CN104134812A - Fiber-net-reinforced polymer electrolyte membrane and preparation method thereof - Google Patents
Fiber-net-reinforced polymer electrolyte membrane and preparation method thereof Download PDFInfo
- Publication number
- CN104134812A CN104134812A CN201310157568.XA CN201310157568A CN104134812A CN 104134812 A CN104134812 A CN 104134812A CN 201310157568 A CN201310157568 A CN 201310157568A CN 104134812 A CN104134812 A CN 104134812A
- Authority
- CN
- China
- Prior art keywords
- straight chain
- fiber
- ion exchange
- film
- exchange resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to a fiber-net-reinforced polymer electrolyte membrane and a preparation method thereof. The membrane is prepared by employing perfluoro ion exchange resin as a substrate to form the membrane with addition of a fiber net composed of specific fibers inside the membrane. The invention also discloses the preparation method of the reinforced polymer electrolyte membrane. The method mainly includes following steps: enabling a perfluoro ion exchange resin dispersion liquid to form the membrane, spraying a fiber dispersion liquid, and enabling the perfluoro ion exchange resin dispersion liquid to form the membrane. The fiber-net-reinforced polymer electrolyte membrane has a very excellent mechanical strength performance and a very excellent electrical performance. Meanwhile, the fiber-net-reinforced polymer electrolyte membrane has excellent isotropy on not only a size change rate but also a surface electrically-conductive property when an external environment humidity is changed.
Description
Technical field
The invention belongs to field of functional polymer composites, relate to a kind of fleece and strengthen polymer dielectric film and preparation method thereof.
Background technology
Polyelectrolyte membranes is comprising fuel cell, brine electrolysis or chloric alkali electrolysis, and synthetic grade of organic electrochemistry played vital effect in interior electrochemical reactor.Particularly fuel cell is directly converted into chemical energy the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy as a kind of by electrochemical means, is considered to the cleaning of 21 century first-selection, efficient generation technology.Proton exchange membrane (proton exchange membrane, PEM) is the critical material of Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, PEMFC).
The perfluorosulfonic acid proton exchange film using now has good proton-conducting and chemical stability under (80 ℃) and higher humidity at a lower temperature.But they also have a lot of defects: as poor dimensional stability, mechanical strength are not high, poor chemical stability etc.Film water absorption rate and size of causing because of water suction under different humidity expand also different, and when film is during at different operating mode down conversion, therefore the size of film also will change.So repeatedly, finally cause proton exchange membrane generation mechanical damage.In addition, the reaction of the positive pole of fuel cell usually produces the material that a large amount of hydroxyl free radicals and hydrogen peroxide etc. have strong oxidizing property, and non-fluorin radical on these materials meeting attack film-forming resin molecules, causes film generation chemical degradation and damaged, foaming.Finally, when the working temperature of perfluorinated sulfonic acid exchange membrane is during higher than 90 ℃, because the rapid dehydration of film causes the proton-conducting of film sharply to decline, thereby the efficiency of fuel cell is declined greatly.But high working temperature can improve the resistance to carbon monoxide of fuel-cell catalyst greatly.Be exactly that existing perfluoro sulfonic acid membrane has certain hydrogen or methanol permeability in addition, especially, in direct methanol fuel cell, methanol permeability is very large, and this becomes fatal problem.Therefore the permeability etc. that, how to improve proton conduction efficiency under intensity, dimensional stability and the high temperature of perfluorosulfonic acid proton exchange film, reduces working media becomes the key subjects that fuel cell industries faces.
People have proposed certain methods and have solved these problems at present.As adopting perfluorinated sulfonic resin to flood the porous media that polytetrafluoroethylene (PTFE) makes, Japan Patent JP-B-5-75835 strengthens film strength.Yet the porous media of this PTFE is because PTFE material is relatively soft, humidification is insufficient, still fails to address the above problem.
The Gore-Select series composite membrane liquid of W.L.Gore company exploitation adopts porous teflon to fill the method (seeing US5547551, US5635041, US5599614) of Nafion ionic conductivity liquid.This film has higher proton conductive and larger dimensional stability, but at high temperature teflon creep is very large, causes hydraulic performance decline.
Japan Patent JP-B-7-68377 also proposed a kind of method, the porous media made from proton exchange resins filled polyolefin, but its chemical durability is not enough, thereby have problems aspect long-time stability.And owing to not possessing the adding of porous media of proton conductive ability, proton conduction path is reduced, cause the proton exchange ability of film to decline.
In addition, Japan Patent JP-A-6-231779 has proposed another kind of Enhancement Method, is to use fluororesin fiber.The amberplex that it adopts the fluorocarbon polymer reinforcing material of fibrillation form to strengthen.But this method must add relatively a large amount of reinforcing materials, in this case, the processing characteristics of film is tending towards difficulty, and film resistance increase occurs possibly.
European patent EP 0875524B1 discloses the technology of utilizing glass fibre membrane prepared by glass fibre non-woven technology to strengthen nafion film, mentions in the method the oxides such as silicon dioxide simultaneously.But in this patent, non-woven glass fibre cloth is the base material that must use, and this will limit the scope of application of described enhancing film greatly.
US Patent No. 6692858 discloses the technology of polytetrafluoroethylene fibre enhancing perfluorinated sulfonic resin.In this technology, by perfluor sulfonyl fluororesin and polytetrafluoroethylene fibre mix, extrude, making the transition makes fibre-reinforced perfluorinated sulfonic resin.The method is because transformation process is consuming time and can not produce continuously.
But fiber reinforcement or perforated membrane enhancing often exist phase-splitting between reinforcement and film-forming resin, also just there is very large gap, thereby cause become film to there is high gas permeability.
Crosslinking technological can improve the mechanical strength of the thermal stability of polymer, the swelling that reduces solvent, raising polymer.Therefore, crosslinking technological has been widely used in the fields such as separated absorption and various rubber elastomers.At present, for solving the existing problem of perfluorosulfonic acid proton exchange film, explored and studied multiple crosslinking technological.
US20070031715 has described the crosslinked cross-linking method that generates sulphonyl acid anhydride of sulfonic acid chloride, formed sulphonyl acid anhydride cross-linked structure can improve the mechanical strength of film effectively in the method, but this cross-linked structure has obvious shortcoming: sulphonyl acid anhydride unit is unsettled to alkali.
US20030032739 is connected and is reached crosslinked object by the alkyl between strand of the sulfonyl on macromolecular chain.This crosslinked solvent swell that can reduce well film.But for obtaining not suitability for industrialized process of the required a lot of steps of this cross-linked structure.
US6733914 discloses the perfluor sulfonyl fluorine type film melt extruding has been soaked to the proton exchange membrane that forms sulfimide cross-linked structure in ammoniacal liquor, and the perfluoro sulfonic acid membrane of so processing has good mechanical strength and dimensional stability.But utilize the resulting film of this patent to be inhomogeneous film, because ammonia enters film by the method for infiltration, in the process of infiltration, ammonia meeting and sulfuryl fluoride react, the sulfuryl fluoride of reaction is by the further diffusion that stops ammonia to film inside, thereby the surface at film forms very high crosslink density, and the inside of film does not almost occur to be cross-linked.The large crosslinked conductivity of film that makes in surface sharply declines.
CN200710013624.7 and US7259208 disclose and have contained triazine ring cross-linked structure perfluoro sulfonic acid membrane, have equally good mechanical strength and dimensional stability.
Only adopt the crosslinked film of chemical bonding, often can not form the very high degree of cross linking, limited to improving the performance of film.The performance of telolemma can not reach the requirement of use.
Chinese patent 200810138430.4 discloses a kind of chemical bonding and has been cross-linked and fiber and the common multi-layer perfluor sulfonate film strengthening of microporous barrier.Although used chemical bonding crosslinked and tunica fibrosa, microporous barrier multiple means to carry out modification, the performance of film is greatly improved on basis in the past, film still exists film-forming resin to be combined the problem such as not firm with fiber and perforated membrane.
For the perfluorinated sulfonic acid ionic membrane of fuel cell, need to meet the demands: stable, high conductivity, high mechanical properties.Generally speaking, when ion-exchange capacity raises, the equivalent value of (per) fluoropolymer declines, and (equivalent value EW value reduces, ion exchange capacity IEC=1000/EW), film strength also reduces simultaneously, and the also rising thereupon of the gas permeability of film, this will produce very serious impact on fuel cell.Therefore, preparation has macroion exchange capacity, the film of the Mechanics of Machinery intensity that had and air-tightness, the stability that had is fuel cell, and the fuel cell especially using on the delivery vehicles such as automobile is able to practical key.
(this film is in preparing production process due to the reason of the processing technology of reinforcing material itself for the polyelectrolyte film that tradition ePTFE microporous barrier strengthens, the longitudinal stretching of film is far longer than the cross directional stretch of film, the degree of crystallinity that molecule in film has been had in the vertical, simultaneously the micropore in film also demonstrates longitudinal aperture much larger than horizontal aperture) size changing rate of film differs very large on transverse and longitudinal while making sheet conductance, Mechanics of Machinery character, the suction-dehydration of formed enhancing film.For example, more than the polyelectrolyte film longitudinal strength that ePTFE film strengthens can reach 40MPa, but transverse strength is often less than 25MPa; Elongation at break is laterally again much larger than longitudinally.When eluting water, lateral dimension changes also than longitudinally much larger.So just make to be easy to the horizontal direction generation deformation at film when assembling film pile and membrane module, even film destroys.And film causes that because humidity changes difference swelling or contraction very greatly also occurs in transverse and longitudinal direction for water suction or dehumidification in battery context, flanging place of film in pile or assembly will be born very large, inhomogeneous mechanical stress like this, the destruction that long-term use finally causes film.
Summary of the invention
For the deficiencies in the prior art, polymer dielectric film that a kind of fleece of the present invention strengthens and preparation method thereof.
Because spraying coating process has been taked in fibroreticulate moulding, make polymer dielectric film that fleece strengthens no matter in mechanical property, or on size changing rate, and on electrochemical properties, there is isotropic characteristic.Technical assignment of the present invention is the polymer dielectric film strengthening by fleece, the shortcoming such as the air-tightness that not only solves conventional film is bad, Mechanics of Machinery character is poor, also solved while adopting polytetrafluoroethyltwo two-way stretch film (ePTFE) to strengthen polymer dielectric film in the past, because the anisotropy of ePTFE film own causes film, the problems such as Mechanics of Machinery fatigue, damage easily occur because each stress is different in use.
Technical scheme of the present invention is as follows:
The polymer dielectric film that fleece strengthens, this film is to take perfluorinated ion exchange resin as matrix formation film, the inside of film is added with fleece; Described perfluorinated ion exchange resin is selected from one or more the mixing in perfluorinated sulfonic resin, perfluor phosphoric acid resin, perfluorinated sulfonic acid-perfluor phosphoric acid copolymer resins, described fibroreticulate composition fiber is selected from one or more in polytetrafluoroethylene fibre, perfluoroethylene-propylene fiber (FEP), poly-perfluoro propyl vinyl ether fiber, perfluorinated alkoxy vinyl ether copolymer fiber (PFA), ceramic fibre, mineral fibres or oxide fibre, fibre diameter is 0.005 micron～50 microns, and fibre length is 0.05 micron～3 millimeters.
The present invention strengthens polymer dielectric film with fibroreticulate form, and it is arbitrary position that matrix forms film that fleece is arranged in perfluorinated ion exchange resin, preferred, and it is the centre that matrix forms film that fleece is positioned at perfluorinated ion exchange resin; Such as, in fibrous fleece both sides, having respectively one deck perfluorinated ion exchange resin is the film that matrix forms, fleece is positioned at the centre of two-layer base film.
According to the present invention, preferably, described perfluorinated sulfonic resin is that the polymer that one or more and the tetrafluoroethene multi-component copolymer in following formula (A), (B), (C), (D) function monomer obtains makes through hydrolysis acidification, and the number-average molecular weight of polymer is between 140,000～500,000;
Described perfluor phosphoric acid resin is that the polymer being obtained by monomer shown in formula (E) and tetrafluoroethene copolymerization makes through acidification hydrolization, and the number-average molecular weight of polymer is between 140,000～500,000;
Described perfluorinated sulfonic acid-perfluor phosphoric acid copolymer resins is to carry out multi-component copolymer by being selected from one or more monomers in above-mentioned formula (A), (B), (C), (D) and formula (E) and tetrafluoroethene, the polymer that copolymerization obtains makes through hydrolysis acidification, and the number-average molecular weight of polymer is between 140,000～500,000.
Copolyreaction of the present invention is the common practise in organic chemistry field of polymer technology, as long as clear and definite comonomer specifically, to those skilled in the art, can according to prior art, select suitable copolyreaction condition apparently, as temperature, time, solvent, initator etc., thereby obtain perfluorinated ion exchange resin of the present invention.
According to the present invention, preferred, the ion exchange capacity of described perfluorinated ion exchange resin is at 0.85～1.60mmol/g, more preferably 1.05～1.55mmol/g.
According to the present invention, preferred, the surface of described fibroreticulate composition fiber silicifies, the hydrophilic modifying of sulfonation, sulphation or phosphorylation; The existing surface modifying method for polytetrafluoroethylene comprises that modified with reduction method, laser emission modification method, plasma modification method or the silicic acid activation method of sodium naphthalene solution are all suitable for the modification to fiber of the present invention.More preferably silicic acid activation method is carried out modification to fiber of the present invention because it can be on fluorine carbon fiber surface the silicon dioxide of water conservation on Direct precipitation.Other method of modifying by modification after, fiber surface has produced hydrophilic group, preferably carries out on this basis further modification again, such as by the fiber of modification at tetraethoxysilane, ZrOCl
2-H
3pO
4or carry out further modification in titanate esters etc.
According to the present invention, preferably, take perfluorinated ion exchange resin when matrix forms film, also add the oxide of one or more elements in metal elements W, Ir, Y, Mn, Ru, V, Ce, Zn, La or the additive that complex compound forms, in described additive, metallic element accounts for 0.01%～10% of perfluorinated ion exchange resin gross mass.Preferred oxide addition is selected from MnO
2, CeO
2or LaO
2in one or more.In preferred Complex Additive, ligand has but is not limited to one or more in benzimidazole, porphyrin ring, three azo-cycles, schiff base of salicylaldehyde, phenol oxygen dialdehyde schiff base structure unit, and the structure of ligand is selected from but is not limited to one or more in following formula I～V compound.
I
In formula I, R
1, R
2, R
3, R
4can independently be selected from the straight chain of H, C1～C10 or the straight chain that replace or that part halogen replaces or with alkyl, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or with alkylene, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or the amido that replaces with aryl, sulfonic group, carboxylic acid group, phosphate, amino or the alkyl of straight chain with the alkyl of straight chain, alkylene, aryl, perhalogeno element.
II
In formula II, R
5, R
1, R
2can independently be selected from the straight chain of H, C1～C10 or the straight chain that replace or that part halogen replaces or with alkyl, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or with alkylene, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or the amido that replaces with aryl, sulfonic group, carboxylic acid group, phosphate, amino or the alkyl of straight chain with the alkyl of straight chain, alkylene, aryl, perhalogeno element.
III
In formula III, R
6, R
7can independently be selected from the straight chain of H, C1～C10 or the straight chain that replace or that part halogen replaces or with alkyl, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or with alkylene, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or the amido that replaces with aryl, sulfonic group, carboxylic acid group, phosphate, amino or the alkyl of straight chain with the alkyl of straight chain, alkylene, aryl, perhalogeno element.
IV
M, x can independently be selected from 1～10 integer.
V
The alkyl of R=C1～C10.
In described Complex Additive, ligand accounts for 0.01%～10% of perfluorinated ion exchange resin gross mass.These additives can effectively be eliminated the peroxide that fuel cell electrochemical process produces, and diaphragm is not subject to their corrosion.
According to the present invention, the preparation method of the polymer dielectric film that a kind of fleece strengthens, mainly comprises perfluorinated ion exchange resin dispersion liquid film forming, fiber dispersion spraying, perfluorinated ion exchange resin dispersion liquid, and step is as follows:
(1) perfluorinated ion exchange resin is distributed in solvent to the dispersion liquid B that the dispersion liquid A that the content of preparing perfluorinated ion exchange resin is 10～40wt% and the content of perfluorinated ion exchange resin are 0.1～2wt%; Described solvent is selected from 1,2-tri-chloro-1, one or more in 2,2-HFC-143a (F113), dimethyl formamide, dimethylacetylamide, methylformamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or glycerol;
(2) by the dispersion liquid A in step (1), the mode by cast, spin coating, curtain coating, silk screen printing, spraying or dipping forms after liquid film on flat board, at 20～100 ℃, preferably 30～50 ℃ of heat treatment is 10～120 seconds, preferably 10～30 seconds, forms the not completely crued film in surface;
(3) fiber is evenly spread in the described dispersion liquid B of step (1) by strong stirring or ultrasonic processing; The fiber dispersion that formation fiber content is 1～20wt%; Described fiber is selected from one or more in polytetrafluoroethylene fibre, perfluoroethylene-propylene fiber (FEP), poly-perfluoro propyl vinyl ether fiber, perfluorinated alkoxy vinyl ether copolymer fiber (PFA), ceramic fibre, mineral fibres or oxide fibre;
(4) fiber dispersion step (3) being obtained is sprayed on the formed surface of step (2) not on the surface of completely crued film, and at 20～100 ℃, preferably 30～50 ℃ of heat treatment is 10～120 seconds, preferably 30～60 seconds, forms fleece;
(5) by the dispersion liquid of the perfluorinated ion exchange resin forming in step (1), the mode by cast, spin coating, curtain coating, silk screen printing, spraying or dipping forms and the perfluorinated ion exchange resin liquid film of step (2) equal thickness be placed in 50～250 ℃ on the formed fleece of step (4), heat treatment 0.1～600 minute, obtains the present invention and strengthens polymer dielectric film.
According to the present invention, preferably, in the dispersion liquid A of described step (1), also add by metallic element: the additive that the oxide of one or more elements in W, Ir, Y, Mn, Ru, V, Ce, Zn, La or complex compound form, in described additive, metallic element accounts for 0.01%～10% of perfluorinated ion exchange resin gross mass.
According to the present invention, preferred, in described step (3), the diameter of fiber is 0.005 micron～50 microns, and fibre length is 0.05 micron～3 millimeters.
The thickness of the formed enhancing polymer dielectric film of the present invention is 5～250 microns, and fleece is 1～50g/m at the content of polymer dielectric film
2, preferred 1～10g/m
2.
The invention has the beneficial effects as follows:
1, the polymer dielectric film that fleece strengthens for the present invention, has very excellent mechanical strength properties and electric property, on size changing rate when externally ambient humidity changes simultaneously or sheet conductance all shows excellent isotropism in nature.
2, there is not anisotropic factor in Enhancement Method used in the present invention, thus strong solution the drawback of traditional enhancement method.Simultaneously because fiber is overlapping mutually, overlapping place connects by very thin perfluorinated ion exchange resin, this layer of attachment material not only played the effect of binder fibre but also played the effect of conducting ion, thereby avoided traditional ePTFE film to strengthen polymer dielectric film owing to existing a large amount of nonconducting nodes to hinder the problem that ion transmits in film.In addition, between fiber, mutual overlapping formation fleece can play the collaborative effect strengthening in polymer dielectric film.
3, the intensity of enhancing polymer dielectric film of the present invention and dimensional stability also far above simply by fiber dispersion in polymer poly compound dielectric film, fiber-fiber spacing is from far and any mutually collaborative problem do not occur.In addition, fiber is also very likely distributed on the surface that strengthens film, thereby has reduced the contact area of film and catalyst or collector and the resistance rising that causes.
Embodiment
By the following examples the present invention is further described, but those skilled in the art are known, the following examples are only for explaining, and not the spirit and scope of the present invention are limited.In embodiment, if no special instructions, described percentage composition (%) is mass percent.
Embodiment 1:
The perfluorinated sulfonic resin that the exchange capacity that formula (C) and TFE copolymer hydrolysis acidification are obtained is 1.50mmol/g is dissolved in the dispersion liquid A that forms 25wt% in dimethyl formamide (DMF); The perfluorinated sulfonic resin that the exchange capacity that formula (C) and TFE copolymer hydrolysis acidification are obtained is 1.26mmol/g is dissolved in the dispersion liquid B that forms 1.5wt% in dimethyl formamide (DMF); To adding average grain diameter in dispersion liquid A, be the MnO of 0.5 μ m
2particle, dispersing and dissolving is prepared film forming dispersion liquid 1; MnO
2the mass ratio of particle and perfluorinated sulfonic resin is 3:100.
By length, be 30 microns, diameter is the polytetrafluoroethylene fibre of 1 micron, is distributed to and in dispersion liquid B, forms the polytetrafluoroethylene fibre suspension 1 that polytetrafluoroethylene fibre content is 5wt%.
Dispersion liquid 1 curtain coating on plate glass is formed to the liquid film of 100 micron thickness, be then placed in after 50 ℃ of baking ovens heat 30s and take out, form fleeces in its surface by sprayed suspension 1 and at 80 ℃ of dry 100s, fibroreticulate fiber content is 5g/m
2.
On fleece, curtain coating forms the liquid film of the dispersion liquid 1 of 100 micron thickness again, is then placed in the baking oven of 160 ℃ and heats 200min, obtains the polyelectrolyte film that PTFE web strengthens.
Embodiment 2:
The perfluorinated sulfonic resin that the exchange capacity that formula (A), (C) and tetrafluoroethylene terpolymer hydrolysis acidification are obtained is 1.30mmol/g is dissolved in the dispersion liquid A that forms 30wt% in water-propyl alcohol mixed solvent; The perfluorinated sulfonic resin that the exchange capacity that formula (A) and TFE copolymer hydrolysis acidification are obtained is 1.05mmol/g is dissolved in the dispersion liquid B that forms 1.5wt% in dimethyl formamide (DMF); To adding average grain diameter in dispersion liquid A, be the CeO of 0.5 μ m
2particle, dispersing and dissolving is prepared film forming dispersion liquid 2; CeO
2the mass ratio of particle and perfluorinated sulfonic resin is 1:100.
By length, be 100 microns, diameter is the PFA fiber of 2 microns, is distributed to and in dispersion liquid B, forms the PFA fibrous suspension 2 that PFA fiber content is 5wt%.
Dispersion liquid 2 curtain coating on plate glass is formed to the liquid film of 150 micron thickness, be then placed in after 50 ℃ of baking ovens heat 30s and take out, form fleeces in its surface by sprayed suspension 2 and at 80 ℃ of dry 100s, fibroreticulate fiber content is 10g/m
2.
On fleece, curtain coating forms the liquid film of the dispersion liquid 2 of 150 micron thickness again, is then placed in the baking oven of 160 ℃ and heats 200min, obtains the polyelectrolyte film that PFA fleece strengthens.
Embodiment 3:
The perfluorinated sulfonic resin that the exchange capacity that formula (A), (B) and tetrafluoroethylene terpolymer hydrolysis acidification are obtained is 1.24mmol/g is dissolved in the dispersion liquid A that forms 10wt% in water-propyl alcohol mixed solvent; The perfluorinated sulfonic resin that the exchange capacity that formula (A) and TFE copolymer hydrolysis acidification are obtained is 1.05mmol/g is dissolved in the dispersion liquid B that forms 1.5wt% in dimethyl formamide (DMF); To adding average grain diameter in dispersion liquid A, be the LaO of 0.5 μ m
2particle, dispersing and dissolving is prepared film forming dispersion liquid 3; LaO
2the mass ratio of particle and perfluorinated sulfonic resin is 1:100.
By length, be 50 microns, diameter is the FEP fiber of 5 microns, is distributed to and in dispersion liquid B, forms the FEP fibrous suspension 3 that FEP fiber content is 5wt%.
Dispersion liquid 3 curtain coating on plate glass is formed to the liquid film of 150 micron thickness, be then placed in after 50 ℃ of baking ovens heat 30s and take out, form fleeces in its surface by sprayed suspension 3 and at 80 ℃ of dry 100s, fibroreticulate fiber content is 2g/m
2.
On fleece, curtain coating forms the liquid film of the dispersion liquid 3 of 150 micron thickness again, is then placed in the baking oven of 160 ℃ and heats 200min, obtains the polyelectrolyte film that FEP fleece strengthens.
Embodiment 4:
The perfluorinated sulfonic resin that the exchange capacity that formula (A), (B) and tetrafluoroethylene terpolymer hydrolysis acidification are obtained is 1.24mmol/g is dissolved in the dispersion liquid A that forms 10wt% in water-propyl alcohol mixed solvent; The perfluorinated sulfonic resin that the exchange capacity that formula (A) and TFE copolymer hydrolysis acidification are obtained is 1.05mmol/g is dissolved in the dispersion liquid B that forms 1.5wt% in dimethyl formamide (DMF); To adding average grain diameter in dispersion liquid A, be the LaO of 0.5 μ m
2particle, dispersing and dissolving is prepared film forming dispersion liquid 4; LaO
2the mass ratio of particle and perfluorinated sulfonic resin is 1:100.
By length, be 50 microns, diameter is the zirconia ceramic fiber of 5 microns, is distributed to and in dispersion liquid B, forms the zirconia ceramic fibrous suspension 4 that zirconia ceramic fiber content is 5wt%.
Dispersion liquid 4 curtain coating on plate glass is formed to the liquid film of 150 micron thickness, be then placed in after 50 ℃ of baking ovens heat 30s and take out, form fleeces in its surface by sprayed suspension 4 and at 80 ℃ of dry 100s, fibroreticulate fiber content is 20g/m
2.
On fleece, curtain coating forms the liquid film of the dispersion liquid 4 of 150 micron thickness again, is then placed in the baking oven of 160 ℃ and heats 200min, obtains the polyelectrolyte film that zirconia ceramic fleece strengthens.
Comparative example 1:
The perfluorinated sulfonic resin that the exchange capacity that formula (A), (B) and tetrafluoroethylene terpolymer hydrolysis acidification are obtained is 1.24mmol/g is dissolved in the dispersion liquid that forms 10wt% in water-propyl alcohol mixed solvent, the thick eptfe film (porosity 80%) of 20 μ m is placed in to above-mentioned solution to be soaked approximately 1 hour, then the film soaking is dried to processing on 160 ℃ of heating 200min, obtains the microporous barrier that 25 μ m are thick and strengthen amberplex.
The performance characterization of film
Performance to the film of embodiment 1-4 and comparative example 1 preparation characterizes, and the results are shown in Table 1.The performance characterizing comprises 95 ℃ of conductivity, hot strength, the size changing rate of different directions.Wherein the test of size changing rate is to cut 5 * 5cm
2film be placed in the water 1 hour of 100 ℃, measure the elongated rate of change (direction of blade applicator walking when x direction refers to masking curtain coating; Y direction refers to the direction perpendicular to x direction).The formula of rate of change is as follows: Δ L=(L
t-L
0)/L
0* 100% (Lt be water suction after length, L
0the length before water suction).The test of conductivity is the sheet conductance using in four electrode method test x and y direction.Hot strength comprises the intensity of x direction and the intensity of y direction.
From the data of table 1, the polyelectrolyte film that tradition use expanded PTFE microporous barrier strengthens is because the anisotropy of expanded PTFE makes polyelectrolyte film electrical conductance, dimensional stability and intensity in the x and y direction all occur anisotropy.
The various films of table 1 characterize
Claims (10)
1. the polymer dielectric film that fleece strengthens, this film is to take perfluorinated ion exchange resin as matrix formation film, there is fleece the inside of film; Described perfluorinated ion exchange resin is selected from one or more the mixing in perfluorinated sulfonic resin, perfluor phosphoric acid resin, perfluorinated sulfonic acid-perfluor phosphoric acid copolymer resins, described fibroreticulate composition fiber is selected from one or more in polytetrafluoroethylene fibre, perfluoroethylene-propylene fiber (FEP), poly-perfluoro propyl vinyl ether fiber, perfluorinated alkoxy vinyl ether copolymer fiber (PFA), ceramic fibre, mineral fibres or oxide fibre, fibre diameter is 0.005 micron～50 microns, and fibre length is 0.05 micron～3 millimeters.
2. polymer dielectric film according to claim 1, is characterized in that, it is arbitrary position that matrix forms film that described fleece is arranged in perfluorinated ion exchange resin, preferably centre position.
3. polymer dielectric film according to claim 1, it is characterized in that, described perfluorinated sulfonic resin is that the polymer that one or more and the tetrafluoroethene multi-component copolymer in following formula (A), (B), (C), (D) function monomer obtains makes through hydrolysis acidification, and the number-average molecular weight of polymer is between 140,000～500,000;
Described perfluor phosphoric acid resin is that the polymer being obtained by monomer shown in formula (E) and tetrafluoroethene copolymerization makes through acidification hydrolization, and the number-average molecular weight of polymer is between 140,000～500,000;
Described perfluorinated sulfonic acid-perfluor phosphoric acid copolymer resins is to carry out multi-component copolymer by being selected from one or more monomers in above-mentioned formula (A), (B), (C), (D) and formula (E) and tetrafluoroethene, the polymer that copolymerization obtains makes through hydrolysis acidification, and the number-average molecular weight of polymer is between 140,000～500,000.
4. polymer dielectric film according to claim 1, is characterized in that, the ion exchange capacity of described perfluorinated ion exchange resin is at 0.85～1.60mmol/g, preferably 1.05～1.55mmol/g.
5. polymer dielectric film according to claim 1, is characterized in that, hydrophilic modifying is carried out on the surface of described fibroreticulate composition fiber; Preferably adopt silicic acid activation method to carry out modification to fiber.
6. polymer dielectric film according to claim 1, it is characterized in that, take perfluorinated ion exchange resin when matrix forms film, also add by metallic element: the additive that the oxide of one or more elements in W, Ir, Y, Mn, Ru, V, Ce, Zn, La or complex compound form, in described additive, metallic element accounts for 0.01%～10% of perfluorinated ion exchange resin gross mass; Preferred oxide addition is selected from MnO
2, CeO
2or LaO
2in one or more; In Complex Additive, ligand is one or more in benzimidazole, porphyrin ring, three azo-cycles, schiff base of salicylaldehyde, phenol oxygen dialdehyde schiff base structure unit, and preferred ligand is selected from one or more in following formula I～V compound;
I
In formula I, R
1, R
2, R
3, R
4can independently be selected from the straight chain of H, C1～C10 or the straight chain that replace or that part halogen replaces or with alkyl, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or with alkylene, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or the amido that replaces with aryl, sulfonic group, carboxylic acid group, phosphate, amino or the alkyl of straight chain with the alkyl of straight chain, alkylene, aryl, perhalogeno element;
II
In formula II, R
5, R
1, R
2can independently be selected from the straight chain of H, C1～C10 or the straight chain that replace or that part halogen replaces or with alkyl, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or with alkylene, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or the amido that replaces with aryl, sulfonic group, carboxylic acid group, phosphate, amino or the alkyl of straight chain with the alkyl of straight chain, alkylene, aryl, perhalogeno element;
III
In formula III, R
6, R
7can independently be selected from the straight chain of H, C1～C10 or the straight chain that replace or that part halogen replaces or with alkyl, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or with alkylene, the perhalogeno element straight chain that replace or that part halogen replaces of straight chain or the amido that replaces with aryl, sulfonic group, carboxylic acid group, phosphate, amino or the alkyl of straight chain with the alkyl of straight chain, alkylene, aryl, perhalogeno element;
IV
M, x can independently be selected from 1～10 integer;
V
The alkyl of R=C1～C10;
In described Complex Additive, ligand accounts for 0.01%～10% of perfluorinated ion exchange resin gross mass.
7. a preparation method for the polymer dielectric film described in claim 1～6 any one, mainly comprises perfluorinated ion exchange resin dispersion liquid film forming, fiber dispersion spraying, perfluorinated ion exchange resin dispersion liquid film forming; Step is as follows:
(1) perfluorinated ion exchange resin is distributed in solvent to the dispersion liquid B that the dispersion liquid A that the content of preparing perfluorinated ion exchange resin is 10～40wt% and the content of perfluorinated ion exchange resin are 0.1～2wt%; Described solvent is selected from 1,2-tri-chloro-1, one or more in 2,2-HFC-143a (F113), dimethyl formamide, dimethylacetylamide, methylformamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or glycerol;
(2) by the dispersion liquid A in step (1), the mode by cast, spin coating, curtain coating, silk screen printing, spraying or dipping forms after liquid film on flat board, at 20～100 ℃, preferably 30～50 ℃ of heat treatment is 10～120 seconds, preferably 10～30 seconds, forms the not completely crued film in surface;
(3) fiber is evenly spread in the described dispersion liquid B of step (1) by strong stirring or ultrasonic processing; The fiber dispersion that formation fiber content is 1～20wt%; Described fiber is selected from one or more in polytetrafluoroethylene fibre, perfluoroethylene-propylene fiber (FEP), poly-perfluoro propyl vinyl ether fiber, perfluorinated alkoxy vinyl ether copolymer fiber (PFA), ceramic fibre, mineral fibres or oxide fibre;
(4) fiber dispersion step (3) being obtained is sprayed on the formed surface of step (2) not on the surface of completely crued film, and at 20～100 ℃, preferably 30～50 ℃ of heat treatment is 10～120 seconds, preferably 30～60 seconds, forms fleece;
(5) by the dispersion liquid of the perfluorinated ion exchange resin forming in step (1), the mode by cast, spin coating, curtain coating, silk screen printing, spraying or dipping forms and the perfluorinated ion exchange resin liquid film of step (2) equal thickness be placed in 50～250 ℃ on the formed fleece of step (4), heat treatment 0.1～600 minute, obtains.
8. the preparation method of enhancing polymer dielectric film according to claim 7, it is characterized in that, in the dispersion liquid A of described step (1), also add by metallic element: the additive that the oxide of one or more elements in W, Ir, Y, Mn, Ru, V, Ce, Zn, La or complex compound form, in described additive, metallic element accounts for 0.01%～10% of perfluorinated ion exchange resin gross mass.
9. the preparation method of enhancing polymer dielectric film according to claim 7, is characterized in that, in described step (3), the diameter of fiber is 0.005 micron～50 microns, and fibre length is 0.05 micron～3 millimeters.
10. the preparation method of enhancing polymer dielectric film according to claim 7, is characterized in that, the thickness of formed enhancing polymer dielectric film is 5～250 microns, and fleece is 1～50g/m at the content of polymer dielectric film
2; Preferably, described fleece is 1～10g/m at the content of polymer dielectric film
2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310157568.XA CN104134812B (en) | 2013-05-02 | 2013-05-02 | Fiber-net-reinforced polymer electrolyte membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310157568.XA CN104134812B (en) | 2013-05-02 | 2013-05-02 | Fiber-net-reinforced polymer electrolyte membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104134812A true CN104134812A (en) | 2014-11-05 |
| CN104134812B CN104134812B (en) | 2017-02-08 |
Family
ID=51807403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310157568.XA Active CN104134812B (en) | 2013-05-02 | 2013-05-02 | Fiber-net-reinforced polymer electrolyte membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104134812B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285541A (en) * | 2017-12-29 | 2018-07-17 | 山东东岳高分子材料有限公司 | The exchange membrane containing fluorine and preparation method thereof of nanofiber enhancing |
| CN109346751A (en) * | 2018-09-10 | 2019-02-15 | 中原工学院 | A kind of preparation method of composite proton exchange membrane for fuel cell |
| CN110444793A (en) * | 2019-08-16 | 2019-11-12 | 上海元城汽车技术有限公司 | A kind of durability proton exchange, preparation method and applications |
| CN113699600A (en) * | 2021-08-26 | 2021-11-26 | 东华大学 | Protective product with mustard gas/bacterium/virus protection function and preparation method thereof |
| CN115991820A (en) * | 2021-10-18 | 2023-04-21 | 山东东岳未来氢能材料股份有限公司 | Polymeric phosphonic acid ionic membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010026883A1 (en) * | 2000-03-31 | 2001-10-04 | Asahi Glass Company, Ltd. | Electrolyte membrane for polymer electrolyte fuel cell and producing method thereof |
| CN1902777A (en) * | 2003-12-17 | 2007-01-24 | 百拉得动力系统公司 | Reduced degradation of ion-exchange membranes in electrochemical fuel cells |
| CN102522576A (en) * | 2011-12-24 | 2012-06-27 | 山东东岳高分子材料有限公司 | Fuel cell membrane with high tolerance and its preparation method |
-
2013
- 2013-05-02 CN CN201310157568.XA patent/CN104134812B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010026883A1 (en) * | 2000-03-31 | 2001-10-04 | Asahi Glass Company, Ltd. | Electrolyte membrane for polymer electrolyte fuel cell and producing method thereof |
| CN1902777A (en) * | 2003-12-17 | 2007-01-24 | 百拉得动力系统公司 | Reduced degradation of ion-exchange membranes in electrochemical fuel cells |
| CN102522576A (en) * | 2011-12-24 | 2012-06-27 | 山东东岳高分子材料有限公司 | Fuel cell membrane with high tolerance and its preparation method |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285541A (en) * | 2017-12-29 | 2018-07-17 | 山东东岳高分子材料有限公司 | The exchange membrane containing fluorine and preparation method thereof of nanofiber enhancing |
| CN109346751A (en) * | 2018-09-10 | 2019-02-15 | 中原工学院 | A kind of preparation method of composite proton exchange membrane for fuel cell |
| CN110444793A (en) * | 2019-08-16 | 2019-11-12 | 上海元城汽车技术有限公司 | A kind of durability proton exchange, preparation method and applications |
| CN110444793B (en) * | 2019-08-16 | 2021-02-05 | 上海元城汽车技术有限公司 | Durable proton exchange membrane, preparation method and application thereof |
| CN113699600A (en) * | 2021-08-26 | 2021-11-26 | 东华大学 | Protective product with mustard gas/bacterium/virus protection function and preparation method thereof |
| CN115991820A (en) * | 2021-10-18 | 2023-04-21 | 山东东岳未来氢能材料股份有限公司 | Polymeric phosphonic acid ionic membrane and preparation method thereof |
| CN115991828A (en) * | 2021-10-18 | 2023-04-21 | 山东东岳未来氢能材料股份有限公司 | Perfluorinated sulfonic acid resins containing phosphonic acid structural units |
| CN115991821A (en) * | 2021-10-18 | 2023-04-21 | 山东东岳未来氢能材料股份有限公司 | Proton exchange membrane containing phosphonic acid structural unit and preparation method thereof |
| CN115991822A (en) * | 2021-10-18 | 2023-04-21 | 山东东岳未来氢能材料股份有限公司 | Ionic polymer membrane containing perfluorobutyl ethyl ether and preparation method thereof |
| CN115991829A (en) * | 2021-10-18 | 2023-04-21 | 山东东岳未来氢能材料股份有限公司 | Multi-copolymer containing perfluorobutyl ethyl ether, fluorine-containing resin and preparation method |
| CN115991827A (en) * | 2021-10-18 | 2023-04-21 | 山东东岳未来氢能材料股份有限公司 | Multi-copolymer containing sulfonyl fluoride, ion exchange resin and preparation method |
| CN115991821B (en) * | 2021-10-18 | 2023-12-22 | 山东东岳未来氢能材料股份有限公司 | Proton exchange membrane containing phosphonic acid structural unit and preparation method thereof |
| CN115991820B (en) * | 2021-10-18 | 2024-01-05 | 山东东岳未来氢能材料股份有限公司 | Polymeric phosphonic acid ionic membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104134812B (en) | 2017-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9793564B2 (en) | Composite having ion exchange function and preparation method and use thereof | |
| US9325027B2 (en) | Preparation method of fluorine-containing ionomer composite material with ion exchange function | |
| CN101728549B (en) | High-temperature proton exchange compound film | |
| CN100580987C (en) | Microporous-film-reinforced fluorine-containing cross-linking ion-exchange membrane and preparation method thereof | |
| KR20150086384A (en) | Fluorine-based polymer electrolyte membrane | |
| CN104134812B (en) | Fiber-net-reinforced polymer electrolyte membrane and preparation method thereof | |
| JP5748844B2 (en) | Fluorine-containing ionomer complex having ion exchange function, preparation method and use thereof | |
| JP4771702B2 (en) | Polymer solid electrolyte membrane with reinforcing material | |
| JP2006269266A (en) | Compound solid polyelectrolyte membrane having reinforcement material | |
| CN101745321B (en) | Micro-porous membrane reinforced perfluorinated cross-linking ion exchange membrane and preparation method thereof | |
| CN101764232B (en) | Fluorinated proton exchange membrane with cross-linked network structure and preparation thereof | |
| KR102125412B1 (en) | Method for manufacturing hydrocarbon based reinforced polymer electrolyte membrane for fuel cell and reinforced polymer electrolyte membrane manufactured thereby | |
| CN101350419A (en) | Fiber-reinforced fluorine-containing cross-linking ionic membrane and preparation method thereof | |
| CN102013499B (en) | Fluorine-containing ionomer composite material with function of ion exchange and preparation method and application thereof | |
| CN102010555B (en) | Fluorine-containing ionomer composite with ion exchange function as well as preparation method and application thereof | |
| CN101745323B (en) | Fiber reinforced composite multi-layer total fluoride crosslinking ionic membrane and preparation method thereof | |
| CN102013498B (en) | Fluorine-containing ionomer composite material with ion exchange function as well as preparation method and application thereof | |
| KR102154101B1 (en) | A composite membrane comprising nonwoven PAN support and hydrocarbon-based electrolyte impregnated therein and the use thereof | |
| CN101733015B (en) | Micro-porous membrane reinforced multi-layer fluorine-containing cross-linking ionic membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |