WO2011156934A1 - Proton exchange membrane, its preparing method and use - Google Patents
Proton exchange membrane, its preparing method and use Download PDFInfo
- Publication number
- WO2011156934A1 WO2011156934A1 PCT/CN2010/000892 CN2010000892W WO2011156934A1 WO 2011156934 A1 WO2011156934 A1 WO 2011156934A1 CN 2010000892 W CN2010000892 W CN 2010000892W WO 2011156934 A1 WO2011156934 A1 WO 2011156934A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- resin
- exchange membrane
- single layer
- proton exchange
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- 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.
- 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.
- 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.
- PTFE polytetrafluoroethylene
- 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.
- JP-A-6-231779 proposes another reinforcing method using fluororesin fibers.
- 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.
- 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.
- 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.
- 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%.
- 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.
- Proton exchange membranes for fuel cells need to meet the following requirements: Stable, high electrical conductivity, and high mechanical strength.
- Stable high electrical conductivity
- 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.
- 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 are provided.
- 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 are examples of 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.
- intersection network structure may be one or more of the structures shown by the formulas (1), (11), (111), (IV) and (V):
- G ⁇ PG 2 is CF 2 or O, respectively, and R f is a C chain;
- R is methylene or perfluoromethylene, n is 0-10
- 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 ⁇ m, preferably 0.05 to 2 ⁇ m, 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:
- A perfluorosulfonic acid monomer
- B perfluorosulfonic acid monomer
- C perfluorosulfonic acid monomer
- 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, ⁇ , and La elements.
- 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 ⁇ m, preferably from 10 to 50 ⁇ m.
- 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.
- the perfluoroolefin is selected from one or more of tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, hexafluoropropylene and vinylidene fluoride.
- the perfluoroolefin is tetrafluoroethylene.
- trifluoro of the functional group-containing perfluoroolefin monomer is selected from one or more of the structures shown in formulas (VII), (VIII) and (IX):
- 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 consist
- the perfluoroolefin monomer having a crosslinking site is selected from one or more of the structures represented by the following formulas ( ⁇ ) and (XI):
- 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:
- the finally obtained composite film comprises 2-40 single layer films, at least Single layer film
- 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 is provided.
- the steps (1) and (2) may be carried out simultaneously, or the step (1) may be performed first and then the step (2).
- 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.
- 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;
- step (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;
- crosslinked network structure is as shown in formulas (1), (11), (111),
- GPG 2 is CF 2 or O, respectively, and R f is a chain;
- R is methylene or perfluoromethylene, n 0-10
- 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).
- 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.
- the method of melt extrusion and hot pressing is as follows:
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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 ⁇ m, preferably from 0.05 to 2 ⁇ m; 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.
- 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):
- 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, ⁇ , and La elements , phosphate, acetate and combined double salt, W, Ir, Y, Mn, Ru, V, ⁇ , and La elements of the highest and intermediate valences of cyclodextrin, crown ether, acetylacetone, nitrogen-containing crown Ether and nitrogen-containing
- 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 ⁇ m, preferably 10 to 50 ⁇ m.
- 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.
- 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):
- 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 ⁇ group; X is selected from the group consisting of F, Cl, Br and I; Y, ⁇ 2 and ⁇ 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, Li
- the perfluoroolefin monomer having a crosslinking site is selected from one or more of the structures represented by the following formulas ( ⁇ ) and (XI):
- 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 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.
- 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.
- 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.
- 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.
- 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.
- 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
- Example 1 The present invention is further described in detail with reference to the preferred embodiments of the present invention.
- Example 1 The present invention is further described in detail with reference to the preferred embodiments of the present invention.
- 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 ⁇ m (the weight ratio to the resin is 3:100), and 5 wt% of propanol Aqueous solution.
- Example 2 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 ⁇ m, that is, the proton exchange membrane of the present invention, which is referred to as Al.
- Example 2 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 ⁇ m, that is, the proton exchange membrane of the present invention, which is referred to as Al.
- Example 2 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 ⁇ m, that is, the proton exchange
- 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 # ).
- EW 1200 perfluoro ion exchange resin and tetraphenyltin were extruded into a film of 20 ⁇ m 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 ⁇ m, which is the present invention.
- Proton exchange membrane denoted as ⁇ 2.
- This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
- 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 ⁇ m, that is, the proton exchange membrane of the present invention. Recorded as A3.
- Example 4
- This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
- a mixture of modified polyvinylidene fluoride fiber (diameter 5 ⁇ , length ⁇ , 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 ⁇ .
- 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 Example 5
- This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
- 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 0.8 ⁇ (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 ⁇ m (monolayer film 8#).
- Example 4 The resin of Example 4, ⁇ -mordenite powder having a particle size of 5 ⁇ m (the weight with the resin) was used.
- the above ionic membrane was again placed in the perfluoro ion exchange resin of the present example, yttrium-montmorillonite having a particle diameter of ⁇ (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)
- 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 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.
- This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
- the modified polytetrafluoroethylene fiber (diameter 15 ⁇ m, length ⁇ , mass ratio of resin to resin: 3:100) was mixed. After the mixture was uniformly mixed, a film having a thickness of 20 ⁇ m 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.
- a crosslinked three-layer perfluorosulfonic acid film having a thickness of 60 ⁇ m 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 ⁇ 6.
- This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
- 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 3 ⁇ (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 ⁇ 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.
- Example 8 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 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 Example 8
- This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
- a crosslinked three-layer doped perfluorosulfonic acid film of 60 ⁇ m 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 ⁇ 8.
- 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 ⁇ m 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#).
- EW 1200 perfluoro ion exchange resin and ethyl phosphate and tetraethyl orthosilicate gel-spun modified polytetrafluoroethylene fiber (diameter 0.05 ⁇ , 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.
- 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#).
- the crosslinked fiber-reinforced hexa-layer film having a thickness of 300 ⁇ m is obtained, which is the film of the present invention.
- This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
- 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 ⁇ m in diameter, 0.07 ⁇ m in length, and a total weight ratio of resin: 25:100) was added.
- Example 11 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 ⁇ 10.
- Example 11 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 ⁇ 10.
- Example 11 Example 11
- This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
- 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 8 ⁇ 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 ⁇ m (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 ⁇ m (weight ratio to resin of 1:1) and the ion-exchangeable fiber (CN101003588A) (diameter 15 ⁇ , 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 ⁇ m , a three-layer fiber-reinforced perfluorinated ion exchange membrane was obtained.
- Example 12 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 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 Example 12
- This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
- 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
- the exchange resin is mixed with Zr0 2 (weight ratio of resin to resin: 9:100) having a particle diameter of 0.01 ⁇ m, 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 ⁇ m in diameter, 3 ⁇ m 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 ⁇ m 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 ⁇ m, that is, the proton exchange membrane of the present invention, which is referred to as A13.
- Example 14
- 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 ⁇ m was added to the solution (the weight ratio to the resin was 6).
- a sulfur trioxide-modified polytetrafluoroethylene fiber (0.01 ⁇ m in diameter, 120 ⁇ m 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.
- Example 15 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 The proton exchange membrane of the invention is designated A14.
- 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 Comparative example 1
- This comparative example is used to illustrate the existing proton exchange membrane and its preparation method.
- silicic acid-modified polytetrafluoroethylene fiber (diameter 0.2 ⁇ , length 80 ⁇ , weight ratio of resin to resin: 7:100) was cast at 170 ° C for 60 min.
- 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.
- the test method for hydrogen permeation current is electrochemical method (Electrochemical and Solid-State Letters, vol. 10, Issue 5, B101-B104, 2007). Table 1
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
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
一种质子交换膜及其制备方法和应用 技术领域 Proton exchange membrane and preparation method and application thereof
本发明涉及一种质子交换膜及其制备方法和应用。 背景技术 The invention relates to a proton exchange membrane and a preparation method and application thereof. Background technique
质子交换膜燃料电池 ( proton exchange membrane fuel cell, PEMFC )是 一种通过电化学方式直接将化学能转化为电能的发电装置, 被认为是 21 世 纪首选的洁净、 高效的发电技术。 质子交换膜 ( proton exchange membrane, PEM )是质子交换膜燃料电池的关键材料。 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.
目前使用的全氟磺酸质子交换膜在较低温度下(不高于 8(TC )和较高的 湿度下具有良好的质子传导性, 但也存在很多不足, 例如尺寸稳定性差、 机 械强度不高、 化学稳定性差等。 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.
膜在不同的湿度下吸水率和因吸水而导致的尺寸膨胀不同, 当膜在不同 工作状况下变换时, 膜的尺寸也将因此发生变化, 如此反复最终将导致质子 交换膜的机械破损。 此外, 燃料电池的正极反应常常产生大量的氢氧自由基 和过氧化氢等具有强氧化性的物质,这些物质会进攻成膜树脂分子中的非氟 基团, 导致膜的化学降解、 破损或起泡。 此外, 高的工作温度可以大大提高 燃料电池催化剂的耐一氧化碳性,但是当全氟磺酸交换膜的工作温度高于 90 °C时, 由于膜的迅速失水导致膜的质子传导性急剧下降, 从而使燃料电池的 效率大大下降。 另外, 现有的全氟磺酸膜都有一定的氢气或甲醇渗透性, 尤 其是在直接甲醇燃料电池中, 甲醇渗透率十分大, 成为致命的问题。 因此, 如何提高全氟磺酸质子交换膜的强度、 尺寸稳定性及高温下的质子传导效 率, 降低工作介质的渗透性等是燃料电池工业所面临的重大课题。 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.
目前已经提出了一些方法来解决这些问题。如 JP-B-5-75835釆用全氟磺 酸树脂来浸渍聚四氟乙烯 (PTFE ) 制成的多孔介质来增强膜的强度。 然而, 这种 PTFE的多孔介质由于 PTFE材料相对较软, 增强作用不充分, 仍未能 彻底解决上述问题。 W. L. Gore公司开发的 Gore-Select系列复合膜液釆用多 孔特氟隆填充 Nafion离子导电液的方法 (US 5547551、 US 5635041和 US 5599614 ), 这种膜具有较高的质子导电性和较大的尺寸稳定性, 但在高温下 特氟隆蠕变很大, 导致性能下降。 JP-B-7-68377还提出过一种方法, 用质子 交换树脂填充聚烯烃制成的多孔介质, 但是其化学耐久性不足, 因而长期稳
定性方面存在问题; 并且由于不具备质子导电能力的多孔介质的加入, 使得 质子传导通路减少, 膜的质子交换能力下降。 此外, JP-A-6-231779 还提出 了另一种增强方法, 使用氟树脂纤维。 釆用原纤维形式的氟烃聚合物增强材 料的机械强度。 但这种方法必须加入相对大量的增强材料, 这种情况下, 薄 膜的加工趋于困难,并且很可能会发生膜电阻增大。 EP 0875524B1公开了一 种利用玻璃纤维无纺技术制备的玻璃纤维膜增强 Nafion膜的技术,在该专利 中同时提到了使用二氧化硅等氧化物。 不足的是该方法中无纺玻璃纤维布是 必须使用的基材,这将大大限制增强膜的使用范围。 US 6733914公开的将熔 融挤出的全氟磺酰氟型膜在氨水中浸泡形成磺酰亚胺交联结构的质子交换 膜, 这样处理的全氟磺酸膜具有好的机械强度和尺寸稳定性。 但是利用该方 法得到的膜是不均匀的膜, 因为氨气通过渗透的方法进入薄膜, 在渗透的过 程中氨气会和磺酰氟发生反应, 反应的磺酰氟将阻止氨气进一步向膜内部的 扩散,从而在膜的表面形成很高的交联密度,而膜的内部几乎没有发生交联。 表面很高的交联密度使得膜的电导率急剧下降。 CN 200710013624.7和 US 7259208公开的含有三嗪环交联结构的全氟磺酸膜同样具有较好的机械强度 和尺寸稳定性。 但是, 仅仅釆用化学键合交联的膜, 往往不能形成很高的交 联度, 对改善膜的性能有限, 使得该膜的性能仍不能达到使用的要求。 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.
为了改善全氟磺酸膜的高温质子传导行为, 向全氟磺酸交换膜中加入了 很多具有辅助质子传导功能的物质。选取的辅助质子传导物质粒子必须具有 如下特征: (1)粒子具有较好的保水能力, 也就是有较高的失水温度; (2)与 质子交换树脂具有较好的相溶性; (3)粒子具有一定的传导质子能力; (4)易 于获得纳米级粒子; (5)粒子结构稳定性好, 在吸、 脱水过程中不伴随明显的 结构变化; (6)有利于保持或提高质子交换膜的力学强度或物理尺寸稳定性。 通常釆用的无机保水粒子是 Si02、 Ti02、 Zr(HP04)2或 Zr02粒子, 杂多酸或 固体酸粒子,沸石族矿物粒子,蒙脱石等层型粘土矿物及其插层粘土矿物等。 例如 CN 1862857公开了向全氟磺酸树脂中加入 Si02等辅助质子传导物质可 以提高质子交换膜的高温导电性能。 J. Electrochem. Soc. (VI 54, 2007, P B288-B295)中描述了 Nafion树脂和磷酸锆复合成膜, 该膜在相对湿度小于 13%时仍然有很高的电导性。 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%.
不足的是, 简单加入上述物质常常使膜的机械性能劣化, 无法满足实际 操作、 安装的需要。 CN 200810138186.1公开了一种化学键合交联和纤维增 强并掺杂有辅助质子传导物质的多层全氟磺酸膜。该膜虽然使用了化学键合
交联和纤维多种手段进行改性, 膜的性能在以往的基础上有了很大的提高, 但是该膜仍然存在成膜树脂与纤维结合不牢等问题。 发明内容 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
用于燃料电池的质子交换膜需要满足如下要求: 稳定、 电导率高、 机械 强度高。 一般而言, 当离子交换能力升高时, 全氟聚合物的当量值下降(当 量值 EW值减小, 离子交换容量 IEC=1000/EW ) 同时膜的强度也降低。 膜 的气体渗透性也随之上升, 这会对燃料电池产生非常严重的影响。 因此, 制 备具有高离子交换能力, 同时具有好的机械力学强度和气密性, 同时还具有 好的稳定性的膜是燃料电池, 尤其是在汽车等运载工具上使用的燃料带吃实 用的关键。 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.
因此, 本发明的目的是克服现有技术的质子交换膜机械强度不高、 高温 传导性差和气密性差的缺点,提供一种在具有高离子交换能力的同时具有良 好的机械强度、高温传导性和气密性的质子交换膜以及该膜的制备方法和应 用。 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.
本发明提供了一种质子交换膜, 包括 2-40 层以全氟离子交换树脂为基 体的单层膜, 其中, 至少一层单层膜具有交联网状结构, 至少一层单层膜含 有表面修饰的辅助质子传导物质, 至少一层单层膜含有改性纤维, 至少一层 单层膜含有高价金属化合物。 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.
根据本发明提供的质子交换膜, 其中, 以 100重量份的全氟离子交换树 脂为基准,所述表面修饰的辅助质子传导物质的含量可以为 0.05-50重量份, 优选为 1-15重量份;所述改性纤维的含量可以为 0.5-50重量份,优选为 1-20 重量份;所述高价金属化合物的含量可以为 0.0001-5重量份,优选为 0.001-1 重量份。 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.
其中, 所述交联网状结构可以为式 (1 )、 (11 )、 (111 )、 ( IV ) 和 ( V )所 示结构中的一种或多种: Wherein, the intersection network structure may be one or more of the structures shown by the formulas (1), (11), (111), (IV) and (V):
( I )
其中 G^P G2分别为 CF2或 O, Rf为 C 链; (I) Wherein G^PG 2 is CF 2 or O, respectively, and R f is a C chain;
(II) (ΠΙ) (II) (ΠΙ)
R为亚甲基或全氟亚甲基, n为 0-10 R is methylene or perfluoromethylene, n is 0-10
, 其中, 所述表面修饰的 Where the surface modification
质包括被无机掺杂物修饰的氧化物、 正磷酸盐、缩聚磷酸盐、 多 多酸盐、 硅酸盐、 硫酸盐、 ***盐和砷化物, 优选为氧化物、 正磷酸盐、 缩聚磷酸 盐、 多酸和多酸盐, 更优选为氧化物、 正磷酸盐和缩聚磷酸盐; 所述无机掺 杂物为 Si02、 Zr02、 Ti02、 BP04、 Zr3(P04)4、 Zr(HP04)2、 HZr2(P04)3、 Ti(HP04)2、 和 Zr2H(P301())2中的一种或多种。 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 .
根据本发明提供的质子交换膜, 其中, 所述改性纤维选自被具有离子交 换功能的单体改性的氟碳聚合物纤维中的一种或多种, 如聚四氟乙烯纤维、 聚全氟乙丙烯纤维和聚全氟丙基乙烯基醚纤维。 纤维的直径可以为 0.005-5μηι, 优选为 0.05-2μηι; 长度可以为 0.03-3mm, 优选为 0.05-lmm。 所述具有离子交换功能的单体可以为二氧化硫、 三氧化硫, 以及结构如下的 全氟磺酸单体(A )、 全氟磺酸单体(B )和全氟磺酸单体(C ) 中的一种或 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
其中, h = 0-l, i= 1-5, 八为 、 Cl、 Br、 OH、 氧甲基( OCH3 )或 ONa; j = 0-l, k= 1-5, B为甲基(Me)、 H或乙基(Et); 1=1-5, D为 H、 甲基(Me) 或乙基(Et)。 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).
根据本发明提供的质子交换膜, 其中, 所述高价金属化合物可以为 W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元素的最高价态和中间价态的硝酸盐、 硫酸 盐、 碳酸盐、 磷酸盐、 醋酸盐和组合复盐, W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La 元素的最高价态和中间价态的环糊精、 冠醚、 乙酰丙酮、 含氮冠醚及含 氮杂环、 乙二胺四乙酸、 二甲基甲酰胺和二甲基亚砜络合物, 以及 W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元素的最高价态和中间价态的具有钙钛矿结构的 氧化物中的一种或多种。 其中, 所述 W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元 素的最高价态和中间价态的具有钙钛矿结构的氧化物包括但不限于如下化 合物: CexTi(1-x)02 (x = 0.25-0.4) 、 Ca06La027TiO3、 La(i-y)CeyMn03 (y = 0.1-0.4) 、 La07Ce015Ca0 15MnO3。 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 .
根据本发明提供的质子交换膜, 其中, 该质子交换膜优选地包括 2-20 层, 更优选为 2-5层以全氟离子交换树脂为基体的单层膜。 该质子交换膜的 厚度可以为 5-300μηι, 优选为 10-50μηι。 其中, 各层可以由一种全氟离子交 换树脂形成也可以由多种全氟离子交换树脂混合形成,各层可以都形成交联 结构也可以部分层不形成交联结构。 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.
所述全氟离子交换树脂是由全氟烯烃、 一种或多种含功能基团的全氟烯 单体和一种或多种含交联位点的全氟烯单体共聚形成的, 或者是上述共聚物 的混合物, 其 EW值可以为 600-1300, 优选为 700-1200。 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.
其中, 所述全氟烯烃选自: 四氟乙烯、 三氟氯乙烯、 三氟乙烯、 六氟丙 烯和偏氟乙烯中的一种或多种,优选地,所述全氟烯烃为四氟乙烯和 /或三氟 所述含功能基团的全氟烯单体选自式(VII)、 (VIII)和(IX)所示的结 构中的一种或多种:
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) (VII)
R。CF=CF(CF2)dY2 R. CF=CF(CF 2 ) d Y 2
(IX) (IX)
其中, a、 b、 c各自独立地为 0或 1, 但不同时为零; d为 0-5白 n为 0或 1; Rfl、 Re和 分别选自全氟垸基和氟氯垸基; X选自 F、 Cl、 Br和 I; Y2和 Y3各自独立地选自 S02M、 COOR3、 和 PO(OR4)(OR5), 其中: M选自 F、 Cl、 0R、 NRiR2; R选自甲基、 乙基、 丙基、 H、 Na、 Li、 K和铵根; R PR2分别选自 11、 甲基、 乙基和丙基; R3选自 H、 Na、 Li、 K、 铵根、 甲基、 乙基和丙基; R4和 R5分别选自 11、 Na、 Li、 K和铵根。 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.
所述的含交联位点的全氟烯单体选自如下式 (Χ)、 (XI)所示的结构中的 一种或多种: The perfluoroolefin monomer having a crosslinking site is selected from one or more of the structures represented by the following formulas (Χ) and (XI):
F2C^=CFRf4Y4 F 2 C^=CFRf 4 Y4
(X) (X)
Y5(CF2)a,(CFRf5)b,(CFRf6)c,O(CFCF2O)n,—— C=CF2 Y 5 (CF 2 ) a , (CFR f5 ) b , (CFR f6 ) c , O(CFCF 2 O) n , — C=CF 2
(XI) (XI)
其中, Y4和 Y5可以分别选自 Cl、 Br、 I和 CN; a,、 b,和 c,分别为 0或 1, 但 a,+b,+c,≠0; 选自 F、 Cl、 Br和 I; n,为 0或 1; Rf4、 Rf5和 Rf6各自 独立地选自全氟垸基。 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.
本发明还提供了上述质子交换膜的制备方法, 该方法包括: The invention also provides a preparation method of the above proton exchange membrane, the method comprising:
( 1 )使用含有全氟离子交换树脂的溶液或熔融物形成单层膜, 其中, 该溶液或熔融物还选择性地含有表面修饰的辅助质子传导物质、 改性纤维和 高价金属化合物中的一种或多种; (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)在步骤(1 ) 制得单层膜中形成交联网状结构; (2) forming a cross-linked network structure in the monolayer film obtained in the step (1);
(3)使用步骤(1 )和 /或(2)得到的单层膜与步骤(2)得到单层膜复
合, 和 /或使用步骤( 1 )所述的溶液或熔融物在步骤(2 )得到的单层膜上形 成单层膜, 使最终得到的复合膜包括 2-40 层单层膜, 其中至少一层单层膜 (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 OOSNM
含有表面修饰 HNI 的辅助质子传导物质, 至少一层单层膜含有改性纤维, 至少一 层单层膜含有高 OOSNM价金属化合物。 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.
根据本发明提供的方法, 其中, 步骤(1 )和(2 )可以同时进行, 也可 以先进行步骤( 1 ) 再进行步骤( 2 )。 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).
其中, 步骤(1 ) 中形成单层膜的方法为浇铸、 熔融挤出、 热压、 旋涂、 流延、 丝网印刷、 喷涂和浸渍中的一种或多种。 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.
优选地, 所述流延、 浇注、 丝网印刷、 旋涂、 喷涂或浸渍的方法如下: ( a )将全氟离子交换树脂, 作为增强物的纤维, 辅助质子传导物质, 交联剂, 酸或自由基引发剂和高价金属化合物中的一种或多种分散到溶剂中 形成混和物; 混合物中全氟离子交换树脂的固含量可以为 1-80重量%, 所用 的溶剂可以为二甲基甲酰胺、 二甲基乙酰胺、 甲基甲酰胺、 二甲基亚砜、 N- 甲基吡咯垸酮、 六甲基磷酸胺、 丙酮、 水、 乙醇、 甲醇、 丙醇、 异丙醇、 乙 二醇和丙三醇中的一种或多种; 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 )利用步骤(a ) 中制备溶液在平板上或已制备的单层或多层膜上通 过溶液流延、 溶液浇注、 丝网印刷、 旋涂、 喷涂或浸渍工艺成膜; 成膜时要 在 30-250°C的温度下热处理 0.01-600分钟,优选为在 100-200 °C下热处理 1-30 分钟; (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;
可以在成膜中或成膜后交联, 所述交联网状结构如式 (1 )、 (11)、 (111)、 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)和 (V)所示: (IV) and (V):
、「ι , "
ΐ ΧΑΛΛΛΛΛ ( J ) ΐ ΧΑΛΛΛΛΛ ( J )
其中, G P G2分别为 CF2或 O , Rf为 链; Wherein, GPG 2 is CF 2 or O, respectively, and R f is a chain;
(IV) (v)。 其中, 形成式 (I )所示的交联结构的方法包括热、 光、 电子辐射、 等 离子体、 X射线、 或自由基引发剂, 也可以在一种或多种交联剂存在时通过 热、 光、 电子辐射、 等离子体、 X射线、 或自由基引发剂的作用形成交联 构。 其中所使用的交联剂的结构如下式 (VI )所示。 (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).
X2Rf7X3 ( VI ) 其中, X2和 X3各自独立地为 CI, Br或 I; ¾7为全氟)^ X 2 R f7 X 3 ( VI ) wherein X 2 and X 3 are each independently CI, Br or I; 3⁄47 is perfluoro)^
优选地,所述的自由基引发剂为有机过氧化物或偶氮类引发剂;优选地, 引发剂为有机氧化物引发剂; 更优选地, 引发剂为全氟有机过氧化物。 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.
形成 (11)、 (III)交联结构的方法是: 利用磺酰氟、 磺酰氯、 磺酰溴型树脂 与氨、 肼、 有机二胺或能够经化学处理释放出氨、 肼、 有机二胺的物质反应 得到。 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.
所述的有机二胺为 C1-C10的垸基二胺或全氟垸基二胺, 所述的能够经 化学处理释放出氨、 肼、 有机二胺的物质包括但不限于氨, 肼、 有机二胺的 有机或无机酸酸盐、 尿素、 或胍。 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.
形成 (IV)交联结构的方法是全氟磺酸树脂利用氯磺酸处理得到。 The method of forming the (IV) crosslinked structure is obtained by treating a perfluorosulfonic acid resin with chlorosulfonic acid.
形成 (V)交联结构的方法是含腈基位点的全氟磺酸树脂或含腈基位点的 全氟磺酰氟树脂、 含磺酰氯树脂、 含磺酰溴树脂在热或酸的作用下形成。 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.
所述的酸为强的质子酸或路易斯酸; 其中质子酸选自 H2S04、 CF3S03H 和:¾?04; 路易斯酸选自 ZnCl2、 FeCl3、 A1C13、 有机锡、 有机锑和有机碲。 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.
优选地, 所述熔融挤出和热压的方法如下: Preferably, the method of melt extrusion and hot pressing is as follows:
( a )根据多层交联全氟离子交换膜中各层配方的需要制备适合的磺酰 氟、 磺酰氯、 磺酰溴树脂, 改性纤维、 表面修饰的辅助质子传导物质、 交联 剂、 酸或自由基引发剂和高价金属化合物中的一种或多种的混合物, 利用双
螺杆挤出机、 密炼机或开炼机在 200-28(TC混合; (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 )将步骤(a ) 混合好的树脂利用螺杆挤出机或平板硫化机成膜; 该方法也可以在成膜中或成膜后交联, 得到如上所述的交联单层膜。 根据本发明提供的方法, 其中, 步骤(3 ) 中复合的方式可以为单层膜 复合、 多层膜与单层膜复合、 多层膜与多层膜复合, 以及使用溶液或熔融物 在单层膜或多层膜上直接形成单层膜的方法中的一种或多种。 也就是说, 各 单层膜可以通过溶液或熔融物的浇铸、 挤出、 热压、 旋涂、 流延、 丝网印刷 工艺、 喷涂或浸渍工艺制成; 多层膜的制备是通过单层膜间复合, 多层膜与 单层膜间复合、 或多层膜与多层膜间复合, 也可以直接在已制得的单层膜或 多层膜上利用溶液或熔融物的浇铸、 挤出、 热压、 旋涂、 流延、 丝网印刷工 艺、 喷涂或浸渍工艺制备。 (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.
优选地, 在复合前可以将制得的单层膜先转化为酸型, 也可先与其它的 膜复合后再转化为酸型。 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.
也可以将树脂挤出形成单层膜后, 水解转化为氢型膜, 再将该膜浸泡在 高价金属化合物的溶液中达到形成物理键合交联的目的。 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.
优选地, 步骤(2 ) 中所述的交联是指利用上述的各种交联手段交联。 根据本发明提供的方法, 其中, 所述表面修饰的辅助质子传导物质包括 被无机掺杂物修饰的氧化物、 正磷酸盐、 缩聚磷酸盐、 多酸、 多酸盐、 硅酸 盐、 硫酸盐、 ***盐和砷化物, 优选为氧化物、 正磷酸盐、 缩聚磷酸盐、 多酸和多酸盐, 更优选为氧化物、 正磷酸盐和缩聚磷酸盐; 所述无机掺杂物 为 Si02、 Zr02、 Ti02、 BP04、 Zr3(P04)4、 Zr(HP04)2、 HZr2(P04)3、 Ti(HP04)2、 和 Zr2H(P301())2中的一种或多种。 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 .
上述辅助质子传导物质的表面可通过共凝胶、共沉淀或共水热解等方法 修饰上具有离子交换功能或酸性的基团。例如,在本发明的一些实施方式中, 具体的制备方法可以为: 将磷酸甲酯或硫酸甲酯和硅酸乙酯或氯化氧锆或钛 酸酯等在碱性条件下凝胶得到表面修饰的辅助质子传导物质。表面修饰的辅 助质子传导物质可以和高价金属化合物及树脂中酸***换基团形成物理交 联。 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.
根据本发明提供的方法, 其中, 所述改性纤维选自被具有离子交换功能 的物质改性的氟碳聚合物纤维中的一种或多种, 如聚四氟乙烯纤维、 聚全氟 乙丙烯纤维和聚全氟丙基乙烯基醚纤维。 纤维的直径可以为 0.005-5μηι, 优 选为 0.05-2μηι; 长度可以为 0.03-3mm, 优选为 0.05-lmm。 具体的改性方法 可以为: 将纤维与具有离子交换功能的单体在热、 光、 电子辐射、 等离子体、
X射线、 自由基引发剂等手段的作用下发生反应, 然后将改性后的纤维在酸 或碱的作用下产生离子交换基团。 其中, 所述具有离子交换功能的单体可以 为二氧化硫、 三氧化硫, 以及结构如下的全氟磺酸单体(A)、 全氟磺酸单体 (B)和全氟磺酸单体(C) 中的一种或多种: 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):
其中, h = 0-l, i=l-5, A为 F、 Cl、 Br、 OH、 氧甲基(OCH3)或 ONa; j = 0-1, k= 1-5, B为甲基(Me) 、 H或乙基( Et ) ; 1=1-5, D为 H、 甲 基(Me)或乙基(Et) 。 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).
作为增强物的纤维优选具有离子交换能力或表面具有保水基团的纤维。 如 CN101003588A中公开的具有离子交换功能的纤维, 表面硅酸化、 磺化、 硫酸化、 磷酸化、 亲水改性的氟碳聚合物纤维, 表面进行硅酸化、 磺化、 硫 一、 根据本发明提供的质子交换膜,一其中, 所述高价金属化合物可以为 W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元素的最高价态和中间价态的硝酸盐、 硫酸 盐、 碳酸盐、 磷酸盐、 醋酸盐和组合复盐, W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元素的最高价态和中间价态的环糊精、 冠醚、 乙酰丙酮、 含氮冠醚及含 氮杂环、 乙二胺四乙酸、 二甲基甲酰胺和二甲基亚砜络合物, 以及 W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元素的最高价态和中间价态的具有钙钛矿结构的 氧化物中的一种或多种。 其中, 所述 W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元 素的最高价态和中间价态的具有钙钛矿结构的氧化物包括但不限于如下化 合物: CexTi(1-x)02 (x = 0.25-0.4) 、 Ca。6La。27Ti03、 La(1-y)CeyMn03 (y = 0.1-0.4) 、 La0.7Ce015Ca015MnO3。 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 .
根据本发明提供的质子交换膜, 其中, 该质子交换膜优选地包括 2-5层 以全氟离子交换树脂为基体的单层膜。该质子交换膜的厚度可以为 5-300μηι, 优选为 10-50μηι。
根据本发明提供的质子交换膜, 其中, 所述全氟离子交换树脂是由全氟 烯烃单体、 一种或多种含功能基团的全氟烯单体和一种或多种含交联位点的 全氟烯单体共聚形成的, 或者是上述共聚物的混合物, 其 EW值可以为 600-1300, 优选为 700-1200。 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.
其中, 所述全氟烯烃单体选自: 四氟乙烯、 三氟氯乙烯、 三氟乙烯、 六 氟丙烯和偏氟乙烯中的一种或多种, 优选地, 所述全氟烯烃单体为四氟乙烯 所述 ^功能基团的全氟烯单体选自式(VII)、 (VIII)和(IX)所示的结 构中的一种或多种:
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) (VII)
R。CF=CF(CF2)dY2 R. CF=CF(CF 2 ) d Y 2
(IX) (IX)
其中, a、 b、 c各自独立地为 0或 1, 但不同时为零; d为 0-5的整数; n为 0或 1; Rfl、 Re和 分别选自全氟垸基和氟氯垸基; X选自 F、 Cl、 Br和 I; Y、 Υ2和 Υ3各自独立地选自 S02M、 COOR3、 和 PO(OR4)(OR5), 其中: M选自 F、 Cl、 OR、 NRiR2; R选自甲基、 乙基、 丙基、 H、 Na、 Li、 K和铵根; 和 分别选自 11、 甲基、 乙基和丙基; R3选自 H、 Na、 Li、 K、 铵根、 甲基、 乙基和丙基; R4和 R5分别选自 11、 Na、 Li、 K和铵根。 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.
所述的含交联位点的全氟烯单体选自如下式 (Χ)、 (XI)所示的结构中的 一种或多种: The perfluoroolefin monomer having a crosslinking site is selected from one or more of the structures represented by the following formulas (Χ) and (XI):
F2C^=CFRf4Y4 F 2 C^=CFRf 4 Y4
(XI)
其中, Y4和 Y5可以分别选自 Cl、 Br、 I和 CN; a,、 b,和 c,分别为 0或 1 , 但 a,+b,+c,≠0; 选自 F、 Cl、 Br和 I; n,为 0或 1 ; Rf4、 Rf5和 Rf6各自 独立地选自全氟垸基。 (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.
根据本发明提供的方法, 其中, 所述全氟离子交换树脂是由全氟烯烃单 体、 一种或多种含功能基团的全氟烯单体以及一种或多种含交联位点的全氟 烯单体共聚形成的,或者是上述共聚物的混合物,其環值可以为 600-1300, 优选为 700-1200。 其中, 所述全氟烯烃、 含功能基团的全氟烯单体和含交联 位点的全氟烯单体的定义如前文所述。 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.
本发明还提供了本发明的质子交换膜或者根据本发明提供的制备方法 制备的质子交换膜在质子交换膜燃料电池中的应用。 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.
在本发明提供的质子交换膜使用增强纤维、 化学键合交联和高价金属化 合物与酸***换基团形成的物理键合交联的方式在改善质子传导性能的同 时极大提高了离子膜的机械强度。特别是釆用了高价金属化合物与酸***换 基团间的物理键合交联具有高的交联度而且能够实现层层间的交联, 再加上 如酰胺化学键合交联中的酰胺基团、 三嗪环键合交联中的三嗪基团还能够和 高价金属化合物形成配位, 这样就进一步改善了膜的性能。 尤其要强调的是 表面被具有酸***换基团修饰的纤维能够通过物理键合和高价金属化合物 及成膜树脂形成物理键合交联。这样就解决了传统上纤维增强全氟磺酸膜的 气体渗透率高的问题。这可能的原因 1.表面功能化的纤维与成膜树脂结合力 提高了; 2.由于纤维的表面具有功能基团可以和金属化合物形成键合结构, 进一步减小了树脂和纤维间的空隙。 以往加入辅助质子传导物质的膜尽管高 温质子传导性有所提高, 但机械力学性质下降比较明显。 在我们的发明中由 于上面的交联改性, 同时又由于某些辅助质子传导物质表面被活性基团修 饰, 可以和高价金属化合物形成物理交联结构。 从而保证了它们不仅仅能够 对膜的质子传导有贡献, 而且对膜的机械力学性质也有很大贡献。 因此, 本 发明提供的质子交换膜在具有高离子交换能力的同时具有 好的机械强度、 高温传导性和气密性。 实施发明的最佳方式 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
下面结合具体实施方式对本发明进行进一步的详细描述, 给出的实施例 仅为了阐明本发明, 而不是为了限制本发明的范围。
实施例 1 The present invention is further described in detail with reference to the preferred embodiments of the present invention. Example 1
本实施例用于说明本发明提供的质子交换膜及其制备方法 This embodiment is used to illustrate the proton exchange membrane provided by the present invention and a preparation method thereof
将重复单元为 Will repeat the unit as
子交换树脂和碳酸亚铈(与树脂的重量比为: 1: 100 )、 粒度为 0.005μηι的 Zr(HP04)2 (与树脂的重量比为 3:100 ) 制成 5重量%的丙醇水溶液。 然后配 制浓度为 5重量%的过氧化全氟丙二酰的 DMF溶液, 向上述溶液中加入表 CF2=CFO(CF2CFO)h(CF2)1S02A 面被 CF3 (其中, h=0, i=2, A=OH )改性的聚四 氟乙烯纤维 (直径 Ιμηι, 长度 50μηι, 与树脂的重量比为 7: 100 ), 后浇铸 到水平放置的聚四氟乙烯铸模内,经过 80°C真空干燥 12小时后,将膜剥离, 得到单层全氟磺酸交联为第 (I )种的掺杂离子膜(单层膜 1 # )。 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.
将两张上述单层膜 1 #叠置进行热压, 制得厚度为 30μηι的铈离子键合 双层纤维增强全氟交联离子膜, 即本发明的质子交换膜, 记作 Al。 实施例 2 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
本实施例用于说明本发明提供的质子交换膜及其制备方法 This embodiment is used to illustrate the proton exchange membrane provided by the present invention and a preparation method thereof
— [-CF CFr]7-CF广 CF—— 将重复单元为 OCF2CF2CF2SG2f , EW=800的全氟离 子交换树脂和粒度为 0.03μηι的 Si02 (与树脂的重量比为 5:100 ), 表面被 CF2=CFO(CF2CFO)h(CF2)1S02A — [-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
CF3 (其中 h=0, i=4, A=ONa )修饰的聚全氟乙 丙烯纤维(直径 0.05μηι长度 5um, 与树脂的重量比为 1:40 ) 混合挤出得到 厚度为 30μηι的膜。 将该膜在 150°C真空烘箱中放置 1小时后浸泡于 NH4C1 的 DMF溶液中 5小时。 将浸泡后的膜在 200°C下置于三乙胺中 2小时, 得 交联的膜。 将得到的膜依次用 KOH溶液、 盐酸溶液处理, 得到交联结构为
第 (II )种的离子交换膜(单层膜 2 # )。 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 # ).
将重复单元为 Will repeat the unit as
CF。 CF.
EW=1200的全氟离子交换树脂与四苯基锡用双螺杆挤出机挤出成 20μηι的 膜, 然后将该膜加热到 230°C保持 10小时得交联结构为第(V )种的膜。 将 该膜依次用 LiOH和硝酸溶液处理得到交联离子膜(单层膜 3 # )。 将单层膜 2 #和3#重叠、 热压, 并浸泡在硝酸锰溶液中 1小时, 得到厚度为 50μηι的 锰离子键合的交联两层掺杂纤维增强离子交换膜, 即本发明的质子交换膜, 记作 Α2。 实施例 3 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
本实施例用于说明本发明提供的质子交换膜及其制备方法。 This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
将重复单元为 Will repeat the unit as
-CF2CF2 CF2CF~["CF2CF2+CF2CF—— -CF 2 CF 2 CF 2 CF~["CF 2 CF 2 +CF 2 CF -
OCFpCF Br OCF2CFOCF2CF2S03H OCFpCF Br OCF 2 CFOCF 2 CF 2 S0 3 H
CF, , EW=1100的全氟离 子交换树脂、 醋酸镧 (与树脂的重量比为 0.001: 100 )和 H3PW1204o (与树 脂的重量比为 1:100 ) 配制成树脂含量为 3重量%的溶液 (溶剂为水:乙醇 =1:1(重量比)), 浇铸成膜, 然后将此膜经 50KGy辐射交联得到 ΙΟμηι交联结 构为第 (I )种的离子膜(单层膜 4 # )。 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 # ).
-重复单元为
EW=940的全 氟离子交换树脂、 Ce(III)-DMSO络合物 (与树脂的重量比为 0.1:100 )和 H3PWi204o (与树脂的重量比为 20:100 ) 配制成树脂含量为 30重量%的
CF2=CFO(CF2CFO)h(CF2)1S02A - 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溶液, 向该溶液中加入表面被
h=l , i=2, A=F ) 改性的聚四氟乙烯纤维(直径 0.2μηι, 长度 80μηι, 与聚合 物的重量比为 7:100 ),通过浇铸的方法在 170°C , 60分钟制得 ΙΟμηι的膜(单 层膜 5 # )。 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.
将单层膜按照 4 # -4 # -5 #的顺序叠放进行热压,得到厚度为 30μηι的高 价金属离子键合纤维增强三层交联掺杂离子膜, 即本发明的质子交换膜, 记 作 A3。 实施例 4 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
本实施例用于说明本发明提供的质子交换膜及其制备方法。 This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
子交换树脂、 HP04)2 (与树脂的重量比为 0.1: 100 )、 18-冠 -6络合的 Υ(ΠΙ)化合物(与树
Sub-exchange resin, HP0 4 ) 2 (weight ratio to resin: 0.1: 100), 18-crown-6 complexed ruthenium (ΠΙ) compound (with tree
改性的聚偏氟乙烯纤维 (直径 5μηι, 长度 ΙΟΟμηι, 与树脂的重量比为 1 :5 ) 的混合物于 DMF中配制成树脂含量为 20重量%的溶液, 浇铸成膜, 成膜时 间为 1小时,然后在 120°C下处理 10分钟得到厚度为 ΙΟμηι的纤维增强的单 层全氟磺酸离子膜。 将该离子交换膜浸渍于氯磺酸中得交联结构为式 (IV ) 的膜(单层膜 6# )。 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).
将单层膜 6#置于实施例 1的树脂和 0.1%过氧化全氟月桂二酰、 5%1,4- 二碘八氟丁垸的 DMF溶液中浸泡 0.5小时, 取出后干燥, 重复上述步骤; 然后将膜在 120°C下处理 300分钟,得到单层膜 7#。再将单层膜 7#与单层膜 4#热压, 得到本发明的质子交换膜, 记作 A4。 实施例 5 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
本实施例用于说明本发明提供的质子交换膜及其制备方法。
CF2CF2 7CF2CF— j-CF2CF2†CF2CF' 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 OCF2CFOCF2CF2S〇3H 将重复单元为 CF3 ,CI OCF 2 CFOCF 2 CF 2 S〇 3 H The repeating unit is CF 3 ,
EW=1300的全氟离子交换树脂与乙酰丙酮 -Ce(III)络合物 (与树脂的重量比 为 0.01:100 )、 表面硫酸改性的粒径为 0.8μηι的 Zr02 (与树脂的重量比为 2:100 )、 偶氮二异戊腈(与树脂的重量比为 0.1 :100 )、 1,4-二碘八氟丁垸(与 树脂的重量比为 5:100 )溶解于 DMF中配制成树脂含量为 20重量%的溶液, 浇铸成膜, 成膜温度为 170°C , 时间为 60分钟, 制得厚度为 20μηι的膜(单 层膜 8# )。 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#).
使用实施例 4中的树脂、 粒径为 5μηι的 Η-丝光沸石粉末(与树脂的重 The resin of Example 4, Η-mordenite powder having a particle size of 5 μm (the weight with the resin) was used.
0 量比为 1:1 )和表面被0^0^^172)1^^ ( 1=1 , D=Me ) 改性的聚四氟 乙烯-乙烯纤维(直径 5μηι, 长度 ΙΟΟμηι, 与树脂的重量比为 1:100 )混合于 Ν-甲基吡咯垸酮中, 配制成树脂含量为 15重量%的溶液, 将该溶液在单层 膜 8#的两个表面旋涂形成厚度为 30μηι的膜,制备得到三层全氟离子交换膜 (多层膜 1# )。 将多层膜 1#在69°〇下处理 2.4小时, 得到金属离子键合三层 的交联结构为式 (I ) 的全氟磺酸膜。 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.
将上述离子膜再次置于由本实施例的全氟离子交换树脂、 粒径为 ΙΟμηι 的 Η-蒙脱石(与树脂的重量比为 0.5:100 )、 偶氮二异戊腈(与树脂的重量比 为 0.1:100 )、 1,4-二碘八氟丁垸(与树脂的重量比为 5:100 ) 和 DMF-Ce(m) 络合物 (与树脂的重量比为 0.02: 100 ) 溶解于 DMF中制得的树脂含量为 25 重量%的溶液中, 浸泡 0.5小时后将膜取出干燥, 重复上述步骤, 然后将膜 在 120°C下处理 300分钟, 得到金属离子键合五层纤维增强全氟磺酸交联离 子膜(多层膜 2# )。 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#).
将多层膜 1#和2#进行热压, 制得金属离子键合的十层纤维增强全氟磺 酸交联离子掺杂膜, 即本发明的质子交换膜, 记作 A5。 实施例 6 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
本实施例用于说明本发明提供的质子交换膜及其制备方法。 This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
将重复单元为
, EW=1300的全氟 离子交换树脂和
(y=0.5) , 与树脂的重量比为 0.01: 100)分 散于六甲基磷酸胺形成 29%的树脂溶液, 然后加入粒径为 0.7μηι的 Η-蒙脱 石 (与树脂的重量比为 10:100)和在等离子体作用下经全氟磺酸单体( I )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
CF2=CFO(CF2CFO) (CF2) S02F CF 2 =CFO(CF 2 CFO) (CF 2 ) S0 2 F
改性的聚四氟乙烯纤维(直径 15μηι,长度 ΙΟΟμηι,与树脂的质量比为 3:100) 混合。混合均匀后,通过真空喷涂方法得到厚度为 20μηι的膜。将该膜在 230°C 下处理 100min。 得到交联结构为式 (I) 的单层全氟磺酸膜(单层膜 9#)。 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.
在单层膜 9#的两个表面再次通过喷涂工艺方法,制得厚度为 60μηι的交 联的三层全氟磺酸膜,再在其两个表面热压单层膜 9#, 制得纤维增强交联五 层全氟磺酸掺杂膜, 即本发明的质子交换膜, 记作 Α6。 实施例 7 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
本实施例用于说明本发明提供的质子交换膜及其制备方法。 This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
将重复单元为 Will repeat the unit as
—— |~CF2CF2 CF2CF~["CF2CF2+6CF2CF—— —— |~CF 2 CF 2 CF 2 CF~["CF 2 CF 2 + 6 CF 2 CF -
OCF2Br OCF2CFOCF2CF2CF2S03H OCF 2 Br OCF 2 CFOCF 2 CF 2 CF 2 S0 3 H
CF3 , EW=1300的全 氟离子交换树脂和 La(OH)3(与树脂的重量比为: 0.5:100)、过氧化苯甲酰(与 树脂的重量比为 0.1:100)、 1,14-二碘二十氟十垸(与树脂的重量比为 5:100) 溶解于二甲基亚砜(树脂含量为 35重量%) 中, 然后加入聚四氟乙烯纤维 (与树脂的重量比为 2:100)及表面被 W离子交换的具有离子交换功能的纤 维(与树脂的重量比为 1 :5 ), 再和粒径为 3μηι的 Ti02 (与树脂的重量比为: 15:100) 混合, 浇铸成膜, 成膜温度是 160°C, 时间为 3分钟。 得到交联的 30μηι掺杂纤维增强全氟磺酸膜。 (单层膜 10#)。
将单层膜 10#置于由本实施例的树脂、沸石(与树脂的重量比为 0.4: 100 ) 和过氧化苯甲酰(与树脂的重量比为 0.1 :100 )、 1,14-二碘二十氟十垸(与树 脂的重量比为 5:100 )的二甲基亚砜溶液(树脂含量为 35重量%)中浸泡 0.5 小时, 将膜取出干燥, 重复上述步骤, 然后将膜在 120°C下处理 300分钟, 得到三层全氟磺酸交联掺杂离子膜(多层膜 3# )。 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#).
将三张多层膜 3#叠置进行热压,制得增强的九层纤维增强全氟磺酸交联 掺杂离子膜, 即本发明的质子交换膜, 记作 A7。 实施例 8 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
本实施例用于说明本发明提供的质子交换膜及其制备方法。 This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
将重复单元为 Will repeat the unit as
—— [~CF2CF24 CF2CF~["CF2CF2+2CF2CF—— —— [~CF 2 CF 2 4 CF 2 CF~["CF 2 CF 2 + 2 CF 2 CF -
OCF2CF2CF2l OCF2CFOCF2CF2CF2SO3H OCF 2 CF 2 CF 2 l OCF2CFOCF2CF2CF2SO3H
CF3 , EW=1250 的全氟离子交换树脂、 吡啶 -Ru络合物溶液(与树脂的重量比为 0.63:100 ) 和 CsH2P04 (与树脂的重量比为 20:100 )混合, 然后溶解于六甲基磷酸胺中 得到树脂含量为 30重量%的溶液, 向该溶液中加入聚全氟乙丙烯纤维(直 径 30μηι长度 3mm, 与树脂的重量比为 0.01:100 ), 浇铸成膜, 得到厚度为 ΙΟμηι的膜。 将该膜在 230°C下处理 100分钟, 得到交联的单层纤维增强掺 杂全氟磺酸膜(单层膜 11# )。 其中, 所用的聚全氟乙丙烯纤维在电子辐射作 用下经全氟羧酸单体(II ) 改性: 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 CF = CFO(CF CFO) ( ¥^CQ 2 H
( II ) 。 (II).
使用形成单层膜 11#的溶液在单层膜 11#的两个表面通过喷涂方法, 制 得 60μηι的交联的三层掺杂全氟磺酸膜。 在该三层膜的两个表面热压单层膜 11#, 制得交联五层纤维增强掺杂全氟磺酸膜, 即本发明的质子交换膜, 记 作 Α8。 实施例 9
本实施例用于说明本发明提供的质子交换膜及其制备方法 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
子交换树脂和粒径为 0.03μηι的 Si02 (与树脂的重量比为 5:100 )在 270°C下 挤出成膜。 将该膜浸泡于 10%NH3的 DMF溶液中 5小时。 在 200°C下得到 第(II)种交联结构的膜。 将该膜用碱液, 酸液处理后浸泡在乙酰丙酮 -lr(m) 的 DMF溶液(浓度为 0.05重量%) 中得到金属离子键合的交联膜(单层膜 12#)。 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#).
将重复单元结构为 Will repeat the unit structure as
-CF-CF2-]-CF ■CF— •CF2" 3: CF--CF-CF 2 -]-CF ■CF— •CF 2 " 3 : CF-
5.5 5.5
0CF CF CF S0J OCF2Cj;FOCF2CF2CN 0CF CF CF S0J OCF 2 Cj;FOCF 2 CF 2 CN
CF CF
, EW=1200 的全氟离子交换树脂与磷酸乙酯与正硅酸乙酯凝胶抽丝的改性聚四氟乙烯 纤维(直径 0.05μηι, 长度 5um, 与树脂的重量比为 1:40) 和四苯基锡 (与 树脂的重量比为 0.1:100)用双螺杆挤出机混合,热压成膜,将膜加热到 230°C 保持 10小时得到第 (V)种交联结构的膜。 将该膜置于 35重量%的水合肼 中 10小时, 取出后在 280°C下加热 5小时得到同时有第(V)种交联结构和 第(III)种交联结构的膜, 该膜用碱液, 酸液处理后将膜浸泡在硝酸钌溶液 (浓度为 0.5重量%)中 2小时,得到钌离子键合的掺杂交联膜 (单层膜 13#)。 , 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#).
按照单层膜 12#-单层膜 13#-实施例 8的膜 A8-实施例 5的膜 A5的顺序 叠放热压得到厚度为 300μηι的交联纤维增强十六层膜, 即本发明的质子交 换膜, 记作 Α9。
实施例 10 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
本实施例用于说明本发明提供的质子交换膜及其制备方法。 This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
, EW=1300的全氟离 子交换树脂(两者的重量比为 1:0.2 )与含氮冠醚 -Ce络合物(与树脂的总重 量之比为 1:100 )、 磷酸改性的粒径为 10nm的 Zr02 (与树脂的总重量之比为 2:100 )和偶氮二异戊腈(与树脂的总重量之比为 0.1:100 )混合,溶解于 DMF 中配制成树脂总含量为 20重量%的溶液, 加入在光作用下经三氧化硫改性 的聚全氟丙基乙烯基醚纤维(直径 0.005μηι, 长度 0.07微米, 与树脂的总重 量之比为 25:100 ), 浇铸成膜, 140°C加热得到厚度为 50μηι的含有第(I )种 交联结构的单层全氟磺酸膜, 再将该膜放于氯磺酸中得到同时含有第 (I ) 种和第 (IV )种交联结构的膜(单层膜 14# )。 , 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#).
将单层膜 14#与实施例 2制得的膜 Α2热压, 制得金属离子键合的五层 全氟磺酸纤维增强交联离子膜, 即本发明的质子交换膜, 记作 Α10。 实施例 11 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
本实施例用于说明本发明提供的质子交换膜及其制备方法。 This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
, EW=1200的全氟离子交换树脂、 Mn(OH)3 (与树脂的重量比为 2:100 ) 与 三苯基氢氧化锡 (与树脂的重量比为 0.1:100 )及粒径为 8μηι的 Zr02 (与树 脂的重量比为 2:100 ), 分散于 DMF中, 形成树脂含量为 30重量%的溶液, 浇铸成膜, 并在 170°C下处理 60min制得厚度为 20μηι的具有第 (V )种交 联结构的膜(单层膜 15# )。 , 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#).
使用实施例 4中的树脂和粒径为 5μηι的 Η-丝光沸石粉末(与树脂的重 量比为 1:1 )和被钛离子交换的具有离子交换功能的纤维(CN101003588A ) (直径 15μηι, 长度 20mm, 与树脂的重量比为 0.5:5 )混合于 N-甲基吡咯垸 酮中, 形成树脂含量为 27重量%的溶液, 在单层膜 15#的两个表面旋涂形成 厚度为 30μηι的膜, 得到三层纤维增强全氟离子交换膜。 将该膜在 190 °C下 处理 2.4小时, 得到锰离子键合的三层交联纤维增强全氟磺酸膜, 即本发明 的质子交换膜, 记作 All。 实施例 12 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
本实施例用于说明本发明提供的质子交换膜及其制备方法。 This embodiment is for explaining the proton exchange membrane provided by the present invention and a preparation method thereof.
将重复单元为 Will repeat the unit as
的全氟离子交换树脂与粒径为 0.02μηι的 Ή02 (与树脂的重量比为 3: 100 )、 被 Ti02改性的聚四氟乙烯纤维(直径 0.01微米, 长度 120微米, 与树脂的 重量比为 5:100 )混合用熔融挤出的方法制备单层膜,然后将该膜在 280°C下 处理 3个小时得到交联结构为式 II的单层膜 16#。 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.
在单层膜 16#的两个表面分别叠放一层实施例 3 制得的膜 A3 , 并在
120°C下热压处理 3分钟, 然后水解酸化得到四层交联全氟磺酸纤维增强膜, 即本发明的质子交换膜, 记作 A12。 实施例 13 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
本实施例用于 This embodiment is used for
将重复单元为
交换树 脂与粒径 0.01微米的 Zr02 (与树脂的重量比为 9:100 )、 环糊精 -W(III)络合 物 (与树脂的重量比为 0.034:100 ) 混合后分散于 N-甲基吡咯垸酮中形成固 含量为 30重量%的分散液, 再将经过二氧化硫改性的聚四氟乙烯纤维(直 径 0.5微米,长度为 3亳米, 与树脂的重量比为 2:100 ) 混合于上述溶液中,在 190°C浇铸成膜 (单层膜 17#)。 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#).
上述全氟离子交换树脂同重复单元为 The above perfluoro ion exchange resin has the same repeating unit
的全氟离子交换树脂 按重量比为 1:5的比例混合后分散于 DMSO中, 形成树脂总含量为 20重量 %的溶液, 向该溶液中加入粒径为 0.05微米的 Zr3(P04)4 (与树脂的重量比为 12:100 ), 再加入有机锑催化剂后通过流延法成膜, 并使膜在 230°C下形成三 嗪交联环, 得到单层膜 18#。 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#.
将两层单层膜 17#和三层单层膜 18#交替叠放热压复合得到厚度为 50微米 的五层膜, 即本发明的质子交换膜, 记作 A13。 实施例 14 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
本实施例用于说明本发明提供的质子交换膜及其制备方法
将重复单元为
EW=900 的全: 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:
:子交换 脂与重复单元为 : Sub-exchange grease and repeat unit are
氟离子交换树脂按照重量比为 6: 1混合后分散于 DMSO中,形成树脂总含量 为 35重量%的溶液, 再向该溶液中加入粒径 0.01微米的 Zr02 (与树脂的重 量比为 6: 100 )和三氧化硫改性的聚四氟乙烯纤维(直径为 0.01微米, 长度 为 120微米, 与树脂的重量比为 3: 100 ), 通过流延法制备单层膜, 然后将该 膜 50KGy辐射交联得到交联结构为第 (V )种的单层膜 19#。 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.
在单层膜 19#的两个表面分别叠放实施例 3制得的膜 A3 , 在 120°C热压 处理 3分钟, 然后水解酸化得到七层交联全氟磺酸纤维增强膜, 即本发明的 质子交换膜, 记作 A14。 实施例 15 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
本实施例用于说明本发明提供的质子交换膜及其制备方法 This embodiment is used to illustrate the proton exchange membrane provided by the present invention and a preparation method thereof
将重复单元为
的全氟离 子交换树脂与粒径为 0.02微米的 Si02 (与树脂的重量比为 3: 100 ), 和 S02 改性的聚全氟丙烯乙烯基醚纤维(直径 0.01微米, 长度 120微米, 与树脂的 重量比为 5: 100 )混合用熔融挤出的方法制备单层膜,然后将该膜在 250°C下 处理 3小时得到交联结构为式 (I ) 的单层膜 20#。 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).
在单层膜 20#的两个表面分别叠放实施例 3制得的膜 A3 , 在 120°C热压 处理 3分钟, 然后水解酸化得到七层交联全氟磺酸纤维增强膜, 即本发明的 质子交换膜, 记作 A15。 对比例 1 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
本对比例用于说明现有的质子交换膜及其制备方法。 This comparative example is used to illustrate the existing proton exchange membrane and its preparation method.
利用 10重量%的 nafion®DMF溶液, 硅酸改性的聚四氟乙烯纤维(直径 0.2μηι, 长度 80μηι, 与树脂的重量比为 7: 100 )在 170°C下, 60min浇铸得到 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.
30微米厚的纤维增强离子交换膜, 记作 Cl。 膜的性能表征 A 30 micron thick fiber reinforced ion exchange membrane, designated Cl. Membrane performance characterization
测定实施例 1-15制得的质子交换膜 A1-A15和对比例 1制得的质子交换 膜 C1的 95 °C电导率、 拉伸强度、 氢气渗透电流, 尺寸变化率, 结果见表 1。 其中, 两项电导率值的测试条件分别为: T=95 °C , 饱和湿度下, 以及 T=25 °C ,干燥器干燥两天后;拉伸强度的测试方法为国标法(GB/T20042.3-2009 ); 氢气渗透电流的测试方法为电化学方法 ( Electrochemical and Solid-State Letters, vol.10, Issue 5, B101-B104, 2007 )。
表 1 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
由表 1可以看出, 本发明的质子交换膜的 95 °C电导率、 拉伸强度、 氢气 渗透电流和尺寸变化率等性能均优于普通纤维增强的多层全氟交联掺杂离 子膜。
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
1、一种 HNI质子交换膜,包括 2-40层以全氟离子交换树脂为基体的单层膜, 其特征在于, 至少一层单层膜含有表面 修饰的辅助质子传导物质, 至少一层单层膜含有改性纤维, 至少一层单层膜 含有高价金属化合物。 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.
2、 根据权利要求 1所述的质子交换膜, 其中, 以 100重量份的全氟离 子交换树脂为基准, 所述表面修饰的辅助质子传导物质的含量为 0.05-50重 量份, 所述改性纤维的含量为 0.5-50重量份, 所述高价金属化合物的含量为 0.001-5重量份。 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.
3、 根据权利要求 1或 2所述的质子交换膜, 其中, 所述交联网状结构 为式 (1)、 (11)、 (111)、 (IV)和 (V)所示结构 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 w w1 ( I ) Ij ww 1 ( I )
其中, G P G2分别为 CF2或 O, Rf C2-C1()的全氟碳链或含氯全氟碳链; Wherein GPG 2 is a perfluorocarbon chain or a chlorine-containing perfluorocarbon chain of CF 2 or O, R f C 2 -C 1 () ;
其中, R为亚甲基或全氟亚甲基, n为 0-10 Wherein R is a methylene group or a perfluoromethylene group, and n is 0-10
4、 根据权利要求 1至 3中任一项所述的质子交换膜, 其中, 所述表面 修饰的辅助质子传导物质包括被无机掺杂物修饰的氧化物、 正磷酸盐、 缩聚 磷酸盐、 多酸、 多酸盐、 硅酸盐、 硫酸盐、 ***盐和砷化物, 优选为氧化 物、 正磷酸盐、 缩聚磷酸盐、 多酸和多酸盐, 更优选为氧化物、 正磷酸盐和 缩聚磷酸盐;所述无机掺杂物为 Si02、Zr02、Ti02、BP04、Zr3(P04)4、Zr(HP04)2、 HZr2(P04)3、 Ti(HP04)2和 Zr2H(P301())2中的一种或多种。 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 .
5、 根据权利要求 1至 4中任一项所述的质子交换膜, 其中, 所述改性 纤维选自被具有离子交换功能的单体改性的氟碳聚合物纤维中的一种或多 种, 如聚四氟乙烯纤维、 聚全氟乙丙烯纤维和聚全氟丙基乙烯基醚纤维; 纤 维的直径为 0.005-5μηι, 长度为 0.03-3mm; 所述具有离子交换功能的单体为 二氧化硫、三氧化硫, 以及结构如下的全氟磺酸单体( A )、全氟磺酸单体(B ) 和全氟磺酸单体(C ) 中的一种或多种: 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:
CF2=CFO(CF2CFO)h(CF2)1SO2A CF 2 =CFO(CF 2 CFO) h (CF 2 ) 1 SO 2 A
( A ) (A)
其中, h = 0-l , i = 1-5 , 入为 、 Cl、 Br、 OH、 氧甲基或 ONa; j = 0-1 k = 1-5 , B为甲基、 H或乙基; 1 = 1-5 , D为 H、 甲基或乙基。 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.
6、 根据权利要求 1至 5中任一项所述的质子交换膜, 其中, 所述高价 金属化合物为 W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元素的最高价态和中间价 态的硝酸盐、 硫酸盐、 碳酸盐、 磷酸盐、 醋酸盐和组合复盐; W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元素的最高价态和中间价态的环糊精、 冠醚、 乙酰丙 酮、 含氮冠醚及含氮杂环、 乙二胺四乙酸、 二甲基甲酰胺和二甲基亚砜络合 物; 以及 W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元素的最高价态和中间价态的 具有钙钛矿结构的氧化物中的一种或多种。 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.
7、 根据权利要求 1至 6中任一项所述的质子交换膜, 其中, 该质子交 换膜包括 2-5层以全氟离子交换树脂为基体的单层膜; 该质子交换膜的厚度 为 5-300μηι, 优选为 10-50μηι。 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.
8、 根据权利要求 1至 7中任一项所述的质子交换膜, 其中, 所述全氟 离子交换树脂是由全氟烯烃单体、 一种或多种含功能基团的全氟烯单体和一 种或多种含交联位点的全氟烯单体共聚形成, 或者是上述共聚物的混合物, EW值为 600-1300, 优选为 700-1200。 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.
9、 权利要求 1至 8中任一项所述质子交换膜的制备方法, 其特征在于, 该方法包括: The method of preparing a proton exchange membrane according to any one of claims 1 to 8, characterized in that the method comprises:
( 1 )使用含有全氟离子交换树脂的溶液或熔融物形成单层膜, 其中, 该溶液或熔融物还选择性地含有表面修饰的辅助质子传导物质、 改性纤维和 高价金属化合物中的一种或多种; (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 )在步骤(1 ) 制得单层膜中形成交联网状结构; (2) forming a crosslinked network structure in the monolayer film obtained in the step (1);
( 3 )使用步骤(1 )和 /或 (2 )得到的单层膜与步骤(2 )得到单层膜复 合, 和 /或使用步骤( 1 )所述的溶液或熔融物在步骤(2 )得到的单层膜上形 成单层膜, 使最终得到的复合膜包括 2-40层单层膜, 其中至少一层单层膜 含有表面修饰的辅助质子传导物质, 至少一层单层膜含有改性纤维, 至少一 层单层膜含有高价金属化合物。 (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、 根据权利要求 9所述的方法, 其中, 所述交联网状结构为式 (1 )、10. The method according to claim 9, wherein the intersection network structure is the formula (1),
( 11 )、 (111 )、 (IV )和 (V )所示结构中的一种或多种: One or more of the structures shown in (11), (111), (IV), and (V):
其中, R为亚甲基或全 , n为 0-10 Where R is methylene or all, n is 0-10
11、 根据权利要求 9或 10所述的方法, 其中, 步骤(1 ) 中形成单层膜 的方法为浇铸、 挤出、 热压、 旋涂、 流延、 丝网印刷、 喷涂和浸渍中的一种 或多种; 优选地, 当使用浇铸、 旋涂、 流延、 丝网印刷、 喷涂或浸渍成膜时 在 30-300°C下热处理 0.1-600分钟,更优选为 100-200°C下热处理 1-30分钟。 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.
12、 根据权利要求 9至 11中任一项所述的方法, 其中, 步骤(2 ) 中复 合的方式为单层膜复合、 多层膜与单层膜复合、 多层膜与多层膜复合, 以及 使用溶液或熔融物在单层膜或多层膜上直接形成单层膜的方法中的一种或 多种。 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.
13、 根据权利要求 9至 12中任一项所述的方法, 其中, 步骤(3 ) 成式 (I )所示的交联网状结构的方法包括: 利用热、 光、 电子辐射、 子体、 X射线、 自由基引发剂, 以及在一种或多种交联剂的存在下通过热、 光、 电子辐射、 等离子体、 X射线、 自由基引发剂的作用形成交联网状结构, 其中, 所述自由基引发剂为有机过氧化物和偶氮类引发剂中的一种或多种, 优选为有机氧化物引发剂, 更优选为全氟有机过氧化物引发剂; 所述交联剂 的结构为式 (VI )所示结构中的一种或多种: 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):
X2Rf7X3 X 2 R f7 X 3
( VI ) ( VI )
其中, X2和 X3各自独立地为 Cl、 Br或 I; Rfv为全氟垸基或氟氯垸基; 形成式 (II )和 (III )所示的交联网状结构的方法包括: 使用磺酰氟、 磺酰氯、 磺酰溴型树脂与氨、 肼、 有机二胺或能够释放出氨、 肼或有机二胺 的有机过氧化物反应; 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;
形成式(IV )所示的交联网状结构的方法包括: 用氯磺酸处理全氟磺酸 树脂; The method of forming the crosslinked network structure represented by the formula (IV) comprises: treating the perfluorosulfonic acid resin with chlorosulfonic acid;
形成式 (V )所示的交联网状结构的方法包括: 用热或酸处理含腈基位 点的全氟磺酸树脂、 全氟磺酰氟树脂、 含磺酰氯树脂和含磺酰溴树脂中的一 种或多种。 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.
14、 根据权利要求 9至 13中任一项所述的方法, 其中, 所述表面修饰 的辅助质子传导物质包括被无机掺杂物修饰的氧化物、 正磷酸盐、 缩聚磷酸 盐、 多酸、 多酸盐、 硅酸盐、 硫酸盐、 ***盐和砷化物, 优选为氧化物、 正磷酸盐、 缩聚磷酸盐、 多酸和多酸盐, 更优选为氧化物、 正磷酸盐和缩聚 磷酸盐; 所述无机掺杂物为 Si02、 Zr02、 Ti02、 BP04、 Zr3(P04)4、 Zr(HP04)2、 HZr2(P04)3、 Ti(HP04)2和 Zr2H(P3O10)2中的一种或多种; 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 ;
所述改性纤维选自被具有离子交换功能的物质改性的氟碳聚合物纤维 中的一种或多种, 如聚四氟乙烯纤维、 聚全氟乙丙烯纤维和聚全氟丙基乙烯 基醚纤维; 纤维的直径为 0.005-5μηι, 长度为 0.03-3mm; 所述具有离子交换 功能的物质为二氧化硫、 三氧化硫, 以及结构如下的全氟磺酸单体(A )、 全 氟磺酸单体(B )和全氟磺酸单体(C ) 中的一种或多种: 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):
CF2=CFO(CF2†FO)h(CF2)1SO2A CF 2 =CFO(CF 2 †FO) h (CF 2 ) 1 SO 2 A
CF2=CF0(CFJ ( C ) 其中, h = 0-l, i= 1-5, A为 F、 Cl、 Br、 OH、 氧甲基或 ONa; j = 0-1, k= 1-5, B为甲基、 H或乙基; 1=1-5, 0为 11、 甲基或乙基; 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;
所述高价金属化合物为 W、 Ir、 Y、 Mn、 Ru、 V、 Zn和 La元素的最高 价态和中间价态的硝酸盐、 硫酸盐、 碳酸盐、 磷酸盐、 醋酸盐和组合复盐; W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元素的最高价态和中间价态的环糊精、 冠醚、 乙酰丙酮、 含氮冠醚及含氮杂环、 乙二胺四乙酸、 二甲基甲酰胺和二 甲基亚砜络合物; 以及 W、 Ir、 Y、 Mn、 Ru、 V、 Ζη和 La元素的最高价态 和中间价态的具有钙钛矿结构的氧化物中的一种或多种。 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.
15、 根据权利要求 9至 14中任一项所述的方法, 其中, 所述全氟离子 交换树脂是由全氟烯烃单体、 一种或多种含功能基团的全氟烯单体和一种或 多种含交联位点的全氟烯单体共聚形成, 或者是上述共聚物的混合物, EW 值为 600-1300, 优选为 700-1200。 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.
16、权利要求 1-8中任意一项所述的或者由权利要求 9-15中任意一项所 述方法制备的质子交换膜在质子交换膜燃料电池中的应用。 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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2010/000892 WO2011156934A1 (en) | 2010-06-18 | 2010-06-18 | Proton exchange membrane, its preparing method and use |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2010/000892 WO2011156934A1 (en) | 2010-06-18 | 2010-06-18 | Proton exchange membrane, its preparing method and use |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011156934A1 true WO2011156934A1 (en) | 2011-12-22 |
Family
ID=45347615
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2010/000892 WO2011156934A1 (en) | 2010-06-18 | 2010-06-18 | Proton exchange membrane, its preparing method and use |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2011156934A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103752189A (en) * | 2014-01-17 | 2014-04-30 | 山东东岳高分子材料有限公司 | Preparation method of microporous membrane with ion exchange function |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1675292A (en) * | 2002-08-21 | 2005-09-28 | 3M创新有限公司 | Process for preparing multi-layer proton exchange membranes and membrane electrode assemblies |
CN101320817A (en) * | 2008-07-11 | 2008-12-10 | 山东东岳神舟新材料有限公司 | Fibre reinforced multi-layer fluorine-contained cross-linking doping ionic membrane and preparation method thereof |
CN101733003A (en) * | 2009-12-10 | 2010-06-16 | 山东东岳神舟新材料有限公司 | Fiber-reinforced multi-layer long-service life fluorine-containing ion exchange membrane |
CN101733010A (en) * | 2009-12-10 | 2010-06-16 | 山东东岳神舟新材料有限公司 | Doped double cross-linking reinforced perfluorinated proton exchange membrane and preparation method thereof |
-
2010
- 2010-06-18 WO PCT/CN2010/000892 patent/WO2011156934A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1675292A (en) * | 2002-08-21 | 2005-09-28 | 3M创新有限公司 | Process for preparing multi-layer proton exchange membranes and membrane electrode assemblies |
CN101320817A (en) * | 2008-07-11 | 2008-12-10 | 山东东岳神舟新材料有限公司 | Fibre reinforced multi-layer fluorine-contained cross-linking doping ionic membrane and preparation method thereof |
CN101733003A (en) * | 2009-12-10 | 2010-06-16 | 山东东岳神舟新材料有限公司 | Fiber-reinforced multi-layer long-service life fluorine-containing ion exchange membrane |
CN101733010A (en) * | 2009-12-10 | 2010-06-16 | 山东东岳神舟新材料有限公司 | Doped double cross-linking reinforced perfluorinated proton exchange membrane and preparation method thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103752189A (en) * | 2014-01-17 | 2014-04-30 | 山东东岳高分子材料有限公司 | Preparation method of microporous membrane with ion exchange function |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Yao et al. | Superacidic electrospun fiber‐nafion hybrid proton exchange membranes | |
JP5638692B2 (en) | Complex having ion exchange function and preparation method and use thereof | |
Liu et al. | Eco-friendly polyvinyl alcohol/cellulose nanofiber–Li+ composite separator for high-performance lithium-ion batteries | |
CN101728549B (en) | High-temperature proton exchange compound film | |
WO2011156937A1 (en) | Fluorine containing ionomer composite with ion exchange function, preparation method and use thereof | |
CN101330150B (en) | Inorganic doping cross-linking multilayer ion membrane containing fluorine and preparation method thereof | |
WO2011156938A1 (en) | Fluorine containing ionomer composite with ion exchange function, preparation method and use thereof | |
CN101721922A (en) | Microporous film enhanced multilayer fluorine-containing crosslinked ion-doped film and preparation method thereof | |
CN102008905B (en) | Proton exchange film as well as preparation method and application thereof | |
CN104134812B (en) | Fiber-net-reinforced polymer electrolyte membrane and preparation method thereof | |
CN101350417A (en) | Microporous-film-reinforced multilayer fluorine-containing cross-linking doping ionic membrane and preparation method thereof | |
CN101670246A (en) | Multilayer fluorine-contained crosslinking doping ionic membrane with reinforced microporous membrane and preparation method thereof | |
WO2011156934A1 (en) | Proton exchange membrane, its preparing method and use | |
CN101350415A (en) | Microporous-film-reinforced fluorine-containing cross-linking doping ion-exchange membrane and preparation method thereof | |
WO2011156935A1 (en) | Proton exchange membrane, preparation process and use thereof | |
JP4747647B2 (en) | POLYMER ELECTROLYTE MEMBRANE AND METHOD FOR PRODUCING THE SAME | |
Asghar et al. | A review of advancements in commercial and non-commercial Nafion-based proton exchange membranes for direct methanol fuel cells | |
CN101733012B (en) | Micro-porous membrane compounded multi-layer fluorine-containing cross-linking doped ionic membrane | |
CN101733019B (en) | Microporous membrane reinforced fluorine-containing crosslinked and doped ion exchange membrane and preparation method thereof | |
CN102019147B (en) | Proton exchange membrane as well as preparation method and application thereof | |
CN101757862B (en) | Microporous membrane reinforcing fluorine-containing cross linking doping ion exchange membrane and preparation method thereof | |
CN101333322B (en) | Mineral-doped fluor-containing cross-linking ion exchanger membrane and method for preparing same | |
CN101745323B (en) | Fiber reinforced composite multi-layer total fluoride crosslinking ionic membrane and preparation method thereof | |
CN101685868B (en) | Microporous membrane enhanced multilayer fluorine-containing cross-linked doped ion-exchange membrane and preparation method thereof | |
CN101733018B (en) | Microporous membrane reinforced perfluorinated chain crosslinked and doped perfluoro ion exchange membrane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10853044 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10853044 Country of ref document: EP Kind code of ref document: A1 |