WO2011156934A1

WO2011156934A1 - Proton exchange membrane, its preparing method and use

Info

Publication number: WO2011156934A1
Application number: PCT/CN2010/000892
Authority: WO
Inventors: 张永明; 唐军柯; 刘萍; 张恒; 王军
Original assignee: 山东东岳神舟新材料有限公司
Priority date: 2010-06-18
Filing date: 2010-06-18
Publication date: 2011-12-22

Abstract

A proton exchange membrane, its preparing method and use in a proton exchange membrane fuel cell are provided. The proton exchange membrane includes 2-40 monolayer membranes using perfluoro ion exchange resin as their base, wherein at least a monolayer membrane has a crosslinking net structure, at least a monolayer membrane has auxiliary proton conducting substances with modified surface, at least a monolayer membrane has modified fibers and at least a monolayer membrane has high valent metal compounds. The proton exchange membrane of the invention has improved proton conductivity and also greatestly improved mechanical strength of the membrane by using reinforced fibers, chemical bonding crosslinking and physical bonding crosslinking formed by high valent metallic compounds and acidic exchange groups.

Description

Proton exchange membrane and preparation method and application thereof

The invention relates to a proton exchange membrane and a preparation method and application thereof. Background technique

The proton exchange membrane fuel cell (PEMFC) is a power generation device that directly converts chemical energy into electrical energy by electrochemical means. It is considered to be the clean, efficient power generation technology of choice in the 21st century. Proton exchange membrane (PEM) is a key material for proton exchange membrane fuel cells.

The perfluorosulfonic acid proton exchange membranes currently used have good proton conductivity at lower temperatures (not higher than 8 (TC) and higher humidity, but there are also many disadvantages such as poor dimensional stability and mechanical strength. High, poor chemical stability, etc.

The water absorption of the film at different humidity levels and the dimensional expansion due to water absorption are different. When the film is changed under different working conditions, the size of the film will also change, and the repetition will eventually lead to mechanical breakage of the proton exchange membrane. In addition, the positive electrode reaction of a fuel cell often generates a large amount of highly oxidizing substances such as hydroxyl radicals and hydrogen peroxide, which attack the non-fluorine groups in the film-forming resin molecules, resulting in chemical degradation or damage of the film. Foaming. In addition, high operating temperatures can greatly improve the carbon monoxide resistance of fuel cell catalysts, but when the operating temperature of the perfluorosulfonic acid exchange membrane is higher than 90 °C, the proton conductivity of the membrane drops sharply due to the rapid dehydration of the membrane. Thereby the efficiency of the fuel cell is greatly reduced. In addition, the existing perfluorosulfonic acid membranes have a certain hydrogen or methanol permeability, especially in a direct methanol fuel cell, and the methanol permeability is very large, which is a fatal problem. Therefore, how to improve the strength and dimensional stability of the perfluorosulfonic acid proton exchange membrane and the proton conductivity at high temperatures and reduce the permeability of the working medium are major issues facing the fuel cell industry.

Some methods have been proposed to solve these problems. For example, JP-B-5-75835 uses a perfluorosulfonic acid resin to impregnate a porous medium made of polytetrafluoroethylene (PTFE) to enhance the strength of the film. However, this porous medium of PTFE has not completely solved the above problems because the PTFE material is relatively soft and the reinforcing effect is insufficient. The Gore-Select series of composite membrane liquids developed by WL Gore uses a porous Teflon-filled Nafion ion conductive liquid (US 5,547,551, US 5,653,041 and US 5,599,614), which has high proton conductivity and large Dimensional stability, but Teflon creeps at high temperatures, resulting in reduced performance. JP-B-7-68377 also proposes a method of filling a porous medium made of polyolefin with a proton exchange resin, but having insufficient chemical durability and thus long-term stability There are problems in qualitative aspects; and because of the addition of porous media that do not have proton conductivity, the proton conduction pathway is reduced and the proton exchange capacity of the membrane is reduced. Further, JP-A-6-231779 proposes another reinforcing method using fluororesin fibers. The mechanical strength of the fluorocarbon polymer reinforcement in the form of fibrils. However, this method requires the addition of a relatively large amount of reinforcing material. In this case, the processing of the film tends to be difficult, and the increase in film resistance is likely to occur. EP 0875524 B1 discloses a glass fiber membrane reinforced Nafion membrane prepared by a glass fiber nonwoven technique, in which an oxide such as silica is also mentioned. What is insufficient is that the nonwoven glass fiber cloth in this method is a substrate that must be used, which will greatly limit the range of use of the reinforcing film. US 6733914 discloses a melt-extruded perfluorosulfonyl fluoride type membrane immersed in aqueous ammonia to form a proton exchange membrane of a sulfonimide crosslinked structure, and the thus treated perfluorosulfonic acid membrane has good mechanical strength and dimensional stability. . However, the membrane obtained by this method is a non-uniform membrane because the ammonia gas enters the membrane by the permeation method, and the ammonia gas reacts with the sulfonyl fluoride during the permeation process, and the reacted sulfonyl fluoride will prevent the ammonia gas from further moving toward the membrane. The internal diffusion forms a high crosslink density on the surface of the film, and almost no cross-linking occurs inside the film. The high crosslink density of the surface causes the conductivity of the film to drop dramatically. CN 200710013624.7 and the perfluorosulfonic acid membrane containing a triazine ring crosslinked structure disclosed in US Pat. No. 7,259,208 also have good mechanical strength and dimensional stability. However, the use of a chemically bonded crosslinked film often does not result in a high degree of crosslinking, and the performance of the film is limited, so that the performance of the film still does not meet the requirements for use.

In order to improve the high-temperature proton conduction behavior of the perfluorosulfonic acid membrane, a plurality of substances having an auxiliary proton conduction function are added to the perfluorosulfonic acid exchange membrane. The selected auxiliary proton conductive material particles must have the following characteristics: (1) The particles have better water retention capacity, that is, have higher water loss temperature; (2) have better compatibility with proton exchange resins; (3) Particles have certain ability to conduct protons; (4) easy to obtain nano-sized particles; (5) good structural stability of particles, no obvious structural changes during absorption and dehydration; (6) favorable for maintaining or improving proton exchange membrane Mechanical strength or physical dimensional stability. The inorganic water-retaining particles usually used are Si0 ₂ , Ti0 ₂ , Zr(HP0 ₄ ) ₂ or Zr0 ₂ particles, heteropoly acid or solid acid particles, zeolite group mineral particles, smectite and other layered clay minerals and intercalation layers thereof. Clay minerals, etc. For example, CN 1862857 discloses that the addition of an auxiliary proton conductive material such as SiO ₂ to a perfluorosulfonic acid resin can improve the high temperature conductivity of the proton exchange membrane. A composite film of Nafion resin and zirconium phosphate is described in J. Electrochem. Soc. (VI 54, 2007, P B288-B295), which still has a high electrical conductivity at a relative humidity of less than 13%.

The shortcoming is that simply adding the above substances often deteriorates the mechanical properties of the film, and cannot meet the needs of actual operation and installation. CN 200810138186.1 discloses a multilayer perfluorosulfonic acid membrane which is chemically bonded and crosslinked and fiber reinforced and doped with an auxiliary proton conducting material. The film uses chemical bonding Cross-linking and fiber modification have been carried out, and the performance of the film has been greatly improved on the basis of the past, but the film still has problems such as poor bonding of the film-forming resin to the fiber. Summary of the invention

Proton exchange membranes for fuel cells need to meet the following requirements: Stable, high electrical conductivity, and high mechanical strength. In general, when the ion exchange capacity is increased, the equivalent value of the perfluoropolymer decreases (when the amount of EW decreases, the ion exchange capacity IEC = 1000/EW) and the strength of the membrane also decreases. The gas permeability of the membrane also increases, which can have a very serious effect on the fuel cell. Therefore, the preparation of a membrane having high ion exchange capacity while having good mechanical strength and airtightness, as well as good stability, is the key to fuel cells, especially for fuels used in vehicles such as automobiles.

Therefore, the object of the present invention is to overcome the shortcomings of the prior art proton exchange membranes which have low mechanical strength, poor high temperature conductivity and poor air tightness, and provide a good mechanical strength, high temperature conductivity and gas while having high ion exchange capacity. A dense proton exchange membrane and a preparation method and application of the membrane.

The present invention provides a proton exchange membrane comprising 2-40 layers of a monolayer film based on a perfluoro ion exchange resin, wherein at least one single layer membrane has a crosslinked network structure, and at least one single layer membrane contains a surface The modified auxiliary proton conducting material, at least one single layer film containing modified fibers, and at least one single layer film containing high valent metal compounds.

The proton exchange membrane according to the present invention, wherein the surface-modified auxiliary proton conductive material may be contained in an amount of 0.05 to 50 parts by weight, preferably 1 to 15 parts by weight based on 100 parts by weight of the perfluoro ion exchange resin. The modified fiber may be contained in an amount of 0.5 to 50 parts by weight, preferably 1 to 20 parts by weight; and the high-valent metal compound may be contained in an amount of 0.0001 to 5 parts by weight, preferably 0.001 to 1 part by weight.

Wherein, the intersection network structure may be one or more of the structures shown by the formulas (1), (11), (111), (IV) and (V):

(I) Wherein G^PG ₂ is CF ₂ or O, respectively, and R _f is a C chain;

(II) (ΠΙ)

R is methylene or perfluoromethylene, n is 0-10

Where the surface modification

Included are oxides, orthophosphates, polyphosphates, polyacid salts, silicates, sulfates, selenites and arsenides modified with inorganic dopants, preferably oxides, orthophosphates, polycondensed phosphoric acids a salt, a polyacid and a polyacid salt, more preferably an oxide, an orthophosphate or a polyphosphate; the inorganic dopants are Si0 ₂ , Zr0 ₂ , Ti0 ₂ , BP0 ₄ , Zr ₃ (P0 ₄ ) ₄ , One or more of Zr(HP0 ₄ ) ₂ , HZr ₂ (P0 ₄ ) ₃ , Ti(HP0 ₄ ) ₂ , and Zr ₂ H(P ₃ 0 ₁₍₎ ) ₂ .

A proton exchange membrane according to the present invention, wherein the modified fiber is selected from one or more of a fluorocarbon polymer fiber modified by a monomer having an ion exchange function, such as polytetrafluoroethylene fiber, poly Perfluoroethylene propylene fibers and polyperfluoropropyl vinyl ether fibers. The fiber may have a diameter of 0.005 to 5 μm, preferably 0.05 to 2 μm, and a length of 0.03 to 3 mm, preferably 0.05 to 1 mm. The monomer having an ion exchange function may be sulfur dioxide, sulfur trioxide, and a perfluorosulfonic acid monomer (A), a perfluorosulfonic acid monomer (B), and a perfluorosulfonic acid monomer (C) having the following structure: One of or

Wherein, h = 0-l, i = 1-5, VIII, Cl, Br, OH, oxymethyl (OCH ₃ ) or ONa; j = 0-l, k = 1-5, B is methyl ( Me), H or ethyl (Et); 1 = 1-5, D is H, methyl (Me) or ethyl (Et).

A proton exchange membrane according to the present invention, wherein the high-valent metal compound may be a nitrate, a sulfate, or a carbon of a highest valence state and a middle valence state of W, Ir, Y, Mn, Ru, V, Ζ, and La elements. Acidate, phosphate, acetate and combined double salt, W, Ir, Y, Mn, Ru, V, Ζ and La elements of the highest valence state and intermediate valence of cyclodextrin, crown ether, acetylacetone, Nitrogen crown ether and nitrogen-containing heterocycle, ethylenediaminetetraacetic acid, dimethylformamide and dimethyl sulfoxide complex, and the highest valence of W, Ir, Y, Mn, Ru, V, Ζ and La elements One or more of the oxides having a perovskite structure in the state and the intermediate valence state. Wherein, the oxides having a perovskite structure of the highest and intermediate valence states of the W, Ir, Y, Mn, Ru, V, Ζ, and La elements include, but are not limited to, the following compounds: Ce _x Ti _{(1- x)} 0 ₂ (x = 0.25-0.4), Ca ₀₆ La ₀₂₇ TiO ₃ , La ₍ i _-y) Ce _y Mn ₀ ₃ (y = 0.1-0.4), La ₀₇ Ce ₀₁₅ Ca _{0 15} MnO ₃ .

The proton exchange membrane according to the present invention, wherein the proton exchange membrane preferably comprises 2 to 20 layers, more preferably 2 to 5 layers of a monolayer film based on a perfluoro ion exchange resin. The proton exchange membrane may have a thickness of from 5 to 300 μm, preferably from 10 to 50 μm. Here, each layer may be formed of a perfluoro ion exchange resin or a mixture of a plurality of perfluoro ion exchange resins, and each layer may form a crosslinked structure or a partial layer may not form a crosslinked structure.

The perfluoro ion exchange resin is formed by copolymerization of a perfluoroolefin, one or more functional group-containing perfluoroolefin monomers, and one or more perfluoroolefin monomers having a crosslinking site, or It is a mixture of the above copolymers, which may have an EW value of from 600 to 1300, preferably from 700 to 1200.

Wherein, the perfluoroolefin is selected from one or more of tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, hexafluoropropylene and vinylidene fluoride. Preferably, the perfluoroolefin is tetrafluoroethylene. And/or trifluoro of the functional group-containing perfluoroolefin monomer is selected from one or more of the structures shown in formulas (VII), (VIII) and (IX):

(VII)

R. CF=CF(CF ₂ ) _d Y ₂

( VIII )

(IX)

Wherein a, b, c are each independently 0 or 1, but are not simultaneously zero; d is 0-5 white n is 0 or 1; R _fl , Re and are respectively selected from perfluorodecyl and fluorochloroindolyl X is selected from the group consisting of F, Cl, Br, and I; Y ₂ and Y ₃ are each independently selected from the group consisting of S0 ₂ M, COOR ₃ , and PO(OR ₄ )(OR ₅ ), wherein: M is selected from the group consisting of F, Cl, and 0R NRiR ₂ ; R is selected from the group consisting of methyl, ethyl, propyl, H, Na, Li, K and ammonium; R PR _{2 is} respectively selected from the group consisting of 11, methyl, ethyl and propyl; R _{3 is} selected from H, Na, Li, K, ammonium, methyl, ethyl and propyl; R ₄ and R ₅ are each selected from the group consisting of 11, Na, Li, K and ammonium.

The perfluoroolefin monomer having a crosslinking site is selected from one or more of the structures represented by the following formulas (Χ) and (XI):

F ₂ C^=CFRf ₄ Y4

(X)

Y ₅ (CF ₂ ) _a , (CFR _f5 ) _b , (CFR _f6 ) _c , O(CFCF ₂ O) _n , — C=CF ₂

(XI)

Wherein Y ₄ and Y ₅ may be selected from Cl, Br, I and CN, respectively; a, b, and c are 0 or 1, respectively, but a, +b, +c, ≠0; selected from F, Cl , Br and I; n, are 0 or 1; R _f4 , R _f5 and R _f6 are each independently selected from perfluorodecyl.

The invention also provides a preparation method of the above proton exchange membrane, the method comprising:

(1) forming a monolayer film using a solution or a melt containing a perfluoro ion exchange resin, wherein the solution or melt further optionally contains one of a surface-modified auxiliary proton conductive substance, a modified fiber, and a high-valent metal compound Species or more;

(2) forming a cross-linked network structure in the monolayer film obtained in the step (1);

(3) obtaining a single layer film using the single layer film obtained in the steps (1) and/or (2) and the step (2) And/or forming a single layer film on the single layer film obtained in the step (2) using the solution or the melt described in the step (1), so that the finally obtained composite film comprises 2-40 single layer films, at least Single layer film

OOSNM

An auxiliary proton conducting material containing surface modified HNI, at least one single layer film containing modified fibers, and at least one single layer film containing a high OOSNM valence metal compound.

According to the method provided by the present invention, the steps (1) and (2) may be carried out simultaneously, or the step (1) may be performed first and then the step (2).

Wherein, the method of forming the single layer film in the step (1) is one or more of casting, melt extrusion, hot pressing, spin coating, casting, screen printing, spraying, and dipping.

Preferably, the casting, casting, screen printing, spin coating, spraying or dipping methods are as follows: (a) a perfluoro ion exchange resin, a fiber as a reinforcement, an auxiliary proton conducting substance, a crosslinking agent, an acid Or one or more of a free radical initiator and a high-valent metal compound are dispersed in a solvent to form a mixture; the solid content of the perfluoro ion exchange resin in the mixture may be 1-80% by weight, and the solvent used may be dimethyl Formamide, dimethylacetamide, methylformamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylphosphoric acid amine, acetone, water, ethanol, methanol, propanol, isopropanol, B One or more of a diol and glycerol;

(b) forming a film by solution casting, solution casting, screen printing, spin coating, spraying or dipping on the plate or the prepared single layer or multilayer film by using the solution prepared in the step (a); Heat treatment at a temperature of 30-250 ° C for 0.01-600 minutes, preferably at 100-200 ° C for 1-30 minutes;

It may be crosslinked in film formation or after film formation, and the crosslinked network structure is as shown in formulas (1), (11), (111),

(IV) and (V):

, "

ΐ ΧΑΛΛΛΛΛ ( J )

Wherein, GPG ₂ is CF ₂ or O, respectively, and R _f is a chain;

(in) Wherein R is methylene or perfluoromethylene, n 0-10

(IV) (v). Wherein the method of forming the crosslinked structure represented by the formula (I) includes heat, light, electron radiation, plasma, X-ray, or a radical initiator, and may also pass heat in the presence of one or more crosslinking agents. The interaction of light, electron radiation, plasma, X-rays, or a free radical initiator forms a cross-linkage. The structure of the crosslinking agent used therein is as shown in the following formula (VI).

^X 2 ^R f7 ^X 3 ( VI ) wherein X ₂ and X ₃ are each independently CI, Br or I; 3⁄47 is perfluoro)^

Preferably, the radical initiator is an organic peroxide or an azo initiator; preferably, the initiator is an organic oxide initiator; more preferably, the initiator is a perfluoroorganic peroxide.

The method for forming the (11) and (III) crosslinked structures is: using a sulfonyl fluoride, a sulfonyl chloride, a sulfonyl bromide type resin with ammonia, hydrazine, an organic diamine or capable of chemically releasing ammonia, hydrazine, and an organic diamine. The material reaction is obtained.

The organic diamine is a C1-C10 decyl diamine or a perfluorodecyl diamine, and the substances capable of chemically releasing ammonia, hydrazine, and organic diamine include, but are not limited to, ammonia, hydrazine, organic An organic or inorganic acid salt of a diamine, urea, or hydrazine.

The method of forming the (IV) crosslinked structure is obtained by treating a perfluorosulfonic acid resin with chlorosulfonic acid.

The method for forming the (V) crosslinked structure is a perfluorosulfonic acid resin containing a nitrile group or a perfluorosulfonyl fluoride resin containing a nitrile group, a sulfonyl chloride resin, a sulfonyl bromide resin in heat or acid Formed under the action.

The acid is a strong protic acid or a Lewis acid; wherein the protonic acid is selected from the group consisting of H ₂ S0 ₄ , CF ₃ S0 ₃ H and: _3⁄4 ?0 ₄ ; the Lewis acid is selected from the group consisting of ZnCl ₂ , FeCl ₃ , A1C1 ₃ , organotin , organic cockroaches and organic cockroaches.

Preferably, the method of melt extrusion and hot pressing is as follows:

(a) Preparing suitable sulfonyl fluoride, sulfonyl chloride, sulfonyl bromide resin, modified fiber, surface-modified auxiliary proton conductive material, crosslinking agent according to the requirements of each layer of the multi-layer cross-linked perfluorinated ion exchange membrane. a mixture of one or more of an acid or a free radical initiator and a high valence metal compound, utilizing a double Screw extruder, internal mixer or open mill at 200-28 (TC mixing;

(b) The resin mixed in the step (a) is formed into a film by a screw extruder or a flat vulcanizer; the method may also be crosslinked in a film formation or after film formation to obtain a crosslinked single layer film as described above. According to the method provided by the present invention, the method of compounding in the step (3) may be a single layer film composite, a multilayer film and a single layer film composite, a multilayer film and a multilayer film composite, and a solution or a melt in a single film. One or more of the methods of directly forming a single layer film on a film or a multilayer film. That is to say, each single layer film can be formed by casting, extrusion, hot pressing, spin coating, casting, screen printing process, spraying or dipping process of solution or melt; multilayer film is prepared by single layer Inter-membrane recombination, composite between multilayer film and single-layer film, or composite film between multi-layer film and multi-layer film, can also directly use casting or extruding of solution or melt on the obtained single-layer film or multi-layer film. Prepared by hot pressing, spin coating, casting, screen printing, spraying or dipping.

Preferably, the obtained monolayer film may be first converted into an acid form prior to recombination, or may be first combined with other films and then converted into an acid form.

It is also possible to extrude the resin to form a monolayer film, hydrolyze it into a hydrogen type film, and then soak the film in a solution of a high-valent metal compound to achieve physical bonding crosslinking.

Preferably, the crosslinking described in the step (2) means crosslinking using various crosslinking means as described above. The method according to the present invention, wherein the surface-modified auxiliary proton conductive substance comprises an oxide modified by an inorganic dopant, an orthophosphate, a polycondensation phosphate, a polyacid, a polyacid salt, a silicate, a sulfate And selenite and arsenide, preferably oxides, orthophosphates, polycondensed phosphates, polyacids and polyacid salts, more preferably oxides, orthophosphates and polycondensed phosphates; Si0 ₂ , Zr0 ₂ , Ti0 ₂ , BP0 ₄ , Zr ₃ (P0 ₄ ) ₄ , Zr(HP0 ₄ ) ₂ , HZr ₂ (P0 ₄ ) ₃ , Ti(HP0 ₄ ) ₂ , and Zr ₂ H (P ₃ 0 One or more of ₁₍₎ ) ₂ .

The surface of the above-mentioned auxiliary proton conductive substance may be modified with a group having an ion exchange function or an acidity by a method such as cogelation, coprecipitation or hydrothermal pyrolysis. For example, in some embodiments of the present invention, the specific preparation method may be: gelating methyl phosphate or methyl sulfate and ethyl silicate or zirconyl chloride or titanate under alkaline conditions to obtain a surface Modified auxiliary proton conducting material. The surface-modified auxiliary proton conductive material can physically form a crosslink with the high-valent metal compound and the acidic exchange group in the resin.

According to the method of the present invention, wherein the modified fiber is selected from one or more of fluorocarbon polymer fibers modified by a substance having an ion exchange function, such as polytetrafluoroethylene fiber, polyperfluoroethylene Propylene fiber and polyperfluoropropyl vinyl ether fiber. The fibers may have a diameter of from 0.005 to 5 μm, preferably from 0.05 to 2 μm; and may have a length of from 0.03 to 3 mm, preferably from 0.05 to 1 mm. The specific modification method may be: using fibers and ions having ion exchange function in heat, light, electron radiation, plasma, The reaction takes place under the action of X-rays, a radical initiator or the like, and then the modified fiber generates an ion exchange group under the action of an acid or a base. Wherein, the monomer having an ion exchange function may be sulfur dioxide, sulfur trioxide, and a perfluorosulfonic acid monomer (A), a perfluorosulfonic acid monomer (B), and a perfluorosulfonic acid monomer having the following structure ( One or more of C):

Wherein, h = 0-l, i=l-5, A is F, Cl, Br, OH, oxymethyl (OCH ₃ ) or ONa; j = 0-1, k = 1-5, B is methyl (Me), H or ethyl ( Et ); 1 = 1-5, D is H, methyl (Me) or ethyl (Et).

The fiber as the reinforcement is preferably a fiber having an ion exchange capacity or a water-retaining group on the surface. A fiber having an ion exchange function as disclosed in CN101003588A, surface silicate, sulfonated, sulfated, phosphorylated, hydrophilically modified fluorocarbon polymer fiber, surface silicidated, sulfonated, sulfur, according to the invention Providing a proton exchange membrane, wherein the high-valent metal compound may be a nitrate, a sulfate or a carbonate of a highest valence state and a middle valence state of W, Ir, Y, Mn, Ru, V, Ζ, and La elements , phosphate, acetate and combined double salt, W, Ir, Y, Mn, Ru, V, Ζ, and La elements of the highest and intermediate valences of cyclodextrin, crown ether, acetylacetone, nitrogen-containing crown Ether and nitrogen-containing heterocycles, ethylenediaminetetraacetic acid, dimethylformamide and dimethyl sulfoxide complexes, and the highest valence states of W, Ir, Y, Mn, Ru, V, Ζ and La elements One or more of intermediate oxides having a perovskite structure. Wherein, the oxides having a perovskite structure of the highest and intermediate valence states of the W, Ir, Y, Mn, Ru, V, Ζ, and La elements include, but are not limited to, the following compounds: Ce _x Ti _{(1- x)} 0 ₂ (x = 0.25-0.4), Ca. ₆ La. ₂₇ Ti0 ₃ , La _(1-y) Ce _y Mn0 ₃ (y = 0.1-0.4), La ₀ . ₇ Ce ₀₁₅ Ca ₀₁₅ MnO ₃ .

A proton exchange membrane according to the present invention, wherein the proton exchange membrane preferably comprises 2 to 5 layers of a monolayer membrane based on a perfluoro ion exchange resin. The proton exchange membrane may have a thickness of 5 to 300 μm, preferably 10 to 50 μm. A proton exchange membrane according to the present invention, wherein the perfluoro ion exchange resin is a perfluoroolefin monomer, one or more functional group-containing perfluoroolefin monomers, and one or more crosslinks The mixture of sites of perfluoroolefin monomers, or a mixture of the above copolymers, may have an EW value of from 600 to 1300, preferably from 700 to 1200.

Wherein the perfluoroolefin monomer is selected from one or more of tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, hexafluoropropylene and vinylidene fluoride, preferably, the perfluoroolefin monomer The perfluoroolefin monomer which is a functional group of tetrafluoroethylene is selected from one or more of the structures represented by the formulae (VII), (VIII) and (IX):

(VII)

R. CF=CF(CF ₂ ) _d Y ₂

( VIII )

(IX)

Wherein a, b, c are each independently 0 or 1, but are not simultaneously zero; d is an integer from 0 to 5; n is 0 or 1; R _fl , Re and are respectively selected from perfluorodecyl and fluorochloro垸 group; X is selected from the group consisting of F, Cl, Br and I; Y, Υ ₂ and Υ ₃ are each independently selected from S0 ₂ M, COOR ₃ , and PO(OR ₄ )(OR ₅ ), wherein: M is selected from F , Cl, OR, NRiR ₂ ; R is selected from the group consisting of methyl, ethyl, propyl, H, Na, Li, K and ammonium; and is selected from the group consisting of 11, methyl, ethyl and propyl, respectively; R _{3 is} selected from H, Na, Li, K, ammonium, methyl, ethyl and propyl; R ₄ and R ₅ are each selected from the group consisting of 11, Na, Li, K and ammonium.

F ₂ C^=CFRf ₄ Y4

(X)

(XI) Wherein Y ₄ and Y ₅ may be selected from the group consisting of Cl, Br, I and CN, respectively; a, b, and c are 0 or 1, respectively, but a, +b, +c, ≠0; selected from F, Cl , Br and I; n, are 0 or 1; R _f4 , R _f5 and R _f6 are each independently selected from a perfluorodecyl group.

The method according to the present invention, wherein the perfluoro ion exchange resin is a perfluoroolefin monomer, one or more functional group-containing perfluoroolefin monomers, and one or more crosslinking sites. The copolymer of perfluoroolefin monomers or a mixture of the above copolymers may have a ring number of from 600 to 1300, preferably from 700 to 1200. Here, the definition of the perfluoroolefin, the functional group-containing perfluoroolefin monomer, and the crosslinking site-containing perfluoroolefin monomer is as described above.

The present invention also provides the use of the proton exchange membrane of the present invention or the proton exchange membrane prepared according to the preparation method provided by the present invention in a proton exchange membrane fuel cell.

The proton exchange membrane provided by the present invention greatly enhances the mechanical strength of the ion membrane while improving the proton conductivity while using the reinforcing fibers, the chemical bonding crosslinking, and the physical bonding cross-linking of the high-valent metal compound with the acidic exchange group. . In particular, the physical bonding between the high-valent metal compound and the acidic exchange group has a high degree of crosslinking and can achieve cross-linking between the layers, together with an amide group in the chemical bonding of the amide. The triazine group in the triazine ring-bonding crosslink can also form a coordination with the high-valent metal compound, which further improves the performance of the film. In particular, it is emphasized that the surface is modified by an acidic exchange group to form a physical bond crosslink by physical bonding with a high-valent metal compound and a film-forming resin. This solves the problem of the high gas permeability of the conventional fiber-reinforced perfluorosulfonic acid membrane. The possible causes are as follows: 1. The surface-functionalized fiber has a strong adhesion to the film-forming resin; 2. Since the surface of the fiber has a functional group, it can form a bonding structure with the metal compound, further reducing the gap between the resin and the fiber. In the past, the membrane with the auxiliary proton-conducting substance was added, although the high-temperature proton conductivity was improved, but the mechanical properties were significantly reduced. In our invention, the cross-linking modification as described above, and at the same time, due to the modification of the surface of some of the auxiliary proton-conducting substances by the reactive groups, can form a physical cross-linking structure with the high-valent metal compound. This ensures that they not only contribute to the proton conduction of the membrane, but also contribute to the mechanical properties of the membrane. Therefore, the proton exchange membrane provided by the present invention has high mechanical strength, high temperature conductivity and airtightness while having high ion exchange capacity. The best way to implement the invention

The present invention is further described in detail with reference to the preferred embodiments of the present invention. Example 1

This embodiment is used to illustrate the proton exchange membrane provided by the present invention and a preparation method thereof

Will repeat the unit as

The sub-exchange resin and the cerium carbonate (weight ratio to the resin: 1:100), Zr(HP0 ₄ ) ₂ having a particle size of 0.005 μm (the weight ratio to the resin is 3:100), and 5 wt% of propanol Aqueous solution. Then, a DMF solution of perfluoro-malonyl peroxide having a concentration of 5% by weight is prepared, and a CF ₂ =CFO(CF ₂ CFO) _h (CF ₂ ) ₁ S0 ₂ A surface is added to the above solution to be ^CF 3 (where h=0, i=2, A=OH) modified polytetrafluoroethylene fiber (diameter Ιμηι, length 50μηι, weight ratio with resin: 7: 100), post-cast into a horizontally placed polytetrafluoroethylene mold After drying under vacuum at 80 ° C for 12 hours, the film was peeled off to obtain a doped ion film (monolayer film 1 # ) in which a single layer of perfluorosulfonic acid was crosslinked to the (I) species.

Two of the above-mentioned single-layer films 1 # were stacked and hot pressed to obtain a yttrium ion-bonded double-layer fiber-reinforced perfluoro crosslinked ion film having a thickness of 30 μm, that is, the proton exchange membrane of the present invention, which is referred to as Al. Example 2

— [-CF CF _r ] ₇ -CF广CF - The repeating unit is OCF ₂ CF ₂ CF ₂ SG ₂ f , _EW=800 perfluoro ion exchange resin and SiO ₂ with a particle size of 0.03μηι (with resin weight) The ratio is 5:100), and the surface is CF ₂ =CFO(CF ₂ CFO) _h (CF ₂ ) ₁ S0 ₂ A

CF ₃ (where _h=0 , i= ₄ , A=ONa ) modified perfluoroethylene propylene fibers (diameter 0.05 μm length 5 μm, weight ratio to resin 1:40) mixed extrusion to obtain a film having a thickness of 30 μm . The film was placed in a vacuum oven at 150 ° C for 1 hour and then immersed in a solution of NH ₄ C1 in DMF for 5 hours. The soaked film was placed in triethylamine at 200 ° C for 2 hours to obtain a crosslinked film. The obtained film was sequentially treated with a KOH solution or a hydrochloric acid solution to obtain a crosslinked structure. An ion exchange membrane of the (II) species (monolayer membrane 2 # ).

Will repeat the unit as

— [-C

CF.

EW=1200 perfluoro ion exchange resin and tetraphenyltin were extruded into a film of 20 μm by a twin-screw extruder, and then the film was heated to 230 ° C for 10 hours to obtain a crosslinked structure of the (V) species. membrane. The film was sequentially treated with LiOH and a nitric acid solution to obtain a crosslinked ion film (monolayer film 3 # ). The single layer films 2 # and 3# were overlapped, hot pressed, and immersed in a manganese nitrate solution for 1 hour to obtain a manganese ion-bonded crosslinked two-layer doped fiber-reinforced ion exchange membrane having a thickness of 50 μm, which is the present invention. Proton exchange membrane, denoted as Α2. Example 3

This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.

Will repeat the unit as

-CF ₂ CF ₂ CF ₂ CF~["CF ₂ CF ₂ +CF ₂ CF -

OCFpCF Br OCF ₂ CFOCF ₂ CF ₂ S0 ₃ H

CF, , EW=1100 perfluoro ion exchange resin, barium acetate (weight ratio to resin: 0.001:100) and H ₃ PW ₁₂ 0 ₄ o (weight ratio to resin: 1:100) 3 wt% solution (solvent: water = 1:1 (weight ratio)), cast into a film, and then the film was cross-linked by 50 KGy radiation to obtain a ruthenium (N) cross-linked structure of the (I) ion film (single Layer film 4 # ).

- the repeating unit is

EW=940 perfluoro ion exchange resin, Ce(III)-DMSO complex (weight ratio to resin: 0.1:100) and H ₃ PWi ₂ 0 ₄ o (weight ratio to resin: 20:100) The resin content is 30% by weight CF ₂ =CFO(CF ₂ CFO) _h (CF ₂ ) ₁ S0 ₂ A

DMSO solution, adding surface to the solution

h=l , i=2, A=F ) modified polytetrafluoroethylene fiber (diameter 0.2μηι, length 80μηι, weight ratio to polymer: 7:100), by casting method at 170 ° C, 60 A film of ΙΟμηι (single layer film 5 # ) was obtained in minutes.

The single layer film is stacked in the order of 4 # -4 # -5 # and hot pressed to obtain a high-valent metal ion-bonded fiber-reinforced three-layer crosslinked doped ion film having a thickness of 30 μm, that is, the proton exchange membrane of the present invention. Recorded as A3. Example 4

Will repeat the unit as

_{? EW=700} full

Sub-exchange resin, HP0 ₄ ) ₂ (weight ratio to resin: 0.1: 100), 18-crown-6 complexed ruthenium (ΠΙ) compound (with tree

A mixture of modified polyvinylidene fluoride fiber (diameter 5 μηι, length ΙΟΟμηι, weight ratio of resin to 1:5) was formulated into a solution having a resin content of 20% by weight in DMF, and cast into a film, and the film formation time was 1 After hours, it was then treated at 120 ° C for 10 minutes to obtain a fiber-reinforced monolayer perfluorosulfonic acid ion membrane having a thickness of ΙΟμηι. The ion exchange membrane was immersed in chlorosulfonic acid to obtain a membrane (monolayer membrane 6#) having a crosslinked structure of the formula (IV).

The single layer film 6# was placed in the DMF solution of the resin of Example 1 and 0.1% perfluoroperyl laurethoyl, 5% 1,4-diiodooctafluorobutane, and immersed for 0.5 hour, taken out, dried, and the above was repeated. Step; The film was then treated at 120 ° C for 300 minutes to obtain a single layer film 7#. Further, the single layer film 7# and the single layer film 4# were heat-pressed to obtain a proton exchange membrane of the present invention, which was designated as A4. Example 5

This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof. CF ₂ CF ₂ 7CF ₂ CF— j-CF ₂ CF ₂ †CF ₂ CF'

CI OCF ₂ CFOCF ₂ CF ₂ S〇 ₃ H The repeating unit is ^CF 3 ,

EW=1300 perfluoro ion exchange resin and acetylacetone-Ce(III) complex (weight ratio of resin to 0.01:100), surface sulfuric acid modified Zr0 ₂ with particle size of 0.8μη (with resin weight) A ratio of 2:100), azobisisovaleronitrile (weight ratio to resin: 0.1:100), 1,4-diiodooctafluorobutane (5:100 by weight to resin) dissolved in DMF A solution having a resin content of 20% by weight was prepared and cast into a film at a film forming temperature of 170 ° C for 60 minutes to prepare a film having a thickness of 20 μm (monolayer film 8#).

The resin of Example 4, Η-mordenite powder having a particle size of 5 μm (the weight with the resin) was used.

0 volume ratio is 1:1) and the surface is modified by ⁰ ^ ⁰ ^^ ¹⁷² ) ¹ ^^ ( 1 = 1, D = Me ) PTFE-ethylene fiber (diameter 5μηι, length ΙΟΟμηι, with resin The weight ratio was 1:100) mixed in Ν-methylpyrrolidone to prepare a solution having a resin content of 15% by weight, and the solution was spin-coated on both surfaces of the single layer film 8# to form a film having a thickness of 30 μm. A three-layer perfluoro ion exchange membrane (multilayer membrane 1#) was prepared. The multilayer film 1# was treated at 69 ° C for 2.4 hours to obtain a perfluorosulfonic acid film of the formula (I) in which the metal ion-bonded three layers had a crosslinked structure.

The above ionic membrane was again placed in the perfluoro ion exchange resin of the present example, yttrium-montmorillonite having a particle diameter of ΙΟμηι (weight ratio of 0.5:100 to resin), azobisisovaleronitrile (weight of resin) The ratio is 0.1:100), 1,4-diiodooctafluorobutane (5:100 by weight to resin) and DMF-Ce(m) complex (weight ratio to resin: 0.02:100) In a solution prepared in DMF having a resin content of 25% by weight, the film was taken out and dried after soaking for 0.5 hours, the above procedure was repeated, and then the film was treated at 120 ° C for 300 minutes to obtain a metal ion-bonded five-layer fiber reinforcement. Perfluorosulfonic acid crosslinked ion membrane (multilayer film 2#).

The multilayer films 1# and 2# were hot pressed to obtain a metal ion-bonded ten-layer fiber-reinforced perfluorosulfonic acid cross-linked ion doped film, i.e., the proton exchange membrane of the present invention, designated as A5. Example 6

Will repeat the unit as

, EW=1300 perfluorinated ion exchange resin and

(y=0.5), the weight ratio to the resin is 0.01: 100) dispersed in hexamethylphosphoric acid to form a resin solution of 29%, and then yttrium-montmorillonite having a particle diameter of 0.7 μm (the weight ratio to the resin is 10:100) and perfluorosulfonic acid monomer (I) under the action of plasma

CF ₂ =CFO(CF ₂ CFO) (CF ₂ ) S0 ₂ F

The modified polytetrafluoroethylene fiber (diameter 15 μm, length ΙΟΟμηι, mass ratio of resin to resin: 3:100) was mixed. After the mixture was uniformly mixed, a film having a thickness of 20 μm was obtained by a vacuum spraying method. The film was treated at 230 ° C for 100 min. A single-layer perfluorosulfonic acid membrane (monolayer film 9#) having a crosslinked structure of the formula (I) was obtained.

On the two surfaces of the single layer film 9#, a crosslinked three-layer perfluorosulfonic acid film having a thickness of 60 μm was again produced by a spray coating method, and then a single layer film 9# was heat-pressed on both surfaces thereof to obtain a fiber. The crosslinked five-layer perfluorosulfonic acid doped film, that is, the proton exchange membrane of the present invention, is referred to as Α6. Example 7

Will repeat the unit as

—— |~CF ₂ CF ₂ CF ₂ CF~["CF ₂ CF ₂ + ₆ CF ₂ CF -

OCF ₂ Br OCF ₂ CFOCF ₂ CF ₂ CF ₂ S0 ₃ H

CF ₃ , EW=1300 perfluoro ion exchange resin and La(OH) ₃ (weight ratio to resin: 0.5:100), benzoyl peroxide (weight ratio to resin: 0.1:100), 1, 14-Diiodo-decafluorodecene (5:100 by weight to resin) Dissolved in dimethyl sulfoxide (resin content of 35% by weight), and then added polytetrafluoroethylene fiber (weight ratio to resin) It is 2:100) and the ion exchange function of the surface is ion exchanged (the weight ratio of the resin is 1:5), and the Ti0 ₂ with the particle size of 3μη (the weight ratio to the resin is: 15:100) The mixture was cast into a film, and the film formation temperature was 160 ° C for 3 minutes. A crosslinked 30 μηι doped fiber reinforced perfluorosulfonic acid membrane was obtained. (single layer film 10#). The single layer film 10# was placed in the resin, zeolite (0.4:100 by weight to the resin) and benzoyl peroxide (weight ratio to resin: 0.1:100), 1,14-diiodine, from the present example. Soaking the dimethyl sulfoxide solution (resin ratio of resin: 5:100) in a dimethyl sulfoxide solution (resin content of 35% by weight) for 0.5 hour, taking out the film and drying, repeating the above steps, and then placing the film at 120 The mixture was treated at ° C for 300 minutes to obtain a three-layer perfluorosulfonic acid cross-linked doped ion film (multilayer film 3#).

The three multilayer films 3# were stacked and hot pressed to obtain a reinforced nine-layer fiber-reinforced perfluorosulfonic acid cross-linked ion-exchange film, i.e., the proton exchange membrane of the present invention, designated A7. Example 8

Will repeat the unit as

—— [~CF ₂ CF ₂ 4 CF ₂ CF~["CF ₂ CF ₂ + ₂ CF ₂ CF -

OCF ₂ CF ₂ CF ₂ l OCF2CFOCF2CF2CF2SO3H

CF ₃ , EW=1250 perfluoro ion exchange resin, pyridine-Ru complex solution (weight ratio of resin to 0.63:100) and CsH ₂ P0 ₄ (weight ratio of resin to resin: 20:100), then The solution was dissolved in hexamethylphosphoric acid to obtain a solution having a resin content of 30% by weight, and a polyperfluoroethylene propylene fiber (having a length of 30 μm and a length of 3 mm and a weight ratio of 0.01:100) was added to the solution, and the film was cast. A film having a thickness of ΙΟμηι was obtained. The film was treated at 230 ° C for 100 minutes to obtain a crosslinked single-layer fiber-reinforced doped perfluorosulfonic acid film (monolayer film 11#). Wherein the polyperfluoroethylene propylene fibers used are modified by perfluorocarboxylic acid monomer (II) under the action of electron radiation:

CF = CFO(CF CFO) ( ¥^CQ ₂ H

(II).

A crosslinked three-layer doped perfluorosulfonic acid film of 60 μm was produced by a spraying method on both surfaces of the single layer film 11# using a solution forming the single layer film 11#. The single layer film 11# was heat-pressed on both surfaces of the three-layer film to obtain a crosslinked five-layer fiber-reinforced doped perfluorosulfonic acid film, that is, the proton exchange membrane of the present invention, which was designated as Α8. Example 9 This embodiment is used to illustrate the proton exchange membrane provided by the present invention and a preparation method thereof

The sub-exchange resin and SiO ₂ (weight ratio to resin: 5:100) having a particle diameter of 0.03 μm were extruded at 270 ° C to form a film. The film was immersed in 10% NH ₃ in DMF for 5 hours. A film of the (II) crosslinked structure was obtained at 200 °C. The membrane was treated with an alkali solution and an acid solution, and then immersed in a DMF solution (concentration: 0.05% by weight) of acetylacetone-lr (m) to obtain a metal ion-bonded crosslinked film (monolayer film 12#).

Will repeat the unit structure as

-CF-CF ₂ -]-CF ■CF— •CF ₂ " ₃ : CF-

5.5

0CF CF CF S0J OCF ₂ Cj;FOCF ₂ CF ₂ CN

CF

, EW=1200 perfluoro ion exchange resin and ethyl phosphate and tetraethyl orthosilicate gel-spun modified polytetrafluoroethylene fiber (diameter 0.05μηι, length 5um, weight ratio of resin to 1:40) And tetraphenyltin (weight ratio to resin: 0.1:100) was mixed with a twin-screw extruder, hot pressed to form a film, and the film was heated to 230 ° C for 10 hours to obtain a film of the (V) crosslinked structure. . The film was placed in a 35 wt% hydrazine hydrate for 10 hours, and after removal, it was heated at 280 ° C for 5 hours to obtain a film having both the (V) crosslinked structure and the (III) crosslinked structure. After the treatment with an alkali solution and an acid solution, the film was immersed in a cerium nitrate solution (concentration: 0.5% by weight) for 2 hours to obtain a cerium ion-bonded doped crosslinked film (monolayer film 13#).

According to the film A8 of the single layer film 12#-monolayer film 13#-the film A8 of the embodiment 8 and the film A5 of the embodiment 5, the crosslinked fiber-reinforced hexa-layer film having a thickness of 300 μm is obtained, which is the film of the present invention. Proton exchange membrane, denoted as Α9. Example 10

Perfluorinated ion

, EW=1300 perfluoro ion exchange resin (the weight ratio of the two is 1:0.2) and the nitrogen-containing crown ether-Ce complex (the ratio of the total weight to the resin is 1:100), phosphoric acid modified particles Mixing 10 nm of Zr0 ₂ (2:100 to the total weight of the resin) and azobisisovaleronitrile (0.1:100 to the total weight of the resin), dissolved in DMF to form the total resin content a 20% by weight solution, a polyperfluoropropyl vinyl ether fiber modified by sulfur trioxide (0.55 μm in diameter, 0.07 μm in length, and a total weight ratio of resin: 25:100) was added. Casting into a film, heating at 140 ° C to obtain a single-layer perfluorosulfonic acid film containing the (I) cross-linking structure having a thickness of 50 μm, and then placing the film in chlorosulfonic acid to obtain both the (I) species and A film of the (IV) crosslinked structure (monolayer film 14#).

The monolayer film 14# and the film 2 obtained in Example 2 were heat-pressed to obtain a metal ion-bonded five-layer perfluorosulfonic acid fiber-reinforced crosslinked ion membrane, i.e., the proton exchange membrane of the present invention, which was designated as Α10. Example 11

Will repeat the unit as

, EW=1200 perfluoro ion exchange resin, Mn(OH) ₃ (weight ratio to resin: 2:100) and triphenyltin hydroxide (weight ratio to resin: 0.1:100) and particle size of 8μηι Zr0 ₂ (weight ratio to resin: 2:100), dispersed in DMF, forming a solution having a resin content of 30% by weight, cast into a film, and treated at 170 ° C for 60 min to obtain a thickness of 20 μm (V) a film of a crosslinked structure (monolayer film 15#).

The resin of Example 4 and the cerium-mordenite powder having a particle diameter of 5 μm (weight ratio to resin of 1:1) and the ion-exchangeable fiber (CN101003588A) (diameter 15 μηι, length 20 mm) exchanged with titanium ions were used. , the weight ratio to the resin is 0.5:5) mixed in N-methylpyrrolidone to form a solution having a resin content of 27% by weight, and spin-coated on both surfaces of the single layer film 15# to form a film having a thickness of 30 μm , a three-layer fiber-reinforced perfluorinated ion exchange membrane was obtained. The film was treated at 190 ° C for 2.4 hours to obtain a manganese ion-bonded three-layer crosslinked fiber-reinforced perfluorosulfonic acid film, i.e., the proton exchange membrane of the present invention, which is referred to as All. Example 12

Will repeat the unit as

Perfluoro ion exchange resin and Ή02 with a particle size of 0.02 μηη (3:100 by weight of resin), PTFE-modified polytetrafluoroethylene fiber (0.01 μm in diameter, 120 μm in length, weight ratio to resin) A single layer film was prepared by melt extrusion for 5:100), and then the film was treated at 280 ° C for 3 hours to obtain a single layer film 16# having a crosslinked structure of the formula II.

A film A3 prepared in Example 3 is stacked on both surfaces of the single layer film 16#, and The mixture was autoclaved at 120 ° C for 3 minutes, and then hydrolyzed and acidified to obtain a four-layer crosslinked perfluorosulfonic acid fiber reinforced film, that is, the proton exchange membrane of the present invention, which was designated as A12. Example 13

This embodiment is used for

Will repeat the unit as

The exchange resin is mixed with Zr0 ₂ (weight ratio of resin to resin: 9:100) having a particle diameter of 0.01 μm, and cyclodextrin-W (III) complex (0.034:100 by weight to resin), and dispersed in N- A dispersion having a solid content of 30% by weight is formed in methylpyrrolidone, and a PTFE-modified polytetrafluoroethylene fiber (0.5 μm in diameter, 3 μm in length, and 2:100 by weight of resin) is formed. The film was mixed in the above solution and cast at 190 ° C (monolayer film 17#).

The above perfluoro ion exchange resin has the same repeating unit

The perfluoro ion exchange resin was mixed in a ratio of 1:5 by weight and dispersed in DMSO to form a solution having a total resin content of 20% by weight, and Zr ₃ (P0 ₄ ) having a particle diameter of 0.05 μm was added to the solution. ₄ (weight ratio to resin: 12:100), an organic rhodium catalyst was further added, and a film was formed by a casting method, and a film was formed at 230 ° C to form a triazine crosslinked ring to obtain a monolayer film 18#.

The two-layer single-layer film 17# and the three-layer single-layer film 18# were alternately laminated and hot-pressed to obtain a five-layer film having a thickness of 50 μm, that is, the proton exchange membrane of the present invention, which is referred to as A13. Example 14

This embodiment is used to illustrate the proton exchange membrane provided by the present invention and a preparation method thereof Will repeat the unit as

EW=900's full:

^: Sub-exchange grease and repeat unit are

The fluorine ion exchange resin was mixed in a weight ratio of 6:1 and dispersed in DMSO to form a solution having a total resin content of 35% by weight, and then a Zr0 ₂ particle size of 0.01 μm was added to the solution (the weight ratio to the resin was 6). : 100 ) and a sulfur trioxide-modified polytetrafluoroethylene fiber (0.01 μm in diameter, 120 μm in length, and a weight ratio of resin to resin: 3:100), a monolayer film is prepared by a casting method, and then the film is prepared. 50KGy radiation cross-linking results in a single layer film 19# having a crosslinked structure of the (V) species.

The film A3 prepared in Example 3 was stacked on both surfaces of the single layer film 19#, and subjected to hot pressing treatment at 120 ° C for 3 minutes, and then hydrolyzed and acidified to obtain a seven-layer crosslinked perfluorosulfonic acid fiber reinforced film, that is, The proton exchange membrane of the invention is designated A14. Example 15

Will repeat the unit as

a perfluoro ion exchange resin with a particle size of 0.02 μm of SiO ₂ (weight ratio to resin of 3:100), and S0 ₂ modified polyperfluoropropene vinyl ether fiber (0.01 μm in diameter, 120 μm in length, The weight ratio to the resin was 5:100). A single layer film was prepared by melt extrusion, and then the film was treated at 250 ° C for 3 hours to obtain a single layer film 20# having a crosslinked structure of the formula (I).

The film A3 prepared in Example 3 was placed on both surfaces of the single layer film 20#, and subjected to hot pressing treatment at 120 ° C for 3 minutes, and then hydrolyzed and acidified to obtain a seven-layer crosslinked perfluorosulfonic acid fiber reinforced film, that is, The proton exchange membrane of the invention is referred to as A15. Comparative example 1

This comparative example is used to illustrate the existing proton exchange membrane and its preparation method.

Using 10% by weight of nafion® DMF solution, silicic acid-modified polytetrafluoroethylene fiber (diameter 0.2μηι, length 80μηι, weight ratio of resin to resin: 7:100) was cast at 170 ° C for 60 min.

A 30 micron thick fiber reinforced ion exchange membrane, designated Cl. Membrane performance characterization

The 95 °C conductivity, tensile strength, hydrogen permeation current, and dimensional change rate of the proton exchange membranes A1 obtained in Examples 1-15 and the proton exchange membrane C1 prepared in Comparative Example 1 were measured, and the results are shown in Table 1. Among them, the test conditions of the two conductivity values are: T=95 °C, saturated humidity, and T=25 °C, after drying the dryer for two days; the tensile strength test method is GB/T20042. 3-2009); The test method for hydrogen permeation current is electrochemical method (Electrochemical and Solid-State Letters, vol. 10, Issue 5, B101-B104, 2007). Table 1

It can be seen from Table 1 that the 95 °C conductivity, tensile strength, hydrogen permeation current and dimensional change rate of the proton exchange membrane of the present invention are superior to those of the conventional fiber-reinforced multi-layer perfluoro-crosslinked doped ion membrane. .

Claims

杈利 demands OOSRM

1. A HNI proton exchange membrane comprising 2-40 layers of a perfluoro ion exchange resin-based monolayer film, characterized in that at least one monolayer film comprises a surface-modified auxiliary proton-conducting substance, at least one layer The film contains modified fibers, and at least one single layer film contains a high-valent metal compound.

The proton exchange membrane according to claim 1, wherein the surface-modified auxiliary proton conductive material is contained in an amount of 0.05 to 50 parts by weight based on 100 parts by weight of the perfluoro ion exchange resin, and the modification The content of the fiber is from 0.5 to 50 parts by weight, and the content of the high-valent metal compound is from 0.001 to 5 parts by weight.

The proton exchange membrane according to claim 1 or 2, wherein the crosslinked network structure is a structure represented by the formulas (1), (11), (111), (IV) and (V)

Ij ww ¹ ( I )

Wherein GPG ₂ is a perfluorocarbon chain or a chlorine-containing perfluorocarbon chain of CF ₂ or O, R _f C ₂ -C _{1 ()} ;

Wherein R is a methylene group or a perfluoromethylene group, and n is 0-10

The proton exchange membrane according to any one of claims 1 to 3, wherein the surface-modified auxiliary proton conductive substance comprises an oxide modified by an inorganic dopant, an orthophosphate, a polyphosphate, and a plurality Acids, polyacid salts, silicates, sulfates, selenites and arsenides, preferably oxides, orthophosphates, polycondensation phosphates, polyacids and polyacid salts, more preferably oxides, orthophosphates And polyphosphate; the inorganic dopants are Si0 ₂ , Zr0 ₂ , Ti0 ₂ , BP0 ₄ , Zr ₃ (P0 ₄ ) ₄ , Zr(HP0 ₄ ) ₂ , HZr ₂ (P0 ₄ ) ₃ , Ti (HP0 ₄ ) One or more of ₂ and Zr ₂ H(P ₃ 0 ₁₍₎ ) ₂ .

The proton exchange membrane according to any one of claims 1 to 4, wherein the modified fiber is one or more selected from the group consisting of a monomer-modified fluorocarbon polymer fiber having an ion exchange function. , such as polytetrafluoroethylene fiber, polyperfluoroethylene propylene fiber and polyperfluoropropyl vinyl ether fiber; fiber diameter of 0.005-5μηι, length of 0.03-3mm; the ion exchange function of the monomer is Sulfur dioxide, sulfur trioxide, and one or more of perfluorosulfonic acid monomer (A), perfluorosulfonic acid monomer (B), and perfluorosulfonic acid monomer (C) having the following structure:

CF ₂ =CFO(CF ₂ CFO) _h (CF ₂ ) ₁ SO ₂ A

(A)

Wherein, h = 0-l, i = 1-5, in, Cl, Br, OH, oxymethyl or ONa; j = 0-1 k = 1-5, B is methyl, H or ethyl; 1 = 1-5 and D is H, methyl or ethyl.

The proton exchange membrane according to any one of claims 1 to 5, wherein the high-valent metal compound is a highest valence state and a middle valence of W, Ir, Y, Mn, Ru, V, Ζ, and La elements. Nitrate, sulphate, carbonate, phosphate, acetate and combined double salt; the highest valence and intermediate valence of W, Ir, Y, Mn, Ru, V, Ζ and La Fine, crown ether, acetylacetone, nitrogen-containing crown ether and nitrogen-containing heterocycle, ethylenediaminetetraacetic acid, dimethylformamide and dimethyl sulfoxide complex; and W, Ir, Y, Mn, Ru, One or more of the highest valence state of the V, Ζη, and La elements and the oxide having a perovskite structure in the intermediate valence state.

The proton exchange membrane according to any one of claims 1 to 6, wherein the proton exchange membrane comprises 2 to 5 layers of a perfluoro ion exchange resin as a matrix; the thickness of the proton exchange membrane is 5-300 μηι, preferably 10-50 μηι.

The proton exchange membrane according to any one of claims 1 to 7, wherein the perfluoro ion exchange resin is a perfluoroolefin monomer, one or more functional group-containing perfluoroolefins The body is formed by copolymerization of one or more perfluoroolefin monomers containing a crosslinking site, or a mixture of the above copolymers, and has an EW value of from 600 to 1300, preferably from 700 to 1200.

The method of preparing a proton exchange membrane according to any one of claims 1 to 8, characterized in that the method comprises:

(2) forming a crosslinked network structure in the monolayer film obtained in the step (1);

(3) using the single layer film obtained in the steps (1) and/or (2) to obtain a single layer film composite with the step (2), and/or using the solution or the melt described in the step (1) in the step (2) Forming a single layer film on the obtained single layer film, so that the finally obtained composite film comprises 2-40 single layer films, wherein at least one single layer film contains surface modified auxiliary proton conductive material, and at least one single layer film contains The fibrous, at least one single layer film contains a high-valent metal compound.

10. The method according to claim 9, wherein the intersection network structure is the formula (1),

One or more of the structures shown in (11), (111), (IV), and (V):

Where R is methylene or all, n is 0-10

The method according to claim 9 or 10, wherein the method of forming the single layer film in the step (1) is casting, extrusion, hot pressing, spin coating, casting, screen printing, spraying, and dipping One or more; preferably, heat-treated at 30-300 ° C for 0.1-600 minutes, more preferably 100-200 ° C when cast, spin-coated, cast, screen printed, spray coated or impregnated. Heat treatment for 1-30 minutes.

The method according to any one of claims 9 to 11, wherein the composite method in the step (2) is a single layer film composite, a multilayer film and a single layer film composite, and a multilayer film and a multilayer film composite. And one or more of the methods of forming a single layer film directly on a single layer film or a multilayer film using a solution or a melt.

The method according to any one of claims 9 to 12, wherein the method of forming the cross-network structure shown in the formula (I) comprises: using heat, light, electron radiation, a daughter, an X-ray, a free radical initiator, and a crosslinked network structure formed by the action of heat, light, electron radiation, plasma, X-ray, or a free radical initiator in the presence of one or more crosslinking agents, Wherein the radical initiator is one or more of an organic peroxide and an azo initiator, preferably an organic oxide initiator, more preferably a perfluoroorganic peroxide initiator; The structure of the binder is one or more of the structures shown in formula (VI):

^X 2 ^R f7 ^X 3

( VI )

Wherein X ₂ and X ₃ are each independently Cl, Br or I; Rfv is perfluorodecyl or fluorochloroindolyl; and the method of forming the crosslinked network structure represented by formulas (II) and (III) comprises: Sulfonyl fluoride, sulfonyl chloride, sulfonyl bromide type resin reacted with ammonia, hydrazine, organic diamine or organic peroxide capable of releasing ammonia, hydrazine or organic diamine;

The method of forming the crosslinked network structure represented by the formula (IV) comprises: treating the perfluorosulfonic acid resin with chlorosulfonic acid;

The method for forming the crosslinked network structure represented by the formula (V) comprises: treating a nitrile group-containing perfluorosulfonic acid resin, a perfluorosulfonyl fluoride resin, a sulfonyl chloride resin, and a sulfonyl bromide resin by heat or acid One or more of them.

The method according to any one of claims 9 to 13, wherein the surface-modified auxiliary proton conductive substance comprises an oxide modified by an inorganic dopant, an orthophosphate, a polyphosphate, a polyacid, Polyacid salts, silicates, sulfates, selenites and arsenides, preferably oxides, orthophosphates, polycondensed phosphates, polyacids and polyacid salts, more preferably oxides, orthophosphates and polycondensates Phosphate; the inorganic dopants are Si0 ₂ , Zr0 ₂ , Ti0 ₂ , BP0 ₄ , Zr ₃ (P0 ₄ ) ₄ , Zr(HP0 ₄ ) ₂ , HZr ₂ (P0 ₄ ) ₃ , Ti(HP0 ₄ ) One or more of ₂ and Zr ₂ H(P ₃ O ₁₀ ) ₂ ;

The modified fiber is selected from one or more of fluorocarbon polymer fibers modified by a substance having an ion exchange function, such as polytetrafluoroethylene fiber, polyperfluoroethylene propylene fiber, and polyperfluoropropyl ethylene. a fiber having a diameter of 0.005 to 5 μm and a length of 0.03 to 3 mm; the substance having an ion exchange function is sulfur dioxide, sulfur trioxide, and a perfluorosulfonic acid monomer (A) and perfluorosulfonic acid having the following structure; One or more of acid monomer (B) and perfluorosulfonic acid monomer (C):

CF ₂ =CFO(CF ₂ †FO) _h (CF ₂ ) ₁ SO ₂ A

CF ₃ ( A )

(B) O

_CF2 = _CF0(CF J _{( C )} where h = 0-l, i= 1-5, A is F, Cl, Br, OH, oxymethyl or ONa; j = 0-1, k= 1-5 , B is methyl, H or ethyl; 1 = 1-5, 0 is 11, methyl or ethyl;

The high-valent metal compound is a nitrate, a sulfate, a carbonate, a phosphate, an acetate, and a complex of the highest and intermediate valence states of the W, Ir, Y, Mn, Ru, V, Zn, and La elements. Salt; the highest and intermediate valences of W, Ir, Y, Mn, Ru, V, Ζ, and La, cyclodextrin, crown ether, acetylacetone, nitrogen-containing crown ether, and nitrogen-containing heterocycle, ethylenediamine Tetraacetic acid, dimethylformamide and dimethyl sulfoxide complex; and the highest valence state and intermediate valence of W, Ir, Y, Mn, Ru, V, Ζ and La elements with perovskite structure One or more of the oxides.

The method according to any one of claims 9 to 14, wherein the perfluoro ion exchange resin is a perfluoroolefin monomer, one or more functional group-containing perfluoroolefin monomers, and One or more perfluoroolefin monomers containing a crosslinking site are copolymerized, or a mixture of the above copolymers, having an EW value of from 600 to 1300, preferably from 700 to 1200.

Use of a proton exchange membrane as claimed in any one of claims 1 to 8 or prepared by the method of any one of claims 9 to 15 in a proton exchange membrane fuel cell.