CN102324534B - Polyamide membrane with proton conduction property, and preparation method thereof - Google Patents
Polyamide membrane with proton conduction property, and preparation method thereof Download PDFInfo
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- CN102324534B CN102324534B CN201110219457.8A CN201110219457A CN102324534B CN 102324534 B CN102324534 B CN 102324534B CN 201110219457 A CN201110219457 A CN 201110219457A CN 102324534 B CN102324534 B CN 102324534B
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention belongs to modification of polyamide membranes, relates to a preparation of a functional polyamide membrane, and in particular relates to a polyamide membrane with proton conduction property, and a preparation method thereof, namely, an acid-doping modified polyamide membrane with proton conduction property, and a preparation method thereof. The polyamide membrane with proton conduction property is of a phosphoric acid or sulfuric acid-doping polyamide membrane and has a continuous and uniform porous structure, and the proton conductivity of the polyamide membrane with proton conduction property is 1.92*10<-3>-8.74*10<-2>.S.cm<-1>. The preparation method of the polyamide membrane with proton conduction property comprises the steps of preparing polyamide into a membrane with the thickness of 50-150mu m, and doping phosphoric acid and sulfuric acid into a polymer membrane, and leading the polymer membrane to obtain the proton conduction capability. The polyamide membrane after being acid-doped has higher proton conductivity; and the preparation method is simple to operate, and has no special requirements on equipment, thus having lower cost.
Description
Technical field
The invention belongs to the modification of polyamide membrane, relate to a kind of preparation of functional polyamide membrane, particularly relate to a kind of polyamide membrane with proton conduction property and preparation method thereof, specifically a kind of have polyamide membrane of proton conduction property and preparation method thereof by sour doping vario-property.
Background technology
It is the serious test that development of world economy faces that energy shortage, biological environment continue the problem such as deteriorations, thus the develop energy utilance is high and eco-friendly novel energy becomes day by day necessary with urgently.Fuel cell has been subject to people's extensive concern as a kind of clean, efficient, safe novel energy, and has manifested the good prospect of marketing.Wherein Proton Exchange Membrane Fuel Cells is because its energy density is high, environmental pollution is little and electrolyte used is solid thereby to low the gaining great popularity of corrosivity of material.
Proton exchange membrane is the core component of Proton Exchange Membrane Fuel Cells, is determining the combination property of battery.Expensive through commercial full fluorin proton exchange film, methanol permeability is high, and under high temperature, uses again.So high-performance polymer is adulterated to obtain proton-conducting by acid, alkali, thereby it is more and more concerned to be applied to this research direction of proton exchange membrane.
The base polymer that polyamide is syntheticly obtained, contained amide groups (CONH-) in the constitutional repeating unit of molecular backbone by binary acid and diamine, comprise fatty polyamide, fat-aromatic polyamide and fully aromatic polyamide.As the polymer of high crystalline, polyamide has the good performances such as high strength, wear-resisting, heat-resisting, oil resistant and resistance to chemical attack.Due to excellent combination property, therefore preparing the polyamide with specific function by modification becomes current study hotspot.
Hiroshi, M. wait people (J.Polym.Sci., Part A:Polym.Chem., 1990,28 (3): 465-477) in the side chain of polyamide, introduce the flexible structure of polarity, the conformation that reduces intermolecular interaction, increase molecule segment by destroying full rigid structure is improved its dissolubility.
The people such as Liaw (Polymer, 2006,47 (7): 2337-2348) trifluoromethyl substituent is introduced in the strand of polyamide, improved heat resistance, mechanical performance and the solubility property in organic solvent of polymer, and reduced dielectric constant and the moisture absorption of polymer.
But existing study on the modification mainly concentrates on dissolubility, raising thermal endurance and the aspects such as anti-flammability, reduction polymer dielectric constant of improving polyamide, there are no by sour doping vario-property, making it possess the report of proton conductivity.
Summary of the invention
The invention provides a kind of polyamide membrane with proton conduction property and preparation method thereof, specifically a kind of have polyamide membrane of proton conduction property and preparation method thereof by sour doping vario-property.Technical problem to be solved by this invention is the preparation of acid doping polyamide membrane, and the employing dissolubility is good, the polyamide casting film of excellent heat resistance, after the acid doping, has higher proton conductivity; This preparation method is simple to operate, and to equipment, without specific (special) requirements, cost is lower.
A kind of polyamide membrane with proton conduction property of the present invention, be the polyamide membrane of phosphoric acid or sulfuric acid doping, possesses the loose structure of continuous uniform, and the described proton conductivity with polyamide membrane of proton conduction property is 1.92 * 10
-3～8.74 * 10
-2s.cm
-1, can be applicable to the proton exchange membrane in fuel cell.
As preferred technical scheme:
A kind of thickness with polyamide membrane of proton conduction property as above is 50～150 μ m.
The present invention also provides a kind of preparation method with polyamide membrane of proton conduction property, polyamide is dissolved in organic solvent, obtain the solution that mass fraction is 5～10wt%, adopt solution-cast film forming legal system to obtain the thick film of 50～150 μ m, then respectively with phosphoric acid and the sulfuric acid described polymer film that adulterates, make described polymer film obtain proton conductivity; Can be applicable to the proton exchange membrane in fuel cell.
Describedly by the concrete steps of phosphoric acid and sulfuric acid doped polymer membrane, be respectively: soak in the phosphate aqueous solution that is 2M～10M in molar concentration by described polymer film or aqueous sulfuric acid 20～100 hours, take out after drying the polyamide membrane with proton conduction property that obtains phosphoric acid or sulfuric acid doping; The described proton conductivity with polyamide membrane of proton conduction property is 1.0 * 10
-3～9.0 * 10
-2s.cm
-1.
Wherein, a kind of preparation method with polyamide membrane of proton conduction property as above, the preparation method of described polymer film is that masking production method or solution-cast film build method are extruded in industrialization.Can adopt ripe industrialization to extrude the masking production method, also can adopt the method film forming of solution-cast.For the sample of a small amount of polymer, be applicable to adopting the method film forming of solution-cast.
A kind of preparation method with polyamide membrane of proton conduction property as above, described solution-cast film build method comprises the steps: polyamide is dissolved in organic solvent, obtain the solution that mass fraction is 5～10wt%, pour in smooth culture dish, dry and put 15～25 hours in 90～150 ℃ of baking ovens, treat that solvent volatilizees fully, make the thin polymer film that thickness is 50～150 μ m; Can carry out by controlling solution concentration the thickness of controlling diaphragm;
Described organic solvent is 1-METHYLPYRROLIDONE, DMA or methyl-sulfoxide.
Beneficial effect
(1) the acid doping polyamide membrane that prepared by the present invention possesses proton conductivity;
(2) this preparation method is simple to operate, and to equipment, without specific (special) requirements, cost is lower.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
A kind of polyamide membrane with proton conduction property of the present invention, be the polyamide membrane of phosphoric acid or sulfuric acid doping, possesses the loose structure of continuous uniform, and the described proton conductivity with polyamide membrane of proton conduction property is 1.92 * 10
-3～8.74 * 10
-2s.cm
-1, can be applicable to the proton exchange membrane in fuel cell.
Wherein, the described thickness with polyamide membrane of proton conduction property is 50～150 μ m.
Embodiment 1
The preparation of polymer film adopts the solution-cast film build method, take a certain amount of polyamide in beaker, add N, N-dimethylacetylamide (DMAc) is mixed with the polymer solution that mass fraction is 8wt%, pour in the even curface ware, dry and put 25 hours in 90 ℃ of baking ovens, treat that solvent volatilizees fully, make the thin polymer film of thickness at 104 μ m.The thin polymer film obtained being soaked 48 hours in the phosphate aqueous solution of 2M, make phosphate-doped polyamide film, by electrochemical workstation, record its proton conductivity, is 5.97 * 10
-3.
Embodiment 2
The preparation of polymer film adopts the solution-cast film build method, take a certain amount of polyamide in beaker, add 1-METHYLPYRROLIDONE (NMP) to be mixed with the polymer solution that mass fraction is 5wt%, pour in the even curface ware, dry and put 15 hours in 110 ℃ of baking ovens, treat that solvent volatilizees fully, make the thin polymer film of thickness at 50 μ m.The thin polymer film obtained is soaked 20 hours in the phosphate aqueous solution of 6M, make phosphate-doped polyamide film, recording its proton conductivity by electrochemical workstation is 4.97 * 10
-2.
Embodiment 3
The preparation of polymer film adopts industrialization to extrude the masking production method, and by a certain amount of polyamide casting film-forming after twin-screw extrusion, the thickness of film is 150 μ m.The thin polymer film obtained is soaked 100 hours in the phosphate aqueous solution of 10M, make phosphate-doped polyamide film, recording its proton conductivity by electrochemical workstation is 8.74 * 10
-2.
Embodiment 4
The preparation of polymer film adopts the solution-cast film build method, take a certain amount of polyamide in beaker, add N, N-dimethylacetylamide (DMAc) is mixed with the polymer solution that mass fraction is 6wt%, pour in the even curface ware, dry and put 15 hours in 120 ℃ of baking ovens, treat that solvent volatilizees fully, make the thin polymer film of thickness at 95 μ m.The thin polymer film obtained is soaked 25 hours in the aqueous sulfuric acid of 3M, make the polyamide film of sulfuric acid doping, recording its proton conductivity by electrochemical workstation is 1.92 * 10
-3.
Embodiment 5
The preparation of polymer film adopts the solution-cast film build method, take a certain amount of polyamide in beaker, add 1-METHYLPYRROLIDONE (NMP) to be mixed with the polymer solution that mass fraction is 10wt%, pour in the even curface ware, dry and put 20 hours in 130 ℃ of baking ovens, treat that solvent volatilizees fully, make the thin polymer film of thickness at 115 μ m.The thin polymer film obtained is soaked 50 hours in the aqueous sulfuric acid of 6M, make the polyamide film of sulfuric acid doping, recording its proton conductivity by electrochemical workstation is 2.13 * 10
-2.
Embodiment 6
The preparation of polymer film adopts the solution-cast film build method, take a certain amount of polyamide in beaker, add methyl-sulfoxide (DMSO) to be mixed with the polymer solution that mass fraction is 7wt%, pour in the even curface ware, dry and put 15 hours in 150 ℃ of baking ovens, treat that solvent volatilizees fully, make the thin polymer film of thickness at 100 μ m.The thin polymer film obtained is soaked 80 hours in the aqueous sulfuric acid of 9M, make the polyamide film of sulfuric acid doping, recording its proton conductivity by electrochemical workstation is 3.51 * 10
-2.
Claims (2)
1. the preparation method with polyamide membrane of proton conduction property, it is characterized in that: described preparation method makes the thick polymer film of 95～150 μ m by polyamide, then respectively with phosphoric acid or the sulfuric acid described polymer film that adulterates, make it obtain proton conductivity;
By the adulterate concrete steps of described polymer film of phosphoric acid and sulfuric acid, be respectively: soak in the phosphate aqueous solution that is 2M～10M in molar concentration by described polymer film or aqueous sulfuric acid 25～100 hours, take out after drying the polyamide membrane with proton conductivity that obtains phosphoric acid or sulfuric acid doping; The described proton conductivity with polyamide membrane of proton conduction property is 1.92 * 10
-3～8.74 * 10
-2scm
-1;
The preparation method of described polymer film comprises the steps: polyamide is dissolved in organic solvent, obtain the solution that mass fraction is 5～10wt%, pour in smooth culture dish, dry and put 15～25 hours in 90～150 ℃ of baking ovens, treat that solvent volatilizees fully, make the thin polymer film that thickness is 95～150 μ m;
Wherein, described organic solvent is 1-METHYLPYRROLIDONE, DMA or methyl-sulfoxide.
2. a kind of preparation method with polyamide membrane of proton conduction property according to claim 1, is characterized in that, the described thickness with polyamide membrane of proton conduction property is 95～150 μ m.
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|---|---|---|---|
| CN201110219457.8A CN102324534B (en) | 2011-08-02 | 2011-08-02 | Polyamide membrane with proton conduction property, and preparation method thereof |
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| CN201110219457.8A CN102324534B (en) | 2011-08-02 | 2011-08-02 | Polyamide membrane with proton conduction property, and preparation method thereof |
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|---|---|
| CN102324534A CN102324534A (en) | 2012-01-18 |
| CN102324534B true CN102324534B (en) | 2014-01-08 |
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| CN109786791B (en) * | 2019-01-28 | 2021-08-17 | 江苏乾景新能源产业技术研究院有限公司 | Method for enhancing operation stability of fuel cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817944A (en) * | 2005-02-07 | 2006-08-16 | 财团法人工业技术研究院 | Proton conducting membrane and production |
| CN101673831A (en) * | 2008-09-11 | 2010-03-17 | 元智大学 | Composite proton exchange membrane of acidic nanofiber/alkaline high polymer and preparation method thereof |
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| AU5480300A (en) * | 1999-06-11 | 2001-01-02 | Penn State Research Foundation, The | Proton conducting polymer membranes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817944A (en) * | 2005-02-07 | 2006-08-16 | 财团法人工业技术研究院 | Proton conducting membrane and production |
| CN101673831A (en) * | 2008-09-11 | 2010-03-17 | 元智大学 | Composite proton exchange membrane of acidic nanofiber/alkaline high polymer and preparation method thereof |
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