CN101350420B - Inorganics doping multi-layer fluorine-containing ion-exchange film - Google Patents

Inorganics doping multi-layer fluorine-containing ion-exchange film Download PDF

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CN101350420B
CN101350420B CN2008101384323A CN200810138432A CN101350420B CN 101350420 B CN101350420 B CN 101350420B CN 2008101384323 A CN2008101384323 A CN 2008101384323A CN 200810138432 A CN200810138432 A CN 200810138432A CN 101350420 B CN101350420 B CN 101350420B
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film
solution
ion exchange
resin
layer
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CN101350420A (en
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张永明
王军
唐军柯
王汉利
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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

Abstract

The invention relates to an inorganic-matter doped multi-layer fluoric ion-exchange film and a preparation method thereof, pertaining to the field of functional macromolecular composite materials. The film is in a multi-layer structure, composed of fluoric ion-exchange resin and inorganic substance. The ion-exchange film prepared by the method has sound water-retaining performance, relatively high mechanical performance, chemical and mechanical stability, and is capableof preventing the penetration of hydrogen and methanol effectively.

Description

A kind of inorganics doped multi-layer fluorine ion exchange containing film
Technical field
The invention belongs to field of functional polymer composites, relate to a kind of multi-layer fluorine-contained ionic exchange film, particularly exchange membrane containing fluorine of inorganic doping 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.
Though the perfluorinated sulfonic acid proton exchange membrane of using is used for many years now, but still exists deficiency not reach the commercialization requirement,, poor dimensional stability low as the high temperature proton conductivity, mechanical strength are not high.Especially dimensional stability aspect, film are also different because of the different swelling ratios of water absorption rate under different humidity.In addition, when the perfluorinated sulfonic acid exchange membrane is worked under higher temperature,, 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 of fuel-cell catalyst greatly.In addition, existing perfluoro sulfonic acid membrane has certain hydrogen or methanol permeability, and especially in direct methanol fuel cell, methanol permeability is very big, becomes fatal problem.Therefore, how to improve perfluorinated sulfonic acid proton exchange film strength, dimensional stability, the permeability of reduction working media etc. is the key subjects that fuel cell industries faces.
For solving the high temperature proton conduction behavior of perfluoro sulfonic acid membrane, the inorganic additive that much has the high-temp water-preserving ability is added in the perfluorinated sulfonic acid exchange membrane.Choosing these inorganic water conservation machines of inorganic water conservation particle requirement must have: (1) particle has the better water holding capacity that gets, 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 good stability is not accompanied tangible structural change in suction, dehydration; (6) help keeping or improving the mechanical strength or the physical size stability of proton exchange membrane.Usually the inorganic water conservation particle that adopts is SiO 2, TiO 2, Zr (HPO 4) 2Or ZrO 2Particle, heteropoly acid or solid acid particle, zeolite family mineral particle, stratotype clay mineral such as montmorillonite and intercalation clay mineral thereof etc.
For example Chinese patent CN1862857 discloses and added SiO in perfluorinated sulfonic resin 2Can be etc. inorganic water-loss reducer to improve the high-temperature electric conduction performance of proton exchange membrane.
J.Electrochem.Soc. (V154,2007, p.B288-B295) nafion resin and basic zirconium phosphate composite membrane-forming have been described.Because this film still has very high electrical conductance in relative humidity less than 13%.
And European patent EP 0875524B1 discloses, and utilizes the technology of the glass fibre membrane enhancing nafion film of glass fibre non-woven technology preparation, mentions oxides such as silicon dioxide in this patent simultaneously.But non-woven glass fibre cloth is the base material that must use in this patent, and this will limit its scope of application greatly.
Summary of the invention
The perfluorinated sulfonic acid ionic membrane that is used for fuel cell need meet the demands: high temperature low humidity water retention property, high conductivity, high mechanical properties preferably.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 a macroion exchange capacity, can keep mechanical strength simultaneously, and the ionic membrane with good water retention property and high proton conductivity is very important.
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of mineral-doped fluor-containing multilayer amberplex and preparation method with better conductivity and mechanical strength.Amberplex adopts MULTILAYER COMPOSITE can effectively stop penetrating of hydrogen and methyl alcohol, improves the mechanical stability of film, layer with layer effectively mechanical damaged the spreading of block film of interface.
The invention provides a kind of mineral-doped fluor-containing multilayer amberplex, with the EW value is the multilayer film of the 2-40 layer that forms of 600～1300 ion exchange fluoro resin, have at least 1 layer of interpolation to have the inorganic doping thing of water retaining function or proton exchange function, gross thickness 10～300 μ m, conductivity 40-150ms/cm, hot strength 10-60MPa; Described ion exchange fluoro resin is to be formed by Fluorine containing olefine, one or more fluorine-containing alkene monomer copolymerization that contain functional group, also can be the mixture of above-mentioned copolymer.
Described Fluorine containing olefine is selected from: tetrafluoroethene, and chlorotrifluoroethylene, trifluoro-ethylene, hexafluoropropylene, and/or in the vinylidene one or more, preferred, Fluorine containing olefine is selected from tetrafluoroethene or chlorotrifluoroethylene; Described contain the fluorine-containing alkene monomer of functional group be general formula (I), (II) and/or (III) in one or more:
Figure S2008101384323D00021
R f3CF＝CF(CF 2) dY 2
(II)
Figure S2008101384323D00022
Wherein, a, b, c are 0 or 1, but can not be zero simultaneously;
D is 0～5 integer;
N is 0 or 1;
R F1, R F2And R F3Be selected from perfluoroalkyl or dichlorodifluoromethan base respectively; Perfluoroalkyl or the dichlorodifluoromethan base of preferred C1～C10;
X is selected from F, Cl, Br, or I;
Y 1, Y 2, Y 3Be selected from SO 2M, COOR 3, or PO (OR 4) (OR 5), wherein:
M is selected from F, Cl, OR or NR 1R 2Described R is selected from methyl, ethyl or propyl group, H, Na, Li, K or ammonium root; R 1And R 2Be selected from H, methyl, ethyl or propyl group respectively; R 3Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group; R 4, R 5Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group.
Preferably, ion exchange fluoro resin EW value is 700～1200.
The inorganic doping thing comprises oxide, orthophosphates and condensed phosphate, polyacid, multi-acid salt, silicate, sulfate selenite and/or arsenide; Wherein preferred oxides, orthophosphates, condensed phosphate, polyacid and/or multi-acid salt, preferred oxide, orthophosphates and/or the condensed phosphate of selecting.
Below above various inorganic doping things are further specified in detail:
(1) oxide is shown in general formula: QO E/2E=1～8; Wherein Q can be second and third, a kind of element in four, five major elements and the transition elements or multiple element e=1～8 as: SiO 2, Al 2O 3, Sb 2O 5, SnO 2, ZrO 2, TiO 2, MoO 3, ZrCeO, 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.As: 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 20Zr 5(P 3O 10) 4, ZrHP 3O 10
(3) polyacid, multi-acid salt and hydrate thereof are shown in general formula: A iB jC kO lMH 2O.Wherein A can be first, second, third and fourth, five major elements, transition elements or, two, three, four, pentavalent group; B, C can be second and third, four, five, six major elements, transition elements; I=1～10, j=0～50, k=0～50, l=2～100, m=0～50.As: 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 3, H 2MoO 4
(4) silicate comprises zeolite, zeolite (NH 4 +), phyllosilicate, web-like silicon hydrochlorate, H-sodalite, H-modenite, NH 4-analcime, NH 4-sodalite, NH 4-gallate or H-montmorillonite.
(5) sulfate is shown in general formula: D oH pS qO rWherein D can be first, second, third and fourth, five major elements, transition elements or, two, three, four, pentavalent group; O=1～10, p=0～10, q=1～5, r=2～50.As: CsHSO 4, Fe (SO 4) 2, (NH 4) 3H (SO 4) 2, LiHSO 4, NaHSO 4, KHSO 4, RbSO 4, LiN 2H 5SO 4, NH 4HSO 4
(6) selenite and arsenide are shown in general formula: E sH tF uO vWherein E can be first, second, third and fourth, five major elements, transition elements or, two, three, four, pentavalent group; F can be As or Se; S=1～10, t=0～10, u=1～5, v=2～50.As: (NH 4) 3H (SeO 4) 2, (NH 4) 3H (SeO 4) 2, KH 2AsO 4, Cs 3H (SeO 4) 2, Rb 3H (SeO 4) 2
To sum up, concrete preferred inorganic doping thing is SiO among the present invention 2, ZrO 2, TiO 2, BPO 4, Zr 3(PO 4) 4, Zr (HPO 4) 2, HZr 2(PO 4) 3, Ti (HPO 4) 2Or Zr 2H (P 3O 10) 2In one or more.
Preferably, the mass ratio of described inorganic doping material and ion exchange fluoro resin is 0.1～100: 100, preferred 0.5～50: 100, more excellent 1～25: 100. The particle diameter of the inorganic doping thing that is added is 0.005～50 μ m.
A kind of fibre-reinforced multi-layer fluorine-contained cross-linking doping ionic membrane that invention provides, each layer can be formed also can be mixed by various kinds of resin and form by a kind of resin, each layer can contain a kind of inorganic water conservation thing, also can contain several water-loss reducers, also can certain which floor contain water-loss reducer but each tunic of preferred multilayer film all has inorganic water conservation material.
The number of plies of multilayer film is 2～40 layers, gross thickness 10～300 μ m, wherein preferred 10～50 μ m.
Preferably, the number of plies of multilayer film is 2～20 layers.More preferably 2～10 layers.
The present invention also provides a kind of preparation method of multilayer fluorine-contained doped ion-exchange membrane, it is characterized in that, each monofilm utilize solution or fused mass casting, extrude, hot pressing, curtain coating, silk-screen printing technique, spin coating, spraying or impregnation technology make; The preparation of multilayer film is by compound between monofilm, compound between compound or multilayer film and multilayer film between multilayer film and monofilm, also can 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 preparation.
Preferably, the step of solution casting, solution casting, silk-screen printing technique, spin coating, spraying or dipping is as follows:
(1) ion exchange fluoro resin and inorganic doping thing are distributed to solvent formation mixture; Ion exchange fluoro resin content is 1～80% in the mixture, weight ratio;
(2) utilize the middle preparation of step (1) solution passing through solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology film forming on the flat board or on the single or multiple lift film that has prepared; To under 30～300 ℃ temperature, heat treatment handle film forming in 10～100 minutes during film forming.
Preferably, the used solvent of step (1) 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 and/or the glycerol;
Preferably, the single or multiple lift film of (2) preparation is compound, obtain fibre reinforcement inorganics doped multi-layer fluorine ion exchange containing film of the present invention.
Preferably, will be under 80～250 ℃ temperature during film forming in the step (2) heat treatment 20～60 minutes.
Preferably, melt extrude with the step of pressure sintering as follows:
(1). suitable ion exchange fluoro resin and the inorganic doping thing mixture of needs preparation according to each layer formula in the multilayer fluorine-contained doped ion-exchange membrane, utilize double screw extruder, banbury or mill 200～280 ℃ of mixing; Described ion exchange fluoro resin is sulfuryl fluoride, sulfonic acid chloride or sulfonic acid bromide resin;
(2) resin that step (1) is mixed utilizes screw extruder or vulcanizing press film forming;
Preferably, the monofilm of step (2) preparation is compound, obtain described fibre reinforcement inorganics doped multi-layer fluorine ion exchange containing film.
Preferably, the film of gained can be converted in advance acid type and other film is compound, also can be earlier and the compound acid type that transfers to again of other film.
The present invention-multilayer fluorine-contained doped ion-exchange membrane, the means of employing multilayer film have improved the mechanical strength of ionic membrane.Simultaneously, our fuel permeability that can also find film descends greatly than the result of various technology in the past.Though the existence of inorganic additive can reduce fuel permeability to a certain extent, the multi-layer film structure among the present invention also makes the infiltration of fuel must overcome interfacial resistance, thereby reaches the purpose that reduces fuel permeability.In addition, the moisture in the film that the existence of interfacial structure also makes is difficult for running off because of interfacial resistance becomes, and the high temperature or the conductivity under the low humidity of adding the feasible film that is obtained of existence of water retaining function inorganic doping thing are higher than general amberplex far away.
Embodiment:
By the following examples the present invention is further specified, but the present invention is not limited only to following embodiment.
Embodiment 1:
With repetitive be
Figure S2008101384323D00051
E.W.=900g/mmol polymer dissolution in dimethyl sulfoxide (DMSO), form the solution of 26% weight ratio, adding diameter in above-mentioned solution is 0.005 μ m SiO 2(SiO 2With the mass ratio of perfluorinated sulfonic resin be 1: 5) under vigorous stirring, disperse dispersion liquid 1.With 190 ℃ of dispersion liquid 1 methods by solution casting, 30min prepares the monofilm 1 of 25 μ m.With repetitive be
Figure S2008101384323D00052
The polymer manufacture of E.W.=1000g/mmol becomes the DMF of 15% weight ratio, and adding diameter in DMF solution is the Zr of 0.05 μ m 3(PO 4) 4Powder makes inorganic powder: perfluorinated sulfonic resin=1: 10, weight ratio is prepared dispersion 2 under vigorous stirring.Utilize the method that sprays at 120 ℃ dispersion 2,15min prepares the monofilm 2 of 10 μ m.Utilize the method for hot pressing to spend 120 monofilm 1 and monofilm 2,3.5MPa, 4min obtain inorganics doped two-layer perfluorinated ion-exchange membrane.
Embodiment 2:
Repetitive is
Figure S2008101384323D00053
The polymer dissolution of E.W.=800g/mmol forms the solution of 30% weight ratio in ethylene glycol, adding diameter in above-mentioned solution is 0.03 μ m ZrO 2(ZrO 2With the mass ratio of perfluorinated sulfonic resin be 2: 5) under vigorous stirring disperse system 1.With 150 ℃ of the method for disperse system 1 by silk screen printing, 5min prepares the monofilm 3 of 30 μ m.
Repetitive is
Figure S2008101384323D00054
The polymer of E.W.=950g/mmol adds BPO 170 ℃ of fusions 4(diameter is 0.1 μ m), wherein BPO 4Powder: the perfluor sulfonyl fluororesin is 3: 10 weight ratios) mix the monofilm of extruding by screw extruder 4, monofilm 3 and monofilm 4 utilize the method for hot pressing at 150 degree, and 2.5MPa, 1min obtain inorganics doped two-layer perfluorinated ion-exchange membrane.Two-layer perfluorinated ion-exchange membrane must mix after the two membranes that hot pressing is good is handled with NaOH and sulfuric acid solution successively.
Embodiment 3:
With repetitive be
Figure S2008101384323D00055
The polymer of E.W.=1150g/mmol and etc. the repetitive of quality be
Figure S2008101384323D00061
The polymer dissolution of E.W.=850g/mmol is in methylformamide, and adding diameter in above-mentioned solution is 0.08 μ mZr (HPO 4) 2With diameter be 0.2 μ mH 3SiW 12O 40β H 2O ((Zr (the HPO of β=21-29) 4) 2And H 3SiW 12O 40β H 2The mass ratio of O and perfluorinated sulfonic resin is 0.7: 0.8: 10) must disperse system 1 under vigorous stirring.With 170 ℃ of disperse system 1 methods by casting, 60min prepares the monofilm 5 of 10 μ m.With repetitive be
Figure S2008101384323D00062
E.W.=700g/mmol polymer dissolve at ethylene glycol, add zeolite powder (diameter is 0.6 μ m), wherein zeolite powder: polymer be 2: 10 weight ratios) disperse system 2.Monofilm 5 direct impregnation that film is peeled off from substrate are handled 110min and are prepared inorganics doped two-layer perfluorinated ion-exchange membrane for 200 ℃ behind the 10min disperse system 2.
Embodiment 4:
With repetitive be
Figure S2008101384323D00063
The polymer of E.W.=700g/mmol and 0.8 μ mZr (H 2PO 4) 3(Zr (H 2PO 4) 3And the mass ratio of resin is 1: 4) mix the film 1 that is extruded into 10 μ m.With repetitive be
Figure S2008101384323D00064
The polymer of E.W.=1200g/mmol and 5 μ mTiO 2Powder (TiO 2And the mass ratio of resin is 1: 2) mix the film 2,3 that is extruded into 20 μ m.The both sides that film 2,3 is placed film 1 are through hot pressing, hydrolysis, and acidification prepares inorganics doped three layers of perfluorinated ion-exchange membrane.
Embodiment 5:
With repetitive be
Figure S2008101384323D00065
The polymer of E.W.=600g/mmol and 10 μ mTi (HPO 4) 2(Ti (HPO 4) 2And the mass ratio of resin is 1: 100) mix and be scattered in the N-methyl pyrrolidone, the thickness that utilizes the method system of curtain coating is the film 1 of 30 μ m.With repetitive be
The polymer of E.W.=1000g/mmol is mixed in the N-methyl pyrrolidone in ethylene glycol dissolving and becomes the film of 15 μ m in film 1 both sides spin coating, prepares inorganics doped three layers of perfluorinated ion-exchange membrane.
Embodiment 6:
With repetitive be
Figure S2008101384323D00071
The polymer of E.W.=700g/mmol and repetitive are
Figure S2008101384323D00072
The polymer of E.W.=1200g/mmol (mass ratio is 1: 2), LiHSO 4(LiHSO 4And the mass ratio of resin is 1: 100) mix and be scattered in dimethylacetylamide, utilize the method for dipping on ptfe substrate, to form the film that thickness is 50 μ m, then it is peeled off film 1.
With repetitive be
Figure S2008101384323D00073
The polymer of E.W.=950g/mmol with repetitive be
Figure S2008101384323D00074
The hybrid resin of the perfluor sulfonyl fluororesin of E.W.=1100g/mmol (mass ratio is 1: 2) and 10 μ m H-montmorillonites (mass ratio of H-montmorillonite and resin is 0.1: 50) be blended in 170 ℃ melt extrude film 2.The both sides that two films 1 are placed film 2 are through hot pressing, hydrolysis, and acidification prepares inorganics doped three layers of perfluorinated ion-exchange membrane that thickness is 150 μ m.
Embodiment 7:
With repetitive be
Figure S2008101384323D00075
The polymer of E.W.=1100g/mmol and multiple unit are
Figure S2008101384323D00076
The polymer dissolution of E.W.=1000g/mmol forms the solution of 10% weight ratio in dimethyl sulfoxide (DMSO), add 5 μ m (NH to above-mentioned solution 4) 3H (SeO 4) 2((NH 4) 3H (SeO 4) 2With the mass ratio of perfluorinated sulfonic resin be 1: 1), under agitation disperse disperse system 1.With 1 190 ℃ of methods by solution casting, 30min prepares the film 2 of 80 μ m.
Repetitive is
Figure S2008101384323D00081
The polymer of E.W.=800g/mmol adds H 2MoO 4Powder, inorganic powder: perfluorinated sulfonic resin=0.5: 10, weight ratio, melt extrude two extruded films, is the inorganics doped three layers of perfluorinated ion-exchange membrane of 150 μ m with these two extruded films with placing the compound heating in film 2 both sides, NaOH hydrolysis, HCl acidifying to obtain gross thickness.
Embodiment 8:
With repetitive be
Figure S2008101384323D00082
The polymer of E.W.=600g/mmol and 20 μ m Zr 2H (P 3O 10) 2With 10 μ m OsO 4(Zr 2H (P 3O 10) 2: OsO 4The mass ratio of resin is 0.1: 0.1: 100) mix and to be scattered in methylformamide and the ethanol mixed solvent, utilizing the thickness of the method system of casting is the film 1 of 60 μ m.With repetitive be again
Figure S2008101384323D00083
The polymer of E.W.=1000g/mmol and 0.8 μ m MgHPO 4Powder (MgHPO 4And the mass ratio of resin is 1: 1) be mixed in the N-methyl pyrrolidone and make 10 μ m films 2 with the method system of casting.Repetitive is
Figure S2008101384323D00084
The polymer of E.W.=1000g/mmol is by melt extruding the film 3 that makes 15 μ m, and with film 1,2, hot pressing after 3 sequence arrangement of pressing, hydrolysis, acidifying obtain the inorganics doped three layers of perfluorinated ion-exchange membrane of 85 μ m.
Embodiment 9:
With repetitive be
Figure S2008101384323D00085
The polymer of E.W.=1200g/mmol and 1 μ m Zr (H 2PO 4) 3(Zr (H 2PO 4) 3And the mass ratio of resin is 1: 4) mix the film 1 that is extruded into 10 μ m.
With repetitive be
The polymer of E.W.=1200g/mmol and 5 μ m H-modenite powder (mass ratio of H-modenite and resin is 1: 1) are mixed in 120 ℃ of the methods of N-methyl pyrrolidone spraying, and 300min prepares the film 2 of 30 μ m.
Repetitive is
Figure S2008101384323D00091
The polymer mixed of E.W.=960g/mmol is (with 20 μ m MoO 3(MoO 3With the mass ratio of resin be 5: 100) mix and to be scattered in the mixed solvent of dimethyl formamide and propyl alcohol, utilizing the thickness of the method system of casting is the film 3 of 30 μ m.With film 1,2, hot pressing after 3 sequence arrangement of pressing, hydrolysis, acidifying obtain the inorganics doped three layers of perfluorinated ion-exchange membrane of 60 μ m.
Embodiment 11:
With repetitive be
Figure S2008101384323D00092
The polymer of E.W.=700g/mmol and 20 μ m ZrHP 3O 10With 10 μ m OsO 4(ZrHP 3O 10: OsO 4The mass ratio of resin is 0.1: 0.1: 100) mix and to be scattered in methylformamide and the ethanol mixed solvent, utilizing the thickness of the method system of casting is the film 1 of 60 μ m.Re-use and be repetitive
Figure S2008101384323D00093
The polymer of E.W.=800g/mmol and 0.8 μ m MgHPO 4Powder (MgHPO 4And the mass ratio of resin is 1: 1) be mixed in the N-methyl pyrrolidone and make 10 μ m films 2 with the method system of casting.
With repetitive be
The perfluor sulfonyl fluororesin of E.W.=1100g/mmol is by melt extruding the film 3 that makes 15 μ m, and with film 1,2, hot pressing after 3 sequence arrangement of pressing, LiOH hydrolysis, HCl acidifying obtain the inorganics doped three layers of perfluorinated ion-exchange membrane of fiber reinforcement 85 μ m.
Embodiment 12:
The use repetitive is
Figure S2008101384323D00095
The polymer of E.W.=1100g/mmol and 1 μ m Zr (H 2PO 4) 3(Zr (H 2PO 4) 3And the mass ratio of resin is 1: 4) mix the film 1 that is extruded into 10 μ m.
Repetitive is
The polymer of E.W.=800g/mmol and 5 μ m H-modenite powder (mass ratio of H-modenite and resin is 1: 1) are mixed in 120 ℃ of the methods of N-methyl pyrrolidone spraying, and 300min prepares the film 2 of 30 μ m.
The use repetitive is
The polymer of E.W.=700g/mmol and 20 μ m MoO 3(MoO 3With the mass ratio of resin be 5: 100) mix and to be scattered in the mixed solvent of dimethyl formamide and propyl alcohol, utilizing the thickness of the method system of casting is the film 3 of 30 μ m.With film 1,2, hot pressing after 3 sequence arrangement of pressing, nitrification hydrolysis obtain the inorganics doped three layers of perfluorinated ion-exchange membrane of fiber reinforcement 60 μ m.
Embodiment 13
Get the basic zirconium chloride (ZrOCl of 1.5M 2) solution 100ml evenly mixes with the absolute ethyl alcohol of 400ml, dropwise adds the absolute ethyl alcohol of 400ml and the mixed liquor of 1M phosphoric acid 20ml then, continues to stir 24h under 80 ℃ temperature, obtains containing 0.03 μ m Zr (HPO 4) 2The aqueous solution;
With the perfluorinated sulfonic resin of EW=800, its repeat unit structure is as follows:
Figure S2008101384323D00103
With Zr (HPO 4) 2Press 100: 1 relation of mass ratio with Zr (HPO 4) 2The aqueous solution and 5wt% perfluor sulfoacid resin solution mix, ultrasonic 10min.
With Zr (HPO 4) 2Being cast in the polytetrafluoroethylene mold of horizontal positioned with 5wt% perfluor sulfoacid resin solution mixed liquor,, 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 individual layer dopant ion exchange membrane 1.
With Cs 3H (SeO 4) 2Be cast in the polytetrafluoroethylene mold of horizontal positioned with perfluor sulfoacid resin solution,, film peeled off, get film 2 through 80 ℃ of vacuumizes 12 hours.
With two above-mentioned Cs that make 3H (SeO 4) 2Two individual layer Zr (HPO on (film 2) and the perfluorinated sulfonic resin film therebetween 4) 2Dopant ion exchange membrane (film 1), 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 2.5MPa, and the time is 3 minutes, and 130 ℃ of temperature are taken out stacked after the hot pressing, throw off the polytetrafluoroethylene film on surface, make four layers of perfluorinated ion-exchange membrane of doping of the present invention, thickness 50 μ m.
Embodiment 14
The tetraethoxysilane of 33ml and the absolute ethyl alcohol of 300ml are mixed, and the absolute ethyl alcohol and the molar concentration that dropwise add 240ml then are the mixed liquor of 0.3M hydrochloric acid 60ml, continue to stir 12h under 50 ℃ temperature, obtain containing 0.007 μ mSiO 2Solution.And and SiO 2Tie up to by 1: 1 pass of mass ratio and to add H in the solution 3PW 12O 40, ultrasonic 10min.
Above-mentioned solution is joined the EW=800 repetitive respectively is
Figure S2008101384323D00111
With the EW=1000 repetitive be
Figure S2008101384323D00112
The 5wt% perfluor sulfoacid resin solution in, make wherein SiO 2And H 3PW 12O 40Total amount is that 0.01, two kind of perfluor sulfoacid resin solution of perfluorinated sulfonic resin is labeled as solution 1 and solution 2 respectively.
Solution 1,2 being cast to respectively 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 individual layer doping 1 and individual layer doping 2.
The 5wt% perfluor sulfoacid resin solution of EW=800 and the 5wt% perfluor sulfoacid resin solution of EW=1000 are cast to respectively in the polytetrafluoroethylene mold of horizontal positioned,, film are peeled off make resin molding 1 and resin molding 2 through 80 ℃ of vacuumizes 12 hours.
Place resin molding 1 successively, doping 1, doping 2, resin molding 2, 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, and 125 ℃ of temperature are taken out stacked after the hot pressing, throw off the polytetrafluoroethylene film on surface, make four layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 30 μ m).
Embodiment 15
With the EW=800 repetitive be respectively
Figure S2008101384323D00113
With the EW=1000 repetitive be
Figure S2008101384323D00114
Perfluorinated sulfonic resin make 7% solution, be labeled as solution 1 and solution 2.
Solution 1,2 being cast to respectively 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 resin film 1 and single-layer resin film 2.
In the butyl titanate of 100ml, add the glacial acetic acid of 25ml, and mix, under vigorous stirring, slowly pour in the 600ml water, continue to stir 3h, after the hydrolysis fully, add the nitric acid of 10ml70wt%, continue after being heated to 80 ℃ to stir 2h, make 0.08 μ m TiO 2Colloidal solution.Press TiO 2: 1: 50 mass ratio of perfluorinated sulfonic resin is with TiO in the solution 1 2Colloidal solution mixes with solution 1, ultrasonic 30min.Be cast to afterwards in the polytetrafluoroethylene mold of horizontal positioned,, film peeled off make doping 1 through 80 ℃ of vacuumizes 12 hours.
With the perfluorinated sulfonic resin of EW=1000, its structure is as follows:
Figure S2008101384323D00121
By extruder, mix and extrude with Zirconium powder (diameter is 0.1 μ m) down at 250 ℃, make doping 2.
Place doping 1 successively, resin molding 1, doping 2, resin molding 2, 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, and 125 ℃ of temperature are taken out stacked after the hot pressing, throw off the polytetrafluoroethylene film on surface, make four layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 100 μ m).
Embodiment 16
With the perfluorinated sulfonic resin of EW=970, its structure is as follows:
Figure S2008101384323D00122
Make 12% solution.
Being cast to then 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, the single-layer resin film 1 that makes.
With the perfluorinated sulfonic resin of EW=1030, its structure is as follows:
Figure S2008101384323D00123
By extruder, at 250 ℃ of following and 0.6 μ m montmorillonite and H 3SiW 12O 40(diameter is 0.5 μ m) mixing is extruded, and makes doping 2.
Place resin molding 1 successively, doping 2, doping 2, resin molding 1, 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, and 125 ℃ of temperature are taken out stacked after the hot pressing, throw off the polytetrafluoroethylene film on surface, make four layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 30 μ m).
Embodiment 17
With the EW=800 repetitive be respectively
Figure S2008101384323D00124
The EW=970 repetitive is
Figure S2008101384323D00131
The EW=1000 repetitive is
Figure S2008101384323D00132
The EW=1030 repetitive is
Figure S2008101384323D00133
Four kinds of perfluorinated sulfonic resins make 5% solution, be labeled as solution 1, solution 2, solution 3 and solution 4.
The method of being said by front embodiment prepares 10 μ m TiO respectively 2, 0.3 μ m SiO 2, 0.09 μ m Zr (HPO 4) 2, H 3SiW 12O 40With solution 1, the blended liquid of solution 2, solution 3 and solution 4 is labeled as blended liquid 1, blended liquid 2, and blended liquid 3 and blended liquid 4, wherein the mixed nanometer thing is 1: 100 with the ratio of perfluorinated sulfonic resin.
Then it being cast to respectively 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 individual layer doping 1, individual layer doping 2, individual layer doping 3 and individual layer doping 4.
Place doping 1 successively, doping 2, doping 3, doping 4, 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 3MPa, and the time is 4 minutes, and 130 ℃ of temperature are taken out stacked after the hot pressing, throw off the polytetrafluoroethylene film on surface, make four layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 150 μ m).
Embodiment 18
Get the basic zirconium chloride (ZrOCl of 1.5M 2) solution 100ml evenly mixes with the absolute ethyl alcohol of 400ml, dropwise adds the absolute ethyl alcohol of 400ml and the mixed liquor of 1M phosphoric acid 20ml then, continues to stir 24h under 80 ℃ temperature, obtains containing 0.01 μ m Zr (HPO 4) 2The aqueous solution; With the perfluorinated sulfonic resin of EW=800, its structure is as follows:
Figure S2008101384323D00134
With Zr (HPO 4) 2Press 1: 70 relation of mass ratio with Zr (HPO 4) 2The aqueous solution and 5wt% perfluor sulfoacid resin solution mix, and ultrasonic 10min gets solution 1.
Solution 1 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 individual layer doping 1.
Above-mentioned doping 1 is immersed in the solution 1, after 30 minutes film is taken out, be placed horizontally at and carry out drying on the heating plate, with rubber roll film is carried out roll extrusion therebetween.Film after the roll extrusion is immersed in the solution 1 once more, repeats above-mentioned steps, make three layers of doping proton exchange.
With the perfluorinated sulfonic resin of EW=1030, its structure is as follows:
Figure S2008101384323D00141
With 0.5 μ m SiO 2Press 1: 100 relation of mass ratio with SiO 2The aqueous solution and 5wt% perfluor sulfoacid resin solution mix, and ultrasonic 10min gets solution 2.
Solution 2 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 individual layer doping 2.
Solution 2 in the spraying of a side of doping 2, dry double-deck doping proton exchange.
With three layers of doping proton exchange and double-deck doping proton exchange 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, and 125 ℃ of temperature are taken out stacked after the hot pressing, throw off the polytetrafluoroethylene film on surface, make five layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 40 μ m).
Embodiment 19
With the perfluorinated sulfonic resin of EW=1000, its structure is as follows respectively:
Figure S2008101384323D00142
With the perfluorinated sulfonic resin with EW=1030, its structure is as follows:
Figure S2008101384323D00143
Make 15% solution, be labeled as solution 1 and solution 2.
In the butyl titanate of 100ml, add the glacial acetic acid of 25ml, and mix, under vigorous stirring, slowly pour in the 600ml water, continue to stir 3h, after the hydrolysis fully, add the nitric acid of 10ml70wt%, continue after being heated to 80 ℃ to stir 2h, make 0.08 μ m TiO 2Colloidal solution.Press TiO 2: 1: 40 mass ratio of perfluorinated sulfonic resin is with TiO in the solution 1 2Colloidal solution mixes with solution 1, and ultrasonic 30min gets mixed liquor 1.
With H 3SiW 12O 40Be mixed and made into the solution of perfluorinated sulfonic resin 5wt% with solution 2, mixed liquor 2, wherein H 3SiW 12O 40: the perfluorinated sulfonic resin of EW=1000 is 1: 50 a ratio.
Mixed liquor 1 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 individual layer dopant ion exchange membrane 1.
Above-mentioned individual layer dopant ion exchange membrane is immersed in the solution 1, after 30 minutes film is taken out, be placed horizontally at and carry out drying on the heating plate, with rubber roll film is carried out roll extrusion therebetween.Film after the roll extrusion is immersed in the solution 1 once more, repeats above-mentioned steps, make three layers of doping proton exchange.
Three layers of doping proton exchange are immersed in the mixed liquor 2, after 30 minutes film are taken out, be placed horizontally at and carry out drying on the heating plate, with rubber roll film is carried out roll extrusion therebetween.Film after the roll extrusion is immersed in the mixed liquor 2 once more, repeats above-mentioned steps, make five layers of doping proton exchange (thickness 60 μ m).
Embodiment 20
Respectively with EW=800
And EW=970
Perfluorinated sulfonic resin make 5% solution, be labeled as solution 1 and solution 2.Solution 1 and solution 2 are made solution 3 by 1: 1 mixed.
Solution 1, solution 2 and solution 3 being cast to respectively 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 resin film 1, single-layer resin film 2 and single-layer resin film 3.
The tetraethoxysilane of 33ml and the absolute ethyl alcohol of 300ml are mixed, and the absolute ethyl alcohol and the molar concentration that dropwise add 240ml then are the mixed liquor of 0.3M hydrochloric acid 60ml, continue to stir 12h under 50 ℃ temperature, obtain containing 0.07 μ mSiO 2Solution.With SiO 2Solution respectively with solution 1, solution 2 mixes, and makes SiO 2With the ratio of perfluorinated sulfonic resin be 1: 60, ultrasonic 30min.Be cast to respectively in the polytetrafluoroethylene mold of horizontal positioned,, film peeled off make doping 1, doping 2 through 80 ℃ of vacuumizes 12 hours.
Place resin molding 1 successively, doping 1, resin molding 2, doping 2, resin molding 3, 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, and 125 ℃ of temperature are taken out stacked after the hot pressing, throw off the polytetrafluoroethylene film on surface, make five layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 90 μ m).
Embodiment 21
Respectively with EW=800
Figure S2008101384323D00153
And EW=1000
Figure S2008101384323D00154
Perfluorinated sulfonic resin make 5% solution, be labeled as solution 1 and solution 2.Solution 1 and solution 2 are made solution 3 by 1: 1 mixed.
Solution 1 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 the single-layer resin film.
Above-mentioned single-layer resin film is immersed in the solution 3, after 30 minutes film is taken out, be placed horizontally at and carry out drying on the heating plate, with rubber roll film is carried out roll extrusion therebetween.Film after the roll extrusion is immersed in the solution 3 once more, repeats above-mentioned steps, make three layer proton exchange membranes.
With HTaWO 6In pass into solution 2 and the solution 3, make HTaWO 6With the ratio of perfluorinated sulfonic resin in the solution be 1: 70, mixed liquor 1, mixed liquor 2.With mixed liquor 1, mixed liquor 2 is cast to respectively in the polytetrafluoroethylene mold of horizontal positioned, through 80 ℃ of vacuumizes 12 hours, film is peeled off make doping 1, doping 2.
Place three layers of doping proton exchange successively, doping 2, doping 1, 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, and 125 ℃ of temperature are taken out stacked after the hot pressing, throw off the polytetrafluoroethylene film on surface, make five layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 100 μ m).
Embodiment 22
Respectively with EW=970
Figure S2008101384323D00161
And EW=1030
Figure S2008101384323D00162
Perfluorinated sulfonic resin make 5% solution, be labeled as solution 1 and solution 2.Solution 1 and solution 2 are made solution 3 by 1: 1 mixed.
Get the basic zirconium chloride (ZrOCl of 1.5M 2) solution 100ml evenly mixes with the absolute ethyl alcohol of 400ml, dropwise adds the absolute ethyl alcohol of 400ml and the mixed liquor of 1M phosphoric acid 20ml then, continues to stir 24h under 80 ℃ temperature, obtains containing 0.03 μ m Zr (HPO 4) 2The aqueous solution.With Zr (HPO 4) 2Press 1: 50 relation of mass ratio with nanometer Zr (HPO with the perfluorinated sulfonic resin of EW=1030 4) 2The aqueous solution and solution 1 mix, and ultrasonic 10min makes mixed liquor 1.
Zeolite particles (particle diameter 0.5 μ m) and perfluorinated sulfonic resin respectively are distributed in solution 2 and the solution 3 by mass ratio at 1: 50, make mixed liquor 2 and mixed liquor 3.
Mixed liquor 1 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 individual layer doping 1.
Mixed liquor 2 is cast in the polytetrafluoroethylene mold of horizontal positioned,, film is peeled off make doping 2 through 80 ℃ of vacuumizes 12 hours.
Above-mentioned doping 2 is immersed in the mixed liquor 3, after 30 minutes film is taken out, be placed horizontally at and carry out drying on the heating plate, with rubber roll film is carried out roll extrusion therebetween.Film after the roll extrusion is immersed in the mixing 3 once more, repeats above-mentioned steps, make three layers of doping proton exchange.
Place 1, three layer of doping proton exchange of doping successively, doping 1, 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 3MPa, and the time is 3 minutes, and 130 ℃ of temperature are taken out stacked after the hot pressing, throw off the polytetrafluoroethylene film on surface, make five layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 60 μ m).
Embodiment 23
Three layers of adulterated full fluorin amberplex that two embodiment 4 are made are superimposed with each other, and wherein film 2 parts of a film contact with film 1 part of another film.After hot pressing, make six layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 60 μ m).
Embodiment 24
Three layers of adulterated full fluorin amberplex that two embodiment 6 are made are superimposed with each other, and make six layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 200 μ m) after hot pressing.
Embodiment 25
Five layers of adulterated full fluorin amberplex that two embodiment 16 and 17 are made are superimposed with each other, and make eight layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 150 μ m) after hot pressing.
Embodiment 26
The multi-layer doping perfluorinated ion-exchange membrane that embodiment 8,10,11,13,14 is made is superimposed with each other, and makes 17 layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 200 μ m) after hot pressing.
Embodiment 27
The multi-layer doping perfluorinated ion-exchange membrane that two embodiment 26 are made is superimposed with each other, and makes 34 layers of perfluorinated ion-exchange membrane of doping of the present invention (thickness 300 μ m) after hot pressing.
Comparative example 28:
Utilize 10%nafion
Figure S2008101384323D00171
It is 0.03 μ mSiO that DMF solution adds granularity 2(SiO 2With the mass ratio of perfluorinated sulfonic resin be 7: 100) utilize the method for cast to obtain the inorganics doped amberplex of 60 micron thickness 170 ℃ of processing.
Embodiment 29
Performance to various multilayer films characterizes, and the results are shown in Table 1.As can be seen from Table 1, performance such as 100 of inorganics doped multi-layer fluorine ion exchange containing film ℃ of conductivity, hot strength, hydrogen permeate electric current all is better than common inorganics doped amberplex.
The various films of table 1 characterize
Figure S2008101384323D00172
Figure S2008101384323D00181

Claims (6)

1. inorganics doped multi-layer fluorine ion exchange containing film, with the EW value is the multilayer film of the 2-40 layer that forms of 600～1300 ion exchange fluoro resin, have at least 1 layer of interpolation to have the inorganic doping thing of water retaining function or proton exchange function, gross thickness 10～300 μ m, conductivity 40-150ms/cm, hot strength 10-60MPa;
Described ion exchange fluoro resin is to be formed by Fluorine containing olefine, one or more fluorine-containing alkene monomer copolymerization that contain functional group, or the mixture of above-mentioned copolymer;
Described Fluorine containing olefine is selected from: tetrafluoroethene, chlorotrifluoroethylene, trifluoro-ethylene, hexafluoropropylene, and/or in the vinylidene one or more;
Described contain the fluorine-containing alkene monomer of functional group be general formula (I), (II) and/or (III) in one or more:
Figure FSB00000377470100011
Wherein, a, b, c are 0 or 1, but can not be zero simultaneously;
D is 0～5 integer;
N is 1;
R F1, R F2And R F3Be selected from perfluoroalkyl or dichlorodifluoromethan base respectively;
X is selected from F, Cl, Br or I;
Y 1, Y 2, Y 3Be selected from SO 2M, COOR 3Or PO (OR 4) (OR 5), wherein:
M is selected from F, Cl, OR or NR 1R 2Described R is selected from methyl, ethyl, propyl group, H, Na, Li, K or ammonium root; R 1And R 2Be selected from H, methyl, ethyl or propyl group respectively; R 3Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group; R 4, R 5Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group; Described inorganic matter is selected from: SiO 2, ZrO 2, TiO 2, BPO 4, Zr 3(PO 4) 4, Zr (HPO 4) 2, HZr 2(PO 4) 3, Ti (HPO 4) 2Or Zr 2H (P 3O 10) 2In one or more; The mass ratio of inorganic doping material and ion exchange fluoro resin is 0.1～100: 100.
2. inorganics doped multi-layer fluorine ion exchange containing film as claimed in claim 1 is characterized in that Fluorine containing olefine is selected from tetrafluoroethene or chlorotrifluoroethylene; R F1, R F2And R F3Be selected from perfluoroalkyl or the dichlorodifluoromethan base of C1～C10 respectively.
3. inorganics doped multi-layer fluorine ion exchange containing film as claimed in claim 1 or 2 is characterized in that, the particle diameter of inorganic doping thing is 0.005～50 μ m; The mass ratio of inorganic doping material and ion exchange fluoro resin is 0.5～50: 100.
4. the preparation method of inorganics doped multi-layer fluorine ion exchange containing film as claimed in claim 1 is characterized in that, each monofilm utilize solution or fused mass casting, extrude, hot pressing, curtain coating, silk-screen printing technique, spin coating, spraying or impregnation technology make; The preparation of multilayer film is by compound between monofilm, compound between compound or multilayer film and multilayer film between multilayer film and monofilm, or 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 preparation;
It is characterized in that the step of the casting of solution or fused mass, curtain coating, silk-screen printing technique, spin coating, spraying or impregnation technology is as follows:
(1) ion exchange fluoro resin and inorganic doping thing are distributed to solvent formation mixture; Ion exchange fluoro resin content is 1～80wt% in the mixture; Used solvent 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, ethylene glycol and/or the glycerol;
(2) utilize the solution of preparation in the step (1) passing through solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology film forming on the flat board or on the single or multiple lift film that has prepared; Will be under 80～250 ℃ temperature during film forming heat treatment 20～60 minutes;
The single or multiple lift film of step (2) preparation is compound, obtain inorganics doped multi-layer fluorine ion exchange containing film.
5. the preparation method of inorganics doped multi-layer fluorine ion exchange containing film as claimed in claim 4 is characterized in that, the step of the extruding of solution or fused mass, pressure sintering is as follows:
(1) according to the suitable ion exchange fluoro resin and the inorganic doping thing mixture of needs preparation of each layer formula in the multilayer fluorine-contained doped ion-exchange membrane, utilize double screw extruder, banbury or mill 200～280 ℃ of mixing; Described ion exchange fluoro resin is sulfuryl fluoride, sulfonic acid chloride or sulfonic acid bromide resin;
(2) resin that step (1) is mixed utilizes screw extruder or vulcanizing press film forming;
The monofilm of step (2) preparation is compound, obtain described inorganics doped multi-layer fluorine ion exchange containing film.
6. the preparation method of inorganics doped multi-layer fluorine ion exchange containing film as claimed in claim 4 is characterized in that, with the film of gained be converted in advance acid type and other film is compound, or earlier and other the compound acid type that transfers to again of film.
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