CN105098214A - Proton exchange membrane having self-repairing capability and preparation method thereof - Google Patents
Proton exchange membrane having self-repairing capability and preparation method thereof Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2212—Natural macromolecular compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention belongs to the technical field of polymer composite materials and functional materials, and in particular relates to a proton exchange membrane having the self-repairing capability and a preparation method thereof. The proton exchange membrane disclosed by the invention is mainly composed of two components including a self-repairing material and a proton conducting material, wherein the self-repairing material comprises, but not limited to, polyvinyl alcohol, chitosan, a poly(vinyl furfural)/bismaleimide cross-linked polymer and the like; and the proton conducting material comprises, but not limited to, phosphoric acid, sulphuric acid, sulfosuccinic acid, sulfomalic acid, perfluorinated sulfonic acid resin, sulfonated polybenzimidazole, sulfonated polyether-ether-ketone, sulfonated polyimide and the like. The two components form the membrane by using the existing process after being composited through the methods, such as a blending method, a copolymerizing method and an interpenetrating polymer network method; the membrane has good proton conducting capability and self-repairing capability; after the membrane is damaged, self-repairing can be realized under the excitations of water infiltration, temperature increasing/decreasing circulation and the like; therefore, the service life of the proton exchange membrane is prolonged; the use range of the proton exchange membrane is enlarged; and the proton exchange membrane disclosed by the invention can be used in the fields of fuel cells, ion exchange, catalysts and the like.
Description
Technical field
The invention belongs to polymer composite and technical field of function materials, be specifically related to a kind of proton exchange membrane with self-reparing capability and preparation method thereof.
Background technology
In recent years due to the active demand to new forms of energy, Proton Exchange Membrane Fuel Cells obtains a large amount of concerns, also achieves considerable progress.The perfluorosulfonic acid proton exchange film being representative with the Nafion of du pont company has demonstrated the unlimited prospect of this proton exchanging film fuel battery in actual use to the world.
Proton exchange membrane for material except the requirement of proton exchange ability, also require that it has some strength, this is because also inevitable mechanical damage can be run in the use procedure of film, especially when film by water or other liquid swelling after, mechanical strength can be caused to decline serious, once occur damaged, gas will arrive pole plate opposite side through film, makes battery performance degradation.Current all research directions, are all conceived to the intensity how improving membrane material.Such as Yang great Wei (open application number is the Chinese invention patent of 101906215A) has invented a kind of manufacture method of high-strength composite proton exchange membrane, tetrafluoroethene is strengthened screen cloth and is placed in the template that plate glass makes by the method, then the solution that proton exchange resins is made is poured in a template into, microwave or far infrared is used to carry out double-side radiation heating crystalline to it, after solvent evaporates, resin and tetrafluoroethene strengthen screen cloth and are combined, and be deposited on together on plate glass, generate a kind of high-strength composite proton exchange membrane; Cai Yan etc. (open application number be the Chinese invention patent of 101771159A) prepare a kind of be more than 60% by sulfonation degree and be less than 100% sulfonated polyether-ether-ketone and sulfonation degree be greater than 0 and the high strength proton exchange membrane made of the blend of the sulfonated polyether sulfone of less than 60%.But, all these proton exchange membrane prepared by Enhancement Method, except complex process, high in cost of production shortcoming, in actual use once run into and exceed the damage that it bears the limit, such as Vehicular impact, excessive, the dry wet conversion of cutting, stream pressure are too frequent etc., still can cause the thorough destruction of film, and cause fuel cells fail.
The proton exchange membrane with self-reparing capability prepared by the present invention, combines the technology of preparing of proton exchange membrane and the technology of preparing of novel intelligent self-repair material, for the useful life extending proton exchange membrane provides another kind of very effective solution.The actual effect of selfreparing illustrates see accompanying drawing, does not also have this report with the proton exchange membrane of self-reparing capability at present.
Summary of the invention
The object of the invention is to, for solving the problem lost efficacy after proton exchange membrane material is subject to mechanical damage, provide a kind of proton exchange membrane with self-reparing capability and preparation method thereof.
The proton exchange membrane with self-reparing capability provided by the invention, is composited by the component with self-repair function and the component with proton conductivity, and complex method can be IPN (or Semi-IPN) polymer network, copolymerization, blended etc.Wherein:
The described component with self-repair function, is selected from a kind of of following material or wherein several: (1) is rich in the polymer of hydrogen bond, as polyvinyl alcohol, shitosan, but is not limited only to this; (2) by the polymeric system that reversible chemical key is crosslinked, as polyvinyl alcohol furfural and two/polynary maleimide amine system, both-end furyl polyethylene glycol and two/polynary maleimide amine system, but this is not limited only to.
The described component with proton conductivity, is selected from a kind of of following material or wherein several: the acid of (1) inorganic proton, as boric acid, phosphoric acid, sulfuric acid, but is not limited only to this; (2) organic acid, as sulfosuccinic acid, sulfo group malic acid, but is not limited only to this; (3) sulfonated polymer, as perfluorinated sulfonic resin, sulfonate polybenzimidazole, sulfonated polyether-ether-ketone, sulfonated polyimide, sulfonated polystyrene etc., but is not limited only to this.
The proton exchange membrane with self-reparing capability provided by the invention, the content of its topmost two kinds of components is determined by the system specifically selected, mainly containing two kinds: (1) two component is different material, the constituent mass mark with self-repair function is 30%-70%, and the constituent mass mark with proton conductivity is 30%-70%, concrete content adjusts according to required effect, the component that proton conductivity is very strong can suitably be arranged in pairs or groups the component of self-repair function of more amount, to strengthen selfreparing effect, the component of the good self-repair function of selfreparing effect otherwise the more weak component of proton conductivity should be arranged in pairs or groups, (2) two components are materials of the same race, and in foundation chemical constitution, the group number of same-action does not regulate the effect of selfreparing and proton exchange ability two kinds of functions.
The proton exchange membrane with self-repair function of the present invention, its preparation method needs according to selecting the difference of system and selecting diverse ways, include but not limited to: after two kinds of component compounds, adopt extrude, the conventional film build method such as blowing, casting, painting are scraped, hot pressing.The design parameter of often kind of technique need be determined according to selective system.
The proton exchange membrane with self-repair function of the present invention, according to the difference of process choice in its course of processing, need optionally to add different auxiliary agents, include but not limited to: improve film toughness, need to add plasticizer, as dibutyl phthalate, tributyl phosphate etc.; Improve and extrude processing characteristics, need to add lubricant, as zinc stearate, calcium stearate, Tissuemat E, aliphatic acid etc.; When there is flame-retardancy requirements, fire retardant need be added, as antimonous oxide, tribromphenol, triphenyl phosphate, chlorinated paraffin wax etc.; Other select the auxiliary agent such as antistatic agent, heat stabilizer, the crosslinking agent etc. that add.
The proton exchange membrane with self-reparing capability of the present invention, its selfreparing needs to carry out under suitable environmental stimuli.Environmental stimuli according to the system selected, under including but not limited to be positioned over high humidity environment, high temperature/low-temperature circulating, be immersed in water, hot pressing etc., under proton exchange membrane condition of work, usually just can realize these stimulations, eliminate the puzzlements such as dismounting.
The proton exchange membrane with self-reparing capability of the present invention, the principle of selfreparing, according to the system selected, comprises the effect of reversible chemical key and the supermolecular mechanism such as hydrogen bond action, van der Waals interaction, but is not limited only to this.
Self-reparing capability of the present invention, after mainly referring to that material is subject to mechanical damage, farthest repairs wound and recovers the ability of mechanical property or other performances under certain stimulation.
The invention has the advantages that: by connexus proton exchange technology of preparing, and the technology of preparing of novel intelligent self-repair material, obtaining can the proton exchange membrane of selfreparing.This selfreparing proton exchange membrane, can teaching display stand reparation under certain environmental stimuli after being subject to mechanical damage, farthest recovers initial mechanical and other performances make wound up, extends proton exchange membrane useful life.This invention best applications field is Proton Exchange Membrane Fuel Cells, secondly also the fields such as catalyst, diffusion barrier, amberplex can be used in, for the reliable use of equipment provides safeguard, can greatly reduce maintenance, replacement cost simultaneously, there is very optimistic application prospect.
Accompanying drawing explanation
Fig. 1 is the photo of self-repair procedure at polarized light microscopy Microscopic observation of embodiment 1 sample.
Fig. 2 is photo and the demonstration of the selfreparing effect of embodiment 2 sample.
Fig. 3 is the proton conductivity of embodiment 3 sample and the relation of phosphoric acid addition.
Fig. 4 is the petrographic microscope photo before and after the selfreparing of embodiment 5 sample, and upper figure is damaged membrane sample, and figure below is for repairing rear membrane sample.
Fig. 5 is hot strength and remediation efficiency before and after embodiment 1,2,3,4,5 sample is repaired.
Embodiment
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation.Following examples for illustration of the present invention, but should not be counted as limitation of the present invention.
Polyvinyl alcohol (PVA-124) in embodiment, furoyl chloride, shitosan, BFEE is bought in Aladdin reagent, polyvinyl alcohol (PVA-124) powder is bought in Kuraray company, N, N '-six methine bismaleimides, diaminobenzidine, sulfosuccinic acid is bought in lark prestige reagent, the alcoholic solution of Nafion, Nafion resin is bought in E.I.Du Pont Company, acetic acid, dioxane, absolute ethyl alcohol, anhydrous phosphoric acid, furfural, hydrochloric acid, triphenyl phosphate, calcium stearate, N, N-dimethylformamide (DMF) etc. is bought in Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
The preparation of selfreparing proton exchange membrane: 0.5g polyvinyl alcohol (PVA-124) is dissolved in 70 of 20ml
oin C deionized water, add 0.5g sulfosuccinic acid after cool to room temperature, in 50 after stirring
oat glass plate blade coating under C, film forming after drying.
Selfreparing condition: get damaged film, drip deionized water in breakage, room temperature places 24h post-drying, and reparation completes.
Embodiment 2
The preparation of selfreparing proton exchange membrane: 0.3g shitosan is dissolved in the middle of the acetum of 20ml about 4%, adds the alcoholic solution containing 0.7gNafion under room temperature, pours into Flat Membrane frame, 50 after stirring at room temperature 1h
ofilm forming is dried under C.
Selfreparing condition: get damaged film, drip deionized water in breakage, room temperature places 24h post-drying, and reparation completes.
Embodiment 3
2, the preparation of 2 '-difuryl-5,5 '-benzimidazole: add 2.1643g diaminobenzidine, at N after to be dissolved in the dioxane of 40ml drying
2under protection, add the dioxane solution 40ml being dissolved with 2.6376g furoyl chloride under ice-water bath, half an hour, drips off rear recovery normal temperature and continues reaction 30 minutes.Add 2.9266g boron trifluoride etherate and other 80ml dioxane afterwards.Mixture backflow 3h, products therefrom is poured in cold water, and stirring is spent the night, and obtains product for several times after suction filtration with ethanol, water washing.
Selfreparing proton exchange film preparation: get 2 of above-mentioned preparation, 2 '-difuryl-5,5 '-benzimidazole is dissolved in the DMF of 30ml, add the N of 0.3771g again, N '-six methine bismaleimides, 0.26g anhydrous phosphoric acid, pours into after stirring in glass-film frame 60
ofilm forming is dried under C.
Selfreparing condition: the film of breakage is placed on 150
oprocess 20min in the baking oven of C, then put into 60
oc baking oven 2h, obtains the proton exchange membrane of selfreparing.
Embodiment 4
The preparation of polyvinyl alcohol furfural: the preparation method of polyvinyl alcohol furfural, with reference to described in patent 101732998A, drips salt acid for adjusting pH value to 2 to the poly-vinyl alcohol solution containing 50g3%, then adds furfural 20g, 70
oc reacts 5h, in cold water, separate out polymer, and ethanol surname extraction post-drying is for subsequent use.
Selfreparing proton exchange film preparation: get polyvinyl alcohol furfural 500g, Nafion500g adds 50gN, N '-six methine bismaleimides, 37.5g calcium stearate 10g, triphenyl phosphate 10g, use double screw extruder 150
oc extrudes and film forming, and product is placed on 60
olower 1 day of C, obtains the proton exchange membrane be cross-linked.
Selfreparing condition: the film of breakage is placed on 150
oprocess 20min in the baking oven of C, then put into 60
oc baking oven 2h, obtains the proton exchange membrane of selfreparing.
Embodiment 5
Selfreparing proton exchange film preparation: get polyvinyl alcohol 40kg, obtains component 1 with single screw extrusion machine film extrusion; Get Nafion resin 40kg again, obtain component 2 with single screw extrusion machine film extrusion; Get the component 2 two parts of certain area, the component 1 of getting same area is a, and three is after the order of component 2-component 1-component 2 stacks, in 140
ounder C, 5MPa, hot pressing 10min makes three combine closely, and obtains final products.
Selfreparing condition: get damaged film, drip deionized water in breakage, room temperature places 24h post-drying, and reparation completes.
Claims (7)
1. have a proton exchange membrane for self-reparing capability, it is characterized in that, be composited by the component with self-repair function and the component with proton conductivity, complex method can be interpenetrating polymer networks, copolymerization, blended; Wherein:
The described component with self-repair function, is selected from a kind of of following material or wherein several: (1) is rich in the polymer of hydrogen bond; (2) by polymeric system that reversible chemical key is crosslinked;
The described component with proton conductivity, is selected from a kind of of following material or wherein several: the acid of (1) inorganic proton; (2) organic acid; (3) sulfonated polymer.
2. the proton exchange membrane with self-reparing capability according to claim 1, is characterized in that, the content of described two kinds of components is determined by the system specifically selected, and is divided into two kinds:
(1) two component is different material, and the constituent mass mark with self-repair function is 30%-70%, and the constituent mass mark with proton conductivity is 30%-70%;
(2) two components are materials of the same race, and in foundation chemical constitution, the group number of same-action does not regulate the effect of selfreparing and proton exchange ability two kinds of functions.
3. the proton exchange membrane with self-reparing capability according to claim 1 and 2, is characterized in that, described in have in the component of self-repair function, described in be rich in hydrogen bond polymer be polyvinyl alcohol or shitosan; The described polymeric acceptor crosslinked by reversible chemical key is polyvinyl alcohol furfural and two/polynary maleimide amine system, or both-end furyl polyethylene glycol and two/polynary maleimide amine system.
4. the proton exchange membrane with self-reparing capability according to claim 1 and 2, it is characterized in that, described have in the component of proton conductivity, and described inorganic proton acid is boric acid, phosphoric acid or sulfuric acid, and described organic acid is sulfosuccinic acid or sulfo group malic acid; Described sulfonated polymer is perfluorinated sulfonic resin, sulfonate polybenzimidazole, sulfonated polyether-ether-ketone, sulfonated polyimide or sulfonated polystyrene.
5. the proton exchange membrane with self-reparing capability according to claim 1 and 2, is characterized in that, according to performance requirement, selectivity is added with plasticizer, lubricant, fire retardant, antistatic agent, heat stabilizer and crosslinking agent.
6. the proton exchange membrane with self-reparing capability according to claim 1 and 2, it is characterized in that described selfreparing is carried out under environmental stimuli, described environmental stimuli comprises: high humidity environment, high temperature/low-temperature circulating, be immersed in water, hot pressing.
7. the preparation method with the proton exchange membrane of self-reparing capability as described in one of claim 1-5, is characterized in that, after two kinds of component compounds, adopt extrude, blowing, casting, painting scrape or be hot pressed into membrane process.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105924865A (en) * | 2016-05-12 | 2016-09-07 | 盐城工学院 | Acid proton exchange membrane and preparing method thereof |
| CN106633555A (en) * | 2016-09-14 | 2017-05-10 | 同济大学 | Polyvinyl alcohol membrane with self-repair function implemented by aid of dynamic covalent bonds and method for preparing polyvinyl alcohol membrane |
| CN107834089A (en) * | 2017-10-19 | 2018-03-23 | 武汉氢阳能源有限公司 | A kind of high temperature proton exchange film available for membrane cell and its preparation method and application |
| CN108134116A (en) * | 2017-12-26 | 2018-06-08 | 成都新柯力化工科技有限公司 | A kind of poly- furfuryl alcohol modification fuel battery proton exchange film and its method of modifying |
| CN108199065A (en) * | 2018-01-02 | 2018-06-22 | 吉林大学 | A kind of recoverable compound substance proton exchange and preparation method thereof |
| CN108310460A (en) * | 2018-02-02 | 2018-07-24 | 武汉大学 | Injectable high intensity Thermo-sensitive modified chitin based aquagel and its preparation method and application |
| CN108832160A (en) * | 2018-06-20 | 2018-11-16 | 四川大学 | Polyimide grafted sulfonated polyethylene alcohol copolymer proton exchange membrane and preparation method thereof |
| CN109904500A (en) * | 2019-02-25 | 2019-06-18 | 四川大学 | A kind of side chain type sulfonated polysulfones/polyvinyl alcohol proton exchange membrane and preparation method thereof |
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| CN105924865B (en) * | 2016-05-12 | 2018-04-20 | 盐城工学院 | A kind of acidic proton exchange membrane and preparation method thereof |
| CN106633555A (en) * | 2016-09-14 | 2017-05-10 | 同济大学 | Polyvinyl alcohol membrane with self-repair function implemented by aid of dynamic covalent bonds and method for preparing polyvinyl alcohol membrane |
| CN107834089A (en) * | 2017-10-19 | 2018-03-23 | 武汉氢阳能源有限公司 | A kind of high temperature proton exchange film available for membrane cell and its preparation method and application |
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| CN108134116A (en) * | 2017-12-26 | 2018-06-08 | 成都新柯力化工科技有限公司 | A kind of poly- furfuryl alcohol modification fuel battery proton exchange film and its method of modifying |
| CN108134116B (en) * | 2017-12-26 | 2020-03-20 | 成都新柯力化工科技有限公司 | Poly furfuryl alcohol modified fuel cell proton exchange membrane and modification method thereof |
| CN108199065B (en) * | 2018-01-02 | 2020-03-10 | 吉林大学 | Repairable compound proton exchange membrane and preparation method thereof |
| CN108199065A (en) * | 2018-01-02 | 2018-06-22 | 吉林大学 | A kind of recoverable compound substance proton exchange and preparation method thereof |
| CN108310460A (en) * | 2018-02-02 | 2018-07-24 | 武汉大学 | Injectable high intensity Thermo-sensitive modified chitin based aquagel and its preparation method and application |
| CN108310460B (en) * | 2018-02-02 | 2021-08-03 | 武汉大学 | Injectable high-strength temperature-sensitive modified chitin-based hydrogel and preparation method and application thereof |
| CN108832160A (en) * | 2018-06-20 | 2018-11-16 | 四川大学 | Polyimide grafted sulfonated polyethylene alcohol copolymer proton exchange membrane and preparation method thereof |
| CN109904500A (en) * | 2019-02-25 | 2019-06-18 | 四川大学 | A kind of side chain type sulfonated polysulfones/polyvinyl alcohol proton exchange membrane and preparation method thereof |
| CN109904500B (en) * | 2019-02-25 | 2020-11-24 | 四川大学 | Side chain type sulfonated polysulfone/polyvinyl alcohol proton exchange membrane and preparation method thereof |
| CN113856503A (en) * | 2021-10-18 | 2021-12-31 | 大连理工大学 | Sulfonic acid type cation exchange membrane for reverse electrodialysis technology, preparation method and application thereof |
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