CN101728550A - Fiber-reinforced stably-doped proton exchange membrane - Google Patents
Fiber-reinforced stably-doped proton exchange membrane Download PDFInfo
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- CN101728550A CN101728550A CN200910231122A CN200910231122A CN101728550A CN 101728550 A CN101728550 A CN 101728550A CN 200910231122 A CN200910231122 A CN 200910231122A CN 200910231122 A CN200910231122 A CN 200910231122A CN 101728550 A CN101728550 A CN 101728550A
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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
- 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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Abstract
The invention relates to a fiber-reinforced inorganic substance-doped proton exchange membrane and a method for preparing the same, and belongs to the field of functional polymer composites. The membrane consists of a fluosulfonic acid-containing resin, a reinforced fiber, an auxiliary proton conducting substance and a high-valent metallic compound which can be physically bonded with acidic exchange groups in the membrane to form a cross-linked network. The invention also relates to the method for preparing the proton exchange membrane. The fluosulfonic acid-containing membrane of the invention has good high-temperature proton conductivity, excellent mechanical property and excellent chemical stability.
Description
Technical field
The invention belongs to field of functional polymer composites, relate to a kind of inorganic doping and strengthen proton exchange membrane, particularly fibre-reinforced inorganics doped sulfonic fluoropolymer type proton exchange membrane and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells is a kind ofly directly chemical energy to be converted into the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy by electrochemical means, is considered to the cleaning of 21 century first-selection, generation technology efficiently.(proton exchange membrane PEM) is Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, critical material PEMFC) to proton exchange membrane.
Now the perfluorinated sulfonic acid proton exchange membrane of using has good proton-conducting and chemical stability under (as 80 ℃) and the higher humidity at a lower temperature.But they also have a lot of defectives:, poor chemical stability not high as poor dimensional stability, mechanical strength etc.Especially dimensional stability and chemical stability aspect and since film under different humidity because the water absorption rate difference makes its swelling ratio also different.When film during at different operating mode down conversions, therefore the size of film also will change.Conversion so repeatedly finally causes proton exchange membrane generation mechanical damage or degraded.In addition, the positive pole reaction of fuel cell usually produces the material that a large amount of hydroxyl free radicals or hydrogen peroxide etc. have strong oxidizing property, these materials unstable group on can attack proton exchange membrane, thereby chemical degradation that these unstable groups is come off cause film and breakage, its bubble.In addition, when the working temperature of perfluorinated sulfonic acid exchange membrane is higher than 90 ℃,, thereby the efficient of fuel cell is descended greatly owing to the rapid dehydration of film causes the proton-conducting of film sharply to descend.But high working temperature can improve the anti-carbon monoxide of fuel-cell catalyst greatly.Be exactly that existing perfluoro sulfonic acid membrane all has certain hydrogen or methanol permeability in addition, especially in direct methanol fuel cell, methanol permeability is very big, becomes fatal problem.Therefore, how to improve the proton conduction efficient under perfluorinated sulfonic acid proton exchange film strength, dimensional stability and the high temperature, the permeability of reduction working media etc. and become the key subjects that fuel cell industries faces.
For improving the high temperature proton-conducting of perfluoro sulfonic acid membrane, the inorganic additive that much has the high-temp water-preserving ability can be joined in the perfluorinated sulfonic acid exchange membrane.Selected inorganic water conservation particle should satisfy following performance: (1) particle has water holding capacity preferably, and higher dehydration temperature is just arranged; (2) has intermiscibility preferably with proton exchange resins; (3) particle has certain proton conductivity; (4) be easy to obtain littler nanometer particle; (5) structural stability of particle is good, does not follow tangible structural change in suction, dehydration; (6) help keeping or improving the mechanical strength or the physical size stability of proton exchange membrane.
The inorganic water conservation particle that is adopted is generally SiO
2, TiO
2, Zr (HPO
4)
2Or ZrO
2Stratotype clay minerals such as particle, heteropoly acid or solid acid particle, zeolite family mineral particle, montmorillonite and intercalation clay mineral thereof etc.
For example, Chinese patent CN1862857 discloses and added SiO in perfluorinated sulfonic resin
2Etc. inorganic water-loss reducer, can improve the high-temperature electric conduction performance of proton exchange membrane.
J.Electrochem.Soc.V154,2007, to have described among the p.B288-B295 nafion resin and basic zirconium phosphate complex film forming, this film still has very high electrical conductance in relative humidity less than 13%.
European patent EP 0875524B1 discloses the technology of utilizing the glass fibre non-woven technology to prepare the nafion film of glass fibre membrane enhancing, mentions oxides such as can using silicon dioxide in this patent simultaneously.But non-woven glass fibre cloth is the base material that must use in this patent document, and this has limited the scope of application of reinforcing glass fiber greatly.
U.S. Pat 6692858 discloses uses polytetrafluoroethylene fibre to strengthen the technology of perfluorinated sulfonic resin.In this patent document, with perfluor sulfonyl fluororesin and polytetrafluoroethylene fibre mix, extrude, making the transition makes fibre-reinforced perfluorinated sulfonic resin.This method is because transformation process is consuming time long and can not turn round continuously, and do not add functional inorganic matter and improve electric conductivity.
Chinese patent 200810107853.x discloses a kind of fuel battery proton exchange film that comprises fortifying fibre and auxiliary proton conductive substance simultaneously.In this patent, utilized two kinds of means that fuel cell membranes is carried out modification, obtain containing simultaneously the film of fortifying fibre and auxiliary proton conductive substance, thereby solved the machinery enhancing of film and the problem of high-temperature electric conduction simultaneously.
But above the whole bag of tricks all can't substantially change the chemical stability of film.Because Proton Exchange Membrane Fuel Cells is when work, fuel gas is known from experience the reaction that free radical takes place to generate on electrode:
(1)H
2→2H
·
(2) H
+ O
2(being diffused into anode) → HO by PEM
2
(3)HO
2 ·+H
·→H
2O
2
(4)H
2O
2+M
2+→M
3++
·OH+OH
-·
(5)
·OH+H
2O
2→HO
2 ·+H
2O
These peroxide radicals have very strong oxidizability, and unstable group and non-fluorin radical on can the attack flim forming molecule finally cause degraded, the deterioration of film, thereby influence the various performances of film.
In order to improve the durability of proton exchange membrane, knownly can in macromolecule proton exchange membrane, add the transition metal oxide of degradable hydrogen peroxide or the material that organic phenols, amine etc. have reproducibility, perhaps improve the mechanical performance and the high-temperature electric conduction of film simultaneously as Chinese patent application 200810107853.x.Though these methods have reduced the concentration of free radical in the film to a certain extent, but various patents in the past or document have often only improved the performance of an aspect of film, can not improve film to because the degradation of the free radical that electrode reaction produces, can not fundamentally suppress the degraded of film, even the unstable group on employed some fiber of modification such as the (per) fluoropolymer (being introduced by polymerization reaction) can be degraded also by free radical.Because the degraded of film can be divided into two aspects: mechanical degradation (just film under alternation of wetting and drying conversion environment, cause breakage), the chemical degradation that other aspect was promptly mentioned just now.The degraded of this two aspect is mutually promoted, and the place of mechanical degradation takes place at first, and the oxidation because of free radical causes film to become thinner or the generation bubble often.
Summary of the invention
At the deficiencies in the prior art, the further investigation of inventor's process, and paid a large amount of creative works, thus finished the present invention.
The objective of the invention is to preparation and have the macroion exchange capacity, can keep high mechanical properties simultaneously, and at high temperature have the ionic membrane of good proton conductivity and stability.In addition, because fuel gas can produce a large amount of free radicals when electrochemical reaction takes place, cause that the non-fluorin radical (as sulfonic group and ehter bond) in the flim forming molecule degrades, and ionic membrane provided by the present invention can increase substantially the chemically stable and the Green Tea Extract performance of film, in addition, the present invention also provides the preparation method of described film.
The invention provides a kind of proton exchange membrane of using fortifying fibre, auxiliary proton conductive substance and the common modification of high-valency metal compound.Use these three kinds of materials to improve mechanical strength, high temperature proton conductive and the air-tightness of film simultaneously, the stability of also unexpected discovery film also is significantly increased simultaneously.This is because thereby the sulfonate radical generation physical bond in meeting of employed high-valency metal compound and the film has improved the compactness of film.In addition by the Fenton evidence chemical stability that combination caused of these several factors be higher than the only simple disclosed film of various technology that adds in the past far away.Trace it to its cause, should be that these several factors act synergistically particularly that the high-valency metal compound can form the crosslinked networking of physical bond with the acidic exchange group in the film, and this cross-linked network can not change film conductance, make that the film size changing rate is littler, and make film more fine and close, thereby suppress to a certain extent or blocked the infiltration of oxygen fully film, and then suppress or stopped oxygen anode react generate the hydrop free radical may, it is generally acknowledged that this free radical has the highest oxidability and film destroy.
Sulfonic fluoropolymer type proton exchange membrane of the present invention is made up of sulfonic fluoropolymer resin, fortifying fibre, auxiliary proton conductive substance and high-valency metal compound, wherein, the content of described fortifying fibre is 1～10% of gross mass, the content of described auxiliary proton conductive substance is 1%～20% of gross mass, described high-valency metal compound is 0.001～5% of a sulfonic fluoropolymer type resin quality, and surplus is a sulfonic fluoropolymer type resin.
Described sulfonic fluoropolymer type resin has as shown in the formula the construction unit shown in (I), and its molecular weight is not special to be limited, and for example molecular weight can be 14～450,000:
(I) G=O (CF
2)
mSO
3H or
Wherein, the integer of n=3～15; The integer of m=2～5; P=1 or 2; Q=2 or 3; M=H, Li, Na, K, Rb, Cs, NH
4, NH
3R
1, NH
2R
2R
3, NHR
4R
5R
6, NR
7R
8R
9R
10X, Y are F or Cl independently; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10Be C independently
1～C
20Alkyl.
Described fortifying fibre is selected from: one or more in glass fibre, fluorocarbon polymer fiber, polyphosphazene fiber, polyphenylene sulfide fibre, ceramic fibre, quartz fibre, mineral fibres or the silicon carbide fibre.The diameter of described fortifying fibre is 0.005 μ m～10 μ m, is preferably 0.1 μ m～8 μ m, and more preferably 0.5 μ m～7 μ m most preferably are 1 μ m～5 μ m; Its length is 0.06 μ m～45mm, is preferably 0.1 μ m～35mm, 1 μ m～20mm more preferably, and more preferably 5 μ m～10mm most preferably are 20 μ m～5mm; This fiber quality is 1～10% of a film gross mass.
Described glass fibre is selected from alkali-resistant glass fibre or alkali-free glass fibre; Described fluorocarbon polymer fiber is selected from polytetrafluoroethylene fibre, perfluoroethylene-propylene fiber, according to the fiber with ion exchanging function or the poly-perfluoro propyl vinyl ether fiber of prior art CN101003588A preparation; Described ceramic fibre is selected from natural coal jewel fiber or alumina silicate fibre; Described mineral fibres is selected from quartz fibre, silicon carbide fibre or basalt fibre.
The particle diameter of described auxiliary proton conduction functional mass is 0.005～5 μ m, is preferably 0.1 μ m～4 μ m, and more preferably 0.5 μ m～3 μ m most preferably are 1 μ m～2 μ m; Should the auxiliary doping of proton conductive substance in film be 1wt%～20wt%, for example can be one of following material or combination:
(1) oxide is shown in general formula: MO
E/2E=1～8; Wherein M be second and third, four, five major element or transition elements; Be preferably SiO
2, Al
2O
3, Sb
2O
5, SnO
2, ZrO
2, TiO
2, MoO
3Or OsO
4
(2) phosphate, comprise first, second, third and fourth, the various forms of orthophosphates and the condensed phosphate of five major elements, transition elements.Be preferably BPO
4, Zr
3(PO
4)
4, Zr (HPO
4)
2, HZr
2(PO
4)
3, Ce (HPO
4)
2, Ti (HPO
4)
2, KH
2PO
4, NaH
2PO
4, LiH
2PO
4, NH
4H
2PO
4, CsH
2PO
4, CaHPO
4, MgHPO
4, HSbP
2O
8, HSb
3P
2O
14, H
5Sb
5P
2O
20, Zr
5(P
3O
10)
4Or ZrHP
3O
10
(3) polyacid, multi-acid salt, and hydrate are as general formula A
iB
jC
kO
lMH
2Shown in the O; Wherein A be one, two, three, four, the pentavalent group first, second, third and fourth, five major elements, transition elements; B, C are second and third independently, four, five, six, seven major element or transition elements; I=1～10, j=0～50, k=0～50, l=2～100, m=0～50;
Be preferably H
3PW
12O
40α H
2O (α=21-29), H
3SiW
12O
40β H
2O (β=21-29), HWO
3, HSbWO
6, H
3PMo
12O
40, H
2Sb
4O
11, HTaWO
6, HNbO
3, HTiNbO
5, HTiTaO
5, HSbTeO
6, H
5Ti
4O
9, HSbO
3Or H
2MoO
4
(4) silicate comprises zeolite, NH
4 +The zeolite, phyllosilicate, web-like silicon hydrochlorate, H-sodalite, H-modenite, the NH that handle
4-analcime, NH
4-sodalite, NH
4-gallate or H-montmorillonite;
Described auxiliary proton conduction functional mass is more preferably: SiO
2, ZrO
2, Zr
3(PO
4)
4, H
3PW
12O
40, TiO
2, CsHSO
4, CsH
2PO
4, Zr (HPO
4)
2, HZr
2(PO
4)
3Or Zr
2H (P
3O
10)
2
Described high-valency metal compound is selected from Mn, Ce, La element: ion, oxide, hydroxide or complex compound.
Described cerium ion can be provided by one of following material or combination: Ce (NO
3)
3, Ce (Ac)
3, Ce
2(CO
3)
3, Ce
2(SO
4)
3, CePO
4, Ce (NO
3)
4, Ce (CO
3)
2, Ce (SO
4)
2, (NH
4)
2Ce (NO)
6, LaCe (CO3);
Described manganese ion can be provided by one of following material or combination: Mn (NO
3)
2, Mn (Ac)
2, MnCO
3, MnSO
4, Mn (NO
3)
2, Mn
3(PO
4)
2, MnPO
4, Mn (Ac)
3, Mn
2(CO
3)
3Or Mn
2(SO
4)
3
Described lanthanum ion can be provided by one of following material or combination: LaPO
4, La (Ac)
3, La
2(CO
3)
3Or La
2(SO
4)
3
Described oxide or hydroxide comprise following one or more combination: Ce
2O
3, CeO
2, MnO, Mn
2O
3, La
2O
3, Ce (OH)
3, Ce (OH)
4, Mn (OH)
2, Mn (OH)
3Or La (OH)
3
Wherein, described oxide also can be cerium, manganese and lanthanum element arbitrarily between two or more or and the mixed oxide formed of other elements or the oxide with perovskite structure.
Described mixed oxide can be following several mixed oxide or has the oxide of perovskite structure: Ce
xTi
(1-x)O
2(x=0.25～0.4), Ca0.6La
0.27TiO
3, La
(1-y)Ce
yMnO
3(y=0.1～0.4), La
0.7Ce
0.15Ca
0.15MnO
3
The part of described complex compound can be the one or more combination of following material: cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether, EDTA (ethylenediamine tetra-acetic acid), DMF (N, dinethylformamide) or DMSO (dimethyl sulfoxide (DMSO)).
Described high-valency metal compound can load on the auxiliary proton conductive substance or load on the fortifying fibre.
The preparation method of fiber reinforcement doping proton exchange of the present invention comprises the steps:
(1) the sulfonic fluoropolymer type resin shown in the general formula (I) is dissolved with polar solvent, form the solution of sulfonic fluoropolymer type resin;
(2) will assist proton conductive substance and high-valency metal compound to be scattered in the sulfonic fluoropolymer type resin solution of step (1) preparation;
(3) with fiber dispersion in the employed polar solvent of step (1), mix by ultrasonic or high-speed stirred, obtain fiber dispersion;
(4) fiber dispersion and the solution in the step (2) with step (3) preparation mixes, and adopt casting, curtain coating, silk-screen printing technique, spraying or impregnation technology to form film, and with film heat treatment 0.5～600 minute under 50～300 ℃ temperature, through peeling off, promptly make fibre-reinforced doping proton exchange.
Preferably, for guaranteeing that fiber fully disperses, can add dispersant in solution in the above-mentioned steps (3), described dispersant for example can be polyphosphate sodium, PA 800K or APP.
State in the step (3), described fiber is preferably glass fibre, fluorocarbon polymer fiber, ceramic fibre, quartz fibre, mineral fibres or silicon carbide fibre.
Described polar solvent in above-mentioned steps (1) and (3) can be one or more in dimethyl formamide, dimethylacetylamide, methylformamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or the glycerol.
Sulfonic fluoropolymer resin type content in the sulfonic fluoropolymer type resin solution of above-mentioned steps (1) preparation is 1～80wt%.
Heat treatment temperature in the above-mentioned steps (4) is preferably 80～200 ℃, more preferably 120～190 ℃.
Sulfonic fluoropolymer type proton exchange membrane of the present invention has good high-temperature proton conduction performance, stable mechanical performance, therefore is specially adapted to proton exchange fuel cell.
Embodiment
The invention will be further described below in conjunction with embodiment, but it will be understood by those skilled in the art that these execution modes only are used to exemplify, but not spirit of the present invention and claimed scope are carried out any type of restriction.
Used sulfonic fluoropolymer type resin among the embodiment has as shown in the formula the construction unit shown in (I):
G=O (CF
2)
mSO
3H or
Wherein, n=3～15, m=2～5, p=1 or 2, q=2 or 3, M=H, Li, Na, K, Rb, Cs, NH
4, NH
3R
1, NH
2R
2R
3, NHR
4R
5R
6, NR
7R
8R
9R
10, R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10Be C independently
1～C
20Alkyl, X, Y are F or Cl independently.
Embodiment 1.Fenton reagent method is measured the chemical stability of prepared film
The film of getting certain mass is put into 80 ℃ the Fe that contains 30ppm
3+Mass concentration be in 30% the 500ml hydrogen peroxide, to heat continuously 70 hours, solution is diluted constant volume to 1000ml, utilize fluoride ion selective electrode to measure the concentration (c) of fluorine ion in the solution.The fluorine ion burst size can be by following calculating: F=1000c*19 (mg).
Embodiment 2:
In general formula I, n=13, m=2, X=F, Y=F, molecular weight be 220,000 perfluorinated sulfonic acid type resin dissolves in the N-methyl pyrrolidone, make solid masses content and be 35% solution.Adding particle diameter is the ZrO of 0.007 μ m
2Powder (ZrO
2Quality be resin quality 5%) and account for the Ce of resin quality 0.01%
2(SO
4)
3And obtain dispersion liquid.With particle diameter is that 0.01 μ m and length are that the quartz fibre (quartz fibre quality be resin quality 5%) of 0.08 μ m disperses in the N-methyl pyrrolidone, and adds the dispersant polyphosphate sodium and carry out vigorous stirring fiber is distributed in the solvent fully.This solvent and the resinous and ZrO that will contain fiber
2The above-mentioned dispersion liquid of powder fully mixes.180 ℃ of following heat treatments 10 minutes, prepare thickness was the fabric reinforcement adulterated full fluorin sulfonic acid proton exchange film that contains cerium of 25 μ m to the method for utilizing solution casting with mixed liquor.Its hot strength is 23Mpa, and electricity is led and is 103mS/cm.Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 0.2mg/L.
Embodiment 3:
In general formula I, n=7, m=3, X=F, Y=F and molecular weight be 25 perfectly sound fluosulfonic acid type resin dissolves in methylformamide, make solid masses content and be 33% solution.Adding particle diameter is the Zr of 0.04 μ m
3(PO
4)
4Powder and to account for resin quality be 0.5% Mn
2(CO
3)
3With particle diameter is that 0.05 μ m and length are the alumina silicate fibre (Zr of 0.1 μ m
3(PO
4)
4Quality is for being 3% of resin quality, the alumina silicate fibre quality be resin quality 7%) in methylformamide, disperse, and add dispersant PA 800K vigorous stirring fiber be distributed in the solvent fully.This solvent and the resinous and Zr that will contain fiber
3(PO
4)
4Powder art and Mn (NO
3)
2Above-mentioned dispersion liquid fully mix, 160 ℃ of following heat treatments 30 minutes, for preparing thickness and be 38 μ m contained manganese fiber reinforcement adulterated full fluorin sulfonic acid proton exchange film to the method for utilizing solution casting with mixed liquor.Its hot strength is 25Mpa, and electricity is led and is 98mS/cm.Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 0.8mg/L.
Embodiment 4:
In general formula I, n=5, m=5, X=F, Y=Cl, and molecular weight be 270,000 sulfonic fluoropolymer resin dissolves in dimethyl formamide, make solid masses content and be 33% solution.Adding particle diameter is the HZr of 0.08 μ m
2(PO
4)
3Powder (HZr
2(PO
4)
3Quality be resin quality 7%) and to account for resin quality be 0.005% lanthanum nitrate (III).The silicon carbide fibre (silicon carbide fibre quality be resin quality 10%) of getting particle diameter and be 0.5 μ m and length and be 2 μ m disperses in dimethyl formamide, and adds dispersant APP vigorous stirring fiber is distributed in the solvent fully.This solvent and the resinous and HZr that will contain fiber
2(PO
4)
3Fully mix with the above-mentioned dispersion liquid of lanthanum nitrate, 190 ℃ of following heat treatments 60 minutes, for preparing thickness and be 50 μ m contained lanthanum fiber reinforcement doped fluor-containing sulfonic acid proton exchange film to the method for utilizing solution casting with this mixed liquor.Its hot strength is 23Mpa, and electricity is led and is 120mS/cm.Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 1.0mg/L.
Embodiment 5:
In general formula I, n=5, m=5, X=F, Y=Cl and molecular weight be 170,000 perfluorinated sulfonic acid type resin dissolves in dimethyl sulfoxide (DMSO), making solid, to contain mass content be 25% solution.Adding particle diameter is the HSb of 0.5 μ m
3P
2O
14Powder (HSb
3P
2O
14Quality be resin quality 10%) and Ce
2O
3Powder (account for resin quality 3%).With particle diameter is that 1 μ m and length are that the alkali-free glass fibre (fiber quality be resin quality 15%) of 8 μ m disperses in dimethyl sulfoxide (DMSO), and adds dispersant APP vigorous stirring fiber is distributed in the solvent fully.This solvent and resinous, the HSb that will contain fiber
3P
2O
14Powder and Ce
2O
3Above-mentioned dispersion liquid fully mix, 100 ℃ of following heat treatments 20 minutes, for preparing thickness and be 50 μ m contained cerium fiber reinforcement adulterated full fluorin sulfonic acid proton exchange film to the method for utilizing solution casting with this mixed liquor.Its hot strength is 26Mpa, and electricity is led and is 105mS/cm.Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 1.6mg/L.
Embodiment 6:
In general formula I, n=5, m=5, X=F, Y=F and molecular weight be 300,000 perfluorinated sulfonic acid type resin dissolves in dimethyl sulfoxide (DMSO), make solid masses content and be 25% solution.Adding particle diameter is the HSb of 4 μ m
3P
2O
14Powder and Mn (OH)
2Powder (Mn (OH)
2Addition is 0.01% of a resin quality, HSb
3P
2O
14Quality be resin quality 10%).With particle diameter is that 1 μ m and length are that the alkali-free glass fibre (fiber quality be resin quality 15%) of 8 μ m disperses in dimethyl sulfoxide (DMSO), and adds dispersant APP vigorous stirring fiber is distributed in the solvent fully.This solvent of fiber be will contain and resin, HSb contained
3P
2O
14Powder, Mn (OH)
2Above-mentioned dispersion liquid fully mix, 230 ℃ of following heat treatments 20 minutes, what make thickness and be 150 μ m contained manganese fiber reinforcement adulterated full fluorin sulfonic acid proton exchange film to the method for utilizing solution casting with this mixed liquor.Its hot strength is: 22Mpa, electricity lead and are 114mS/cm..Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 1.4mg/L.
Embodiment 7:
In general formula I, n=5, p=1, X=F, Y=F, q=2, M=H and molecular weight be 240,000 perfluorinated sulfonic acid type resin dissolves in ethanol-water system (mass ratio 1: 1), make solid masses content and be 10% solution.Adding particle diameter is the H of 2 μ m
3SiW
12O
40Powder (H
3SiW
12O
40Quality be resin quality 25%) and (La
1-xNd
x)
0.5Ca
0.5MnO
3(0≤x≤1) perovskite structure oxide (account for resin quality 1%).With particle diameter is that 10 μ m and length are that the polytetrafluoroethylene fibre (polytetrafluoroethylene fibre quality be resin quality 6%) of 50 μ m disperses in ethanol-water system, and adds dispersant APP vigorous stirring fiber is distributed in the solvent fully.This solvent of fiber be will contain and resin, H contained
3SiW
12O
40Powder, (La
1-xNd
x)
0.5Ca
0.5MnO
3The above-mentioned dispersion liquid of (0≤x≤1) fully mixes, and 150 ℃ of following heat treatments 40 minutes, preparing thickness was the (La that contains of 80 μ m with the method for gained mixed liquor utilization casting
1-xNd
x)
0.5Ca
0.5MnO
3Fiber reinforcement adulterated full fluorin sulfonic acid proton exchange film.Its hot strength is: 28Mpa, electricity lead and are 102mS/cm.Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 1.2mg/L.
Embodiment 8:
In general formula I, n=9, X=Cl, Y=F contain m=2, p=1, two kinds of monomers of q=3 simultaneously, M=H and molecular weight be 20 perfectly sound fluosulfonic acid type resin dissolves in propyl alcohol-aqueous systems (mass ratio 1: 1), make solid masses content and be 5% solution.Adding particle diameter is the H of 2 μ m
3PMo
12O
40Powder and Ce (III)-DMSO complex compound (accounting for resin quality 0.1%).The particle diameter that will make according to prior art CN101003588A is that 20 μ m and length are that the fiber with ion exchanging function of 80 μ m disperses in this propyl alcohol-aqueous systems, the fiber that wherein has ion exchanging function is placed in the solution of cerium oxide gel, cover the last layer cerium oxide by sol-gel process, concrete grammar can be referring to 2002 2 phases of Changchun University of Science and Technology's journal.Wherein, H
3PMo
12O
40Quality is 30% of a resin quality.The ion exchanging function fiber that oxidized cerium is covered disperses in the propyl alcohol aqueous systems, and adding dispersant APP vigorous stirring is distributed in the solvent fiber fully.This solvent of fiber be will contain and resin, H contained
3PMo
12O
40The above-mentioned dispersion liquid of powder, Ce (III)-DMSO complex compound (accounting for resin quality 0.1%) complex compound fully mixes, 150 ℃ of following heat treatments 50 minutes, preparing thickness was the fiber reinforcement adulterated full fluorin sulfonic acid proton exchange film that contains cerium of 150 μ m with the method for gained mixed liquor utilization casting.Its hot strength is 29Mpa, and electricity is led and is 113mS/cm.Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 1.4mg/L.
Embodiment 9:
In general formula I, the perfluorinated sulfonic acid type resin dissolves of n=7, m=4, X=F, Y=F, M=H makes solid masses content and is 15% solution in hexamethyl phosphoric acid (mass ratio 1: 1).The surface La that adds particle diameter 0.7 μ m
2O
3Zirconia of modification (diameter is 0.5 μ m, with resin quality ratio be 3: 100) and Ca
0.6La
0.27TiO
3(account for resin quality 0.007%) makes dispersion liquid.With particle diameter is that 400 μ m and length are that the polytetrafluoroethylene fibre (polytetrafluoroethylene fibre quality be resin quality 8%) of 170 μ m disperses in hexamethyl phosphoric acid, and adds dispersant APP vigorous stirring, and fiber is distributed in the solvent fully.This solution and the above-mentioned dispersion liquid that will contain fiber, the method for utilizing silk-screen printing technique were 170 ℃ of following heat treatments 15 minutes, and preparing thickness is the La that contains of 30 μ m
2O
3And Ca
0.6La
0.27TiO
3Fiber reinforcement sulfonic fluoropolymer type proton exchange membrane.Its hot strength is 29Mpa, and electricity is led and is 124mS/cm.Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 1.1mg/L.
Embodiment 10:
In general formula I, n=14, p=2, X=F, Y=Cl, q=2, M=NH
4Perfluorinated sulfonic acid type resin dissolves in hempa acid system (mass ratio 1: 1), make solid masses content and be 19% solution.Adding particle diameter is the HZr of 5 μ m
2(PO
4)
3(HZr
2(PO
4)
3Quality be resin quality 34%) and cerium-beta-cyclodextrin composition (account for resin quality 0.3%).With particle diameter is that 3mm and length are that the alkali-resistant glass fibre (alkali-resistant glass fibre quality be resin quality 11%) of 190 μ m disperses at hexamethyl phosphoric acid, and adds dispersant APP vigorous stirring fiber is distributed in the solvent fully.This solvent of fiber be will contain and resin, HZr contained
2(PO
4)
3The above-mentioned dispersion liquid of powder, cerium-beta-cyclodextrin composition fully mixes and obtains mixed liquor, 170 ℃ of following heat treatments 25 minutes, preparing thickness was the fiber reinforcement doped fluor-containing sulfonic acid proton exchange film that contains cerium complexes of 500 μ m with the method for this mixed liquor utilization dipping skill.Its hot strength is 31Mpa, and electricity is led and is 113mS/cm.Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 0.3mg/L.
Embodiment 11:
In general formula I, the perfluorinated sulfonic acid type resin dissolves of n=9, p=2, X=F, Y=F, q=2, M=Na makes solid masses content and is 24% solution in dimethylacetylamide-aqueous systems (mass ratio 1: 1).Adding particle diameter is the SiO of 0.5 μ m
2(SiO
2Quality be resin quality 9%) and lanthanum acetate (account for resin quality 0.01%), acetylacetone,2,4-pentanedione-Mn (II) part (account for resin quality 0.4%).With particle diameter is that 1 μ m and length are that the perfluoroethylene-propylene fiber (perfluoroethylene-propylene fiber quality be resin quality 14%) of 5 μ m adds in dimethylacetylamide-water, and adds dispersant APP vigorous stirring fiber is distributed in the solvent fully.This solvent of fiber be will contain and resin, SiO contained
2The above-mentioned dispersion liquid of powder, lanthanum acetate, acetylacetone,2,4-pentanedione-Mn (II) part fully mixes, the method of the gained mixed liquor being utilized spraying coating process is 190 ℃ of following heat treatments 45 minutes, and for preparing thickness and be 47 μ m contains lanthanum and manganese fiber reinforcement adulterated full fluorin sulfonic acid proton exchange film.Its hot strength is 25Mpa, and electricity is led and is 132mS/cm.Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 1.6mg/L.
Embodiment 12:
In general formula I, the perfluorinated sulfonic acid type resin dissolves of n=14, p=2, X=F, Y=Cl, q=2, M=H is prepared solid masses content and is 19% solution in hexamethyl phosphoric acid-aqueous systems (mass ratio 1: 1).Adding particle diameter is the HZr of 0.06 μ m
2(PO
4)
3(HZr
2(PO
4)
3Quality be resin quality 34%) and cerous phosphate.With particle diameter is that 2mm and length are that the alkali-resistant glass fibre (alkali-resistant glass fibre quality be resin quality 11%) of 30 μ m disperses in hexamethyl phosphoric acid, and adds dispersant APP vigorous stirring fiber is distributed in the solvent fully.This solvent of fiber be will contain and resin, HZr contained
2(PO
4)
3The above-mentioned dispersion liquid of powder, cerous phosphate fully mixes, and the method for the gained mixed liquor being utilized impregnation technology is 70 ℃ of following heat treatments 500 minutes, and for preparing thickness and be 80 μ m contains cerium fiber reinforcement adulterated full fluorin sulfonic acid proton exchange film.Its hot strength is 27Mpa, and electricity is led and is 117mS/cm.Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 1.3mg/L.
Comparative example 13:
In general formula I, it is 24% solution that the perfluorinated sulfonic acid type resin dissolves of n=9, p=2, X=F, Y=F, q=2, M=H is prepared solid content in dimethylacetylamide-aqueous systems (mass ratio 1: 1).To wherein adding cerous carbonate (account for resin quality 0.01%)., acetylacetone,2,4-pentanedione-Mn (II) part (account for resin quality 0.4%) makes mixed liquor, use this mixed liquor with the method for spraying coating process 190 ℃ of following heat treatments 45 minutes, for preparing thickness and be 47 μ m contains cerium and manganese perfluorinated sulfonic acid type proton exchange membrane.Its hot strength is 20Mpa, and electricity is led and is 89mS/cm.Utilize 80 ℃ of Fenton reagents to handle 72 hours mensuration F ion release rates and be 6.3mg/L.
By embodiment 2-12 and comparative example 13 as can be seen, proton exchange membrane of the present invention is compared than the proton film that does not add the high-valency metal compound, on chemical stability and mechanical strength improve, the improvement of highly significant has then been arranged on chemical stability, thereby improved greatly the service behaviour and the useful life of the fuel cell that uses this proton exchange membrane.
Claims (11)
1. fiber reinforcement non-impurity-doped proton exchange membrane, it is characterized in that: it is the film forming matrix by sulfonic fluoropolymer type resin, mixed to 1～10% fortifying fibre of film gross mass simultaneously, be 1～20% auxiliary proton conductive substance of film gross mass, and contain the high-valency metal compound, described sulfonic fluoropolymer type resin is to be repeated to form by the construction unit shown in the following formula (I):
G=O (CF wherein
2)
mSO
3H or
Wherein, n=3～15, m=2～5, p=1 or 2, q=2 or 3; M=H, Li, Na, K, Rb, Cs, NH
4, NH
3R
1, NH
2R
2R
3, NHR
4R
5R
6, NR
7R
8R
9R
10X, Y are F or Cl independently; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10Independently be C
1～C
20Alkyl.
2. proton exchange membrane as claimed in claim 1 is characterized in that: described high-valency metal compound is eliminated and to be selected from Mn, Ce or La element: ion, oxide, hydroxide or complex compound, perhaps their combination.
3. proton exchange membrane as claimed in claim 2 is characterized in that: described cerium ion is provided by one of following material or combination: Ce (NO
3)
3, Ce (Ac)
3, Ce
2(CO
3)
3, Ce
2(SO
4)
3, CePO
4, Ce (NO
3)
4, Ce (CO
3)
2, Ce (SO
4)
2, (NH4)
2Ce (NO)
6, LaCe (CO3)
3
4. proton exchange membrane as claimed in claim 2 is characterized in that: described manganese ion is provided by one of following material or combination: Mn (NO
3)
2, Mn (Ac)
2, MnCO
3, MnSO
4, Mn (NO
3)
2, Mn
3(PO
4)
2, MnPO
4, Mn (Ac)
3, Mn
2(CO
3)
3Or Mn
2(SO
4)
3
5. as claimed in claim 2 kind of fiber reinforcement non-impurity-doped long-life proton exchange membrane is characterized in that: described lanthanum ion is provided by one of following material or combination: LaPO
4, La (Ac)
3, La
2(CO
3)
3Or La
2(SO
4)
3
6. proton exchange membrane as claimed in claim 2 is characterized in that: described oxide or hydroxide comprise following one or more combination: Ce
2O
3, CeO
2, MnO, Mn
2O
3, La
2O
3, Ce (OH)
3, Ce (OH)
4, Mn (OH)
2, Mn (OH)
3Or La (OH)
3
7. proton exchange membrane as claimed in claim 2 is characterized in that: described oxide is that cerium, manganese or lanthanum element are arbitrarily between two or more or and the mixed oxide formed of other elements or the oxide with perovskite structure.
8. proton exchange membrane as claimed in claim 7 is characterized in that: described mixed oxide is selected from following several mixed oxides or has the oxide of perovskite structure: Ce
xTi
(1-x)O
2(x=0.25～0.4), Ca0.6
La0.27TiO
3, La
(1-y)Ce
yMnO
3(y=0.1～0.4) or La
0.7Ce
0.15Ca
0.15MnO
3
9. as each described proton exchange membrane of claim 6-8, it is characterized in that: described oxide carried on auxiliary proton conductive substance, wherein said auxiliary proton conductive substance can be the one or more combination of following material: SiO
2, ZrO
2, Zr
3(PO
4)
4, H
3PW
12O
40,, CsHSO
4, CsH
2PO
4, Zr (HPO
4)
2, HZr
2(PO
4)
3Or Zr
2H (P
3O
10)
2
10. as each described proton exchange membrane of claim 6-8, it is characterized in that: described oxide carried on fortifying fibre, wherein said fortifying fibre can be the following one or more combination of material down: in glass fibre, fluorocarbon polymer fiber, silicon carbide fibre, ceramic fibre, the mineral fibres.
11. proton exchange membrane as claimed in claim 2 is characterized in that: the part of described complex compound can be the one or more combination of following material: cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether, EDTA, DMF or DMSO.
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| CN2009102311220A CN101728550B (en) | 2009-12-10 | 2009-12-10 | Fiber-reinforced stably-doped proton exchange membrane |
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| CN101728550B CN101728550B (en) | 2011-05-04 |
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