CN102019147B - Proton exchange membrane as well as preparation method and application thereof - Google Patents
Proton exchange membrane as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a proton exchange membrane as well as a preparation method thereof and application thereof in a proton exchange membrane fuel cell. The proton exchange membrane comprises 2-40 single-layer membranes taking perfluoro ion exchange resins as substrates, wherein at least one single-layer membrane is in a crosslinking reticulate structure, at least one single-layer membrane contains auxiliary proton conducting substances with surfaces modified, at least one single-layer membrane contains high-valent metallic compounds, and at least one single-layer membrane is a modified microporous membrane. The proton exchange membrane improves the proton conducting property and also greatly enhances the mechanical strength of ionic membranes in a way of physical bonding crosslinking formed by the modified microporous membrane, chemical bonding crosslinking, the high-valent metallic compounds and acidic exchange radicals.
Description
Technical field
The present invention relates to a kind of PEM and its preparation method and application.
Background technology
(proton exchange membrane fuel cell is a kind ofly directly chemical energy to be converted into the TRT of electric energy by electrochemical means PEMFC) to Proton Exchange Membrane Fuel Cells, is considered to the cleaning of 21 century first-selection, generation technology efficiently.(proton exchangemembrane PEM) is the critical material of Proton Exchange Membrane Fuel Cells to PEM.
At present the perfluorinated sulfonic acid PEM that uses (be not higher than 80 ℃) at a lower temperature and higher humidity under have good proton-conducting, but also have a lot of deficiencies, for example poor dimensional stability, mechanical strength are not high, poor chemical stability etc.
Film water absorption rate and size of causing because of suction under different humidity expand different, and when film during at different operating situation down conversion, therefore the size of film also will change, the mechanical damage that causes PEM repeatedly the most at last like this.In addition, the reaction of the positive pole of fuel cell usually produces the material that a large amount of hydroxyl free radicals and hydrogen peroxide etc. have strong oxidizing property, and the non-fluorin radical in these materials meeting attack film-forming resin molecules causes chemical degradation, breakage or the foaming of film.In addition, high operating temperature can improve the anti-carbon monoxide of fuel-cell catalyst greatly, but when the operating temperature of perfluorinated sulfonic acid exchange membrane is higher than 90 ℃, because the rapid dehydration of film causes the proton-conducting of film sharply to descend, thereby the efficient of fuel cell is descended greatly.In addition, existing perfluoro sulfonic acid membrane has certain hydrogen or methanol permeability, and especially in DMFC, methanol permeability is very big, becomes fatal problem.Therefore, how to improve the proton conduction efficient under perfluorinated sulfonic acid proton exchange film strength, dimensional stability and the high temperature, the permeability of reduction working media etc. is the key subjects that fuel cell industries faces.
Propose certain methods at present and solved these problems.Adopt perfluorinated sulfonic resin to flood the porous media that polytetrafluoroethylene (PTFE) makes as JP-B-5-75835 and strengthen film strength.Yet the porous media of this PTFE is because the PTFE material is softer relatively, and humidification is insufficient, still fails thoroughly 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 (US 5547551, US5635041 and US 5599614) 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.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 long-time stability aspect existing problems; And owing to do not possess the adding of the porous media of proton conductive ability, make the proton conduction path reduce, the proton exchange ability of film descends.In addition, JP-A-6-231779 has also proposed another kind of Enhancement Method, uses fluororesin fiber.Adopt the mechanical strength of the fluorocarbon polymer reinforcing material of fibrillation form.But this method must add a large amount of relatively reinforcing materials, and in this case, the processing of film is tending towards difficulty, and the film resistance increase takes place possibly.Among the US 5834523, Ballard company is the α of sulfonation, β, β-trifluorostyrene sulfonic acid and m-trifluoromethyl-α, β, the methyl alcohol/propanol solution of β-trifluorostyrene copolymer is immersed in the hole of porous PTFE film of swelling, under 50 ℃ of conditions, dry then, obtain composite membrane.But need repeat polymer fully is filled in the hole of PTFE microporous barrier.
In WO 98/51733, the PTFE film of the film of the thick sulfuryl fluoride type of 25 μ m and Gore company by hot pressing under 310 ℃ of vacuum states together.Then film hydrolysis in the KOH of dimethyl sulfoxide (DMSO) solution, make in the film-SO
2The F group changes into-SO
3 -At last be coated with three times 5% sulfonate resin solution in the one side of porous PTFE film, in 150 ℃ of vacuum drying ovens, make film become as a whole.This method is too time-consuming, and microporous barrier is difficult to be filled by sulfonate resin full.
Often there is phase-splitting in the perforated membrane enhancing between enhancing body and film-forming resin, also just have very big gap, thereby the film that causes has high gas permeability.
The crosslinked heat endurance that can improve polymer, the swelling of minimizing solvent, the mechanical strength of raising polymer has been widely used in fields such as separating absorption and various rubber elastomers.At present, for solving the existing problem of perfluorinated sulfonic acid PEM, a lot of crosslinking technologicals also are explored.The cross-linking method of the crosslinked generation sulphonyl of sulfonic acid chloride acid anhydride has been described as US20070031715, formed sulphonyl acid anhydride cross-linked structure can effectively improve the mechanical strength of film in the method, is that sulphonyl acid anhydride unit is unsettled to alkali but this cross-linked structure has significant disadvantages.US 20030032739 then reaches crosslinked purpose by connecting at the alkyl between strand of the sulfonyl on the macromolecular chain.This crosslinked solvent swell that can well reduce film.But need a lot of steps to be not suitable for course of industrialization for obtaining this cross-linked structure.The US 6733914 disclosed perfluor sulfonyl fluorine type films that will melt extrude soak the PEM that forms the sulfimide cross-linked structure in ammoniacal liquor, the perfluoro sulfonic acid membrane of Chu Liing has good mechanical strength and dimensional stability like this, but the film that utilizes this method to obtain is inhomogeneous 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 further to the diffusion of film inside, 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.
US 7259208 and CN 101029144 (application number 200710013624.7) be the disclosed triazine ring cross-linked structure perfluoro sulfonic acid membrane that contains respectively, has good mechanical strength and dimensional stability equally.But only adopt the crosslinked film of chemical bonding, often can not form the very high degree of cross linking, limited to the performance of improving film.The performance of telolemma can not reach the requirement of use.
In order to improve the high temperature proton conduction behavior of perfluoro sulfonic acid membrane, in the perfluorinated sulfonic acid exchange membrane, added the material that much has auxiliary proton conduction function.The auxiliary proton conductive substance particle of choosing must have following feature: (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 conducting ability; (4) be easy to obtain nanometer particle; (5) particle structure good stability is not followed tangible structural change in suction, dehydration; (6) be conducive to keep or improve mechanical strength or the physical size stability of PEM.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 CN 1862857 discloses in perfluorinated sulfonic resin and has added SiO
2Can improve the high-temperature electric conduction performance of PEM etc. auxiliary proton conductive substance.J.Electrochem.Soc. (V154,2007, P B288-B295) described Nafion resin and basic zirconium phosphate composite membrane-forming, this film in relative humidity less than very high electrical conductance was still arranged in 13% o'clock.
Not enough is, simply adds the degraded in mechanical properties that above-mentioned substance usually makes film, can't satisfy the needs of practical operation, installation.The adding of auxiliary proton conductive substance often causes film to become crisp and easily breaks, and Mechanics of Machinery character descends greatly.
Summary of the invention
The PEM that is used for fuel cell need satisfy following requirement: stable, electrical conductivity is high, mechanical strength is high.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.The gas permeability of film also rises thereupon, and this can produce fuel cell and seriously influence very much.Therefore, preparation has the macroion exchange capacity, has good Mechanics of Machinery intensity and air-tightness simultaneously, and the film that also has good stability simultaneously is fuel cell, and especially the fuel tape that uses at delivery vehicles such as automobiles is eaten practical key.
Therefore, the PEM mechanical strength that the objective of the invention is to overcome prior art is not high, the shortcoming of poor chemical stability and poor air-tightness, and a kind of preparation method and application that have excellent mechanical intensity, chemical stability and bubble-tight PEM and this film when having the macroion exchange capacity are provided.
The invention provides a kind of PEM, comprise that the 2-40 layer is the monofilm of basic 5 bodies with perfluorinated ion exchange resin, wherein, at least one deck monofilm has cross-linked structure, at least one deck monofilm contains the auxiliary proton conductive substance of finishing, at least one deck monofilm contains the high-valency metal compound, and having one deck at least is modified micro-pore film.
According to PEM provided by the invention, wherein, with the perfluor ion-exchange of 100 weight portions
Resin is benchmark, and the content of the auxiliary proton conductive substance of described finishing can weigh 0 amount part for 0.05-50, is preferably the 1-15 weight portion; The content of described high-valency metal compound can be the 0.0001-5 weight portion, is preferably the 0.001-1 weight portion.
Wherein, described cross-linked structure can be for formula (I), (II), (III), (IV) and (V)
Shown in the structure one or more:
Wherein, G
1And G
2Be respectively CF
2Or O, R
fBe C
2-C
10Perfluor carbochain or chloride perfluor carbochain;
Wherein, R is methylene or perfluor methylene, and n is the integer of 0-10;
According to PEM provided by the invention, wherein, described auxiliary proton conductive substance is selected from: one or more in oxide, orthophosphates, condensed phosphate, polyacid, multi-acid salt and hydrate thereof, silicate, sulfate, selenite and the arsenide; Be preferably in oxide, orthophosphates, condensed phosphate, polyacid and the multi-acid salt one or more, more preferably one or more in oxide, orthophosphates and the condensed phosphate.
Below, above various auxiliary proton conductive substance are elaborated, but purpose and do not lie in the scope of the present invention that limits:
(1) oxide is shown in general formula: QO
E/2, e=1-8; Wherein, Q can for second and third, four, five major element or transition elements, for example: SiO
2, Al
2O
3, Sb
2O
5, SnO
2, ZrO
2, TiO
2, MoO
3And OsO
4
(2) phosphate, comprise first, second, third and fourth, various forms of orthophosphates and the condensed phosphate of five major elements and transition elements.For example: BPO
4, Zr
3(PO
4)
4, Zr (HPO
4)
2, HZr
2(PO
4)
3, Ce (HPO
4)
2, Ti (HPO
4)
2, KH
2PO
4, NaH
2PO
4, LiH
2PO
4, NH
4H
2PO
4, CsH
2PO
4, CaHPO
4, MgHPO
4, HSbP
2O
8, HSb
3P
2O
14, H
5Sb
5P
2O
20, Zr
5(P
3O
10)
4And Zr
2H (P
3O
10)
2
(3) polyacid, multi-acid salt and hydrate thereof are shown in general formula: A
iB
jC
kO
1.mH
2O, wherein, A can for first, second, third and fourth, five major elements, transition elements or, two, three, four, pentavalent group; B and C can be second and third independently of one another, four, five, six, seven major elements, transition elements; I=1-10, j=0-50, k=0-50, l=2-100, m=0-50, for example: H
3PW
12O
40α H
2O (α=21-29), H
3SiW
12O
40β H
2O (β=21-29), H
xWO
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
3And 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 and H-montmorillonite;
(5) sulfate is shown in general formula: D
oH
pS
qO
r, wherein, D can for 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, for example: CsHSO
4, Fe (SO
4)
2, (NH
4)
3H (SO
4)
2, LiHSO
4, NaHSO
4, KHSO
4, RbSO
4, LiN
2H
5SO
4And NH
4HSO
4
(6) selenite and arsenide are shown in general formula: E
sH
tF
uO
v, wherein A can for 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, for example: (NH
4)
3H (SeO
4)
2, (NH
4)
3H (SeO
4)
2, KH
2AsO
4, Cs
3H (SeO
4)
2And Rb
3H (SeO
4)
2
To sum up, the concrete preferred auxiliary proton conductive substance of the present invention can comprise 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)
2And/or Zr
2H (P
3O
10)
2In one or more.The particle diameter of described auxiliary proton conductive substance can be 0.001-5 μ m, is preferably 0.01-1 μ m.The surface of these materials can by cogelled, co-precipitation or altogether method such as aquathermolysis modify group and/or the acid group with ion exchanging function.For example, in some embodiments of the present invention, concrete preparation method can be the auxiliary proton conductive substance that methyl orthophosphoric acid or Methylsulfate and silester or gel under alkali condition such as zirconyl chloride or titanate esters obtained finishing.
According to PEM provided by the invention, wherein, described high-valency metal compound can be W, Ir, Y, Mn, Ru, V, the highest price attitude of Zn and La element and the nitrate of middle valence state, sulfate, carbonate, phosphate, acetate and combination double salt, W, Ir, Y, Mn, Ru, V, the highest price attitude of Zn and La element and the cyclodextrin of middle valence state, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether and nitrogen heterocyclic ring, ethylenediamine tetra-acetic acid, dimethyl formamide and dimethyl sulfoxide (DMSO) complex compound, and W, Ir, Y, Mn, Ru, V, in the highest price attitude of Zn and La element and the oxide with perovskite structure of middle valence state one or more.Wherein, the oxide with perovskite structure of the highest price attitude of described W, Ir, Y, Mn, Ru, V, Zn and La element and middle valence state includes but not limited to following compound: 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), La
0.7Ce
0.15Ca
0.15MnO
3
According to PEM provided by the invention, wherein, described modified micro-pore film is selected from the monomer modified organic polymer microporous barrier with ion exchanging function, is preferably the fluorocarbon polymer film especially.The aperture of the used microporous barrier of the present invention can be 0.1-10 μ m, is preferably 0.2-3 μ m, and thickness can be 5-100 μ m, is preferably 5-30 μ m, and porosity can be 30-99%, is preferably 70-97%.
Described monomer with ion exchanging function can be sulfur dioxide, sulfur trioxide, and in following perfluorinated sulfonic acid monomer (A), perfluorinated sulfonic acid monomer (B) and the perfluorinated sulfonic acid monomer (C) of structure one or more:
Wherein, h=0-1, i=1-5, A are F, Cl, Br, OH, oxygen methyl (OCH
3) or ONa; J=0-1, k=1-5, B are methyl (Me), H or ethyl (Et); L=1-5, D are H, methyl (Me) or ethyl (Et).
According to PEM provided by the invention, wherein, this PEM preferably includes the 2-20 layer, comprises that more preferably the 2-5 layer is the monofilm of matrix with the perfluorinated ion exchange resin.The thickness of this PEM can be 10-300 μ m, is preferably 10-150 μ m, more preferably 10-50 μ m.
According to PEM provided by the invention, wherein, each layer can be formed also can be mixed by multiple perfluorinated ion exchange resin and form by a kind of perfluorinated ion exchange resin, and each layer can all form cross-linked structure and also can not form cross-linked structure by part layer.In PEM of the present invention, what described perfluorinated ion exchange resin can be at microporous barrier is surface-crosslinked, also can be crosslinked in the space of microporous barrier.Because perforated membrane carried out the surface active modification, have acidity or functional group and make and to form strong crosslinked action by the physical bond of high-valency metal compound between perforated membrane and the film-forming resin.
Described perfluorinated ion exchange resin be by the perfluoroolefine monomer, one or more contain the perfluor alkene monomer of functional group and perfluor alkene monomer copolymerization that one or more contain crosslink sites forms, or the mixture of above-mentioned copolymer, its EW value can be 600-1300, is preferably 700-1200.
Wherein, described perfluoroolefine monomer is selected from: one or more in tetrafluoroethene, CTFE, trifluoro-ethylene, hexafluoropropene and the vinylidene, preferably, described perfluoroolefine monomer is tetrafluoroethene and/or CTFE.
The described perfluor alkene monomer that contains functional group be selected from formula (VII), (VIII) and (IX) shown in structure in one or more:
R
f3CF＝CF(CF
2)
dY
2
(VIII)
Wherein, a, b, c are 0 or 1 independently of one another, but are not zero simultaneously; D is the integer of 0-5; N is 0 or 1; R
F1, R
F2And R
F3Be selected from perfluoroalkyl and dichlorodifluoromethan base respectively; X is selected from F, Cl, Br and I; Y
1, Y
2And Y
3Be selected from SO independently of one another
2M, COOR
3And PO (OR
4) (OR
5), wherein: M is selected from F, Cl, OR, NR
1R
2R is selected from methyl, ethyl, propyl group, H, Na, Li, K and ammonium root; R
1And R
2Be selected from H, methyl, ethyl and propyl group respectively; R
3Be selected from H, Na, Li, K, ammonium root, methyl, ethyl and propyl group; R
4And R
5Be selected from H, Na, Li, K and ammonium root respectively.
The described perfluor alkene monomer that contains crosslink sites is selected from as shown in the formula in the structure shown in (X), (XI) one or more:
F
2C＝CFR
f4Y
4
(X)
Wherein, Y
4And Y
5Can be selected from Cl, Br, I and CN respectively; A ', b ' and c ' are respectively 0 or 1, but a '+b '+c ' ≠ 0; X
1Be selected from F, Cl, Br and I; N ' is 0 or 1; R
F4, R
F5And R
F6Be selected from perfluoroalkyl independently of one another.
The present invention also provides the preparation method of above-mentioned PEM, and this method comprises:
(1) use solution or the fused mass contain perfluorinated ion exchange resin to form monofilm, wherein, described solution or fused mass optionally contain one or more in auxiliary proton conductive substance, modified fibre and the high-valency metal compound of finishing;
(2) make in step (1) and form cross-linked structure in the monofilm;
(3) make at least one deck step (2) obtain monofilm and one deck modified micro-pore film is compound at least, the monofilm that obtains of composite steps (1) and/or (2) therein optionally simultaneously, and/or optionally use the described solution of step (1) or fused mass to form monofilm therein, make the composite membrane that finally obtains comprise 2-40 layer monofilm, wherein one deck monofilm contains the auxiliary proton conductive substance of finishing at least, at least one deck monofilm contains modified fibre, and one deck monofilm contains the high-valency metal compound at least.
Wherein, described cross-linked structure be formula (I), (II), (III), (IV) and (V) shown in the structure one or more:
Wherein, G
1And G
2Be respectively CF
2Or O, R
fBe C
2-C
10Perfluor carbochain or chloride perfluor carbochain;
Wherein, R is methylene or perfluor methylene, and n is the integer of 0-10;
According to method provided by the invention, wherein, step (1) and (2) can be carried out simultaneously, also can carry out step (1) earlier and carry out step (2) again.
Wherein, the method that forms monofilm in the step (1) for cast, melt extrude, in hot pressing, spin coating, curtain coating, serigraphy, spraying and the dipping one or more.
Preferably, the method for described curtain coating, cast, serigraphy, spin coating, spraying or dipping is as follows:
(a) with perfluorinated ion exchange resin, as the fiber of reinforce, auxiliary proton conductive substance, crosslinking agent, one or more in acid or radical initiator and the high-valency metal compound are distributed to and form mixture in the solvent; The solid content of perfluorinated ion exchange resin can be 1-80 weight % in the mixture, and used solvent can be 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 and the glycerine one or more;
(b) utilize in the step (a) preparation solution on flat board or the single or multiple lift film that has prepared by solution casting, solution casting, serigraphy, spin coating, spraying or impregnation technology film forming; Will be under 30-250 ℃ temperature during film forming heat treatment 0.01-600 minute, be preferably at 100-200 ℃ of following heat treatment 1-30 minute;
Can be crosslinked in film forming or after the film forming, described cross-linked structure is suc as formula (I), (II), (III), (IV) with (V):
Wherein, G
1And G
2Be respectively CF
2Or O, R
fBe C
2-C
10Perfluor carbochain or chloride perfluor carbochain;
Wherein, R is methylene or perfluor methylene, and n is the integer of 0-10;
Wherein, the method that forms the cross-linked structure shown in the formula (I) comprises heat, light, electron radiation, plasma, X ray or radical initiator, also can pass through heat, light, electron radiation, plasma, X ray or action of free radical initiator and form cross-linked structure when one or more crosslinking agents exist.Wherein the structure of employed crosslinking agent is as shown in the formula shown in (VI).
X
2R
f7X
3
(VI)
Wherein, X
2And X
3Be Cl independently of one another, Br or I; R
F7Be perfluoroalkyl or dichlorodifluoromethan base;
Preferably, described radical initiator is organic peroxide or azo-initiator; Preferably, initator is the organic oxygen compound initator; More preferably, initator is the perfluor organic peroxide.
The method that forms (II), (III) cross-linked structure is: utilize sulfuryl fluoride, sulfonic acid chloride, sulfonic acid bromide type resin and ammonia, hydrazine, organic diamine or can obtain through the substance reaction that chemical treatment discharges ammonia, hydrazine, organic diamine.
Described organic diamine is alkyl diamine or the perfluoroalkyl diamines of C1-C10, describedly can include but not limited to ammonia through the material that chemical treatment discharges ammonia, hydrazine, organic diamine, organic or inorganic acid hydrochlorate, urea or the guanidine of hydrazine, organic diamine.
The method that forms (IV) cross-linked structure is that perfluorinated sulfonic resin utilizes the chlorosulfonic acid processing to obtain.
The method that forms (V) cross-linked structure be the perfluorinated sulfonic resin in nitrile group-containing site or nitrile group-containing site the perfluor sulfonyl fluororesin, contain the sulfonic acid chloride resin, contain the sulfonic acid bromide resin and under heat or sour effect, form.
Described acid is strong Bronsted acid or lewis acid; Wherein Bronsted acid is selected from H
2SO
4, CF
3SO
3H and H
3PO
4Lewis acid is selected from ZnCl
2, FeCl
3, AlCl
3, organotin, antimony organic and organic tellurium.
Preferably, described melt extrude with the method for hot pressing as follows:
(a) needs according to each layer formula in the multilayer cross-linked perfluorinated ion-exchange membrane prepare sulfuryl fluoride, sulfonic acid chloride, the sulfonic acid bromide resin that is fit to, auxiliary proton conductive substance, crosslinking agent, acid or the radical initiator of modified fibre, finishing and one or more the mixture in the high-valency metal compound utilize double screw extruder, banbury or mill 200-280 ℃ of mixing;
(b) resin that step (a) is mixed utilizes screw extruder or vulcanizing press film forming;
This method also can be crosslinked in film forming or after the film forming, obtains aforesaid crosslinked monofilm.
According to method provided by the invention, wherein, in the step (3) compound mode can be compound for monofilm, multilayer film and monofilm is compound, multilayer film and multilayer film are compound, and use solution or fused mass direct one or more in the method for formation monofilm on monofilm or multilayer film.That is to say, the casting that each monofilm can be by solution or fused mass, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, 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 be directly the 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, before compound, the monofilm that makes can be converted into acid type earlier, also can be earlier and other film be converted into acid type again after compound.
Also can be with behind the resin extruded formation monofilm, hydrolysis is converted into the Hydrogen film, this film is immersed in to reach in the solution of high-valency metal compound again to form the crosslinked purpose of physical bond.
Preferably, crosslinked described in the step (2) refers to utilize above-mentioned various crosslinked means crosslinked.
According to method provided by the invention, wherein, the auxiliary proton conductive substance of described finishing is had the group of ion exchanging function and/or the auxiliary proton conductive substance that acidic-group is modified; Described auxiliary proton conductive substance is selected from: one or more in oxide, orthophosphates, condensed phosphate, polyacid, multi-acid salt and hydrate thereof, silicate, sulfate, selenite and the arsenide; Be preferably in oxide, orthophosphates, condensed phosphate, polyacid and the multi-acid salt one or more, more preferably one or more in oxide, orthophosphates and the condensed phosphate.The object lesson of various auxiliary proton conductive substance as mentioned before.The surface of these materials can by cogelled, co-precipitation or altogether method such as aquathermolysis modify group and/or the acid group with ion exchanging function.For example, in some embodiments of the present invention, concrete preparation method can be the auxiliary proton conductive substance that methyl orthophosphoric acid or Methylsulfate and silester or gel under alkali condition such as zirconyl chloride or titanate esters obtained finishing.The high-valency metal compound can with film in the acidic exchange group to form physical bond crosslinked.This crosslinking method has the bigger degree of cross linking, and does not influence the conductivity of film.
According to PEM provided by the invention, wherein, described high-valency metal compound can be W, Ir, Y, Mn, Ru, V, the highest price attitude of Zn and La element and the nitrate of middle valence state, sulfate, carbonate, phosphate, acetate and combination double salt, W, Ir, Y, Mn, Ru, V, the highest price attitude of Zn and La element and the cyclodextrin of middle valence state, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether and nitrogen heterocyclic ring, ethylenediamine tetra-acetic acid, dimethyl formamide and dimethyl sulfoxide (DMSO) complex compound, and W, Ir, Y, Mn, Ru, V, in the highest price attitude of Zn and La element and the oxide with perovskite structure of middle valence state one or more.Wherein, the oxide with perovskite structure of the highest price attitude of described W, Ir, Y, Mn, Ru, V, Zn and La element and middle valence state includes but not limited to following compound: 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), La
0.7Ce
0.15Ca
0.15MnO
3
According to method provided by the invention, wherein, described modified micro-pore film is selected from the monomer modified organic polymer microporous barrier with ion exchanging function, is preferably the fluorocarbon polymer film especially, and its aperture is 0.1-10 μ m, is preferably 0.2-3 μ m; Thickness is 5-100 μ m, is preferably 5-30 μ m; Porosity is 30-99%, is preferably 70-97%; Described monomer with ion exchanging function is sulfur dioxide, sulfur trioxide, and in following perfluorinated sulfonic acid monomer (A), perfluorinated sulfonic acid monomer (B) and the perfluorinated sulfonic acid monomer (C) of structure one or more:
Wherein, h=0-1, i=1-5, A are F, Cl, Br, OH, oxygen methyl (OCH
3) or ONa; J=0-1, k=1-5, B are methyl (Me), H or ethyl (Et); L=1-5, D are H, methyl (Me) or ethyl (Et).
Microporous barrier as reinforce carries out the surface active modification through the material with ion exchanging function, concrete method of modifying can for: will strengthen microporous barrier and react under the effect of means such as heat, light, electron radiation, plasma, X ray, radical initiator with the monomer with ion exchanging function, then the microporous barrier after the modification be produced ion-exchange group under the effect of acid or alkali.
Employed microporous barrier preferably carries out surperficial silicic acid, sulfonation, sulphation, phosphorylation, hydrophilic modification.Concrete method of modifying can be with reference to prior art.The invention provides following microporous barrier surface modifying method: as to the fluorocarbon polymer film, silicic acid, sulfonation, sulphation, phosphorylation etc. are carried out in the surface.Existing surface modifying method for polytetrafluoroethylene (PTFE) all is suitable for the modification to the fluorocarbon polymer film, comprises reduction modification, laser emission modification, plasma modification and the silicic acid activation method of sodium naphthalene solution.Its mesosilicic acid activation method is first-selected method because it can be on fluorocarbon polymer film surface directly deposits the silica of water conservation.By fluorocarbon polymer film surface after the modification hydrophilic group has been arranged, but preferably on this basis more further modification as with the fiber of modification at ethyl orthosilicate, ZrOCl
2-H
3PO
4Or further modification in the titanate esters etc.For example the concrete grammar of silica modified voided polytetrafluoroethylene film is placed on SiCl with voided polytetrafluoroethylene film exactly
4Be warmed up to 110 ℃ in the atmosphere after 1 hour and kept 1 hour, be cooled to 60 ℃ again after, water spray is handled and is obtained silica modified voided polytetrafluoroethylene film.
Ion exchange fluoro resin in the fluorine-containing cross-linked doped ion-exchange membrane of microporous film enhanced multilayer of the present invention can be at microporous barrier surface-crosslinked, also can be crosslinked in the space of microporous barrier.Because perforated membrane carried out the surface active modification, have acidity or functional group and make and to form strong crosslinked action by the physical bond of high-valency metal compound between perforated membrane and the film-forming resin.
According to PEM provided by the invention, wherein, this PEM preferably includes the 2-20 layer, and more preferably the 2-5 layer is the monofilm of matrix with the perfluorinated ion exchange resin.The thickness of this PEM can be 5-300 μ m, is preferably 10-50 μ m.Wherein, each layer can be formed also can be mixed by multiple perfluorinated ion exchange resin and form by a kind of perfluorinated ion exchange resin, and each layer can all form cross-linked structure and also can not form cross-linked structure by part layer.
According to PEM provided by the invention, wherein, described perfluorinated ion exchange resin be by perfluoroolefine, one or more contain the perfluor alkene monomer of functional group and perfluor alkene monomer copolymerization that one or more contain crosslink sites forms, or the mixture of above-mentioned copolymer, its EW value can be 600-1300, is preferably 700-1200.
Wherein, described perfluoroolefine is selected from: one or more in tetrafluoroethene, CTFE, trifluoro-ethylene, hexafluoropropene and the vinylidene, preferably, described perfluoroolefine is tetrafluoroethene and/or CTFE.
The described perfluor alkene monomer that contains functional group be selected from formula (VII), (VIII) and (IX) shown in structure in one or more:
R
f3CF＝CF(CF
2)
dY
2
(VIII)
Wherein, a, b, c are 0 or 1 independently of one another, but are not zero simultaneously; D is the integer of 0-5; N is 0 or 1; R
F1, R
F2And R
F3Be selected from perfluoroalkyl and dichlorodifluoromethan base respectively; X is selected from F, Cl, Br and I; Y
1, Y
2And Y
3Be selected from SO independently of one another
2M, COOR
3And PO (OR
4) (OR
5), wherein: M is selected from F, Cl, OR, NR
1R
2R is selected from methyl, ethyl, propyl group, H, Na, Li, K and ammonium root; R
1And R
2Be selected from H, methyl, ethyl and propyl group respectively; R
3Be selected from H, Na, Li, K, ammonium root, methyl, ethyl and propyl group; R
4And R
5Be selected from H, Na, Li, K and ammonium root respectively.
The described perfluor alkene monomer that contains crosslink sites is selected from as shown in the formula in the structure shown in (X), (XI) one or more:
F
2C＝CFR
f4Y
4
(X)
Wherein, Y
4And Y
5Can be selected from Cl, Br, I and CN respectively; A ', b ' and c ' are respectively 0 or 1, but a '+b '+c ' ≠ 0; X
1Be selected from F, Cl, Br and I; N ' is 0 or 1; R
F4, R
F5And R
F6Be selected from perfluoroalkyl independently of one another.
Of the present invention a kind of preferred embodiment in, the preparation method of PEM of the present invention can comprise the steps:
(1) use the solution contain perfluorinated ion exchange resin, auxiliary proton conductive substance, high-valency metal compound or fused mass by cast, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology make a plurality of monofilms, also can while and modified micro-pore film composite membrane-forming;
(2) preparation of multilayer film can be by compound the making of monofilm of preparation in (1), the basis of also can be at monofilm or having made multilayer film use the solution described in (1) or fused mass by cast, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology make, equally can by multilayer film and monofilm or multilayer film and multilayer film is compound make, at compound tense, guarantee that having one deck at least in the composite membrane is modified micro-pore film;
(3) when needs added crosslinking agent and/or initator, crosslinking agent and/or initator can add when carrying out step (1) and/or (2), also crosslinking agent and/or initator can be scattered in the solvent to enter in the film by film mode of swelling in solvent;
(4) film after step (2), (3) are handled is handled under the effect of preceding method, form formula (I), (II), (III), (IV) and/or (V) shown in cross-linked structure;
(5) handle the cross-linked perfluorinated ion-exchange membrane that obtains the microporous barrier enhancing through alkali lye, acid solution successively, wherein said acid is preferably hydrochloric acid, sulfuric acid or nitric acid; Described alkali is preferably LiOH, NaOH or KOH; Described alkali lye and acid solution are the aqueous solution.
The application of PEM in Proton Exchange Membrane Fuel Cells that the present invention also provides PEM of the present invention or prepared according to preparation method provided by the invention.
Means act on the very big mechanical strength that improves ionic membrane simultaneously to use microporous barrier at the compound multi-layer perfluorinated cross-linked doped ion-exchange membrane of the present invention-microporous barrier, chemical bonding is crosslinked and high-valency metal compound and the physical bond of acidic exchange group formation be crosslinked etc.Crosslinked between having adopted particularly that physical bond between high-valency metal compound and acidic exchange group is crosslinked and having the high degree of cross linking and can realize layer by layer, add as the amide group in the acid amides chemistry bonding cross-linking, triazine group in the triazine ring bonding cross-linking and can also form coordination with the high-valency metal compound, so just further improved the performance of film.Especially it is crosslinked to be stressed that microporous barrier that the surface is had an acidic exchange base group modification can form physical bond by physical bond and high-valency metal compound and film-forming resin.Microporous barrier strengthens the high problem of gas permeability that perfluoro sulfonic acid membrane strengthens perfluoro sulfonic acid membrane with regard to having solved traditionally like this.This possible reason is: 1, surface-functionalized microporous barrier and film-forming resin adhesion have improved; 2, can form bonding structure with metallic compound because the surface of microporous barrier has functional group, further reduce resin and interfibrous space.Increase although add the film high temperature proton-conducting of auxiliary proton conductive substance in the past, Mechanics of Machinery character suppression ratio is more obvious.In our invention since above cross-linking modified, simultaneously again because some auxiliary proton conductive substance surface is modified by active group, can form the physical crosslinking structure with the high-valency metal compound.Thereby guaranteed that they not only can have contribution to the proton conduction of film, and the Mechanics of Machinery character of film has also been had very big contribution.Therefore, PEM provided by the invention has excellent mechanical intensity, high temperature conductivity and air-tightness when having the macroion exchange capacity.
The specific embodiment
Below in conjunction with the specific embodiment the present invention is further described in detail, the embodiment that provides is only in order to illustrate the present invention, rather than in order to limit the scope of the invention.
Embodiment 1
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.With repetitive be
Getting thickness is 30 μ m, and porosity is 70% quilt
(h=0 wherein, i=2 A=OH) carry out the microporous teflon membran of surface modification, place above-mentioned solution to soak about 1 hour, and the film that will soak drying on heating plate is carried out roll extrusion with rubber roll to film therebetween then.Above-mentioned solution-cast in the polytetrafluoroethylene (PTFE) mold of horizontal positioned,, after 12 hours is peeled off film through 80 ℃ of vacuum drying, and obtaining each individual layer perfluorinated sulfonic acid crosslinked is (I) species complexity ionic membrane (1# film).Carry out hot pressing with above-mentioned two individual layer perfluorinated cross-linked doped ion-exchange membrane is stacked, make PEM of the present invention, note is made A1.
Embodiment 2
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
The perfluorinated ion exchange resin of EW=800 and granularity are the SiO of 0.03 μ m
2(with the weight ratio of resin be 5: 100), surperficial quilt
(A=ONa) the perfluoroethylene-propylene fiber of Xiu Shiing (diameter 0.05 μ m length 5um is 1: 40 with the weight ratio of resin) mixes to extrude and obtains the film that thickness is 30 μ m for h=0 wherein, i=4.
Get by
(h=0 wherein, i=4, A=ONa) thickness that carries out surface active be the porous hexafluoropropene film of 12 μ m and above-mentioned 30 μ m film by hot pressing under 260 ℃ of vacuum states together, in 150 ℃ of vacuum drying ovens, be soaked in NH then in 1 hour
4In the DMF solution of Cl 5 hours.Film after will soaking then placed triethylamine 2 hours at 200 ℃, obtained crosslinked film.The cross-linked structure that this film is handled with KOH solution, hydrochloric acid solution successively is the amberplex (2# film) that (II) plants.
With repetitive be
With 2# and 3# film stack, hot pressing, and be immersed in the manganese nitrate solution 1 hour, obtaining thickness is the PEM of the present invention of 50 μ m, note is made A2.
Embodiment 3
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
With repetitive be
The perfluorinated ion exchange resin of EW=940, Ce (III)-DMSO complex compound (with the weight ratio of resin be 0.1: 100) and H
3PW
12O
40(with the weight ratio of resin be 20: 100) be mixed with the DMSO solution that resin content is 30 weight %, the method by casting is at 170 ℃, makes the film that thickness is 10 μ m (5# film) in 60 minutes.
Put the film that makes into capable hot pressing according to the order stack of 4#-4#-5#, obtaining thickness is the PEM of the present invention of 30 μ m, and note is made A3.
Embodiment 4
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
The 6# film is placed resin and 0.1% peroxidating perfluor bay, two acyls, 5%1 of embodiment 1, soaked 0.5 hour in the DMF solution of 4-diiodo-octafluorobutane, it is dry to take out the back, repeats above-mentioned steps; Then film was handled 300 minutes down at 120 ℃, obtained the 7# film.7# film and the hot pressing of 4# film are obtained the PEM of the present invention that thickness is 35 μ m, and note is made A4.
Embodiment 5
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
The perfluorinated ion exchange resin of EW=1300 and acetylacetone,2,4-pentanedione-Ce (III) complex compound (with the weight ratio of resin be 0.01: 100), the sulfuric acid modified particle diameter in surface is the ZrO of 0.8 μ m
2(with the weight ratio of resin be 2: 100), AMBN (0.1: 100), 1,4-diiodo-octafluorobutane (with the weight ratio of resin be 1: 100) be dissolved in and be mixed with the solution that resin content is 10 weight % among the DMF.
With surperficial quilt
(h=0 wherein, i=4 after A=ONa) polyvinylidene fluoride porous film of grafting (porosity 80%, thickness are 20 μ m) soaks 30min in above-mentioned solution, handle 60min down at 170 ℃ and make the film that thickness is 20 μ m (8# film).
Use resin, particle diameter among the embodiment 4 be 5 μ m H-modenite powder (with the weight ratio of resin be 1: 1) be mixed in the N-methyl pyrrolidone, being mixed with the solution that resin content is 3 weight %, is the film (multilayer film 1#) of 30 μ m with this solution at two surperficial spin coatings formation thickness of 8# film.Multilayer film 1# was handled 2.4 hours down at 69 ℃, and the cross-linked structure that obtains three layers of metal ion bondings is the perfluoro sulfonic acid membrane of formula (I).
Above-mentioned film is placed perfluorinated ion exchange resin by present embodiment again, particle diameter be 10 μ m the H-montmorillonite (with the weight ratio of resin be 0.5: 100), AMBN (with the weight ratio of resin be 0.5: 100), 1,4-diiodo-octafluorobutane (with the weight ratio of resin be 3: 100) and DMF-Ce (III) complex compound (with the weight ratio of resin be 1: 100) to be dissolved in the resin content that makes among the DMF be in the solution of 25 weight %, soak after 0.5 hour film is taken out drying, repeat above-mentioned steps, then film was handled 300 minutes down at 120 ℃, obtained five layers of microporous barrier perfluorinated sulfonic acid of metal ion bonding cross-linking ion membrane (multilayer film 2#).
Multilayer film 1# and 2# are carried out hot pressing, and ten layers of microporous barrier that make the metal ion bonding strengthen perfluorinated sulfonic acid cross-linking ion doping, and namely PEM of the present invention is remembered and made A5.
Embodiment 6
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
The spraying coating process method is passed through on two surfaces at the 9# film again, and making thickness is the crosslinked perfluoro sulfonic acid membrane of 60 μ m, at two surface difference hot pressing 9# film, makes PEM of the present invention again, and note is made A6.
Embodiment 7
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
With surperficial quilt
(A=OH) polytetrafluoroethylene (PTFE) of modification-ethene microporous barrier (porosity 79%, 5 microns in aperture, thickness 30 μ m) is immersed in the above-mentioned solution for h=1 wherein, i=2, handles 3 minutes down at 160 ℃.Obtain 30 crosslinked μ m doped micropore films and strengthen perfluoro sulfonic acid membrane.(10# film).
With the 10# film place by the resin of present embodiment, zeolite (with the weight ratio of resin be 0.4: 100) and benzoyl peroxide (with the weight ratio of resin being: 0.1: 100), 1,14-diiodo-20 fluorine ten alkane (with the weight ratio of resin be 5: 100) dimethyl sulphoxide solution (resin content is 20 weight %) in soaked 0.5 hour, film is taken out dry, repeat above-mentioned steps, then film was handled 300 minutes down at 120 ℃, obtained three layers of perfluorinated sulfonic acid cross-linked doped ion-exchange membrane (multilayer film 3#).
Carry out hot pressing with three multilayer film 3# are stacked, make nine layers of fiber reinforcement perfluorinated sulfonic acid cross-linked doped ion-exchange membrane of enhancing, i.e. PEM of the present invention, note is made A7.
Embodiment 8
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
Be 10 μ m with thickness, porosity is 89% surface quilt
(l=1, D=H) porous of modification tetrafluoroethene-perfluoroalkyl ethylene oxy copolymer film (porosity 79%, 5 microns in aperture) places above-mentioned solution to soak about 1 hour, obtains the film that thickness is 10 μ m.Film is handled 100min down at 230 ℃, obtain crosslinked individual layer micropore and strengthen adulterated full fluorin sulfonate film (11# film).
Use the solution that forms the 11# film to pass through spraying method on two surfaces of 11# film, make three layers of crosslinked adulterated full fluorin sulfonate film of 60 μ m.Two surface difference hot pressing 11# films at this trilamellar membrane make crosslinked five layers of microporous barrier and strengthen the adulterated full fluorin sulfonate film, and namely PEM of the present invention is remembered and made A8.
Embodiment 9
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
Getting thickness is 30 μ m, and porosity is 50% surface quilt
(A=OH) the expanded PTFE microporous barrier of Xiu Shiing and repetitive are for h=0, i=2
The resin of EW=900 and particle diameter are the SiO of 0.03 μ m
2(with the weight ratio of resin be 5: 100) the hot pressing film forming.This film is soaked in NH
3DMF solution (concentration is 10%) in 5 hours.Under 200 ℃, obtain the film that (II) plants cross-linked structure.With this film alkali lye, after handling, acid solution is immersed in the cross linking membrane (12# film) that obtains the metal ion bonding in the DMF solution (concentration is 0.8%) of acetylacetone,2,4-pentanedione-Ir (III).
With repeat unit structure be
Resin, the tetraphenyltin of EW=1200 mix with double screw extruder.Be 50 μ m with thickness then, porosity is 80% surface quilt
(A=OH) microporous teflon membran of modification (porosity 85%, 1 micron in aperture) hot pressing is compound, film is heated to 230 ℃ then for h=1, i=4, keeps obtaining in 10 hours the film that (V) plants cross-linked structure.Again this film was placed 35% hydrazine hydrate 10 hours, taking out the back heating was had (V) to plant the film of cross-linked structure and (III) kind cross-linked structure in 5 hours simultaneously, this film alkali lye, acid solution is immersed in 2h in the nitric acid ruthenium with film after handling, and obtains the doping cross-linking film (13# film) of ruthenium ion bonding.
Press according to the order stack heat release of the film A5 of the film A8-embodiment 5 of monofilm 12#-monofilm 13#-embodiment 8 that to obtain thickness be that the crosslinked microporous barrier of 300 μ m strengthens 16 tunics, i.e. PEM of the present invention, note is made A9.
Embodiment 10
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
The perfluorinated ion exchange resin of EW=700 and repetitive are
Getting thickness is 50 μ m, and porosity is 75% quilt
(l=3, D=H) carry out the expanded microporous polytetra fluoroethylene-EPTEE-hexafluoropropene film (porosity 80% of surface phosphoric acid modification, 0.5 micron in aperture) place above-mentioned solution to soak about 3 hours, 140 ℃ of heating obtain the perfluoro sulfonic acid membrane that (I) plants cross-linked structure that contains that thickness is 50 μ m, this film are put in the film (14# film) that is contained (I) kind and (IV) kind cross-linked structure in the chlorosulfonic acid simultaneously again.
With the film A2 hot pressing that 14# film and embodiment 2 make, the perfluorinated sulfonic acid microporous barrier that makes the metal ion bonding strengthens cross-linking ion membrane, i.e. PEM of the present invention, and note is made A10.
Embodiment 11
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
, the perfluorinated ion exchange resin of EW=1200, Mn (OH)
3(with the weight ratio of resin be 2: 100) with triphenyl tin hydroxide (with the weight ratio of resin be 0.5: 100) and particle diameter be the ZrO of 8 μ m
2(with the weight ratio of resin be 2: 100), be scattered among the DMF, forming resin content is the solution of 25 weight %.
Getting thickness is 20 μ m, and porosity is 65% quilt
(h=0, i=2, A=OH) the porous Teflon microporous barrier (porosity 92%, 0.5 micron in aperture) that carries out surperficial sulphation modification places above-mentioned solution to soak half an hour approximately, handles 60min down at 170 ℃ and makes the film (15# film) that (V) plants cross-linked structure that has that thickness is 20 μ m.
Use the H-modenite powder that resin among the embodiment 4 and particle diameter be 5 μ m (with the weight ratio of resin be 1: 1) be mixed in the N-methyl pyrrolidone, forming resin content is the solution of 15 weight %.
Use perfluorinated sulfonic resin and 5 μ mH-modenite powder (mass ratio of H-modenite and resin is 1: 1) among the embodiment 4 to be mixed in the N-methyl pyrrolidone and become the film of 30 μ m in the spin coating of the both sides of above-mentioned film, prepare three layers of micropore and strengthen perfluorinated ion-exchange membranes.Film is handled 2.4h down at 190 ℃.Three layers of crosslinked microporous barrier that obtain the manganese ion bonding strengthen perfluoro sulfonic acid membrane (multilayer film 14#).Two surperficial spin coatings formation thickness at the 15# film are the film of 30 μ m, obtain three layers of micropore and strengthen perfluorinated ion-exchange membranes.This film was handled 2.4 hours down at 190 ℃, and three layers of crosslinked microporous barrier that obtain the manganese ion bonding strengthen perfluoro sulfonic acid membrane, and namely PEM of the present invention is remembered and made A11.
Embodiment 12
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
Two surfaces at the 16# film stack the film A3 that one deck embodiment 3 makes respectively, and 120 ℃ of following hot-pressing processing 2 minutes, and hydrolysis acidification obtains four layers of cross-linked perfluorinated sulfonic acid microporous barrier and strengthens amberplexes then, i.e. PEM of the present invention, and note is made A12.
Embodiment 13
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
Perfluorinated ion exchange resin and the ZrO of 0.01 micron of particle diameter
2After mixing, (be 9: 100 with the weight ratio of resin), cyclodextrin-W (III) complex compound (be 0.034: 100 with the weight ratio of resin) be scattered in that to form solid content in the N-methyl pyrrolidone be the dispersion liquid of 30 weight %.
Getting thickness is 10 μ m, the quilt of porosity 65%
(l=3, D=H) the expanded ptfe film that carries out the surface phosphoric acid modification places above-mentioned dispersion liquid to soak half an hour approximately, at 190 ℃ of following film forming (17# film).
With above-mentioned perfluorinated ion exchange resin with repetitive be
It is 50 microns five tunics that two-layer 17# film and three layers of 18# film are stacked alternately the compound thickness that obtains of hot pressing, i.e. PEM of the present invention, and note is made A13.
Embodiment 14
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
Two surfaces at the 19# film stack the film A3 that embodiment 3 makes respectively, and 120 ℃ of hot pressing, hydrolysis acidification obtains seven layers of cross-linked perfluorinated sulfonic acid microporous barriers enhancing film then, and namely PEM of the present invention is remembered and made A14.
Embodiment 15
Present embodiment is used for explanation PEM provided by the invention and preparation method thereof.
With repetitive be
Getting thickness is 28 μ m, porosity is two surfaces that 75% the microporous teflon membran that is carried out surface modification by sulfur trioxide is stacked and placed on the 20# film, and 120 ℃ of hot pressing, hydrolysis acidification obtains four layers of cross-linked perfluorinated sulfonic acid microporous barrier and strengthens films then, be PEM of the present invention, note is made A15.
Embodiment 16
Get thickness and be 10 microns by the microporous teflon membran of sulfur trioxide modification (porosity 80%, 1 micron in aperture), at solution be earlier 0.5 rub/liter nitric acid tungsten solution in soaked 50 minutes, then with tensioning apparatus with fixing around it.With the nmp solution of the perfluorinated sulfonic resin of 30 weight % (wherein perfluorinated sulfonic resin is the mixed resin solution with following structural formula, and two kinds of structural resin weight ratios are 4: 1:
A=12, b=5, a '=b '=1, x/ (x+y)=0.5, y/ (x+y)=0.5) be sprayed on by
(l=1, D=Me) and
(A=OH) two surfaces of the above-mentioned microporous teflon membran (porosity 80%, 1 micron in aperture) of common modification obtain thickness and are 12 microns composite membrane for h=0, i=2, i.e. PEM of the present invention, and note is made A16.
Embodiment 17
With repetitive be
The resin of EW=800 and repetitive are
Resin mixed by weight 2: 1, adding particle diameter is the SiO of 0.03 μ m
2(with the ratio of total resin weight be 5: 100), the hot pressing film forming.Be 18 μ m with thickness then, porosity is 80%, quilt
(h=1, i=4 A=OH) are soaked in NH after carrying out the expanded PTFE microporous barrier (porosity 80%, 1 micron in aperture) of surface modification hot pressing being compound
3DMF solution (concentration is 10 weight %) in 5 hours.Under 200 ℃, obtain the film that (I) plants cross-linked structure.With this film alkali lye, after handling, acid solution is immersed in the cross linking membrane that obtains the metal ion bonding in the DMF solution (concentration is 0.1 weight %) of acetylacetone,2,4-pentanedione-Ir (III), i.e. PEM of the present invention, note is made A17.
Comparative Examples 1
This Comparative Examples is used for existing PEM of explanation and preparation method thereof and compares.
With repetitive be
The perfluorinated ion exchange resin of EW=1100 and H
3PW
12O
40Make the DMF solution of 3 weight % in 100: 1 ratio, casting film, it is the ionic membrane (21# film) that (I) plants that this film is obtained 20 μ m cross-linked structures through the 50KGy crosslinking with radiation.
With repetitive be
The perfluorinated ion exchange resin of EW=940 and H
3PW
12O
40Press polymer and H
3PW
12O
40100: 20 ratio of mass ratio is made the DMSO solution of 30 weight %, by the casting method at 170 ℃, 60min makes the film that thickness is 10 μ m (22# film).
With the 2# film, the 21# film, the 22# film is stacked to carry out hot pressing, the film A2 hot pressing that makes with embodiment 2 then, obtaining thickness is three layers of cross-linked doped ion-exchange membrane of microporous barrier of 60 μ m, note is made C1.
Comparative Examples 2
This Comparative Examples is used for existing PEM of explanation and preparation method thereof.
The eptfe film that 30 μ m are thick (porosity 70%) places the nafion of 10 weight %
Soaked about 1 hour in the solution, the film that will soak carries out the microporous barrier enhancing amberplex that dry 170 ℃ of processing 60min obtain 30 micron thickness at heating plate then, and note is made C2.
The performance characterization of film
The PEM C1 that the PEM A1-A17 that mensuration embodiment 1-17 makes and Comparative Examples 1 and 2 make and 95 ℃ of electrical conductivity, hot strength, hydrogen permeate electric current and the size changing rate of C2 the results are shown in Table 1.Wherein, the test condition of two conductivity values is respectively: T=95 ℃, and under the saturated humidity, and T=25 ℃, the drier drying is two days later; The method of testing of hot strength is National Standard Method (GB/T20042.3-2009); The method of testing of hydrogen permeate electric current is electrochemical method (Issue 5, B101-B104,2007 for Electrochemical and Solid-State Letters, vol.10).
Table 1
| PEM | Electrical conductivity (S/cm) | Hot strength (MPa) | Hydrogen permeate electric current (mA/cm 2) | Size changing rate (%) |
| A1 | 0.0495/0.0221 | 45 | 0.02 | 2 |
| A2 | 0.0546/0.0232 | 46 | 0.05 | 1 |
| A3 | 0.0574/0.0251 | 48 | 0.01 | 0.8 |
| A4 | 0.0478/0.0201 | 47 | 0.01 | 3 |
| A5 | 0.0565/0.0213 | 41 | 0.02 | 2.4 |
| A6 | 0.0575/0.0223 | 47 | 0.01 | 1.5 |
| A7 | 0.0576/0.0245 | 44 | 0.01 | 1.3 |
| A8 | 0.0553/0.0237 | 42 | 0.02 | 2.3 |
| A9 | 0.0583/0.0252 | 47 | 0.03 | 3.1 |
| A10 | 0.0548/0.0231 | 46 | 0.04 | 2 |
| A11 | 0.0526/0.0239 | 47 | 0.02 | 1.8 |
| A12 | 0.0535/0.0212 | 39 | 0.01 | 2.7 |
| A13 | 0.0515/0.0212 | 39 | 0.01 | 2.1 |
| A14 | 0.0541/0.0254 | 45 | 0.01 | 2 |
| A15 | 0.0534/0.0213 | 52 | 0.01 | 1.1 |
| A16 | 0.0571/0.0210 | 43 | 0.01 | 1.7 |
| A17 | 0.0531/0.0200 | 52 | 0.02 | 0.9 |
| C1 | 0.0486/0.0241 | 35 | 1.7 | 8 |
| C2 | 0.0016/0.0009 | 21 | ＞5 | 15 |
As can be seen from Table 1,95 of PEM of the present invention ℃ of performances such as electrical conductivity, hot strength, hydrogen permeate electric current and size changing rate all are better than common microporous film enhanced multilayer perfluorinated cross-linked doped ion-exchange membrane.
Claims (18)
1. PEM, comprise that the 2-40 layer is the monofilm of matrix with the perfluorinated ion exchange resin, it is characterized in that, at least one deck monofilm has cross-linked structure, at least one deck monofilm contains the auxiliary proton conductive substance of finishing, at least one deck monofilm contains the high-valency metal compound, having one deck at least is modified micro-pore film, described modified micro-pore film is selected from the monomer modified fluorocarbon polymer film with ion exchanging function, and described monomer with ion exchanging function is one or both in sulfur dioxide and the sulfur trioxide;
The auxiliary proton conductive substance of described finishing is had the group of ion exchanging function and/or the auxiliary proton conductive substance that acidic-group is modified; Described auxiliary proton conductive substance is selected from: one or more in oxide, orthophosphates, condensed phosphate, polyacid, multi-acid salt and hydrate thereof, silicate, sulfate, selenite and the arsenide;
Described high-valency metal compound is the highest price attitude of W, Ir, Y, Mn, Ru, V, Zn and La element and nitrate, sulfate, carbonate, phosphate, acetate and the combination double salt of middle valence state; The highest price attitude of W, Ir, Y, Mn, Ru, V, Zn and La element and cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether and the nitrogen heterocyclic ring of middle valence state, ethylenediamine tetra-acetic acid, dimethyl formamide and dimethyl sulfoxide (DMSO) complex compound; And in the oxide with perovskite structure of the highest price attitude of W, Ir, Y, Mn, Ru, V, Zn and La element and middle valence state one or more.
2. PEM according to claim 1 wherein, is benchmark with the perfluor amberlite of 100 weight portions, and the content of the auxiliary proton conductive substance of described finishing is the 0.05-50 weight portion; The content of described high-valency metal compound is the 0.0001-5 weight portion.
3. PEM according to claim 2 wherein, is benchmark with the perfluor amberlite of 100 weight portions, and the content of the auxiliary proton conductive substance of described finishing is the 1-15 weight portion.
4. PEM according to claim 2 wherein, is benchmark with the perfluor amberlite of 100 weight portions, and the content of described high-valency metal compound is the 0.001-1 weight portion.
5. PEM according to claim 1, wherein, described cross-linked structure be formula (I), (II), (III), (IV) and (V) shown in the structure one or more:
Wherein, G
1And G
2Be respectively CF
2Or O, R
fBe C
2-C
10Perfluor carbochain or chloride perfluor carbochain;
Wherein, R is methylene or perfluor methylene, and n is the integer of 0-10;
6. PEM according to claim 1, wherein, described auxiliary proton conductive substance is one or more in oxide, orthophosphates, condensed phosphate, polyacid and the multi-acid salt.
7. PEM according to claim 6, wherein, described auxiliary proton conductive substance is one or more in oxide, orthophosphates and the condensed phosphate.
8. PEM according to claim 1, wherein, described modified micropore membrane aperture is 0.1-10 μ m; Thickness is 5-100 μ m; Porosity is 30-99%.
9. PEM according to claim 8, wherein, described modified micropore membrane aperture is 0.1-1 μ m.
10. PEM according to claim 8, wherein, described modified micropore film thickness is 5-30 μ m.
11. PEM according to claim 8, wherein, described modified micropore membrane porosity is 70-97%.
12. PEM according to claim 1, wherein, this PEM comprises that the 2-20 layer is the monofilm of matrix with the perfluorinated ion exchange resin; The thickness of this PEM is 5-300 μ m.
13. PEM according to claim 12, wherein, this PEM comprises that the 2-5 layer is the monofilm of matrix with the perfluorinated ion exchange resin.
14. PEM according to claim 12, wherein, the thickness of this PEM is 10-150 μ m.
15. PEM according to claim 12, wherein, the thickness of this PEM is 10-50 μ m.
16. PEM according to claim 1, wherein, described perfluorinated ion exchange resin be by the perfluoroolefine monomer, one or more contain the perfluor alkene monomer of functional group and perfluor alkene monomer copolymerization that one or more contain crosslink sites forms, or the mixture of above-mentioned copolymer, the EW value is 600-1300.
17. PEM according to claim 16, wherein, described EW value is 700-1200.
18. any application of described PEM in Proton Exchange Membrane Fuel Cells among the claim 1-17.
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