to provide a kind of inorganic-organic selfreparing fuel cell proton exchange
Film.
Inorganic-organic selfreparing fuel battery proton exchange film of the present invention, by the raw material preparation including following parts by weight
At：10~30 parts of alum, 1~20 part of dodecyl ethyoxyl sulfobetaines, 2~15 parts of triethanolamine, sodium methyl silicate 5~
15 parts, 5~20 parts of aerosil, 3~18 parts of calcium sulfate, 30~50 parts of sulfonated polyether-ether-ketone.
Sulfonated polyether-ether-ketone（SPEEK）It is to study relatively broad diaphragm in Proton Exchange Membrane Fuel Cells, has good
Chemical stability, high-temperature stability and higher conductivity.In addition, along with sulfonic acid group (- SO3H introducing),
The sulfonation degree of SPEEK correspondingly increases, and significantly improves the proton exchange capacity and ionic conducting property of film.Therefore SPEEK
It is considered as a kind of no fluorine-based polymer material of preparing for being most hopeful to replace PFI.Inorganic-organic selfreparing fuel electricity of the present invention
Pond proton exchange membrane uses SPEEK for organic matrix.
Alum is also known as 12 hydrazine aluminum sulfate potassium, is the double salt of the potassium sulfate containing the crystallization water and aluminum sulfate, is colourless vertical
Square crystal, appearance are in often octahedron, or form combinate form with cube, granatohedron, are similar to six square plate shapes again sometimes, belong to
α type alum class double salt, has glassy lustre, is dissolved in water, does not dissolve in ethyl alcohol.Dodecyl ethyoxyl sulfobetaines is a kind of both sexes
Ionic surface active agent all has excellent stability under acid and alkaline condition, and it is ionic to be presented male and female respectively, often with
Anions and canons and nonionic surfactant are used in combination, and compatibility is good.Triethanolamine i.e. three (2- ethoxys) amine, can be with
Regard the trihydroxy substituent of triethylamine as.It is similar to other aminated compounds, since there are lone pair electrons, three second on nitrogen-atoms
Hydramine has alkalescent, can generate salt with inorganic acid or organic acid reaction, be common chemicals.Sodium methyl silicate is a kind of
Novel rigid material has good penetrant crystalline.The silanol group in silanol group and silicate material in its molecular structure
Dehydrated crosslinking is reacted, to realize that " anti-capillary effect " forms excellent water-repellent layer, while there is microdilatancy, increase compactness
Function.Aerosil is common one of aeroge, is mutually to assemble that be constituted nanometer more with nanometer scale ultramicro powder
Pore network structure, and the lightweight nano solid material full of gaseous state decentralized medium in network pore, although silica airsetting
Glue is a kind of solid, but 99% is made of gas, and it is the same that appearance looks like cloud, has translucent color and ultralight
Weight, be a kind of light nanoporous amorphous solid material that solar heat protection heat-proof quality is very outstanding.
The present invention selects the above alum, dodecyl ethyoxyl sulfobetaines, triethanolamine, sodium methyl silicate, dioxy
The inorganic base of SiClx aeroge and calcium sulfate composition with selfreparing, constantly crystallizes under water environment, not only inhibits sulfonation poly-
The swelling of ether ether ketone at high temperature, and the generation when proton exchange membrane works with dampening can be overcome, inorganic matter crystallizes certainly
Film defect caused by repairing swelling so that inorganic-organic selfreparing fuel battery proton exchange film of the present invention can at high temperature gram
Clothes swelling, extends the service life of film, improves hot operation stability.In addition, specific constituent and content so that
Sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) channel broadens, and proton conductivity increases, and the performance of fuel cell is more preferable.
Preferably, inorganic-organic selfreparing fuel battery proton exchange film of the present invention, by the raw material for including following parts by weight
It is prepared：13~27 parts of alum, 5~15 parts of dodecyl ethyoxyl sulfobetaines, 3~12 parts of triethanolamine, methyl silicon
7~12 parts of sour sodium, 8~15 parts of aerosil, 5~12 parts of calcium sulfate, 35~45 parts of sulfonated polyether-ether-ketone.
Preferably, inorganic-organic selfreparing fuel battery proton exchange film of the present invention, by including following parts by weight
Raw material be prepared：21 parts of alum, 12 parts of dodecyl ethyoxyl sulfobetaines, 8 parts of triethanolamine, sodium methyl silicate 10
Part, 11 parts of aerosil, 10 parts of calcium sulfate, 42 parts of sulfonated polyether-ether-ketone.
Second technical problem that the present invention solves is to provide inorganic-organic selfreparing fuel cell matter of the present invention
The preparation method of proton exchange.
The preparation method of inorganic-organic selfreparing fuel battery proton exchange film of the present invention, includes the following steps：
A, the preparation of inorganic matrix：By alum, dodecyl ethyoxyl sulfobetaines, triethanolamine, sodium methyl silicate, dioxy
SiClx aeroge, calcium sulfate mixing, are ground to nanoscale colloid, obtain inorganic matrix；
B, the preparation of organic matrix：Sulfonated polyether-ether-ketone is dissolved in organic solvent, organic matrix is obtained；
C, composite membrane-forming：Inorganic matrix, organic matrix and auxiliary dispersants are homogenized in homogenizer, cast film forming is dry, obtains
To inorganic-organic selfreparing fuel battery proton exchange film.
The organic solvent that sulfonated polyether-ether-ketone can be dissolved is suitable for the present invention, it is preferred that the organic solvent is two
Methyl sulfoxide（DMSO）, N, N-dimethylformamide（DMF）Or DMAC N,N' dimethyl acetamide (DMAc).
The concentration of sulfonated polyether-ether-ketone will influence subsequent homogeneous and film forming, it is preferred that in the organic matrix, sulfonation is poly-
The mass concentration of ether ether ketone is 5~20%；In more preferable organic matrix, the mass concentration of sulfonated polyether-ether-ketone is 10%.
Auxiliary dispersants can be such that inorganic matrix is dispersed in organic matrix well, and common organic dispersing agent is suitable for
The present invention.Preferably, the auxiliary dispersants are triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, polyacrylamide
Amine, guar gum or fatty acid polyethylene glycol ester etc..
The addition of auxiliary dispersants has large effect to homo-effect, it is preferred that the addition of the auxiliary dispersants
Amount is the 1~5% of organic matrix quality；It is furthermore preferred that the addition of the auxiliary dispersants is the 3% of organic matrix quality.
Homogeneous is also referred to as homogenized, be make dispersion micronized in suspension (or emulsion) system, homogenization it is processed
Journey, it is this to handle while plaing a part of to reduce dispersion scale and improving dispersion distributing homogeneity.Homogeneous of the present invention
It is carried out in homogenizer, the characteristics of by the energy and mechanism used, homogenizer can be divided into rotary and pressure type two major classes.
Rotary-type homogenizer is made of rotor or rotor-stator system, and mechanical kinetic energy is directly passed to the medium being subject to processing by they.
Colloid mill is typical rotary homogenizer.In addition, blender, emulsifying mill also belong to rotary-type homogenizer.Pressure type is equal
Matter equipment makes liquid medium obtain high pressure energy first, and this high pressure energy liquid is when by the homogenizing mechanism of homogenizer, pressure energy
It is converted into kinetic energy, to obtain the effect of fluid force.Pressure-type homogenizer the most typical is high pressure homogenizer, this is all
Most widely used one kind in homogenizer.In addition, ultrasonic emulsator is also a kind of homogenizer of pressure-type.Preferably, originally
The invention homogenizer uses pressure type homogenizer.Pressure type homogenizer commonly used in the art is suitable for the present invention.
Preferably, using two-section pressure, first segment pressure is 23~28MPa, and homogenising time is 1~5h, and second segment is equal
The pressure of matter is 5~8MPa, and homogenising time is 1~5h；It is preferred that first segment pressure is 25MPa, homogenising time 3h, second segment is equal
The pressure of matter is 6MPa, homogenising time 2h.
The temperature of homogenizing has a certain impact to homo-effect, and preferably, the temperature of homogenizing is 40~60 DEG C；It is excellent
The temperature of choosing homogenizing is 50 DEG C.
After homogeneous, film forming can be directly poured into a mould, it is dry, you can to obtain inorganic-organic selfreparing fuel cell of the present invention
The prior art may be used in proton exchange membrane, pouring procedure and drying means, is not described in detail herein.
Compared with prior art, the present invention has the advantages that：
The present invention selects alum, dodecyl ethyoxyl sulfobetaines, triethanolamine, sodium methyl silicate, silica airsetting
The inorganic base of glue and calcium sulfate composition with selfreparing, constantly crystallizes under water environment, not only sulfonated polyether-ether-ketone is inhibited to exist
Swelling under high temperature, and the generation when proton exchange membrane works with dampening can be overcome, inorganic matter repairs swelling from crystallization
Caused by film defect so that inorganic-organic selfreparing fuel battery proton exchange film of the present invention can overcome swelling at high temperature, prolong
It grown the service life of film, improved hot operation stability.In addition, specific constituent and content so that sulfonated polyether
Ether ketone proton exchange membrane channels broaden, and proton conductivity increases, and the performance of fuel cell is more preferable.
The preparation method of inorganic-organic selfreparing fuel battery proton exchange film of the present invention is simple, and raw material is easy to get, can be a large amount of
It applies in Proton Exchange Membrane Fuel Cells.
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
Inorganic-organic selfreparing fuel battery proton exchange film, is prepared by the raw material including following parts by weight：Alum 10
Part, 1 part of dodecyl ethyoxyl sulfobetaines, 15 parts of triethanolamine, 15 parts of sodium methyl silicate, 5 parts of aerosil,
18 parts of calcium sulfate, 30 parts of sulfonated polyether-ether-ketone.
The preparation method of the inorganic-organic selfreparing fuel battery proton exchange film is as follows：
A, the preparation of inorganic matrix：By alum, dodecyl ethyoxyl sulfobetaines, triethanolamine, sodium methyl silicate, dioxy
SiClx aeroge, calcium sulfate mixing, are ground to nanoscale colloid, obtain inorganic matrix.
B, the preparation of organic matrix：Sulfonated polyether-ether-ketone is dissolved in organic solvent, the matter of sulfonated polyether-ether-ketone is obtained
Measure a concentration of 5% organic matrix；The organic solvent is dimethyl sulfoxide (DMSO).
C, composite membrane-forming：In homogenizer by inorganic matrix, organic matrix and auxiliary dispersants triethyl group hexyl phosphoric acid
Change, cast film forming is dry, obtains the inorganic-organic selfreparing fuel battery proton exchange film that thickness is 100 μm.The auxiliary
The addition of dispersant is the 1% of organic matrix quality；The temperature of homogenizing is 40 DEG C；The homogenizer is pressure type homogenizer, is adopted
With two-section pressure, first segment pressure is 23MPa, and the pressure of homogenising time 5h, second segment homogeneous are 5MPa, and homogenising time is
1h。
Under humidified condition（Relative humidity is 80%）, measure the inorganic-organic selfreparing fuel battery proton exchange film and exist
Proton conductivity under different temperatures, the result is shown in tables 1.
Embodiment 2
Inorganic-organic selfreparing fuel battery proton exchange film, is prepared by the raw material including following parts by weight：Alum 30
Part, 20 parts of dodecyl ethyoxyl sulfobetaines, 2 parts of triethanolamine, 5 parts of sodium methyl silicate, 20 parts of aerosil,
3 parts of calcium sulfate, 50 parts of sulfonated polyether-ether-ketone.
The preparation method of the inorganic-organic selfreparing fuel battery proton exchange film is as follows：
A, the preparation of inorganic matrix：By alum, dodecyl ethyoxyl sulfobetaines, triethanolamine, sodium methyl silicate, dioxy
SiClx aeroge, calcium sulfate mixing, are ground to nanoscale colloid, obtain inorganic matrix.
B, the preparation of organic matrix：Sulfonated polyether-ether-ketone is dissolved in organic solvent, the matter of sulfonated polyether-ether-ketone is obtained
Measure a concentration of 20% organic matrix；The organic solvent is N, N-dimethylformamide.
C, composite membrane-forming：In homogenizer by inorganic matrix, organic matrix and auxiliary dispersants lauryl sodium sulfate
Change, cast film forming is dry, obtains the inorganic-organic selfreparing fuel battery proton exchange film that thickness is 100 μm.The auxiliary
The addition of dispersant is the 5% of organic matrix quality；The temperature of homogenizing is 60 DEG C；The homogenizer is pressure type homogenizer, is adopted
With two-section pressure, first segment pressure is 28MPa, and the pressure of homogenising time 1h, second segment homogeneous are 8MPa, and homogenising time is
5h。
Under humidified condition（Relative humidity is 80%）, measure the inorganic-organic selfreparing fuel battery proton exchange film and exist
Proton conductivity under different temperatures, the result is shown in tables 1.
Embodiment 3
Inorganic-organic selfreparing fuel battery proton exchange film, is prepared by the raw material including following parts by weight：Alum 13
Part, 5 parts of dodecyl ethyoxyl sulfobetaines, 12 parts of triethanolamine, 12 parts of sodium methyl silicate, aerosil 15
Part, 5 parts of calcium sulfate, 35 parts of sulfonated polyether-ether-ketone.
The preparation method of the inorganic-organic selfreparing fuel battery proton exchange film is as follows：
A, the preparation of inorganic matrix：By alum, dodecyl ethyoxyl sulfobetaines, triethanolamine, sodium methyl silicate, dioxy
SiClx aeroge, calcium sulfate mixing, are ground to nanoscale colloid, obtain inorganic matrix.
B, the preparation of organic matrix：Sulfonated polyether-ether-ketone is dissolved in organic solvent, the matter of sulfonated polyether-ether-ketone is obtained
Measure a concentration of 8% organic matrix；The organic solvent is DMAC N,N' dimethyl acetamide.
C, composite membrane-forming：Inorganic matrix, organic matrix and auxiliary dispersants methyl anyl alcohol are homogenized in homogenizer, poured into a mould
Film forming, it is dry, obtain the inorganic-organic selfreparing fuel battery proton exchange film that thickness is 100 μm.The auxiliary dispersants
Addition is the 2% of organic matrix quality；The temperature of homogenizing is 50 DEG C；The homogenizer is pressure type homogenizer, using two-period form
Pressure, first segment pressure are 24MPa, and the pressure of homogenising time 3h, second segment homogeneous are 7MPa, homogenising time 3h.
Under humidified condition（Relative humidity is 80%）, measure the inorganic-organic selfreparing fuel battery proton exchange film and exist
Proton conductivity under different temperatures, the result is shown in tables 1.
Embodiment 4
Inorganic-organic selfreparing fuel battery proton exchange film, is prepared by the raw material including following parts by weight：Alum 27
Part, 15 parts of dodecyl ethyoxyl sulfobetaines, 3 parts of triethanolamine, 7 parts of sodium methyl silicate, 8 parts of aerosil,
12 parts of calcium sulfate, 45 parts of sulfonated polyether-ether-ketone.
The preparation method of the inorganic-organic selfreparing fuel battery proton exchange film is as follows：
A, the preparation of inorganic matrix：By alum, dodecyl ethyoxyl sulfobetaines, triethanolamine, sodium methyl silicate, dioxy
SiClx aeroge, calcium sulfate mixing, are ground to nanoscale colloid, obtain inorganic matrix.
B, the preparation of organic matrix：Sulfonated polyether-ether-ketone is dissolved in organic solvent, the matter of sulfonated polyether-ether-ketone is obtained
Measure a concentration of 10% organic matrix；The organic solvent is N, N-dimethylformamide.
C, composite membrane-forming：By inorganic matrix, organic matrix and auxiliary dispersants fatty acid polyethylene glycol ester in homogenizer
Homogenizing, cast film forming is dry, obtains the inorganic-organic selfreparing fuel battery proton exchange film that thickness is 100 μm.It is described auxiliary
The addition of dispersion aids is the 4% of organic matrix quality；The temperature of homogenizing is 55 DEG C；The homogenizer is pressure type homogenizer,
Using two-section pressure, first segment pressure is 26MPa, and the pressure of homogenising time 4h, second segment homogeneous are 6MPa, homogenising time
For 3h.
Under humidified condition（Relative humidity is 80%）, measure the inorganic-organic selfreparing fuel battery proton exchange film and exist
Proton conductivity under different temperatures, the result is shown in tables 1.
Embodiment 5
Inorganic-organic selfreparing fuel battery proton exchange film, is prepared by the raw material including following parts by weight：Alum 15
Part, 11 parts of dodecyl ethyoxyl sulfobetaines, 12 parts of triethanolamine, 7 parts of sodium methyl silicate, aerosil 13
Part, 15 parts of calcium sulfate, 40 parts of sulfonated polyether-ether-ketone.
The preparation method of the inorganic-organic selfreparing fuel battery proton exchange film is as follows：
A, the preparation of inorganic matrix：By alum, dodecyl ethyoxyl sulfobetaines, triethanolamine, sodium methyl silicate, dioxy
SiClx aeroge, calcium sulfate mixing, are ground to nanoscale colloid, obtain inorganic matrix.
B, the preparation of organic matrix：Sulfonated polyether-ether-ketone is dissolved in organic solvent, the matter of sulfonated polyether-ether-ketone is obtained
Measure a concentration of 10% organic matrix；The organic solvent is N, N-dimethylformamide.
C, composite membrane-forming：In homogenizer by inorganic matrix, organic matrix and auxiliary dispersants lauryl sodium sulfate
Change, cast film forming is dry, obtains the inorganic-organic selfreparing fuel battery proton exchange film that thickness is 100 μm.The auxiliary
The addition of dispersant is the 3% of organic matrix quality；The temperature of homogenizing is 45 DEG C；The homogenizer is pressure type homogenizer, is adopted
With two-section pressure, first segment pressure is 25MPa, and the pressure of homogenising time 2h, second segment homogeneous are 5MPa, and homogenising time is
3h。
Under humidified condition（Relative humidity is 80%）, measure the inorganic-organic selfreparing fuel battery proton exchange film and exist
Proton conductivity under different temperatures, the result is shown in tables 1.
Embodiment 6
Inorganic-organic selfreparing fuel battery proton exchange film, is prepared by the raw material including following parts by weight：Obviously alum 21
Part, 12 parts of dodecyl ethyoxyl sulfobetaines, 8 parts of triethanolamine, 10 parts of sodium methyl silicate, aerosil 11
Part, 10 parts of calcium sulfate, 42 parts of sulfonated polyether-ether-ketone.
The preparation method of the inorganic-organic selfreparing fuel battery proton exchange film is as follows：
A, the preparation of inorganic matrix：By alum, dodecyl ethyoxyl sulfobetaines, triethanolamine, sodium methyl silicate, dioxy
SiClx aeroge, calcium sulfate mixing, are ground to nanoscale colloid, obtain inorganic matrix.
B, the preparation of organic matrix：Sulfonated polyether-ether-ketone is dissolved in organic solvent, the matter of sulfonated polyether-ether-ketone is obtained
Measure a concentration of 10% organic matrix；The organic solvent is N, N-dimethylformamide.
C, composite membrane-forming：In homogenizer by inorganic matrix, organic matrix and auxiliary dispersants lauryl sodium sulfate
Change, cast film forming is dry, obtains the inorganic-organic selfreparing fuel battery proton exchange film that thickness is 100 μm.The auxiliary
The addition of dispersant is the 3% of organic matrix quality；The temperature of homogenizing is 50 DEG C；The homogenizer is pressure type homogenizer, is adopted
With two-section pressure, first segment pressure is 25MPa, and the pressure of homogenising time 3h, second segment homogeneous are 6MPa, and homogenising time is
2h。
Under humidified condition（Relative humidity is 80%）, measure the inorganic-organic selfreparing fuel battery proton exchange film and exist
Proton conductivity under different temperatures, the result is shown in tables 1.
Comparative example 1
Sulfonated polyether-ether-ketone is dissolved in organic solvent, cast film forming is dry, obtains sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM).
Under humidified condition（Relative humidity is 80%）, measure the proton electricity of the sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) at different temperatures
Conductance, the result is shown in tables 1.
Table 1
Claims (10)
1. a kind of inorganic-organic selfreparing fuel battery proton exchange film, which is characterized in that by the raw material for including following parts by weight
It is prepared：10~30 parts of alum, 1~20 part of dodecyl ethyoxyl sulfobetaines, 2~15 parts of triethanolamine, methyl silicon
5~15 parts of sour sodium, 5~20 parts of aerosil, 3~18 parts of calcium sulfate, 30~50 parts of sulfonated polyether-ether-ketone.
2. inorganic-organic selfreparing fuel battery proton exchange film according to claim 1, which is characterized in that by including
The raw material of following parts by weight is prepared：13~27 parts of alum, 5~15 parts of dodecyl ethyoxyl sulfobetaines, three ethyl alcohol
3~12 parts of amine, 7~12 parts of sodium methyl silicate, 8~15 parts of aerosil, 5~12 parts of calcium sulfate, sulfonated polyether-ether-ketone
35~45 parts.
3. inorganic-organic selfreparing fuel battery proton exchange film according to claim 1, which is characterized in that by including
The raw material of following parts by weight is prepared：21 parts of alum, 12 parts of dodecyl ethyoxyl sulfobetaines, 8 parts of triethanolamine, first
10 parts of base sodium metasilicate, 11 parts of aerosil, 10 parts of calcium sulfate, 42 parts of sulfonated polyether-ether-ketone.
4. the preparation method of claims 1 to 3 any one of them inorganic-organic selfreparing fuel battery proton exchange film,
It is characterized in that, includes the following steps：
A, the preparation of inorganic matrix：By alum, dodecyl ethyoxyl sulfobetaines, triethanolamine, sodium methyl silicate, dioxy
SiClx aeroge, calcium sulfate mixing, are ground to nanoscale colloid, obtain inorganic matrix；
B, the preparation of organic matrix：Sulfonated polyether-ether-ketone is dissolved in organic solvent, organic matrix is obtained；
C, composite membrane-forming：Inorganic matrix, organic matrix and auxiliary dispersants are homogenized in homogenizer, cast film forming is dry, obtains
To inorganic-organic selfreparing fuel battery proton exchange film.
5. the preparation method of inorganic-organic selfreparing fuel battery proton exchange film according to claim 4, feature exist
In：The organic solvent is dimethyl sulfoxide (DMSO), N, N-dimethylformamide or DMAC N,N' dimethyl acetamide.
6. the preparation method of inorganic-organic selfreparing fuel battery proton exchange film according to claim 4, feature exist
In：In the organic matrix, the mass concentration of sulfonated polyether-ether-ketone is 5~20%.
7. the preparation method of inorganic-organic selfreparing fuel battery proton exchange film according to claim 4, feature exist
In：The auxiliary dispersants be triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, polyacrylamide, guar gum or
Fatty acid polyethylene glycol ester.
8. the preparation method of inorganic-organic selfreparing fuel battery proton exchange film according to claim 7, feature exist
In：The addition of the auxiliary dispersants is the 1~5% of organic matrix quality.
9. the preparation method of inorganic-organic selfreparing fuel battery proton exchange film according to claim 4, feature exist
In：The homogenizer is pressure type homogenizer, and using two-section pressure, first segment pressure is 23~28MPa, homogenising time 1
The pressure of~5h, second segment homogeneous are 5~8MPa, and homogenising time is 1~5h；It is preferred that first segment pressure is 25MPa, homogenising time
Pressure for 3h, second segment homogeneous is 6MPa, homogenising time 2h.
10. the preparation method of inorganic-organic selfreparing fuel battery proton exchange film according to claim 4, feature
It is：The temperature of homogenizing is 40~60 DEG C.
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