CN101851382B - Fiber and modified silica-doped fluorine-containing ion film and preparation method thereof - Google Patents
Fiber and modified silica-doped fluorine-containing ion film and preparation method thereof Download PDFInfo
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- 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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention relates to a fiber and modified silica-doped fluorine-containing ion film and a preparation method thereof and belongs to the technical field of polymer composite materials. The preparation method comprises the following steps of: performing surface modification on powder SiO2 by using fluorine-containing compounds; dissolving hydrogen fluorine-containing sulfonic acid resin and fluorine-containing sulfonic acid metal salt resin by using a polar solvent, and adding a reinforced fiber and powder SiO2 subjected to surface modification by the fluorine-containing compounds, and uniformly mixing the solution through ultrasound or stirring; and forming the film by the solution by adopting the pouring, casting, screen printing, spraying or impregnating technology, and preparing the fiber and modified silica-doped fluorine-containing ion film through stripping. The prepared fluorine-containing sulfonic acid film has the advantages of better water conservation, higher proton conductivity, and higher mechanical properties.
Description
Technical field
The present invention relates to a kind of fiber and modified silica-doped fluorine-containing ion film and preparation method thereof, belong to technical field of polymer composite materials.
Background technology
Fuel cell (Fuel Cell) be a kind of with chemical energy without overheated and be converted into the device of electric energy.It utilizes non-petroleum fuel such as hydrogen, Sweet natural gas, coal gas and methyl alcohol and pure oxygen or air at the two poles of the earth of battery oxidation-reduction reaction to take place respectively, continuously to environment direct current is provided.Fuel cell is considered to after firepower, waterpower and nuclear energy power generation, be hopeful to provide in a large number the 4th kind of generation technology of electric power.Fuel cell has multiple, and the difference between the various fuel cells is that the ionogen that uses is different.Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell, i.e. PEMFC) is an ionogen with the PEM, is characterized in noiselessness, and zero pollutes; Do not have corrosion, the life-span is long.Because its specific power is big, energy efficiency is high, and working temperature is low, and toggle speed is fast, is particularly suitable for as power cell.
Though the sulfonic fluoropolymer PEM is used for many years, but still have low, the poor dimensional stability of high temperature proton conductivity, the not high shortcoming of physical strength does not reach commercial requirement.Especially dimensional stability aspect, film are also different because of the different swelling ratios of water-intake rate under different humidity.In addition, when the sulfonic fluoropolymer exchange membrane is worked under comparatively high temps,, thereby the efficient of fuel cell is descended greatly because the rapid dehydration of film causes the proton-conducting of film sharply to descend.But high working temperature (being higher than 90 ℃) can improve the anti-carbon monoxide property of fuel-cell catalyst greatly.In addition, existing sulfonic fluoropolymer film has certain hydrogen or methanol permeability, and especially in DMFC, methanol permeability is very big, becomes fatal problem.Therefore, how to improve sulfonic fluoropolymer proton exchange film strength, dimensional stability, the perviousness of reduction working medium etc. is the key subjects that fuel cell industries faces.
For solving the high temperature proton conduction behavior of sulfonic fluoropolymer film, the inorganic additive that much has the high-temp water-preserving ability is added in the sulfonic fluoropolymer exchange membrane.Choose the requirement of inorganic water conservation particle: (1) particle has water retention capacity preferably, and higher dehydration temperature is just arranged; (2) has intermiscibility preferably with proton exchange resins; (3) particle has certain proton conducting ability; (4) be easy to obtain nanometer particle; (5) particle structure stability; (6) help keeping or improve the mechanical strength or the physical size stability of PEM; Usually the inorganic water conservation particle that adopts is SiO
2, TiO
2, ZrHPO
4, ZrO
2Particle, heteropolyacid or solid acid particle, zeolite family mineral particle, stratotype clay mineral such as smectite and intercalation clay mineral thereof etc.
Chinese patent CN1862857, CN200810138704.X, CN200810107853.X and CN200810138186.1 etc. disclose and in perfluorinated sulfonic resin, have added SiO
2Can improve the high-temperature electric conduction performance of PEM etc. inorganic water-holding agent, mix fiber to improve the mechanical property of film.But they are not recognized: because the inorganic particulate particle diameter is little, specific surface area is big, in the machine-shaping process, reunite easily; And owing to inorganic particulate tends to be separated with the matrix fluoro-resin, thereby have a strong impact on work-ing life, dimensional stability and the high-temperature electric conduction property of film.
The sulfonic fluoropolymer ionic membrane that is used for fuel cell need satisfy following requirement: high temperature low humidity water retention property, Gaoyou specific conductivity, high mechanical strength preferably.Generally speaking, when ion-exchange capacity raise, the equivalent value of fluoropolymer decline (equivalent value EW value reduces, loading capacity IEC=1000/EW) film strength simultaneously also reduced.Therefore, preparation has a macroion exchange capacity, can exempt to keep physical strength simultaneously, and the ionic membrane with good water retention property and high proton conductivity is very important.
Summary of the invention
The present invention is directed to the deficiency of prior art, a kind of ion-exchange membrane and preparation method with better conductivity and physical strength is provided.The present invention is through carrying out modification to silicon-dioxide; Improve the degree of scatter of silicon dioxide microparticle in perfluorinated sulfonic resin; Strengthen the affinity of particle and matrix resin; And in resin, mix fortifying fibre, finally improved physical strength, water retention property and the proton conductivity of sulfonic fluoropolymer ionic membrane.
A kind of fiber and modified silica-doped fluorine-containing ion film, it is a matrix with Hydrogen sulfonic fluoropolymer resin and sulfonic fluoropolymer metal-salt resin, fortifying fibre and through the SiO of fluorochemicals surface-treated
2Powder is dispersed in the matrix.
Described sulfonic fluoropolymer metal-salt resin is 0.01～10wt% with respect to the content of Hydrogen sulfonic fluoropolymer resin, and the repeating unit number is 10～6000, has as follows (I) structure:
M?M′＝Ce?Mn?La?Zn?W?Ti?V?Cr?Fe?Co?Ni?Cu?Zr?Nb?Mo?Ru?Rh?Pd?Ta?Re?Ir?Pt?H?Na?K
N, m represent the metal valence state;
A, b are not less than 1 integer, c, d=0 or 1 and c+d ≠ 0; (a+b)/(a+b+c+d)=0.5-0.99; (c+d)/(a+b+c+d)=0.01-0.5.
Described Hydrogen sulfonic fluoropolymer resin is repeated to form by the structural unit shown in the following formula II, and the repeating unit number is 30～3000:
Wherein, X=H or F, Y=H, F or Cl, n=3～15, m=2～5, p=1 or 2, q=2 or 3.
Described SiO through the fluorochemicals surface-treated
2Powder makes through following steps:
(1) by amino silicane coupling agent to SiO
2The powder surface hydroxyl carries out amination modified, forms amination SiO
2Powder;
(2) with amination SiO
2Powder and fluorine-containing carboxylic acid reaction dehydration and finally form the SiO of fluorochemicals surface-treated
2Powder;
Said amination SiO
2The amination degree of powder surface hydroxyl is 10～50mol%;
The structural formula of described amino silicane coupling agent is following:
R
1, R
2And R
3Can from alkane, choose, preferred carbonatoms is 1～5; R
4Contain AZA (Cyclo) Alkanes, R for the hydrogeneous alkane of carbonatoms 1～10 or carbonatoms 1～10
4Preferred carbonatoms be 2～6; R
5Alkane or perfluoro alkane for Wasserstoffatoms or carbonatoms 1～10 are preferably Wasserstoffatoms.Most preferred, amino silicane coupling agent is selected from one of γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, phenylamino Union carbide A-162, phenylamino methyltrimethoxy silane, phenylamino methyltrimethoxy silane, aminoethyl aminoethyl aminopropyl trimethoxysilane.
SiO
2There is great amount of hydroxy group in particle surface, can and slough small molecular alcohol with organoalkoxysilane reaction, utilizes this reaction can be easily at SiO
2The surface of powder is introduced amino; Amino can further be sloughed a part water with the perfluorocarboxylic acid reaction again, finally at SiO
2Fluorine-containing molecular chain is introduced on the surface.SiO
2The amination degree of powder surface hydroxyl should be controlled at 10～50mol% usually, the too high then SiO of amination degree
2Lose moisture retention.
Perfluorocarboxylic acid be carbonatoms 1～10 perfluorocarboxylic acid or carbonatoms 1～100 contain the oxygen perfluorocarboxylic acid, like Perfluorocaprylic Acid, perfluoro propene oxid homopolymer carboxylic acid (compound method of perfluoro propene oxid homopolymer can with reference to U.S. Pat 3412148).
The SiO of said fluorochemicals surface-treated
2The mass ratio of powder and perfluorinated sulfonic resin is 0.5～100: 100, and preferred, mass ratio is 0.5～50: 100; SiO
2Particle diameter be 0.05～30 μ m.
Said fortifying fibre is selected from: one or more of spun glass, fluorocarbon polymer fiber, ceramic fiber, silica fiber, mineral fibre or silicon carbide fiber preferably, are selected from one or both of silica fiber or fluorocarbon polymer fiber; The fortifying fibre diameter is 0.005～50 μ m, and length is 0.05～200 μ m, and preferred length is 0.05～80 μ m, and reinforced fiber content is 0.01～35% of a gross weight.
Said spun glass is selected from alkali resistant glass fibre or alkali free glass fibre.
Said fluorocarbon polymer fiber is selected from polytetrafluoroethylene fiber, gathers the perfluoro propyl vinyl fiber, the perfluoroethylene-propylene fiber.
The preparation method of a kind of fiber and modified silica-doped fluorine-containing ion film, step is following:
Sulfonic fluoropolymer metal-salt resin and Hydrogen sulfonic fluoropolymer resin shown in the logical formula I are dissolved with polar solvent, obtain perfluor sulfoacid resin solution; The SiO that in perfluor sulfoacid resin solution, adds dispersion agent, fortifying fibre, fluorochemicals surface-treated then
2Powder, and even through stirring and ultra-sonic dispersion; With the technology film forming of finely dispersed solution through solution-cast, solution casting, silk-screen printing technique, spraying or dipping; And, make fiber and modified silica-doped fluorine-containing ion film through peeling off with film thermal treatment 0.02～800 minute under 30～250 ℃ temperature.
Dispersion agent is selected from: sodium polyphosphate, Rapisol or ammonium polyphosphate, add-on are 0.01～10% of gross weight.Polar solvent is selected from one or more in N, N,N-DIMETHYLACETAMIDE, NMF, DMSO 99.8MIN., N-Methyl pyrrolidone, water, ethanol, methyl alcohol, propyl alcohol, the Virahol.The adding of dispersion agent is for improving the degree of scatter of fiber in resin.
Fiber of the present invention and modified silica-doped fluorine-containing ion film can also be kept high mechanical strength when having the macroion exchange capacity, and have better water retention performance and high proton transmissibility.
Embodiment:
Through embodiment the present invention is further specified below, but institute of the present invention protection domain is not limited only to this.
Embodiment 1
Under 100 ℃ of normal pressures, be 200nm SiO with particle diameter
2Powder and γ-An Bingjisanjiayangjiguiwan obtain amination SiO reflux in toluene 3 hours
2Powder, amination SiO
2The amination degree of powder surface hydroxyl is 10mol%, adds and the equimolar Perfluorocaprylic Acid of γ-An Bingjisanjiayangjiguiwan then, reclaims solvent at 120 ℃ of following decompression vacuum pumpings after keeping refluxing 3 hours, obtains the SiO of fluorochemicals surface-treated
2Powder (content is 10%); To have logical formula I a=1, b=1, c=0; D=1, the sulfonic fluoropolymer metal-salt resin of M=M '=Ce structure with have logical formula II n=9, a p=2; X=F; Y=F, the Hydrogen sulfonic fluoropolymer resin dissolves of q=2 is (the perfluorinated sulfonic resin total concn is 40%) in N, sulfonic fluoropolymer cerium salt resin is 0.3wt% with respect to the content of Hydrogen sulfonic fluoropolymer resin; Obtain perfluor sulfoacid resin solution, under the state of the stirring that keeps 200r/min, add the SiO of fluorochemicals surface-treated successively
2Powder, sodium polyphosphate (account for total mass 5%), diameter are the silica fiber (silica fiber quality account for total mass 5%) of 0.02 μ m length, 0.05 μ m; The method of utilizing spraying coating process is prepared fiber and modified silica-doped fluorine-containing ion film that thickness is 50 μ m 190 ℃ of following thermal treatments 45 minutes.Tensile strength is: 27MPa, electricity lead and are 125mS/cm.
Embodiment 2
Under 100 ℃ of normal pressures, be 5 μ m SiO with particle diameter
2Powder and N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan obtain amination SiO reflux in toluene 3 hours
2Powder, amination SiO
2The amination degree of powder surface hydroxyl is 16.5mol%; Add and N-β (the aminoethyl)-equimolar perfluoro propene oxid homopolymer of γ-An Bingjisanjiayangjiguiwan carboxylic acid (mean polymerisation degree is 6) then; Reclaim solvent at 120 ℃ of following decompression vacuum pumpings after keeping refluxing 3 hours, obtain the SiO of fluorochemicals surface-treated
2Powder (content is 16.5%); To have logical formula I a=1, b=2, c=1; D=1, M=Mn, the sulfonic fluoropolymer metal-salt resin of M '=Zn structure with have a logical formula II n=14; P=2, X=F, Y=Cl; The Hydrogen sulfonic fluoropolymer resin dissolves of q=3 is (the perfluorinated sulfonic resin total concn is 40%) in N,N-DIMETHYLACETAMIDE; Sulfonic fluoropolymer metal-salt resin is 0.25wt% with respect to the content of Hydrogen sulfonic fluoropolymer resin, obtains perfluor sulfoacid resin solution, under the state of the stirring that keeps 178r/min, adds the SiO of fluorochemicals surface-treated successively
2Powder, ammonium polyphosphate (account for total mass 7.6%), diameter are the polytetrafluoroethylene fiber (content that fiber quality accounts for total mass is 10%) of 40 μ m length, 150 μ m; The method of utilizing silk-screen printing technique is prepared fiber and modified silica-doped fluorine-containing ion film that thickness is 30 μ m 170 ℃ of following thermal treatments 15 minutes.Tensile strength is: 33MPa, electricity lead and are 105mS/cm.
Embodiment 3
Under 100 ℃ of normal pressures, be 5 μ m SiO with particle diameter
2Powder and N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan obtain amination SiO reflux in toluene 3 hours
2Powder, amination SiO
2The amination degree of powder surface hydroxyl is 21.5mol%; Add and N-β (the aminoethyl)-equimolar perfluoro propene oxid homopolymer of γ-An Bingjisanjiayangjiguiwan carboxylic acid (mean polymerisation degree is 10) then; Reclaim solvent at 120 ℃ of following decompression vacuum pumpings after keeping refluxing 3 hours, obtain the SiO of fluorochemicals surface-treated
2Powder; To have logical formula I a=2, b=1, c=0.1; D=0.1, M=Mn, the sulfonic fluoropolymer metal-salt resin of M '=Zn structure with have a logical formula II n=5; P=1, X=F, Y=Cl; The Hydrogen sulfonic fluoropolymer resin dissolves of q=2 is (the perfluorinated sulfonic resin total concn is 40%) in ethanol, and sulfonic fluoropolymer metal-salt resin is 0.3wt% with respect to the content of Hydrogen sulfonic fluoropolymer resin, under the state that keeps high-speed stirring, adds the SiO of fluorochemicals surface-treated successively
2Powder (content is 25%), Rapisol (account for total mass 6%), diameter are the polytetrafluoroethylene fiber (fiber quality content is 6%) of 10 μ m length, 50 μ m; The method of utilizing casting is prepared fiber and modified silica-doped fluorine-containing ion film that thickness is 80 μ m 150 ℃ of following thermal treatments 40 minutes.Tensile strength is: 30MPa, electricity lead and are 135mS/cm.
Claims (13)
1. fiber and modified silica-doped fluorine-containing ion film, it is characterized in that: it is a matrix with Hydrogen sulfonic fluoropolymer resin and sulfonic fluoropolymer metal-salt resin, fortifying fibre and through the SiO of fluorochemicals surface-treated
2Powder is dispersed in the matrix;
Described sulfonic fluoropolymer metal-salt resin is 0.01～10wt% with respect to the content of Hydrogen sulfonic fluoropolymer resin, and the repeating unit number is 10～6000, has as follows (I) structure:
M、M′＝Ce、Mn、La、、Zn、W、Ti、V、Cr、Fe、Co、Ni、Cu、Zr、Nb、Mo、Ru、Rh、Pd、Ta、Re、Ir、Pt、Na、K
N, m represent the metal valence state;
A, b are not less than 1 integer, c, d=0 or 1 and c+d ≠ 0; (a+b)/(a+b+c+d)=0.5-0.99; (c+d)/(a+b+c+d)=0.01-0.5;
Described Hydrogen sulfonic fluoropolymer resin, by repeating to form as shown in the formula the structural unit shown in (II), the repeating unit number is 30～3000:
Wherein, X=H or F, Y=H, F or Cl, n=3～15, m=2～5, p=1 or 2, q=2 or 3;
Described SiO through the fluorochemicals surface-treated
2Powder makes through following steps:
(1) by amino silicane coupling agent to SiO
2The powder surface hydroxyl carries out amination modified, forms amination SiO
2Powder;
(2) with amination SiO
2Powder and fluorine-containing carboxylic acid reaction dehydration and finally form the SiO of fluorochemicals surface-treated
2Powder;
Said amination SiO
2The amination degree of powder surface hydroxyl is 10～50mol%.
2. fiber as claimed in claim 1 and modified silica-doped fluorine-containing ion film is characterized in that: the structural formula of described amino silicane coupling agent is following:
R
1, R
4And R
3From alkane group, choose; R
4Be the hydrogeneous alkane group of carbonatoms 1～10 or the nitrogenous alkane group of carbonatoms 1～10; R
5Alkane group or perfluoro alkane group for Wasserstoffatoms or carbonatoms 1～10.
3. fiber as claimed in claim 2 and modified silica-doped fluorine-containing ion film is characterized in that: R
1, R
2And R
3Be selected from carbonatoms and be 1～5 alkane group, R
4Be the hydrogeneous alkane group of carbonatoms 2～6 or the nitrogenous alkane group of carbonatoms 2～6; R
5Be the Wasserstoffatoms group.
4. fiber as claimed in claim 3 and modified silica-doped fluorine-containing ion film is characterized in that: amino silicane coupling agent is selected from one of γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, phenylamino Union carbide A-162, phenylamino methyltrimethoxy silane, aminoethyl aminoethyl aminopropyl trimethoxysilane.
5. fiber as claimed in claim 1 and modified silica-doped fluorine-containing ion film is characterized in that: said contain perfluorocarboxylic acid that carboxylic acid fluoride is a carbonatoms 1～10 or carbonatoms 1～100 contain the oxygen perfluorocarboxylic acid.
6. fiber as claimed in claim 1 and modified silica-doped fluorine-containing ion film is characterized in that: the SiO of said fluorochemicals surface-treated
2The mass ratio of powder and sulfonic fluoropolymer resin is 0.5～100: 100.
7. fiber as claimed in claim 6 and modified silica-doped fluorine-containing ion film is characterized in that: described mass ratio is 0.5～50: 100; SiO
2Particle diameter be 0.05～30 μ m.
8. fiber as claimed in claim 1 and modified silica-doped fluorine-containing ion film is characterized in that: said fortifying fibre is selected from: one or more of spun glass, fluorocarbon polymer fiber, ceramic fiber, silica fiber, mineral fibre or silicon carbide fiber.
9. fiber as claimed in claim 8 and modified silica-doped fluorine-containing ion film is characterized in that: said fortifying fibre is selected from one or both of silica fiber or fluorocarbon polymer fiber; The fortifying fibre diameter is 0.005～50 μ m, and length is 0.05～200 μ m.
10. fiber as claimed in claim 9 and modified silica-doped fluorine-containing ion film is characterized in that: fortifying fibre length is 0.05～80 μ m, and reinforced fiber content is 0.01～35% of a gross weight.
11. fiber as claimed in claim 8 and modified silica-doped fluorine-containing ion film is characterized in that: said spun glass is selected from alkali resistant glass fibre or alkali free glass fibre; Said fluorocarbon polymer fiber is selected from polytetrafluoroethylene fiber, gathers the perfluoro propyl vinyl fiber, the perfluoroethylene-propylene fiber.
12. the preparation method of fiber as claimed in claim 1 and modified silica-doped fluorine-containing ion film, step is following:
(1) sulfonic fluoropolymer metal-salt resin shown in the general formula (I) and Hydrogen sulfonic fluoropolymer resin are dissolved with polar solvent, obtain perfluor sulfoacid resin solution;
(2) in the perfluor sulfoacid resin solution that step (1) makes, add the SiO of dispersion agent, fortifying fibre, fluorochemicals surface-treated
2Powder, and even through stirring and ultra-sonic dispersion;
(3) the finely dispersed solution that step (2) is made passes through the technology film forming of solution-cast, solution casting, silk-screen printing technique, spraying or dipping; And, make fiber and modified silica-doped fluorine-containing ion film through peeling off with film thermal treatment 0.02～800 minute under 30～250 ℃ temperature.
13. the preparation method of fiber as claimed in claim 12 and modified silica-doped fluorine-containing ion film is characterized in that: said dispersion agent is selected from: sodium polyphosphate, Rapisol or ammonium polyphosphate, add-on are 0.01～10% of gross weight; Said polar solvent is selected from one or more in N, N,N-DIMETHYLACETAMIDE, NMF, DMSO 99.8MIN., N-Methyl pyrrolidone, water, ethanol, methyl alcohol, propyl alcohol, the Virahol.
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| CN111129559B (en) * | 2019-12-26 | 2021-06-15 | 佛山市金辉高科光电材料股份有限公司 | Proton exchange membrane for fuel cell and preparation method thereof |
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