CN109346751A - A kind of preparation method of composite proton exchange membrane for fuel cell - Google Patents
A kind of preparation method of composite proton exchange membrane for fuel cell Download PDFInfo
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- CN109346751A CN109346751A CN201811049888.2A CN201811049888A CN109346751A CN 109346751 A CN109346751 A CN 109346751A CN 201811049888 A CN201811049888 A CN 201811049888A CN 109346751 A CN109346751 A CN 109346751A
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- nafion
- solution
- proton exchange
- exchange membrane
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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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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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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- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a kind of preparation methods of composite proton exchange membrane for fuel cell, support membrane is prepared using the common spinning of organic solution of Nafion resin and film forming, the high molecular polymer of good mechanical properties, and then it is formed a film with the organic solution double teeming of Nafion resin, on the one hand the mechanical stability that compound proton exchange membrane can be improved, on the other hand can improve the compatibility between support membrane and Nafion resin；At the same time, the Nafion resin solution of organic solvent dispersion is used to replace regular quality score that can also largely improve compatibility and penetrating power of the Nafion resin in support membrane for 5% Nafion solution casting film forming, finally, Nafion membrane relative to the preparation of direct solution casting method, under same thickness, the dosage of Nafion resin is less in composite membrane prepared by the present invention, this reduces the cost of proton exchange membrane to a certain extent.
Description
Technical field
The invention belongs to electrostatic spinning technique fields, and in particular to a kind of preparation of composite proton exchange membrane for fuel cell
Method.
Background technique
Proton Exchange Membrane Fuel Cells is a kind of energy conversion mode of clean and effective, is the heat of current energy field research
Point and forward position.One of core key material as Proton Exchange Membrane Fuel Cells, proton exchange membrane largely determines
The performance of fuel cell and service life.Perfluorosulfonic acid type proton exchange membrane is with its excellent chemical stability and good proton
Conducting power and be widely used in Proton Exchange Membrane Fuel Cells.However, the water absorption and swelling performance of perfluorinated sulfonic resin material
And the fundamental characteristics such as lower mechanical performance make it be difficult to keep good object in the long-term use under aqueous conditions
Manage structural stability and durability.In numerous physical structure enhancement type composite proton exchanging films, with polytetrafluoroethylene (PTFE)
Perforated membrane is the most extensive as the development of the compound proton exchange membrane of reinforcement, such as Gore company Gore-Select series and
Dupont company XL series multiwell polytetrafluoroethylene (PTFE) (ePTFE) enhancement type composite proton exchanging film.Polytetrafluoro in such composite membrane
The network structure of ethylene perforated membrane can effectively limit perfluorinated sulfonic resin water absorption and swelling.However, polytetrafluoroethylporous porous membrane
The strongly hydrophilic of strong hydrophobicity and proton exchange membrane makes both materials form good interface compatibility to have difficulties, and
And polytetrafluoroethylene (PTFE) itself and do not have proton conductivity, the presence of polytetrafluoroethylene (PTFE) phase can significantly reduce composite proton exchange
The proton conductivity of film.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of preparation of composite proton exchange membrane for fuel cell
Method is prepared using the common spinning of the organic solution of Nafion resin and film forming, the high molecular polymer of good mechanical properties
Support membrane, and then formed a film with Nafion resin organic solution double teeming, the machinery that compound proton exchange membrane on the one hand can be improved is steady
Qualitative energy, on the other hand can improve the compatibility between support membrane and Nafion resin；At the same time, using organic solvent point
Scattered Nafion resin solution replaces the Nafion solution casting film forming that regular quality score is 5% can also be largely
Compatibility and penetrating power of the Nafion resin in support membrane are improved, finally, relative to the preparation of direct solution casting method
Nafion membrane, under same thickness, the dosage of Nafion resin is less in composite membrane prepared by the present invention, this is to a certain extent
Reduce the cost of proton exchange membrane.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of preparation method of composite proton exchange membrane for fuel cell, steps are as follows:
(1) Nafion solution for being 5% by mass fraction, is dried under 50-100 DEG C of vacuum of temperature, removes the solvent in solution,
It is added in organic solvent later, be uniformly dispersed the Nafion organic solvent solution for preparing that mass fraction is 5-10%；
(2) it by the high molecular polymer with good filming performance, is added in organic solvent, is uniformly dispersed and prepares mass fraction
For the organic solvent solution of the high molecular polymer of 20-50%；
(3) Nafion organic solvent solution made from step (1) is added to the organic solvent of the high molecular polymer of step (2)
It in solution, is uniformly mixed and prepares spinning solution, which is poured into injection-tube and carries out electrostatic spinning preparation fiber support film；
(4) fiber support film is taken off from receiver board, fixed surrounding, by the Nafion organic solvent solution stream in step (1)
Prolong the 60-120 DEG C of constant temperature under fiber support film surface, vacuum and keep 6-36h, obtains the composite proton exchange of fuel cell
Film.
The organic solvent is tetrahydrofuran, n,N-Dimethylformamide, n,N-dimethylacetamide, N- crassitude
Ketone, the mixture of one or both of Triton X-100, acetone.
High molecular polymer in the step (2) is polylactic acid, poly lactide-glycolide acid, polylactide, gathers
The mixture of one or both of caprolactone, polyurethane, fluorinated polyurethane.
The mass fraction of high molecular polymer is 10-40% in step (3) spinning solution.
Step (3) spinning condition are as follows: applied voltage 8-20kV, the spacing of syringe needle to receiver board are 8-20cm, relatively
Humidity is 10-30%, and spinning flow velocity is 0.2-1.0ml/h, and the spinning time is 1-10h.
Beneficial effects of the present invention: the present invention uses the polyphosphazene polymer of Nafion resin and film forming, good mechanical properties
The common spinning of organic solution for closing object prepares support membrane, and then with Nafion resin organic solution double teeming film forming, on the one hand can be with
The mechanical stability for improving compound proton exchange membrane, on the other hand can improve compatible between support membrane and Nafion resin
Property；At the same time, use organic solvent dispersion Nafion resin solution replace regular quality score for 5% Nafion solution
Casting film forming can also largely improve compatibility and penetrating power of the Nafion resin in support membrane, finally, phase
For the Nafion membrane of direct solution casting method preparation, under same thickness, Nafion resin in composite membrane prepared by the present invention
Dosage it is less, this reduces the cost of proton exchange membrane to a certain extent；
Possess higher porosity, and supporting layer and proton conductive resin have good compatibility between the two.The composite proton
Exchange membrane shows good proton conductivity.
Detailed description of the invention
Fig. 1 is proton exchange membrane of the present invention and the cell performance curve figure for being commercialized 212 film of Nafion.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
The preparation method of the composite proton exchange membrane for fuel cell of the present embodiment, it is characterised in that steps are as follows:
(1) Nafion solution (Dupont company) for being 5% by a certain amount of mass fraction, is poured into beaker, true at 80 DEG C of temperature
The lower drying of sky, removes the solvent in solution, is added later a certain amount of N-Methyl pyrrolidone (NMP), ultrasonic 20min, be made
Mass fraction is the nmp solution of 5%Nafion；
(2) a certain amount of polylactic acid is taken, a certain amount of NMP is added, be uniformly dispersed the polylactic acid for preparing that mass fraction is 45%
Nmp solution；
(3) nmp solution of the nmp solution and 100g step (2) polylactic acid that take Nafion made from 125g step (1) stirs evenly
Spinning solution is obtained, wherein the mass fraction of polylactic acid is 20%, which is poured into progress electrostatic spinning preparation in injection-tube
Fiber support film；Spinning condition are as follows: applied voltage 10kV, the spacing of syringe needle to receiver board are 10cm, and relative humidity 20% is spun
Silk flow velocity is 0.3ml/h, and the spinning time is 3h.
(4) fiber support film is taken off from receiver board, fixed surrounding is molten by the Nafion organic solvent in step (1)
Liquid stream is prolonged in fiber support film surface, the lower 80 DEG C of drying of vacuum, then is warming up to 120 DEG C of constant temperature 1 hour, and it is multiple that Nafion double teeming is made
Close proton exchange membrane.
The monocell that compound proton exchange membrane assembling monocell and Nafion212 film assemble under the same conditions is carried out
Performance comparison, battery testing condition are that battery operating temperature is 65 DEG C, and hydrogen humidification temperature is 65 DEG C, and oxygen humidification temperature is
65 DEG C, hydrogen, oxygen pressure 0.05MPa(gauge pressure), battery work area is 5cm2.As shown in Figure 1, composite proton of the present invention
Exchange membrane has more preferably battery performance, this has also absolutely proved compound proton exchange membrane proton conductivity with higher.
Embodiment 2
A kind of preparation method of composite proton exchange membrane for fuel cell, steps are as follows:
(1) Nafion solution for being 5% by mass fraction, is dried under temperature 50 C vacuum, removes the solvent in solution, later
It is added in organic solvent N-Methyl pyrrolidone, is uniformly dispersed and prepares the Nafion organic solvent solution that mass fraction is 5%；
(2) by the high molecular polymer polycaprolactone with good filming performance, it is added to organic solvent N-Methyl pyrrolidone
In, it is uniformly dispersed and prepares the organic solvent solution for the high molecular polymer that mass fraction is 40%；
(3) Nafion organic solvent solution made from a certain amount of step (1) is added to having for the high molecular polymer of step (2)
It in solvent solution, is uniformly mixed and prepares spinning solution, the mass fraction of high molecular polymer is 30% in spinning solution, by the spinning
Liquid, which pours into injection-tube, carries out electrostatic spinning preparation fiber support film, spinning condition are as follows: applied voltage 8kV, syringe needle to receiver board
Spacing be 8cm, relative humidity 10%, spinning flow velocity be 0.2ml/h, the spinning time be 1h；
(4) fiber support film is taken off from receiver board, fixed surrounding, by the Nafion organic solvent solution stream in step (1)
Prolong in fiber support film surface, the lower 60 DEG C of constant temperature of vacuum keeps 36h, obtains the compound proton exchange membrane of fuel cell.
Embodiment 3
A kind of preparation method of composite proton exchange membrane for fuel cell, steps are as follows:
(1) Nafion solution for being 5% by mass fraction, is dried under 100 DEG C of vacuum of temperature, removes the solvent in solution, later
It is added in organic solvent n,N-dimethylacetamide, is uniformly dispersed and prepares the Nafion organic solvent solution that mass fraction is 8%；
(2) by the high molecular polymer (polylactic acid and polylactide) with good filming performance, organic solvent N, N- are added to
In dimethyl acetamide, it is uniformly dispersed and prepares the organic solvent solution for the high molecular polymer that mass fraction is 20%；
(3) Nafion organic solvent solution made from 100g step (1) is added to high molecular polymerization made from 100g step (2)
It in the organic solvent solution of object, is uniformly mixed and prepares spinning solution, the mass fraction of high molecular polymer is 10% in spinning solution, will
The spinning solution, which pours into injection-tube, carries out electrostatic spinning preparation fiber support film, spinning condition are as follows: applied voltage 20kV, syringe needle arrive
The spacing of receiver board is 20cm, and relative humidity 30%, spinning flow velocity is 1.0ml/h, and the spinning time is 10h；
(4) fiber support film is taken off from receiver board, fixed surrounding, by Nafion organic solvent solution made from step (1)
Curtain coating keeps 6h, obtains the compound proton exchange membrane of fuel cell in fiber support film surface, the lower 120 DEG C of constant temperature of vacuum.
Embodiment 4
A kind of preparation method of composite proton exchange membrane for fuel cell, steps are as follows:
(1) Nafion solution for being 5% by mass fraction, is dried under 75 DEG C of vacuum of temperature, removes the solvent in solution, later
It is added in tetrahydrofuran and the mixed solution of n,N-Dimethylformamide, is uniformly dispersed and prepares the Nafion that mass fraction is 10%
Organic solvent solution；
(2) by the high molecular polymer poly lactide-glycolide acid with good filming performance, be added to tetrahydrofuran and
In the mixed solution (v:v=1:1) of n,N-Dimethylformamide, it is uniformly dispersed and prepares the high molecular polymer that mass fraction is 50%
Organic solvent solution；
(3) Nafion organic solvent solution made from step (1) is added to the organic solvent of the high molecular polymer of step (2)
It in solution, is uniformly mixed and prepares spinning solution, the mass fraction of high molecular polymer is 40% in spinning solution, which is poured into
Electrostatic spinning is carried out in injection-tube prepares fiber support film, spinning condition are as follows: applied voltage 15kV, the spacing of syringe needle to receiver board
For 10cm, relative humidity 20%, spinning flow velocity is 0.5ml/h, and the spinning time is 5h；
(4) fiber support film is taken off from receiver board, fixed surrounding, by the Nafion organic solvent solution stream in step (1)
Prolong in fiber support film surface, the lower 100 DEG C of constant temperature of vacuum keeps 12h, obtains the compound proton exchange membrane of fuel cell.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (5)
1. a kind of preparation method of composite proton exchange membrane for fuel cell, it is characterised in that steps are as follows:
(1) Nafion solution for being 5% by mass fraction, is dried under 50-100 DEG C of vacuum of temperature, removes the solvent in solution,
It is added in organic solvent later, be uniformly dispersed the Nafion organic solvent solution for preparing that mass fraction is 5-10%；
(2) it by the high molecular polymer with good filming performance, is added in organic solvent, is uniformly dispersed and prepares mass fraction
For the organic solvent solution of the high molecular polymer of 20-50%；
(3) Nafion organic solvent solution made from a certain amount of step (1) is added to the high molecular polymer of step (2)
It in organic solvent solution, is uniformly mixed and prepares spinning solution, which is poured into progress electrostatic spinning in injection-tube and prepares fiber
Support membrane；
(4) fiber support film is taken off from receiver board, fixed surrounding, by the Nafion organic solvent solution stream in step (1)
Prolong the 60-120 DEG C of constant temperature under fiber support film surface, vacuum and keep 6-36h, obtains the composite proton exchange of fuel cell
Film.
2. the preparation method of composite proton exchange membrane for fuel cell according to claim 1, it is characterised in that: described to have
Solvent is tetrahydrofuran, n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, and polyethylene glycol is pungent
The mixture of one or both of base phenyl ether, acetone.
3. the preparation method of composite proton exchange membrane for fuel cell according to claim 1, it is characterised in that: the step
Suddenly the high molecular polymer in (2) be polylactic acid, poly lactide-glycolide acid, polylactide, polycaprolactone, polyurethane,
The mixture of one or both of fluorinated polyurethane.
4. the preparation method of composite proton exchange membrane for fuel cell according to claim 1, it is characterised in that: the step
Suddenly the mass fraction of high molecular polymer is 10-40% in (3) spinning solution.
5. the preparation method of composite proton exchange membrane for fuel cell according to claim 1, it is characterised in that: the step
Suddenly (3) spinning condition are as follows: applied voltage 8-20kV, the spacing of syringe needle to receiver board are 8-20cm, relative humidity 10-30%, are spun
Silk flow velocity is 0.2-1.0ml/h, and the spinning time is 1-10h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110336063A (en) * | 2019-07-16 | 2019-10-15 | 成都新柯力化工科技有限公司 | A kind of method that roll-to-roll printing protective layer prepares fuel battery proton exchange film |
| CN110534779A (en) * | 2019-08-21 | 2019-12-03 | 清华大学 | A kind of enhanced membrane electrode of non-fluorinated polymer and preparation method thereof |
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| CN101367903A (en) * | 2008-08-07 | 2009-02-18 | 同济大学 | Enhancement type composite proton exchanging film based on semi-interpenetrating network |
| CN103469352A (en) * | 2012-06-06 | 2013-12-25 | 华东理工大学 | Preparation method of polymer nanofiber membrane containing perfluorinated sulfonic acid |
| CN104134812A (en) * | 2013-05-02 | 2014-11-05 | 山东东岳高分子材料有限公司 | Fiber-net-reinforced polymer electrolyte membrane and preparation method thereof |
| CN105355949A (en) * | 2015-10-16 | 2016-02-24 | 同济大学 | Preparation method of nanofiber composite proton exchange membrane |
| CN107994244A (en) * | 2016-10-21 | 2018-05-04 | 中国科学院大连化学物理研究所 | The preparation and film and application of a kind of Multi-layer composite proton exchange membrane |
| CN108428837A (en) * | 2018-02-11 | 2018-08-21 | 湖南德沃普新能源有限公司 | A kind of side chain type sulfonated polyimides/perfluorinated sulfonic acid composite membrane and its preparation method and application |
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| US6692858B2 (en) * | 2000-03-31 | 2004-02-17 | Asahi Glass Company, Limited | Electrolyte membrane for polymer electrolyte fuel cell and producing method thereof |
| CN101367903A (en) * | 2008-08-07 | 2009-02-18 | 同济大学 | Enhancement type composite proton exchanging film based on semi-interpenetrating network |
| CN103469352A (en) * | 2012-06-06 | 2013-12-25 | 华东理工大学 | Preparation method of polymer nanofiber membrane containing perfluorinated sulfonic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110336063A (en) * | 2019-07-16 | 2019-10-15 | 成都新柯力化工科技有限公司 | A kind of method that roll-to-roll printing protective layer prepares fuel battery proton exchange film |
| CN110534779A (en) * | 2019-08-21 | 2019-12-03 | 清华大学 | A kind of enhanced membrane electrode of non-fluorinated polymer and preparation method thereof |
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