CN101733006A - Doped and fiber-modified imide cross-linking perfluorinated ion exchange membrane - Google Patents
Doped and fiber-modified imide cross-linking perfluorinated ion exchange membrane Download PDFInfo
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- CN101733006A CN101733006A CN200910231129A CN200910231129A CN101733006A CN 101733006 A CN101733006 A CN 101733006A CN 200910231129 A CN200910231129 A CN 200910231129A CN 200910231129 A CN200910231129 A CN 200910231129A CN 101733006 A CN101733006 A CN 101733006A
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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
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Abstract
The invention relates to a doped and fiber-modified imide cross-linking perfluorinated ion exchange membrane belonging to the field of functional polymer composites. The perfluorinated ion exchange membrane and a high-valent metal compound form a cross-linking network structure; in addition, the perfluorinated ion exchange membrane contains a reinforced fiber and an auxiliary proton transfer substance. The perfluorinated ion exchange membrane prepared by the invention has higher high-temperature conductivity, excellent stability and mechanical strength, in particular extremely excellent gas penetration resistance.
Description
Technical field
The invention belongs to field of functional polymer composites, relate to doping, fiber-modified imide cross-linking exchange membrane containing fluorine and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells is a kind ofly directly chemical energy to be converted into the 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 PEM.
Though now the perfluorinated sulfonic acid PEM that uses is used for many years, but still exist and do not reach many defectives of commercialization requirement:, poor dimensional stability low as the high temperature proton conductivity, mechanical strength are not high.Especially dimensional stability aspect, film cause swelling ratio also different because of water absorption rate is different 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 owing to the rapid dehydration of film causes the proton-conducting of film sharply to descend.But high operating 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 DMFC, methanol permeability is very big, and this becomes fatal problem.Therefore, permeability that how to improve perfluorinated sulfonic acid proton exchange film strength, dimensional stability, reduction working media etc. becomes the key subjects that fuel cell industries faces.
Japan Patent JP-B-5-75835 strengthens film strength by adopting perfluorinated sulfonic resin to flood the porous media that polytetrafluoroethylene (PTFE) makes.Yet this porous media is because the PTFE material is softer relatively, and humidification is also insufficient, still fails to address the above problem.
The Gore-Select series composite membrane liquid of W.L.Gore company exploitation adopts the porous teflon to fill the method (seeing US5547551, US5635041, US5599614) of Nafion ionic conductivity liquid, this film has higher proton conductive and bigger dimensional stability, but teflon creep at high temperature is very big, causes performance to descend.
Japan Patent JP-B-7-68377 also proposed a kind of method, the porous media made from the proton exchange resins filled polyolefin, but its chemical durability deficiency, thereby aspect long-time stability existing problems.And owing to do not possess the adding of the porous media of 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 proposed to use fluororesin fiber other plant Enhancement Method.It adopts the fluorocarbon polymer reinforcing material of fibrillation form to strengthen amberplex.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.
Crosslinking technological can improve the mechanical strength of the heat endurance of polymer, the swelling that reduces solvent, raising polymer etc., therefore has been widely used in fields such as separating absorption and various rubber elastomers.At present, for solving the existing problems of perfluorinated sulfonic acid PEM, a lot of crosslinking technologicals have been explored and have studied.
US20070031715 has described the cross-linking method of the crosslinked generation sulphonyl of sulfonic acid chloride acid anhydride, formed in the method sulphonyl acid anhydride cross-linked structure can improve the mechanical strength of film effectively, but this cross-linked structure has significant disadvantages: sulphonyl acid anhydride unit is unsettled to alkali.
US20030032739 by on the sulfonyl on the macromolecular chain between strand alkyl connect and to reach crosslinked purpose.This crosslinked solvent swell that can reduce film well.But for obtaining not suitability for industrialized process of the required a lot of steps of this cross-linked structure.
US6733914 discloses the perfluor sulfonyl fluorine type film that will melt extrude and has soaked in ammoniacal liquor, thereby forms the PEM of sulfimide cross-linked structure, and so the perfluoro sulfonic acid membrane of handling has excellent mechanical intensity and dimensional stability.But the film that utilizes this method to obtain will be uneven film, because ammonia enters film by the method for infiltration, ammonia meeting and sulfuryl fluoride react in the process of infiltration, the sulfuryl fluoride of reaction will stop ammonia to the inner further diffusion of film, thereby form very high crosslink density on the surface of film, and that the inside of film does not take place almost is crosslinked.The big crosslinked electrical conductivity of film that makes in surface sharply descends.
In order to solve the high temperature proton conduction behavior of perfluoro sulfonic acid membrane, the inorganic additive that much has the high-temp water-preserving ability is joined in the perfluorinated sulfonic acid exchange membrane.Selected inorganic water conservation particle need have following performance: (1) particle has water holding capacity preferably, and higher dehydration temperature is just arranged; (2) has intermiscibility preferably with proton exchange resins; (3) particle has certain proton conductivity; (4) be easy to obtain littler nanometer particle; (5) structural stability of particle is good, does not follow tangible structural change in suction, dehydration; (6) help keeping or improving the mechanical strength or the physical size stability of PEM.The inorganic water conservation particle that adopts is SiO normally
2, TiO
2, Zr (HPO
4)
2Or ZrO
2Stratotype clay minerals such as particle, heteropoly acid or solid acid particle, zeolite family mineral particle, montmorillonite and intercalation clay mineral thereof etc.
Chinese patent CN1862857 discloses and added SiO in perfluorinated sulfonic resin
2Etc. inorganic water-loss reducer, improve the high-temperature electric conduction performance of PEM.
J.Electrochem.Soc. (V154,2007, described Nafion resin and basic zirconium phosphate composite membrane-forming in p.B288-B295).This film still has very high electrical conductance in relative humidity less than 13%.
Chinese patent 200810138424.9 discloses a kind of method of utilizing crosslinked and two kinds of means of fiber reinforcement to improve the Mechanics of Machinery character of film, by in film, adding the method for proton conduction auxiliary substance, improve film proton-conducting at high temperature, obtained result preferably.But it is crosslinked that the employed crosslinked means of this patent are chemical bonding, have some problems aspect the degree of cross linking, the strong oxidizing property material that the unstable group on employed some fortifying fibre such as the (per) fluoropolymer (being introduced by polymerisation) produces when understanding by operation of fuel cells is degraded.Trace it to its cause, or film can not satisfy the harsh requirement of practical application.
But above each patent or document have only improved the performance of an aspect of film, do not improve the dimensional stability of film and the electricity under the high temperature low humidity simultaneously and lead.
The perfluorinated sulfonic acid ionic membrane that is used for fuel cell need satisfy following requirement: stable, high conductivity, high mechanical properties etc.Generally speaking, when ion-exchange capacity raise, the equivalent value of (per) fluoropolymer descends, and (equivalent value EW value reduced, ion exchange capacity IEC=1000/EW), film strength also reduces simultaneously, and the also rising thereupon of the gas permeability of film, and this will produce very fuel cell and seriously influence.Therefore, preparation has the macroion exchange capacity, has good mechanical mechanical strength and air-tightness simultaneously, and the film that also has good stability simultaneously is a fuel cell, becomes the key that fuel cell is especially used on delivery vehicles such as automobile.
Summary of the invention
At the deficiencies in the prior art, the invention provides and a kind ofly use fiber reinforcement simultaneously, chemical bonding is crosslinked and high-valency metal compound and film in acidic exchange group physical bond form multiple enhancing modification mode such as crosslinked, assist the material of conduction function to improve the high-temperature electric conduction performance of film owing to added proton simultaneously.On the crosslinked basis of fiber reinforcement and chemical bonding, the adding of high-valency metal compound can be set up physical bond effectively between the acidic exchange cation exchange groups, make the film abnormal compact that becomes, on original crosslinked and fibre-reinforced basis, further improved the Mechanics of Machinery character of film, and improved air-tightness gas.Simultaneously, the inventor also is surprised to find the stability of film, particularly chemical stability and is also improved greatly, and this may be because film becomes fine and close, thereby makes strong oxidation material be difficult to the result that infiltration diffuses into film.
The purpose of this invention is to provide a kind of doping, fiber reinforcement cross-linked perfluorinated ion-exchange membrane and preparation method.Adopting fiber in return in the enhancing body of film, the chemical crosslinking chain of inertia and high-valency metal compound form physical crosslinking, make polymer film have excellent mechanical strength and low-down gas permeability, and the inorganic doping thing of the auxiliary proton conductive substance of the conduct of adding in the film can increase proton conductive, makes film at high temperature still possess the good proton ability of leading.
Particularly, the invention provides a kind of doping, fiber reinforcement imide cross-linking perfluorinated ion exchange membrane, it is characterized in that: this film is matrix with the perfluorinated ion exchange resin, this resin and crosslinking agent are cross-linked to form cross-linked structure, this cross-linked structure and high-valency metal compound form the physical bond structure of cross-linked network structure [is example with the sulfonate radical] as (I) by physical bond], and added as the fiber of reinforce with as the inorganic doping thing of assisting proton conductive substance.The EW value of wherein said perfluorinated ion exchange resin is not special to be limited, and for example can be 600～1300.
Described perfluorinated ion exchange resin is to be formed by tetrafluoroethene, one or more perfluor alkene monomer copolymerization that contain the acidic exchange group, 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.
The described perfluor alkene monomer that contains the acidic exchange group is selected from as shown in the formula the combination between (A) or different (A):
CF
2＝CFO[CF
2CF(CF
3)]
fO(CF
2)
gSO
2F
F=0 or 1; The integer of g=2～4 (A)
Described cross-linked network structure has and is selected from (II) or cross-bridge (III)
Wherein, R is methylene or perfluor methylene, and n is 0～5 integer.
Form (II) or (III) method of cross-bridge be: utilize sulfuryl fluoride resin and crosslinking agent ammonia, hydrazine, organic diamine or can obtain through the reactions such as material that chemical treatment discharges ammonia, hydrazine, organic diamine.
Described organic diamine is C
1～C
10Alkyl diamine or perfluoroalkyl diamines, described organic or inorganic hydrochlorate, urea or the guanidine that can include but not limited to ammonia, hydrazine, organic amine or diamines through the material that chemical treatment discharges ammonia, hydrazine, organic diamine.
Non-limiting, can be one or more mixing of following substances as the fiber of reinforce: polymer fiber, simple substance fiber, oxide fibre, oxysalt fibrid, carbide fibre, nitride fiber, boride fiber, sulphide fibres, silicide fiber, phosphide fiber.Preferably, be selected from glass fibre, fluorocarbon polymer fiber, ceramic fibre, mineral fibres or the oxide fibre one or more as the fiber of reinforce.Selected glass fibre is selected from alkali-resistant glass fibre or alkali-free glass fibre; Fiber with ion exchanging function or poly-perfluoro propyl vinyl ether fiber that described fluorocarbon polymer fiber is selected from polytetrafluoroethylene fibre, perfluoroethylene-propylene fiber, makes according to prior art CN101003588A; Described ceramic fibre is selected from natural coal jewel fiber or alumina silicate fibre; Described mineral fibres is selected from quartz fibre, silicon carbide fibre or basalt fibre.
Preferably have ion-exchange capacity or surperficial fiber with water conservation group.As the fiber that makes according to prior art CN101003588A with ion exchanging function, the fluorocarbon polymer fiber of the hydrophilic modifying of surface silicon acidifying, sulfonation, sulphation, phosphorylation, the surface silicifies, oxide fibre of sulfonation, sulphation, phosphorylation, carbide fibre, oxysalt fibrid etc.Existing surface modifying method for polytetrafluoroethylene (PTFE) all is suitable for the modification to the fluorocarbon polymer fiber, comprises reduction modification method, laser emission modification method, plasma modification method and the silicic acid activation method etc. of sodium naphthalene solution.Wherein preferred silicic acid activation method is because this method can be at the silica that directly deposits water conservation on the fluorocarbon polymer fiber surface.By fluorine carbon fiber surface after the modification hydrophilic radical has been arranged, but has preferably further carried out modification on this basis again, as with the fiber of modification at ethyl orthosilicate, ZrOCl
2-H
3PO
4Or carry out further modification in the titanate esters etc.
For the surface modification of inorfil, then these fibers directly can be positioned over ethyl orthosilicate, ZrOCl
2-H
3PO
4Or carry out modification in the titanate esters etc., and also can in fiber, add modifier directly to generate modified fibre, as phosphate and ethyl orthosilicate are mixed, obtain the alkali gel, reeling off raw silk from cocoons obtains modified fibre again.
For example, the preparation method of silica modified polytetrafluoroethylene (PTFE) is placed on SiCl with polytetrafluoroethylene fibre exactly
4In the atmosphere after 1 hour, be warmed up to 110 ℃ and kept 1 hour, be cooled to 60 ℃ again, water spray is handled and is obtained silica modified polytetrafluoroethylene fibre.
The method of titania modified alkali-free glass is that 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.
Also has a kind of method of separating out modified fibre jointly, be that triethyl phosphate is mixed with ethyl orthosilicate (by 1: 100 mass ratio), add entry and concentrated ammonia liquor, left standstill gel 12 hours, utilize 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.
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; Its 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 fiber and perfluorinated ion exchange resin is 0.5～50: 100, is preferably 1～40: 100, most preferably be 5～30: 100.
Described inorganic doping thing is selected from: oxide, orthophosphates and condensed phosphate, polyacid, multi-acid salt, silicate, sulfate, selenite and arsenide; Wherein preferred oxides, orthophosphates and condensed phosphate, polyacid, multi-acid salt; More preferably oxide, orthophosphates and condensed phosphate.
For example, this inorganic doping thing can be selected from: SiO
2, ZrO
2, TiO
2, BPO
4, Zr
3(PO
4)
4, Zr (HPO
4)
2, H
3PW
12O
40, CsHSO
4, CsH
2PO
4, H-modenite, H-montmorillonite, HZr
2(PO
4)
3, Zr
3(PO
4)
4, Ce (HPO
4)
2, Ti (HPO
4)
2, and/or Zr
2H (P
3O
10)
2In one or more.
The mass ratio of this inorganic doping thing and perfluorinated ion exchange resin is 0.5～50: 100, is preferably 1～40: 100, more preferably 3～30: 100, most preferably be 6～20: 100; Its particle diameter is 0.001～5 μ m, is preferably 0.01～4 μ m, and more preferably 0.1～3 μ m most preferably is 0.5～2 μ m.
The element of described high-valency metal compound is selected from down one of column element or combination: W, Ir, Y, Mn, Ru, V, Zn or La element, these element compounds account for perfluorinated ion exchange resin quality 0.001～5%, be preferably 0.01～4%, more preferably 0.1～3%, most preferably be 1～2%.
Described high-valency metal compound can load on auxiliary proton conductive substance and/or the fortifying fibre.
Described high-valency metal compound can be a kind of or combination double salt in the nitrate, sulfate, carbonate, phosphate, acetate of the highest price attitude of these metallic elements and middle valence state.
The sub-compound of described high-valency metal also can be the complex compound of cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether and nitrogen heterocyclic ring, EDTA (ethylenediamine tetra-acetic acid), DMF (N, dinethylformamide) or the DMSO (dimethyl sulfoxide (DMSO)) of the highest price attitude of these metallic elements and middle valence state
Described high-valency metal compound also can be the highest price attitude of these metallic elements and the hydroxide of middle valence state.
Described high-valency metal compound also can be the highest price attitude of these metallic elements and the non-limiting ground of the oxide with perovskite structure of middle valence state in addition, for example can be Ce
xTi
(1-x)O
2(x=0.25～0.4), Ca0.6
La0.27TiO
3, La
(1-y)Ce
yMnO
3(y=0.1～0.4) or La
0.7Ce
0.15Ca
0.15MnO
3
The present invention also provides the preparation method of described doping, fiber reinforcement imide cross-linking perfluorinated ion exchange membrane, it is characterized in that: utilize solution or fused mass casting, extrude, hot pressing, curtain coating, silk-screen printing technique, spin coating, spraying or impregnation technology be prepared.
Wherein, the casting of solution or fused mass, curtain coating,, the step of silk-screen printing technique, spin coating, spraying or dipping is as follows:
(1) perfluorinated ion exchange resin, the fiber as reinforce, auxiliary proton conductive substance, crosslinking agent, high-valency metal compound are distributed to solvent and form mixture solution;
(2) mixture solution with preparation in the step (1) forms film by solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology on flat board; Needed under 30～300 ℃ the temperature heat treatment during film forming 0.01～600 minute;
(3) between film forming stage, or crosslinked after the film forming, form formula (II) or cross-linked structure (III).
Preferably, in the step (1), the perfluorinated ion exchange resin mass concentration in the mixture solution is 1～80%;
Preferably, in the step (1), used solvent is one or more in dimethyl formamide, dimethylacetylamide, NMF, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or the glycerine; Crosslinking agent described in the step (1) is selected from ammonia, hydrazine, organic diamine or can discharges the material of ammonia, hydrazine, organic diamine through chemical treatment.
Preferably, the temperature in the step (2) during film forming is preferably 80～250 ℃, more preferably; Processing time is preferably 10～600 minutes, more preferably 20～60 minutes.
Wherein, melt extrude with the step of pressure sintering as follows:
(1). the mixture according to the suitable perfluorinated ion exchange resin of the needs preparation of cross-linked perfluorinated ion-exchange membrane prescription, fabric reinforcement, auxiliary proton conductive substance, crosslinking agent, high-valency metal compound, utilize double screw extruder, banbury or mill to mix at 200～280 ℃;
(2). utilize screw extruder or vulcanizing press to form film the resin that mixes in the step (1);
(3). between film forming stage, or carry out crosslinked after the film forming; Obtain fibre-reinforced perfluorinated cross-linked doped ion-exchange membrane;
Wherein, crosslinked described in the step (3) is meant that to utilize above-mentioned various crosslinked means crosslinked, forms formula (II) or cross-linked structure (III).
The specific embodiment:
Present invention is described and explain for more detailed clearly; by the following examples the present invention is further specified; but it will be understood by those skilled in the art that these embodiments only are used to exemplify, but not spirit of the present invention and claimed scope are limited.Wherein embodiment 1-5 is the preparation that is used for exemplifying the fortifying fibre of multiple modification.
Embodiment 1:
Polytetrafluoroethylene fibre is placed on SiCl
4In the atmosphere after 1 hour, be warmed up to 110 ℃ and kept 1 hour, be cooled to 60 ℃ again after, water spray is handled and is obtained silica modified polytetrafluoroethylene fibre.
Embodiment 2:
Alkali-free glass fibre is placed Ti (OEt)
4In/the water mixed system, under agitation add concentrated ammonia liquor, hydrolysis is left standstill and is obtained the alkali-free glass fibre that titanium dioxide is modified.
Embodiment 3:
Triethyl phosphate mixes with ethyl orthosilicate (by 1: 100 mass ratio) and adds entry and concentrated ammonia liquor, 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 to utilize the document sol-gel process to prepare nano ceric oxide (" technology and market " the 4th phase in 2008) method, 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 that prior art CN101003588A makes is 10% solution 24 hours, obtains the fiber that cerium, manganese or lanthanum ion are modified
Embodiment 6:
With repetitive be
, EW=800 fluoropolymer resin, the surface by perovskite structure La
0.7Ce
0.15Ca
0.15MnO
3The granularity of modifying is the SiO of 0.03 μ m
2(SiO
2With the mass ratio of perfluorinated sulfonic resin be 5: 100), alkali-free glass fibre (diameter is that 0.05 μ m and length are 5 μ m, is 1: 40 with the mass ratio of perfluorinated sulfonic resin) mixes, extrude and obtain the film that thickness is 30 μ m.This film is soaked in NH
4In the DMF solution of Cl 5 hours.Then the film that soaks is placed triethylamine 2 hours at 200 ℃, get crosslinked film.This film is handled with KOH solution, sulfuric acid solution successively, obtained the amberplex of cross-bridge for (II).Embodiment 7:
With repetitive be
, the fluoropolymer resin, zinc hydroxide (account for resin quality 2%) of EW=1100, H
3PW
12O
40(fluoropolymer resin and H
3PW
12O
40Mass ratio 100: 20), (diameter is that 0.005 μ m and length are 0.5 μ m to the fiber of modifying by the manganese of embodiment 5 preparations with ion exchanging function, with the mass ratio of perfluorinated sulfonic resin be 0.5: 10) and urea by hot pressing, make the film that thickness is 100 μ m, heated 5 hours down at 170 ℃ then, and use alkali and acid treatment successively, obtain the ionic membrane of cross-bridge for (II).
Embodiment 8:
With repetitive be
, the fluoropolymer resin of EW=900, particle diameter be the Ce (HPO of 0.03 μ m
4)
2(with the mass ratio of perfluorinated sulfonic resin be 0.5: 100), the reel off raw silk from cocoons SiO of modification of etherophosphoric acid and ethyl orthosilicate gel
2Fiber (diameter is that 0.05 μ m and length are 5mm, is 1: 40 with the mass ratio of perfluorinated sulfonic resin), phosphoric acid ruthenium (account for resin quality 0.067%) fully mix, and extrude and obtain the film that thickness is 50 μ m.This film is immersed in NH
3DMF solution in 5 hours.200 ℃ down have a film of (II) cross-bridge.This film is obtained the ionomer film with alkali lye, acid solution processing.
Embodiment 9:
With repetitive be
, the fluoropolymer resin of EW=900, particle diameter be the ZrO of 8 μ m
2(with the mass ratio of resin be 2: 100), the modification SiO that reels off raw silk from cocoons of etherophosphoric acid and ethyl orthosilicate gel
2(diameter is that 0.05 μ m and length are 5mm to fiber, modification SiO
2The mass ratio of fiber and perfluorinated sulfonic resin is 1: 40), Ca
0.6La
0.27TiO
3(account for resin quality 2.7%) mixed, extruded and obtain the film that thickness is 50 μ m.This film is immersed in NH
3DMF solution in 5 hours.The film that under 200 ℃, is had (II) cross-bridge.This film is obtained the ionomer film with alkali lye, acid solution processing.
Embodiment 10:
With repetitive be
, EW=1200 fluoropolymer resin and particle diameter be the TiO of 0.02 μ m
2Mix (mass ratio is 100: 3), add acetylacetone,2,4-pentanedione-Ir (III) (account for resin quality 3%) then, (diameter is 0.21 μ m to esters of silicon acis modification SiC fiber, length is 120 μ m, account for above-mentioned fluoropolymer resin gross mass 7%), prepare monofilm with the method that melt extrudes, then this film is immersed in NH
3DMF solution in 5 hours, at high temperature handle obtaining having the film that cross-bridge is formula (II) in 3 hours after the immersion.
Embodiment 11:
With repetitive be
Fluoropolymer resin and repetitive be:
Fluoropolymer resin be that 2: 3 ratio is mixed with mass ratio, add Ti (HPO then
4)
2(particle diameter is 0.05 μ m, account for two kinds of total resin weight 12%), SiN (diameter is 0.1 μ m, and length is 300 μ m), SiC fiber (diameter is 0.5 μ m, and length is 3mm), Ce (HPO
4)
2(particle diameter is 0.5 μ m), HTaWO
6(fluoropolymer resin: SiN: SiC: Ce (HPO
4)
2: HTaWO
6Mass ratio be 100: 2: 6: 4: 8), Zn (OH)
2(account for resin quality 0.02%) fully mixes, and mixed melting is extruded and obtained the film that thickness is 50 μ m in sieve bar extruder then.Again above-mentioned film was soaked 30 minutes with the tetrafluoro ethylenediamine, and then under 170 ℃, add the cross-linked doped perfluorinated sulfonic acid ionic membrane of thermosetting structure cross-bridge for (III).
Embodiment 12
With recurring unit be
, the fluoropolymer resin of EW=900, particle diameter be the SiO of 0.03 μ m
2(with the mass ratio of perfluorinated sulfonic resin be 5: 100), (diameter is that 0.05 μ m and length are 5 μ m to alkali-free glass fibre, with the mass ratio of perfluorinated sulfonic resin is 1: 40), carbonic acid vanadium (account for resin quality 1.3%) fully mixes, extrude and obtain the film that thickness is 30 μ m.This film is immersed in 1, in the DMF solution of 2-ethylenediamine 5 hours.Under 200 ℃, handle and obtain having the film of cross-bridge structure for (III).This film is obtained the ionomer film with alkali lye, acid solution processing.
Comparative example 13:
With repetitive be
, the fluoropolymer resin of EW=1100, H
3PW
12O
40(fluoropolymer resin and H
3PW
12O
40Mass ratio 100: 20), (diameter is that 0.005 μ m and length are 0.5 μ m to poly-perfluoro propyl vinyl ether fiber, the mass ratio of poly-perfluoro propyl vinyl ether fiber and perfluorinated sulfonic resin is 0.5: 10) and urea get the film that thickness is 50 μ m by hot pressing, after 5 hours, obtain having the ion ionic membrane of cross-bridge structure with alkali and acid treatment in heating under 170 ℃ successively then for (II).
Comparative example 14:
Utilize 10%nafion
It is 0.03 μ mSiO that solution adds particle diameter
2(SiO
2With the mass ratio of perfluorinated sulfonic resin be 5: 100), utilize the method for cast to handle down and obtain the doping amberplex that thickness is 60 μ m at 170 ℃.
Embodiment 15
Performance to various films characterizes, and the results are shown in Table 1.As can be seen from Table 1, performances such as 95 ℃ of electrical conductivity of the compound-modified fiber reinforcement doping cross-linking of high-valency metal perfluorinated ion-exchange membrane, hot strength, hydrogen permeate electric current all are better than common doping amberplex, especially aspect gas barrier, the raising and the improvement of highly significant have been arranged.
The various films of table 1 characterize
Claims (10)
1. a doping, fiber reinforcement imide cross-linking perfluorinated ion exchange membrane, it is characterized in that: this film is matrix with the perfluorinated ion exchange resin, this resin and crosslinking agent are cross-linked to form cross-linked structure, this cross-linked structure and high-valency metal compound form cross-linked network structure by physical bond, and have added as the fiber of reinforce with as the inorganic doping thing of assisting proton conductive substance;
Described perfluorinated ion exchange resin be by tetrafluoroethene, one or more contain the perfluor alkene monomer copolymerization of acidic exchange group and form;
The described perfluor alkene monomer that contains the acidic exchange group is selected from as shown in the formula the combination between (A) or different (A):
CF
2＝CFO[CF
2CF(CF
3)]
fO(CF
2)
gSO
2F
F=0 or 1; The integer of g=2～4 (A)
Described cross-linked network structure has and is selected from (II) or cross-bridge (III):
Wherein, R is methylene or perfluor methylene, and n is 0～5 integer.
2. amberplex as claimed in claim 1 is characterized in that: as the fiber of reinforce be selected from alkali-resistant glass fibre, alkali-free glass fibre, polytetrafluoroethylene fibre, perfluoroethylene-propylene fiber, in the fiber with ion exchanging function, poly-perfluoro propyl vinyl ether fiber, fluorocarbon polymer fiber, ceramic fibre, mineral fibres or the oxide fibre that make according to prior art CN101003588A one or more.
3. amberplex as claimed in claim 1 is characterized in that: described auxiliary proton conductive substance is selected from: SiO
2, ZrO
2, TiO
2, BPO
4, Zr
3(PO
4)
4, Zr (HPO
4)
2, H
3PW
12O
40, CsHSO
4, CsH
2PO
4, H-modenite, H-montmorillonite, HZr
2(PO
4)
3, Zr
3(PO
4)
4, Ce (HPO
4)
2, Ti (HPO
4)
2Or Zr
2H (P
3O
10)
2In one or more.
4. amberplex as claimed in claim 1 is characterized in that: the element of described high-valency metal compound is selected from down one of column element or combination: W, Ir, Y, Mn, Ru, V, Zn or La element.
5. amberplex as claimed in claim 4 is characterized in that: described high-valency metal compound can load on auxiliary proton conductive substance and/or the fortifying fibre.
6. amberplex as claimed in claim 4 is characterized in that: a kind of or combination double salt in described nitrate with highest price attitude that the high-valency metal compound is selected from these metallic elements and middle valence state, sulfate, carbonate, phosphate, the acetate.
7. amberplex as claimed in claim 4 is characterized in that: described high-valency metal compound is selected from the complex compound of cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether and nitrogen heterocyclic ring, EDTA, DMF and the DMSO of the highest price attitude of these metallic elements and middle valence state.
8. the amberplex as mixing as described in the claim 4, it is characterized in that: described high-valency metal compound is selected from the highest price attitude of these metallic elements and the hydroxide of middle valence state.
9. amberplex as claimed in claim 4 is characterized in that: described high-valency metal compound is selected from the highest price attitude of these metallic elements and the oxide with perovskite structure of middle valence state.
10. amberplex as claimed in claim 9 is characterized in that: described oxide with perovskite structure can be Ce
xTi
(1-x)O
2(x=0.25～0.4), Ca
0.6La
0.27TiO
3, La
(1-y)Ce
yMnO
3(y=0.1～0.4) or La
0.7Ce
0.15Ca
0.15MnO
3
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102311292A CN101733006B (en) | 2009-12-10 | 2009-12-10 | Doped and fiber-modified imide cross-linking perfluorinated ion exchange membrane |
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| CN101733006B CN101733006B (en) | 2011-01-26 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103354814A (en) * | 2010-12-17 | 2013-10-16 | 3M创新有限公司 | Partially fluorinated polysulfinic acids and their salts |
| CN111129559A (en) * | 2019-12-26 | 2020-05-08 | 佛山市金辉高科光电材料股份有限公司 | Proton exchange membrane for fuel cell and preparation method thereof |
| CN114808270A (en) * | 2022-04-29 | 2022-07-29 | 四川大学 | Electrostatic spinning process for preparing sulfonated polymer elastomer nanofiber membrane |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1318593B1 (en) * | 2000-06-23 | 2003-08-27 | Ausimont Spa | FLUORINATED IONOMERS. |
| CN100402132C (en) * | 2003-06-20 | 2008-07-16 | 上海过滤器厂 | Filter material of tefloncomposite membrane |
| CN1631965A (en) * | 2004-11-22 | 2005-06-29 | 上海新特纺织材料研究中心有限公司 | Polytetrafluoroethylene microporous membrane for water sterilization and method for preparing same |
| US9083049B2 (en) * | 2006-10-16 | 2015-07-14 | GM Global Technology Operations LLC | Additives for fuel cell layers |
| CN101320817B (en) * | 2008-07-11 | 2010-04-14 | 山东东岳神舟新材料有限公司 | Fibre reinforced multi-layer fluorine-contained cross-linking doping ionic membrane and preparation method thereof |
| CN101319051B (en) * | 2008-07-15 | 2010-12-29 | 山东东岳神舟新材料有限公司 | Fibre reinforcement inorganics doped multi-layer fluorine ion exchange containing film |
| CN101348574B (en) * | 2008-07-22 | 2011-06-08 | 山东东岳神舟新材料有限公司 | Fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film |
| CN101350418B (en) * | 2008-07-22 | 2010-09-08 | 山东东岳神舟新材料有限公司 | Microporous-film-and-fiber-reinforced multilayer fluorine-containing cross-linking doping ionic membrane and preparation method thereof |
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2009
- 2009-12-10 CN CN2009102311292A patent/CN101733006B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103354814A (en) * | 2010-12-17 | 2013-10-16 | 3M创新有限公司 | Partially fluorinated polysulfinic acids and their salts |
| US9580526B2 (en) | 2010-12-17 | 2017-02-28 | 3M Innovative Properties Company | Partially fluorinated polysulfinic acids and their salts |
| CN111129559A (en) * | 2019-12-26 | 2020-05-08 | 佛山市金辉高科光电材料股份有限公司 | Proton exchange membrane for fuel cell and preparation method thereof |
| CN111129559B (en) * | 2019-12-26 | 2021-06-15 | 佛山市金辉高科光电材料股份有限公司 | Proton exchange membrane for fuel cell and preparation method thereof |
| CN114808270A (en) * | 2022-04-29 | 2022-07-29 | 四川大学 | Electrostatic spinning process for preparing sulfonated polymer elastomer nanofiber membrane |
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|---|---|
| CN101733006B (en) | 2011-01-26 |
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