CN105098214B - A kind of proton exchange membrane and preparation method thereof with self-reparing capability - Google Patents
A kind of proton exchange membrane and preparation method thereof with self-reparing capability 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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- 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
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- 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
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- C08J5/2218—Synthetic macromolecular compounds
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention belongs to polymer composite and technical field of function materials, specially a kind of proton exchange membrane and preparation method thereof with self-reparing capability.The present invention is mainly made of two components: self-repair material, including but not limited to polyvinyl alcohol, chitosan, polyvinyl alcohol furfural/bismaleimide cross-linked polymer etc.；Proton conducting material, including but not limited to phosphoric acid, sulfuric acid, sulfosuccinic acid, sulfo group malic acid, perfluorinated sulfonic resin, sulfonate polybenzimidazole, sulfonated polyether-ether-ketone, sulfonated polyimide etc..It is formed a film after two kinds of components are by being blended, copolymerization, the methods of interpenetrating polymer networks are compound with prior art.The film has good proton conducting ability and self-reparing capability, after film is impaired, selfreparing can be realized under the stimulations such as water infiltration, heating/cooling circulation, to extend the service life of proton exchange membrane, expand proton exchange membrane use scope.The present invention may be used at the fields such as fuel cell, ion exchange, catalyst.
Description
Technical field
The invention belongs to polymer composites and technical field of function materials, and in particular to one kind has self-reparing capability
Proton exchange membrane and preparation method thereof.
Background technique
In recent years due to the urgent need to new energy, Proton Exchange Membrane Fuel Cells has obtained a large amount of concern, also takes
Obtained considerable progress.It has been actually used using the Nafion of DuPont Corporation as the perfluorosulfonic acid proton exchange film of representative
It is middle to demonstrate the unlimited prospect of this proton exchanging film fuel battery to the world.
Proton exchange membrane other than the requirement of proton exchange ability, also requires it with some strength material, this
Be because further encounter inevitable mechanical damage in the use process of film, it is especially molten by water or other liquid when film
After swollen, it is serious to will lead to mechanical strength decline, once there is breakage, gas will pass through film and reach the pole plate other side, so that
Battery performance degradation.Current all research directions, are all conceived to the intensity for how improving membrane material.Such as Yang great Wei
(Chinese invention patent that published application number is 101906215A) has invented a kind of manufacture of high-strength composite proton exchange membrane
Tetrafluoroethene enhancing screen cloth is placed in template made of plate glass by method, this method, then pours into proton friendship in a template
Solution made of resin is changed, double-side radiation heating crystalline, after the solvent is volatilized, resin are carried out to it using microwave or far infrared
It in conjunction with tetrafluoroethene enhancing screen cloth, and is deposited on plate glass together, generates a kind of high-strength composite proton exchange membrane；
Cai Yan etc. (Chinese invention patent that published application number is 101771159A) be prepared for it is a kind of by sulfonation degree be 60% more than and less than
100% sulfonated polyether-ether-ketone and sulfonation degree be greater than 0 and 60% sulfonated polyether sulfone below blend made of high intensity proton
Exchange membrane.However, it is all these by Enhancement Method prepare proton exchange membrane, in addition to complex process, it is at high cost the disadvantages of it
Outside, in actual use once encounter damage more than its power limit, for example, Vehicular impact, cutting, stream pressure it is excessive,
Dry and wet conversion is excessively frequent etc., still will cause the thorough destruction of film, and leads to fuel cells fail.
With the proton exchange membrane of self-reparing capability prepared by the present invention, combine the technology of preparing of proton exchange membrane with
The technology of preparing of novel intelligent self-repair material, for extend the service life of proton exchange membrane provide it is another very effective
Solution.The actual effect of selfreparing does not have this proton exchange with self-reparing capability also referring to Detailed description of the invention at present
The report of film.
Summary of the invention
It is an object of the invention to provide one kind to solve the problems, such as failure after proton exchange membrane material is mechanically damaged
Proton exchange membrane and preparation method thereof with self-reparing capability.
Proton exchange membrane provided by the invention with self-reparing capability by the component with self-repair function and has matter
The component of sub- conducting power is combined, and complex method can be interpenetrating (or Semi-IPN) polymer network, copolymerization, blending etc..Its
In:
The component with self-repair function, one kind selected from following materials or in which it is several: (1) rich in hydrogen bond
Polymer such as polyvinyl alcohol, chitosan, but is not limited only to this；(2) polymeric system that can be crosslinked by reversible chemical key, such as
Polyvinyl alcohol furfural and double/polynary maleimide amine systems, both-end furyl polyethylene glycol and double/polynary maleimide bodies
System, but it is not limited only to this.
The component with proton conductivity, one kind selected from following materials or in which it is several: (1) inorganic proton
Acid such as boric acid, phosphoric acid, sulfuric acid, but is not limited only to this；(2) organic acid such as sulfosuccinic acid, sulfo group malic acid, but is not limited only to
This；(3) sulfonated polymer, such as perfluorinated sulfonic resin, sulfonate polybenzimidazole, sulfonated polyether-ether-ketone, sulfonated polyimide, sulfonation
Polystyrene etc., but it is not limited only to this.
Proton exchange membrane provided by the invention with self-reparing capability, the content of most important two kinds of components is by specific
The system of selection is determining, there are mainly two types of: (1) two components are different materials, the constituent mass score with self-repair function
For 30%-70%, and the constituent mass score with proton conductivity is 30%-70%, and concrete content is according to required effect
Be adjusted, the very strong component of proton conductivity can suitably arrange in pairs or groups more amount self-repair function component, with enhancing from
Repairing effect, the component of the preferable self-repair function of selfreparing effect otherwise the weaker component of proton conductivity should arrange in pairs or groups；
(2) two components are substances of the same race, and the group number according to different role in chemical structure adjusts selfreparing and proton exchange
The effect of two kinds of functions of ability.
Proton exchange membrane of the present invention with self-repair function, preparation method need to be according to the differences of the system of selection
And select different methods, including but not limited to: by two kinds of components it is compound after, scraped using extrusion, blow molding, casting, painting, hot pressing etc.
Conventional film build method.The design parameter of every kind of technique need to be determined according to selective system.
Proton exchange membrane of the present invention with self-repair function, in process not according to process choice
Together, the auxiliary agent for needing selective addition different, including but not limited to: improve film toughness, needs that plasticizer is added, such as adjacent benzene two
Formic acid dibutyl ester, tributyl phosphate etc.；Improve extrusion processability energy, need that lubricant is added, as zinc stearate, calcium stearate,
Polyethylene wax, fatty acid etc.；When with flame-retardancy requirements, fire retardant need to be added, such as antimony oxide, tribromphenol, phosphoric acid triphen
Ester, chlorinated paraffin etc.；The auxiliary agent such as antistatic agent, heat stabilizer, crosslinking agent etc. that other selections are added.
Proton exchange membrane of the present invention with self-reparing capability, selfreparing need under appropriate environmental stimuli into
Row.System of the environmental stimuli according to selection, includes but is not limited to be placed under high humidity environment, high temperature/low-temperature circulating, be immersed in
In water, hot pressing etc., these stimulations can be usually realized under proton exchange membrane operating condition, eliminate the puzzlement such as disassembly.
Proton exchange membrane of the present invention with self-reparing capability, system of the principle of selfreparing according to selection, packet
The supermolecular mechanisms such as the effect of reversible chemical key and hydrogen bond action, van der Waals interaction are included, but are not limited only to this.
Self-reparing capability of the present invention, refer mainly to material it is mechanically damaged after, under certain stimulation utmostly
Reparation wound and restore mechanical property or the ability of other performances.
The present invention has the advantages that by combining proton exchange membrane technology of preparing and novel intelligent self-repair material
Technology of preparing, obtaining can be with the proton exchange membrane of selfreparing.The selfreparing proton exchange membrane is after mechanically damaged, certain
Self-regeneration may be implemented under environmental stimuli, restore initial mechanical and other performances to the greatest extent and make wound up, extend matter
Proton exchange service life.The invention best applications field be Proton Exchange Membrane Fuel Cells, secondly can also be used in catalyst,
The fields such as seperation film, amberplex provide safeguard for the reliable use of equipment, while can substantially reduce maintenance, be replaced with
This, has very optimistic application prospect.
Detailed description of the invention
Fig. 1 is photo of the self-repair procedure in polarized light microscopy microscopic observation of 1 sample of embodiment.
Fig. 2 is photo and the demonstration of the selfreparing effect of 2 sample of embodiment.
Fig. 3 is the proton conductivity of 3 sample of embodiment and the relationship of phosphoric acid additional amount.
Fig. 4 is the petrographic microscope photo before and after the selfreparing of 5 sample of embodiment, and upper figure is damaged membrane sample, and the following figure is
Membrane sample after reparation.
Fig. 5 is that 1,2,3,4,5 sample of embodiment repairs front and back tensile strength and remediation efficiency.
Specific embodiment
With reference to the accompanying drawing and embodiment the present invention is described in further detail.Following embodiment is for illustrating this
Invention, but should not be construed as limiting the invention.
Polyvinyl alcohol (PVA-124), furoyl chloride, chitosan, boron trifluoride ether are bought in Aladdin reagent in embodiment,
The purchase of polyvinyl alcohol (PVA-124) powder is in Kuraray company, N, the N methine of '-six bismaleimide, diamino connection
Aniline, sulfosuccinic acid purchase in lark prestige reagent, the alcoholic solution of Nafion, the purchase of Nafion resin in E.I.Du Pont Company, acetic acid,
Dioxane, dehydrated alcohol, anhydrous phosphoric acid, furfural, hydrochloric acid, triphenyl phosphate, calcium stearate, n,N dimethylformamide (DMF)
Deng purchase in Sinopharm Chemical Reagent Co., Ltd..
Embodiment 1
The preparation of selfreparing proton exchange membrane: 0.5g polyvinyl alcohol (PVA-124) is dissolved in the 70 of 20mloC deionized water
In, 0.5g sulfosuccinic acid is added after being cooled to room temperature, after mixing evenly in 50oIt scratches under C in glass plate, forms a film after drying.
Selfreparing condition: damaged film is taken, deionized water is dripped in breakage, is placed at room temperature for and dries afterwards for 24 hours, repaired
At.
Embodiment 2
The preparation of selfreparing proton exchange membrane: 0.3g chitosan is dissolved in the acetum of 20ml about 4%, at room temperature
The alcoholic solution containing 0.7g Nafion is added, is stirred at room temperature after 1h and pours into plate membrane frame, 50oFilm forming is dried under C.
Selfreparing condition: damaged film is taken, deionized water is dripped in breakage, is placed at room temperature for and dries afterwards for 24 hours, repaired
At.
Embodiment 3
The preparation of 2,2 '-difuryls -5,5 '-benzimidazole: 2.1643g is added in the dioxane dry to 40ml
Diaminobenzidine, it is to be dissolved after in N2The dioxane solution dissolved with 2.6376g furoyl chloride is added under protection, under ice-water bath
40ml, the reaction was continued 30 minutes for recovery room temperature after half an hour drips off.2.9266g boron trifluoride etherate is added later
And other 80ml dioxane.Mixture flows back 3h, and products therefrom pours into cold water, be stirred overnight, after suction filtration with ethyl alcohol,
Water washing obtains product for several times.
Selfreparing proton exchange film preparation: 2,2 '-difuryls -5,5 '-benzimidazole of above-mentioned preparation is taken to be dissolved in 30ml
DMF in, add the N of 0.3771g ,-six methine bismaleimide of N ', 0.26g anhydrous phosphoric acid pours into after mixing evenly
60 in glass-film frameoFilm forming is dried under C.
Selfreparing condition: damaged film is placed on 150o20min is handled in the baking oven of C, is then placed in 60oC baking oven 2h,
Obtain the proton exchange membrane of selfreparing.
Embodiment 4
The preparation of polyvinyl alcohol furfural: described in the preparation method reference patent 101732998A of polyvinyl alcohol furfural,
Salt acid for adjusting pH value is added dropwise to 2 to the poly-vinyl alcohol solution containing 50g 3%, is then added furfural 20g, 70oC reacts 5h, cold
Polymer is precipitated in water, is dried for standby after ethyl alcohol Soxhlet extraction.
Selfreparing proton exchange film preparation: take polyvinyl alcohol furfural 500g, Nafion 500g that 50g N, N '-six is added
Methine bismaleimide, 37.5g calcium stearate 10g, triphenyl phosphate 10g, using double screw extruder 150oC is squeezed out
And form a film, product is placed on 60oThe lower proton exchange membrane 1 day, being crosslinked of C.
Selfreparing condition: damaged film is placed on 150o20min is handled in the baking oven of C, is then placed in 60oC baking oven 2h,
Obtain the proton exchange membrane of selfreparing.
Embodiment 5
Selfreparing proton exchange film preparation: taking polyvinyl alcohol 40kg, obtains component 1 with single screw extrusion machine film extrusion；
Nafion resin 40kg is taken again, obtains component 2 with single screw extrusion machine film extrusion,；2 two parts of component of certain area are taken, are taken
The component 1 of same area is a, after three stacks in the sequence of component 2- component 1- component 2, in 140oC, hot pressing under 5 MPa
10min makes three combine closely, and obtains final products.
Selfreparing condition: damaged film is taken, deionized water is dripped in breakage, is placed at room temperature for and dries afterwards for 24 hours, repaired
At.
Claims (3)
1. a kind of proton exchange membrane with self-reparing capability, which is characterized in that by with self-repair function component with have
The component of proton conductivity is combined, and complex method can be interpenetrating polymer networks, copolymerization, blending；Wherein:
The component with self-repair function, one kind selected from following materials or in which it is several: (1) be rich in the polymerization of hydrogen bond
Object；(2) polymeric system that can be crosslinked by reversible chemical key；
The component with proton conductivity, one kind selected from following materials or in which it is several: (1) inorganic proton acid；
(2) organic acid；(3) sulfonated polymer；
Wherein, in the component with self-repair function, the polymer rich in hydrogen bond is polyvinyl alcohol or chitosan；Institute
Stating can be polyvinyl alcohol furfural and double/polynary maleimide amine systems by polymeric system that reversible chemical key is crosslinked, or
Both-end furyl polyethylene glycol and double/polynary maleimide amine systems；
In the component with proton conductivity, the inorganic proton acid is boric acid, phosphoric acid or sulfuric acid, and the organic acid is
Sulfosuccinic acid or sulfo group malic acid；The sulfonated polymer is perfluorinated sulfonic resin, sulfonate polybenzimidazole, sulfonated polyether ether
Ketone, sulfonated polyimide or sulfonated polystyrene；
The selfreparing carries out under environmental stimuli, and the environmental stimuli includes: high humidity environment, high temperature/low-temperature circulating, immersion
In water, hot pressing；
The content of the component with self-repair function and the component with proton conductivity is true by the system being specifically chosen
It is fixed, it is divided into two kinds:
(1) two component is different material, and the constituent mass score with self-repair function is 30%-70%, and there is proton to pass
The constituent mass score for leading ability is 30%-70%；
(2) two components are substances of the same race, and the group number according to different role in chemical structure adjusts selfreparing and proton
The effect of two kinds of functions of exchange capacity.
2. the proton exchange membrane according to claim 1 with self-reparing capability, which is characterized in that according to performance requirement,
Selectivity is added with plasticizer, lubricant, fire retardant, antistatic agent, heat stabilizer and crosslinking agent.
3. a kind of preparation method of the proton exchange membrane with self-reparing capability as claimed in claim 1 or 2, feature exist
In, by two kinds of components it is compound after, scraped using extrusion, blow molding, casting, painting or hot pressing film-forming process.
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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 |
| CN107834089B (en) * | 2017-10-19 | 2022-02-18 | 武汉氢阳能源有限公司 | High-temperature proton exchange membrane for membrane fuel cell and preparation method and application thereof |
| 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 |
| 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 |
| CN108832160B (en) * | 2018-06-20 | 2020-09-11 | 四川大学 | Polyimide grafted sulfonated polyvinyl alcohol copolymer 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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| CN1775838A (en) * | 2005-12-15 | 2006-05-24 | 北京航空航天大学 | Method for preparing chitose proton exchange membrance for fuel cell |
| CN101864085A (en) * | 2010-03-10 | 2010-10-20 | 合肥科振实业发展有限公司 | Method for manufacturing covalent cross-linked proton exchange membrane (PEM) for fuel cell |
| CN101887979A (en) * | 2009-05-13 | 2010-11-17 | 财团法人工业技术研究院 | Proton exchange membrane with high proton conductivity |
| CN102504310A (en) * | 2011-10-19 | 2012-06-20 | 西南科技大学 | Preparation method of sulfonated polyimide/chitosan composite proton conducting film |
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| CN1775838A (en) * | 2005-12-15 | 2006-05-24 | 北京航空航天大学 | Method for preparing chitose proton exchange membrance for fuel cell |
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| CN101864085A (en) * | 2010-03-10 | 2010-10-20 | 合肥科振实业发展有限公司 | Method for manufacturing covalent cross-linked proton exchange membrane (PEM) for fuel cell |
| CN102504310A (en) * | 2011-10-19 | 2012-06-20 | 西南科技大学 | Preparation method of sulfonated polyimide/chitosan composite proton conducting film |
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