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CN101728551B - Enhanced multi-layer fluorine-containing ion exchange membrane - Google Patents

Enhanced multi-layer fluorine-containing ion exchange membrane Download PDF

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Publication number
CN101728551B
CN101728551B CN2009102311254A CN200910231125A CN101728551B CN 101728551 B CN101728551 B CN 101728551B CN 2009102311254 A CN2009102311254 A CN 2009102311254A CN 200910231125 A CN200910231125 A CN 200910231125A CN 101728551 B CN101728551 B CN 101728551B
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amberplex
film
fiber
fibre
ion
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CN101728551A (en
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张永明
唐军柯
刘萍
张恒
王军
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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Shandong Dongyue Shenzhou New Material Co Ltd
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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-enhanced multi-layer fluorine-containing ion exchange membrane which is stable to free radicals, belonging to the field of functional polymer composite materials. The membrane is a multi-layer structure membrane which consists of fluorine-containing ion exchange resin, enhancing fibers and free radical removing substances. The prepared ion exchange membrane has high proton conductivity, high mechanical performance, strong resistance to the free radicals, and mechanical stability and can effectively prevent the penetration of hydrogen and methanol.

Description

A kind of enhancing multi-layer fluorine-contained ionic exchange film
Technical field
The invention belongs to field of functional polymer composites, relate to exchange membrane containing fluorine of a kind of fiber-reinforced multi-layer Green Tea Extract 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 have 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.Film water absorption rate and size of causing because of suction under different humidity expand also different, and when film during at different operating mode down conversion, the size of film also will so change.Finally cause proton exchange membrane generation mechanical damage or degraded so repeatedly.In addition, the positive pole reaction of fuel cell usually produces the material that a large amount of hydroxyl free radicals and hydrogen peroxide etc. have strong oxidizing property, unstable group such as non-fluorin radical or sulfonic acid group or ehter bond on these materials meeting attack film resin molecules, thus be chemical degradation and damaged, the foaming that these unstable groups come off and cause film.At last, 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, and this 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.
People have proposed some solutions in order to improve film strength at present.Gore-Select series composite membrane as the exploitation of W.L.Gore company adopts the porous teflon to fill the method (seeing US5547551, US5635041 or US5599614) of Nafion ionic conductivity liquid, this film has higher proton conductive and dimensional stability preferably, but teflon creep at high temperature is very big, causes decreased performance.
Japan Patent JP-B-7-68377 has proposed a kind of method, makes porous media with the proton exchange resins filled polyolefin, but its chemical durability deficiency, thereby aspect long-time stability, have problems.And owing to added the porous media that does not possess the proton conductive ability, make the proton conduction path reduce, thereby cause the proton exchange ability drop of film.
In addition, Japan Patent JP-A-6-231779 has proposed another kind of Enhancement Method, promptly uses fluororesin fiber.The proton exchange membrane that it adopts the fluorocarbon polymer reinforcing material of fibrillation form to strengthen.But this method must add a large amount of relatively reinforcing materials, and in this case, the processing characteristics of film is tending towards difficulty, and the film resistance increase takes place possibly.
European patent EP 0875524B1 discloses and has utilized the glass fibre non-woven technology to prepare the method that glass fibre membrane strengthens the nafion film, has mentioned oxides such as can using silicon dioxide in the method simultaneously.But non-woven glass fibre cloth is the base material that must use in this method, and this has limited the scope of application of this film greatly.
Chinese patent 200810138296.8 provides a kind of fibre-reinforced sandwich construction proton exchange membrane, and it adopts the mechanical mechanics property that adds fortifying fibre and this special mode of multilayer film and improved film.
But above the whole bag of tricks all can't substantially change the chemical stability of film.Because Proton Exchange Membrane Fuel Cells fuel gas when work can generate the reaction of free radical at electrode:
(1)H 2→2H ·
(2) H + O 2(being diffused into anode) → HO2 by PEM
(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, particularly hydrop free radical (HO 2), unstable group and non-fluorin radical (as sulfonic acid group and ehter bond) on can the attack flim forming molecule, thus the degraded of film finally caused, cause deterioration.
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.Though these methods have reduced the concentration of free radical in the film to a certain extent, but can not fundamentally suppress the degraded of film, because the degraded of film can be divided into two aspects: mechanical damage (just film cause under alternation of wetting and drying conversion environment mechanical damage or degraded) is exactly the above-mentioned chemical degradation of mentioning in addition.The degraded of this two aspect is mutually promoted, and the place that mechanical damage takes place at first is often because of the oxidation of free radical, and makes the film attenuation or produce bubble.
The whole bag of tricks is in the past often only paid attention to the improvement of some aspects performance, promptly only relates to improving mechanical strength or Green Tea Extract ability, and fails these combined factors to be got up to take in and solve.Although Chinese patent 200810138296.8 has adopted the method for fiber reinforcement and multilayer film, in the mechanical performance that improves film, also improved the air-tightness of film owing to the existence at multilayer interface.But this modification of being carried out can not improve film to because the degradation of the free radical that electrode reaction produces, even the unstable group on employed some fiber of modification such as the (per) fluoropolymer (being introduced by polymerization reaction) also can be degraded by free radical.The final like this mechanical strength of film that causes descends and the generation breakage.And only add the method for free radical cracking material for some, though reduced the concentration of free radical and the chemical oxidation of radical pair film in the film to a great extent, but can not fundamentally suppress the degraded and the breakage of film equally, because the degraded of film and breakage can be divided into two aspects as mentioned above, the one, because swelling constantly takes place in film under dry wet alternating environment, contraction finally causes breakage, the chemical degradation of promptly mentioning just now in addition.Although add the free radical cracking that the free radical cracking material has suppressed film, can not suppress the breakage that the change in size of film causes.
The perfluorinated sulfonic acid ionic membrane that is used for fuel cell need satisfy the requirement of high mechanical properties.Generally speaking, when ion-exchange capacity raise, the equivalent value of (per) fluoropolymer decline (equivalent value EW value reduces, ion exchange capacity IEC=1000/EW) film strength simultaneously also reduced.Therefore, preparation has the macroion exchange capacity, and the ionic membrane that can keep mechanical strength simultaneously is very important.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of multilayer proton exchange membrane of using fiber and the common modification of free radical cracking material.By using fiber and free radical cracking material and having adopted this special membrane structure of multilayer film, improved the performance of aspects such as the ability of Green Tea Extract of mechanical strength, film of film and fuel gas air-tightness simultaneously.Stoped the damage of the film that the synergy of breakage two aspects that film causes because of free radical cracking and change in size causes.The present invention finds that this Several Factors combines, also improved the ability (than only using resistance Hydrogen Energy power to increase many times) of the resistance hydrogen permeate of film greatly with fibre-reinforced multilayer film, this may be because employed free degradation agent all is the polyvalent metal ion or derivatives thereof, sulfonate radical generation bonding action in these materials meetings and the film has improved film compactness.The Fenton test shows that the combination of these several factors also is higher than the performance of the film that only adds the free radical cracking material far away for the raising of anti-ability of freely degrading in addition, trace it to its cause, should be these several factors synergies (the particularly structure of sandwich construction) make film at size changing rate littler and become fine and close more in, sandwich construction also fundamentally suppresses the infiltration of oxygen to film owing to increased the interface, and then suppressed oxygen and react at anode and generate the hydrop free radical, and it is generally acknowledged that this free radical has the highest oxidability and to the destructiveness of film.
The invention provides a kind of fibre reinforced multi-layer fluorine-contained ionic exchange film, comprising 2～40 layers is the monofilm of matrix with the ion exchange fluoro resin, be preferably 2～5 layers, it is characterized in that: have at least one deck monofilm to add fiber, have at least 1 layer of monofilm to add and have the material that promotes free radical cracking as reinforce.
Described ion exchange fluoro resin is to be formed by one or more Fluorine containing olefines, one or more fluorine-containing alkene monomer copolymerization that contain functional group, also can be the mixture of one or more above-mentioned copolymers.The copolyreaction that forms this ion exchange resin is the common practise in the organic chemistry field of polymer technology, as long as clear and definite comonomer specifically, then to those skilled in the art, select suitable copolyreaction condition according to prior art with may be obvious that, as temperature, time, solvent, initator etc., thereby obtain perfluorinated ion exchange resin of the present invention.
Described Fluorine containing olefine is selected from: tetrafluoroethene, chlorotrifluoroethylene, trifluoro-ethylene, hexafluoropropylene or vinylidene; Preferably, it is selected from tetrafluoroethene or chlorotrifluoroethylene.
The described fluorine-containing alkene monomer of functional group that contains is general formula (I) with following structure, (II) or (III):
Figure G2009102311254D00031
R f3CF＝CF(CF 2) dY 2
(II)
Wherein, a, b, c are 0 or 1 independently, but can not be zero simultaneously;
D is 0～5 integer
N is 0 or 1;
R F1, R F2, R F3Be perfluoroalkyl or dichlorodifluoromethan base independently;
X is selected from F, Cl, Br or I;
Y 1, Y 2, Y 3Be independently selected from SO 2M, COOR 3Or PO (OR 4) (OR 5), wherein:
M is selected from F, Cl, OR, NR 1R 2R is selected from methyl, ethyl, propyl group, H, Na, Li, K or ammonium root; R 1And R 2Be independently selected from H, methyl, ethyl or propyl group; R 3Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group; R 4, R 5Be independently selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group.
Preferred monomer is:
CF 2＝CFO[CF 2CF(CF 3)] aO(CF 2) bSO 2M(A)
Wherein, the gross thickness of described ion exchange fluoro resin is 10～300 μ m, is preferably 30～200 μ m, and more preferably 50～150 μ m most preferably are 70～120 μ m; Its EW value is not special to be limited, and for example can be 600～1300, is preferably 700～1200; The diameter of described fortifying fibre is 0.005 μ m～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; Length is 0.05 μ m～3mm, is preferably 0.1 μ m～1mm, and more preferably 1 μ m～100 μ m most preferably are 10 μ m～50 μ m; The mass ratio of described fortifying fibre and ion exchange fluoro resin is 0.1～60: 100, is preferably 1～25: 100.
Include but not limited to one or more mixing of following substances as the described fiber of reinforce: polymer fiber, simple substance fiber, oxide fibre, oxysalt fibrid, carbide fibre, nitride fiber, boride fiber, sulphide fibres, silicide fiber or phosphide fiber.
Preferably, described fiber is selected from one or more in glass fibre, fluorocarbon polymer fiber, ceramic fibre, mineral fibres or the oxide fibre.
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, self-control has ion exchanging function according to prior art CN101003588A fiber or poly-perfluoro propyl vinyl ether fiber; Described ceramic fibre is selected from natural coal jewel fiber, silicon carbide fibre or alumina silicate fibre; Described mineral fibres is selected from quartz fibre or basalt fibre.
Preferably having ion-exchange capacity, area load has the fiber of auxiliary proton conductive substance or free radical cracking material, as the fiber that makes according to prior art CN101003588A, the fiber of surface silicon acidifying, sulfonation, sulphation, phosphorylation with ion exchanging function.Or these fibers are put into the solution with free radical cracking material material carry out the existing surface modifying method for polytetrafluoroethylene of modification and all be suitable for modification to the fluorocarbon polymer fiber, comprise reduction modification method, laser emission modification method, plasma modification method or the silicic acid activation method of sodium naphthalene solution.Its mesosilicic acid activation method is first-selected method, because it can be at the silicon dioxide that directly deposits water conservation on the fluorine carbon fiber surface.Other method of modifying makes the fluorine carbon fiber surface that hydrophilic radical arranged after by modification, but preferably further carry out again on this basis modification as with the fiber of modification at tetraethoxysilane, ZrOCl 2-H 3PO 4Or carry out modification in the titanate esters etc.
And for the surface modification of inorfil, this can directly be positioned over tetraethoxysilane, ZrOCl with these fibers 2-H 3PO 4Or carry out modification in titanate esters, the cerate etc., and also can in fiber, add modifier and directly generate modified fibre, as phosphate and tetraethoxysilane are mixed, reel off raw silk from cocoons with the alkali gel again and obtain modified fibre.
Described have free radical and eliminate one of the following or combination that the material of function is selected from Mn, Ce, La element: ion, oxide, hydroxide or complex compound.Its account for perfluorinated ion exchange resin quality 0.001～5%, be preferably 0.1～4%, more preferably 0.5～3%, most preferably be 1～2%.
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, (NH4) 2Ce (NO) 6, LaCe (CO3) 3Or Ce 3(PO 4) 4
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 can 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
Described oxide is cerium, manganese and lanthanum element any one or mixed oxide of forming between two or three or with other elements or the oxide with perovskite structure.
Described mixed oxide is following several mixed oxide or the oxide with 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) or La 0.7Ce 0.15Ca 0.15MnO 3
Described oxide can load on the fortifying fibre, and wherein said fortifying fibre can be the one or more combination of following material: glass fibre, fluorocarbon polymer fiber, the fiber with ion exchanging function, polyphosphazene fiber, polyphenylene sulfide fibre, ceramic fibre, quartz fibre, mineral fibres or the silicon carbide fibre that make according to prior art CN101003588A
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)).
The present invention also provides the preparation method of this exchange membrane containing fluorine, it is characterized in that: utilize solution or fused mass casting, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology make each monofilm; The preparation of multilayer film is by compound between compound between compound between monofilm, multilayer film and monofilm or multilayer film and multilayer film, also can be directly on monofilm that has made or multilayer film, utilize solution or fused mass casting, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology prepare multilayer film.
Preferably, the step of described solution casting, solution casting, silk-screen printing technique, spin coating, spraying or dipping preparation is as follows:
(1) with ion exchange fluoro resin, be distributed to as the fiber of reinforce and free radical cracking material and form mixture solution in the solvent; The mass content of ion exchange fluoro resin is 1～80% in the mixture solution;
(2) mixture solution with preparation in the step (1) is forming film by solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology on the flat board or on the single or multiple lift film that has prepared; Need under 30～300 ℃ temperature, heat treatment processing in 0.01～600 minute form film during film forming;
Preferably, the temperature in the step (2) during film forming is 80～250 ℃, is preferably 100～200 ℃; Heat treatment time is 0.1～600 minute, is preferably 1～400 minute, more promising 10～300 minutes.
Preferably, the middle solvent for use of step (2) is 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;
Preferably, the single or multiple lift film of step (2) preparation is carried out compound, thereby obtain fibre reinforced multi-layer fluorine-contained ionic exchange film of the present invention.
Described melt extrude with the step of pressure sintering as follows:
(1). according to the needs preparation of each layer formula in the fibre reinforced multi-layer fluorine-contained ionic exchange film, the mixture of ion exchange fluoro resin, fabric reinforcement and the free radical cracking material that is fit to.Utilize double screw extruder, banbury or mill to mix at 200～280 ℃; Described ion exchange fluoro resin is sulfuryl fluoride, sulfonic acid chloride or sulfonic acid bromide resin;
(2). resin utilizes screw extruder or vulcanizing press to form film with mixing completely in the step (1);
(3). the monofilm that step (2) obtains is compound, thus obtain described multilayer film.
Preferably, the film of gained can be converted in advance acid type again with other film is compound, also can be earlier and other film carry out compoundly, and then transfer acid type to.
When adding the fiber reinforcement amberplex in the prior art, group and ion-exchange group and the free radical cracking function of the fiber that is added because of not having auxiliary proton conduction is so fiber only plays the effect of reinforce in film.Can not play the Green Tea Extract performance that increases proton conduction and film.And some fiber (mainly being the fluorine carbon fiber) that uses also can be by free radical cracking, and left huge cavity descends the performance of film rapidly after these fibers are degraded.And in the present invention, fiber surface is connected the free radical cracking material by functional groupization, has also improved the Green Tea Extract degradation capability of fiber and film in the affinity that increases fiber and ion exchange resin.By Fenton test inventor find surprisingly that the fluorine ion release rate of film only adds the free radical cracking material than those and the film of not doing other modification by much smaller.This because 1, the existence of fortifying fibre increased the film dimensional stability greatly, 2, the existence at a large amount of interface of multi-layer film structure limited the infiltration of passing through film of reacting gas.Simultaneously because those free radical crackings are polyvalent metal elements, they can with sulfonic acid group generation bonding action in the film, film becomes fine and close more as a result, further stoped the infiltration of reacting gas, just oxygen can not be penetrated into anode by film, and the possibility of peroxylradicals also just can't take place to generate at anode.The existence at many interfaces makes the leakage that is kept at the small amount of moisture in the film be suppressed, so the high-temperature electric conduction rate of film also has significant the raising than prior art.
Embodiment:
By the following examples the present invention is further specified, wherein embodiment 1-5 is the preparation that is used for exemplifying the fortifying fibre of multiple modification.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.
Embodiment 1:
Polytetrafluoroethylene fibre is placed on SiCl 4Be warmed up to 110 ℃ in the atmosphere after 1 hour, and kept 1 hour, be cooled to 60 ℃ again after, water spray is handled and to be obtained silica modified polytetrafluoroethylene fibre.
Embodiment 2:
Alkali-free glass fibre is placed Ti (OEt) 4In the water mixed system, add concentrated ammonia liquor down in stirring, hydrolysis is left standstill and is obtained the alkali-free glass fibre that titanium dioxide is modified.
Embodiment 3:
Triethyl phosphate mixes with tetraethoxysilane (1: 100 mass ratio), adds entry and concentrated ammonia liquor and leaves standstill gel 12 hours, utilizes this gel to use electrostatic spinning or the technology of reeling off raw silk from cocoons to obtain the phosphoric acid modification silicon dioxide fibre then.
Embodiment 4:
To gather the tetrafluoro fiber and place cerous nitrate, citric acid, and utilize the existing disclosed sol-gel process of document to prepare nano ceric oxide (" technology and market " the 4th phase in 2008) method and obtain the poly-tetrafluoro fiber that ceria is modified.
Embodiment 5
The mass concentration that will be immersed in cerous nitrate (III) or manganese nitrate (II) or lanthanum nitrate (III) according to the fiber with ion exchanging function of prior art CN101003588A preparation is 10% solution 24 hours, obtains the modified fibre that cerium, manganese or lanthanum ion are modified.
Embodiment 6:
With repetitive be
Figure G2009102311254D00071
The inferior cerium of the fluoropolymer resin of E.W.=900g/mmol, carbonic acid (account for resin quality 0.01%) is dissolved in the dimethyl sulfoxide (DMSO), forms mass concentration and be 26% solution.Through 30 minutes, make thickness was the monofilm 1# of 25 μ m to method by solution casting under 190 ℃.
With repetitive be
Figure G2009102311254D00072
, E.W.=1000g/mmol fluoropolymer resin and with repetitive be
Figure G2009102311254D00073
, E.W.=1100g/mmol fluoropolymer resin be to mix at 1: 2 by mass ratio, again and manganese nitrate (II) (account for resin quality 0.05%) mix, make solid masses content and be 15% DMF solution, adding diameter in DMF solution is that 0.01 μ m and length are the modified Teflon fiber of enforcement 1 preparation of 1 μ m, the mass ratio of described fiber and fluoropolymer resin is 1: 10, and prepares dispersion under vigorous stirring.Utilize spraying method under 120 ℃ through 15 minutes, making thickness is the monofilm 2# of 10 μ m.The method of monofilm 1# and monofilm 2# being utilized hot pressing under 120 ℃ and 3.5Mpa through 4 minutes, the double-deck perfluorinated ion-exchange membrane 3# that is enhanced.
Embodiment 7:
With repetitive be
, the fluoropolymer resin of E.W.=800g/mmol and lanthanum acetate (lanthanum acetate account for resin quality 0.001%) be dissolved in the ethylene glycol, the formation mass concentration is 30% solution, the modification alkali-free glass fibre (diameter is that 0.05 μ m and length are 5 μ m, with the mass ratio of perfluorinated sulfonic resin be 1: 40) that adds embodiment 2 preparation again obtains disperse system.Then by method for printing screen under 150 ℃ through 5 minutes, making thickness is the monofilm 4# of 30 μ m.
With repetitive be
Figure G2009102311254D00082
, E.W.=950g/mmol fluoropolymer resin 170 ℃ of following fusions, the perfluoroethylene-propylene fiber of modifying with the cerium oxide of embodiment 4 methods preparations (diameter is that 0.1 μ m and length are 20 μ m), lanthana (lanthana account for resin quality 5%) mix, wherein the mass ratio of perfluoroethylene-propylene fiber and perfluor sulfonyl fluororesin is 1: 10, extrude by screw extruder then, make monofilm 5#.The method of monofilm 4# and monofilm 5# being utilized hot pressing obtained the double-deck perfluorinated ion-exchange membrane of fiber reinforcement through 1 minute under 150 ℃ and 2.5Mpa.This duplicature that hot pressing is good is that 15% NaOH and mass concentration are that 10% sulfuric acid solution is handled with mass concentration successively, and two-layer exchange membrane containing fluorine 6# is enhanced.
Embodiment 8:
With repetitive be
Figure G2009102311254D00083
, E.w.=1150g/mmol fluoropolymer resin and etc. the repetitive of quality be
, E.W.=850g/mmol perfluorinated sulfonic resin be dissolved in the methylformamide, the formation mass concentration is 10% solution, after under agitation disperseing, the fiber with ion exchanging function (diameter is that 0.005 μ m and length are 0.5 μ m) and the poly-perfluoro propyl vinyl ether fiber (diameter is that 0.05 μ m and length are 0.5 μ m) that add embodiment 5 preparations again fully mix, obtain mixed liquor, resin, the fiber with ion exchanging function and poly-perfluoro propyl vinyl ether fiber three's mass ratio is 1: 0.5: 10.Method by casting made the monofilm 7# that thickness is 10 μ m in 60 minutes at 170 ℃ of following warps.
With repetitive be
Figure G2009102311254D00091
, E.W.=1000g/mmol fluoropolymer resin and LaCe (CO3) 3(account for resin quality 0.05%) disperseed in ethylene glycol, perfluoroethylene-propylene fiber (diameter is that 0.1 μ m and length are 20 μ m) is scattered in the above-mentioned solution, and wherein the mass ratio of perfluoroethylene-propylene fiber and fluoropolymer resin is 3: 10.With the monofilm 7# direct impregnation do not peeled off from substrate above-mentioned disperse system 10 minutes, handled 110 minutes down at 200 ℃ then, make the double-deck exchange membrane containing fluorine 8# of fiber reinforcement.
Embodiment 9:
With repetitive be
Figure G2009102311254D00092
, the fluoropolymer resin of E.W.=700g/mmol, fiber with ion exchanging function (diameter is that 5 μ m and length are 100 μ m, and the mass ratio of fiber and resin is 1: 5) and the La that makes according to prior art CN101003588A 0.6Ce 0.4MnO 3(account for resin quality 0.1%) mixed, extruded and make the monofilm 9# that thickness is 10 μ m.
With repetitive be
Figure G2009102311254D00093
, E.W.=1200g/mmol fluoropolymer resin and Mn (OH) 3(account for resin quality 2%) mixed, extruded and make the monofilm 10# that thickness is 20 μ m.Two monofilm 10# of film are placed the both sides of monofilm 9#, through hot pressing, KOH hydrolysis, HNO 3Acidification makes three layers of exchange membrane containing fluorine 11# of fiber reinforcement.
Embodiment 10:
With repetitive be
Figure G2009102311254D00094
, E.W.=600g/mmol fluoropolymer resin, according to the ZrO of embodiment 2 preparation 2Modified carbonize silica fibre (diameter is that 8 μ m and length are 100 μ m, and the mass ratio of fiber and resin is 1: 50) and Ce 2O 3(account for resin quality 2%) mixed and is scattered in the N-methyl pyrrolidone, utilize the method for curtain coating to make the monofilm 12# that thickness is 30 μ m.
With repetitive be
Figure G2009102311254D00095
, E.W.=1000g/mmol fluoropolymer resin and cyclodextrin-lanthanum (III) complex compound (accounting for the quality 1% of resin) be dissolved in the N-methyl pyrrolidone, becoming thickness in film 12## both sides spin coating then is the film of 15 μ m, makes three layers of exchange membrane containing fluorine 13# of fiber reinforcement.
Embodiment 11:
With repetitive be
Figure G2009102311254D00101
, E.W.=1200g/mmol fluoropolymer resin and La 0.6Ce 0.4MnO 3(La 0.6Ce 0.4MnO 3Account for resin quality 0.1%) be scattered in the glycerol.Utilize the method for dipping on ptfe substrate, to form the film that thickness is 50 μ m, it is peeled off obtain monofilm 14# then.
With repetitive be
Figure G2009102311254D00102
, E.W.=1200g/mmol fluoropolymer resin and repetitive be
Figure G2009102311254D00103
, E.W.=960g/mmol fluoropolymer resin mix (mass ratio of two kinds of fluoropolymer resins is 1: 2), quartz fibre (diameter is that 15 μ m and length are 100 μ m, and the mass ratio of fiber and resin is 3: 100) and Mn (OH) mutually 3(account for resin quality 2%) mixed and is scattered in the dimethylacetylamide.Monofilm 14# was dipped in the above-mentioned dimethylacetamide solution 10 minutes, takes out with KOH hydrolysis, HNO 3Acidification, obtaining thickness is three layers of exchange membrane containing fluorine 15# of fiber reinforcement of 100 μ m.
Embodiment 12:
With repetitive be
Figure G2009102311254D00104
Fluoropolymer resin and the repetitive of E.W.=1200g/mmol be
, E.W.=960g/mmol the fluoropolymer resin mixed dissolution in dimethyl sulfoxide (DMSO), the formation mass concentration is 10% solution, to above-mentioned solution add natural coal jewel fiber and and utilize the fiber that the lanthanum ion of embodiment 5 preparations modifies (mass ratio of two kinds of fibers and perfluorinated sulfonic resin is 1: 5) with ion exchanging function, under agitation decentralized system gets dispersion liquid 1.The method of dispersion liquid 1 by solution casting made the monofilm 16# that thickness is 80 μ m through 30 minutes under 190 ℃.
Be to add the TiO that utilizes embodiment 2 preparations in 10% the dimethyl sulphoxide solution with the mass concentration of above-mentioned two kinds of fluoropolymer resins 2In the alkali-resistant glass fibre of modifying (diameter is 20 μ m, and length is 2000 μ m),, the mass ratio that makes fiber and perfluorinated sulfonic resin is 1: 5, prepares dispersion under vigorous stirring.The method of utilizing spraying is in film 16# both sides film forming, and through 15 minutes, making total thickness was three layers of exchange membrane containing fluorine 18# of 150 μ m fiber reinforcements under 120 ℃.
Embodiment 13:
With repetitive be
Figure G2009102311254D00111
, the fluoropolymer resin of E.W.=700g/mmol, (diameter is that 30 μ m and length are 3mm to basalt fibre, fiber is 0.01: 100 with the mass ratio of resin) and EDTA-Ce (III) complex (EDTA-Ce account for resin quality 5%) mix, be scattered in then in methylformamide and the ethanol mixed solvent, utilize the method for casting to make the monofilm 19# that thickness is 60 μ m.
With repetitive be
, E.W.=800g/mmol fluoropolymer resin and Ce (OH) 4(Ce (OH) 4Account for resin quality 0.003%) be scattered in the N-methyl pyrrolidone, with the casting method make the monofilm 20# that thickness is 10 μ m.
With repetitive be
Figure G2009102311254D00113
, E.W.=1100g/mmol the perfluor sulfonyl fluororesin by melt extruding, making thickness is the monofilm 21# of 15 μ m, monofilm 19#, 20#, 21# are arranged back hot pressing, LiOH hydrolysis, HCl acidifying in order, and obtaining fiber reinforcement thickness is three layers of exchange membrane containing fluorine 22# of 85 μ m.
Embodiment 14
The use repetitive is
Figure G2009102311254D00114
, to make mass concentration be 5% perfluorinated sulfonic resin glycerol solution for the fluoropolymer resin of E.W.=800g/mmol and cerous acetate (IV) (cerous acetate IV account for resin quality 0.001%), places standby.Take by weighing the phosphoric acid modification silicon dioxide fibre (diameter is 1 μ m, and length is 50 μ m) that 0.15 gram embodiment 3 makes, add 3.0 gram deionized waters, make fiber dispersion.
The fiber dispersion of preparation is added in the above-mentioned perfluor sulfoacid resin solution, and the mass ratio that makes fiber and perfluorinated sulfonic resin is 0.01: 100, ultrasonic dispersion 20 minutes, and the vacuum high-speed stirred made blended liquid in 30 minutes.Then blended liquid being cast in the polytetrafluoroethylene mold of horizontal positioned,, after 12 hours film being peeled off through 80 ℃ of vacuumizes, is the H of 0.5M in molar concentration 2SO 4Boil 1 hour in the solution, and use deionized water wash, make single layer fibre and strengthen amberplex 23#.
Perfluor sulfoacid resin solution is cast in the polytetrafluoroethylene mold of horizontal positioned,, film is peeled off individual layer 24# through 80 ℃ of vacuumizes 12 hours.
Two single layer fibres on two above-mentioned 24# monofilm therebetween that make are strengthened amberplex 23#, superimposed after, respectively place the polytetrafluoroethylene film of a same size on its bottom and top, make stacked.
Adopt platen-press to carry out hot pressing to stacked, pressure is 2.5MPa, and the time is 3 minutes, 130 ℃ of temperature are taken out stacked after the hot pressing, throw off the polytetrafluoroethylene film on surface, make four layers of exchange membrane containing fluorine 25# of enhancing of the present invention, thickness 50 is μ m.
Embodiment 15
The use repetitive is
Figure G2009102311254D00121
, EW=800 fluoropolymer resin and EW=1000, repetitive be
Figure G2009102311254D00122
Fluoropolymer resin to prepare total resin quality content be 5% hempa acid amide solution 1.
(diameter is 0.1 μ m to take by weighing 2 part of 0.15 gram polytetrafluoroethylene fibre respectively, length is 10 μ m) and glass fibre (diameter is 0.1 μ m, length is 10 μ m) and 18-hat-6-cerium (III) complex compound (18-hat-6-cerium (III) complex compound account for resin quality 0.003%), add 3.0 gram deionized waters respectively, make polytetrafluoroethylene fibre dispersion liquid and glass fibre dispersion liquid.
The polytetrafluoroethylene fibre dispersion liquid of preparation is joined in the above-mentioned solution that makes 1, and ultrasonic dispersion 20 minutes gets blended liquid 1.The glass fibre dispersion liquid of preparation is joined in the above-mentioned solution that makes 1, ultrasonic dispersion 20 minutes, the vacuum high-speed stirred made blended liquid 2 in 30 minutes.The mass ratio of fiber and perfluorinated sulfonic resin is 5: 100 in two kinds of blended liquids.Then blended liquid 1 and 2 being cast to respectively in the polytetrafluoroethylene mold of horizontal positioned,, after 12 hours film being peeled off through 80 ℃ of vacuumizes, is respectively the H of 0.5M in molar concentration 2SO 4Boil 1 hour in the solution, and use deionized water wash, make individual layer reinforcing membrane 30# that contains polytetrafluoroethylene fibre and the individual layer reinforcing membrane 26# that contains glass fibre respectively.
Solution 1 is cast in the polytetrafluoroethylene mold of two horizontal positioned,, film is peeled off make film 27# and film 28# through 80 ℃ of vacuumizes 12 hours.
Place 24#, 26#, 27# and 28# successively, superimposed after, respectively place the polytetrafluoroethylene film of a same size in its bottom and top, make stacked.
Adopt platen-press to carry out hot pressing to stacked, pressure is 2MPa, and the time is 2 minutes, 125 ℃ of temperature, take out stacked after the hot pressing, throw off the polytetrafluoroethylene film on surface, make four layers of exchange membrane containing fluorine 34# of enhancing of the present invention (thickness is 30 μ m).
Embodiment 16
Described two-layer and three layers of enhancing adulterated full fluorin amberplex that two embodiment 7 and 11 are made are superimposed with each other, and make enhancing doping five layers of long-service life fluorine-containing ion exchange membrane 29# (thickness is 150 μ m) of the present invention after hot pressing.
Embodiment 17
The multilayer that embodiment 8,10,11,13,14 is made strengthens each 1 of adulterated full fluorin amberplex and is superimposed with each other in turn, makes the enhancing of the present invention 15 layers of exchange membrane containing fluorine 30# that mix after hot pressing.
Embodiment 18.Fenton reagent method is measured the chemical stability and the hydrogen transmitance of prepared film
Get the film of certain mass and put into 80 ℃ of Fe that contain 30ppm 3+Mass concentration is in 30% the 500ml hydrogen peroxide, to heat continuously 70 hours, and solution is diluted constant volume to 1000ml, utilizes 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).
Comparative example 19:
With repetitive be
Figure G2009102311254D00131
, E.W.=800g/mmol fluoropolymer resin be dissolved in the ethylene glycol, the formation mass concentration is 30% solution, the modification alkali-free glass fibre (diameter is that 0.05 μ m and length are 5 μ m, and the mass ratio of alkali-free glass fibre and perfluorinated sulfonic resin is 1: 40) that adds embodiment 2 preparations in above-mentioned solution obtains disperse system.Made the monofilm 31# that thickness is 30 μ m then under 150 ℃ of the methods by silk screen printing through 5 minutes.
With repetitive be
Figure G2009102311254D00132
, E.W.=950g/mmol fluoropolymer resin 70 ℃ of fusions, obtain monofilm 32# by screw extruder, the method of monofilm 31# and monofilm 32# being utilized hot pressing through 1 minute, obtains fiber enhanced inorganic adulterated double-deck exchange membrane containing fluorine under 150 ℃ and 2.5Mpa.The duplicature that hot pressing is good is that 15% NaOH and mass concentration are after 10% sulfuric acid solution is handled, must strengthen the double-deck exchange membrane containing fluorine 33# that mixes with mass concentration successively.
Comparative example 20:
With repetitive be
Figure G2009102311254D00133
Perfluorinated sulfonic resin be dissolved in dimethylacetylamide aqueous systems (mass ratio 1: 1) to make solid masses content be 24% solution, in this solution, add cerous carbonate (account for resin quality 0.01%) and acetylacetone,2,4-pentanedione-Mn (II) part (account for resin quality 0.4%) and fully mix.The method of utilizing the spraying skill is 190 ℃ of following heat treatments 45 minutes, and what make thickness and be 47 μ m contains radicals scavenging material cerium and manganese perfluorinated sulfonic acid proton exchange membrane.
Embodiment 21
The performance of the multilayer film that each embodiment is made characterizes, and the results are shown in Table 1.As can be seen from Table 1, fiber reinforcement and the performance of multi-layer fluorine-contained ionic exchange film at aspects such as 100 ℃ of conductivity, hot strength, hydrogen permeate electric currents that added the radicals scavenging material all are better than common single layer fibre and strengthen amberplex.
The various films of table 1 characterize
Figure G2009102311254D00141
Figure G2009102311254D00151

Claims (12)

1. fibre reinforced multi-layer fluorine-contained ionic exchange film that free radical is stable, comprise that the 2-40 layer is the monofilm of matrix with the ion exchange fluoro resin, it is characterized in that: have at least one deck monofilm to add as the fiber of reinforce and had at least 1 layer of monofilm to add and have the material that promotes free radical cracking; Described ion exchange fluoro resin be by Fluorine containing olefine, one or more contain the fluorine-containing alkene monomer copolymerization of ion-exchange group and form;
The material of wherein said promotion free radical cracking is selected from the one of following of Mn, Ce, La element or combination: ion, oxide, hydroxide or complex compound.
2. amberplex as claimed in claim 1 is characterized in that: described amberplex comprises that 2～5 layers is the monofilm of matrix with the ion exchange fluoro resin.
3. amberplex as claimed in claim 1 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) 3Or Ce 3(PO 4) 4
4. amberplex as claimed in claim 1 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. amberplex as claimed in claim 1 is characterized in that: 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
6. amberplex as claimed in claim 1 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. amberplex as claimed in claim 1 is characterized in that: described oxide is cerium, manganese and lanthanum element any one or the mixed oxide formed between two or three or with other elements.
8. amberplex as claimed in claim 1 is characterized in that: described oxide is cerium, manganese and lanthanum element any one or the oxide with perovskite structure formed between two or three or with other elements.
9. amberplex as claimed in claim 8 is characterized in that: described oxide is following oxide or its mixture: Ce with perovskite structure xTi (1-x)O 2, Ca 0.6La 0.27TiO 3, La (1-y)Ce yMnO 3Or La 0.7Ce 0.15Ca 0.15MnO 3, wherein x=0.25～0.4, y=0.1～0.4.
10. as each described amberplex of claim 6-9, it is characterized in that: described oxide carried on fortifying fibre, wherein fortifying fibre comprises the one or more combination of following material: glass fibre, fluorocarbon polymer fiber, silicon carbide fibre or ceramic fibre.
11. amberplex as claimed in claim 1 is characterized in that: the part of described complex compound is the one or more combination of following material: cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, EDTA, DMF or DMSO.
12. amberplex as claimed in claim 11 is characterized in that: crown ether is a nitogen-contained crown ether.
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