CN101864085A - Method for manufacturing covalent cross-linked proton exchange membrane (PEM) for fuel cell - Google Patents
Method for manufacturing covalent cross-linked proton exchange membrane (PEM) for fuel cell Download PDFInfo
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- CN101864085A CN101864085A CN201010143425A CN201010143425A CN101864085A CN 101864085 A CN101864085 A CN 101864085A CN 201010143425 A CN201010143425 A CN 201010143425A CN 201010143425 A CN201010143425 A CN 201010143425A CN 101864085 A CN101864085 A CN 101864085A
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- exchange membrane
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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
- 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
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- 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 discloses a method for manufacturing a covalent cross-linked proton exchange membrane (PEM) for a fuel cell and provides a method for manufacturing a covalent cross-linked proton exchange membrane by performing a condensation reaction on (PVA) polyvinyl alcohol and sulfonated poly-aryl ether sulfone ketone. The method has the advantages of improving electrical performance and enhancing size stability and is hopefully applicable in a PEM field. Moreover, a cross-linked film prepared from the PVA and the sulfonated poly-aryl ether sulfone ketone is also possibly suitable for direct methanol fuel cells because the PVA and the sulfonated poly-aryl ether sulfone ketone have high alcohol resistance.
Description
Technical field:
The present invention relates to a kind of proton exchange membrane of fuel cell, particularly utilize polyvinyl alcohol and sulfonated polyether sulphone ketone generation condensation reaction to make covalent cross-linked proton exchange membrane (PEM).
Background technology:
Fuel cell (FC) is a kind of without burning, directly the chemical energy of fuel and oxygenant is converted into the uninterruptable power generation technology of electric energy with electrochemical means.Owing to be not subjected to the restriction of carnot's working cycle, the energy conversion efficiency height; It is few to discharge pollutants, even can realize zero release, clean environment firendly; The system motion parts are few, and operating noise is low, have outstanding advantage.Therefore, this green novel energy source technology is subjected to the great attention of countries in the world, has become international energy area research hot of research and development, is referred to as the 4th kind of uninterruptable power generation mode after water power, thermal power generation and nuclear energy power generation.Generally believed it is the new millennium to have one of novel energy technology of future most.
According to electrolytical difference, fuel cell can be divided into five types, is respectively alkaline fuel cell (AFC), phosphoric acid type fuel cell (P lamp C), Solid Oxide Fuel Cell (SOFC), molten carbonate fuel cell (MCFC) and Proton Exchange Membrane Fuel Cells (PEMFC).Wherein Proton Exchange Membrane Fuel Cells be after AFC, PAFC, SOFC and MCFC positive fast development the 5th generation fuel cell.Except general advantage with fuel cell, also have working temperature low, start fast, no electrolyte leakage and the burn into life-span is long, the high outstanding advantage of specific power, its application is very extensive, not only can be used for building the decentralized power station, also can be used as the power truck propulsion source, but also be particularly suitable as small-sized portable power source.It is predicted that PEMFC is expected to realize business-like fuel cell the earliest after PAFC.
The critical material of PEMFC and technology comprise eelctro-catalyst, bipolar plates, membrane electrode assembly (MEA) and proton exchange membrane (PEM) etc.Wherein PEM is the core component of PEMFC, it is not a kind of diaphragm material, avoid fuel directly to contact with oxygenant, also be to select the perviousness film, bear the function of proton conducting, also be the substrate of electrode catalyst simultaneously, its performance will directly influence performance, energy conversion efficiency and the work-ing life etc. of battery.With the Nafion series of Dupont company is that the perfluoro sulfonic acid membrane of representative is the outstanding proton exchange membrane of over-all properties so far.Its structure is made of hydrophobic fluorine carbon backbone chain and hydrophilic sulfonic acid group, the former has kept the form of film to give film mechanical property preferably simultaneously, the latter can form hydrophilic passage in film, provide film to transmit the function of proton, therefore, have the electrical property height, dimensional stability is good, physical strength is high, chemical stability and the high outstanding advantage of electrochemical stability.Yet perfluoro sulfonic acid membrane also has important disadvantages: thermostability is not high, is difficult in hot operation, has limited the further raising of battery performance; Electrical property seriously relies on the water-content of film, and performance degradation is serious during dehydration; Fuel, particularly methyl alcohol, rate of permeation is too high, has reduced open circuit voltage, has influenced the performance of direct methanolica cell greatly; In addition, because the monomer purposes is single and synthesis technique is complicated, caused high cost, these defectives have seriously restricted the development of PEMFC.
Above-mentioned shortcoming just because of perfluoro sulfonic acid membrane, impel people to research and develop novel proton exchange membrane, main route comprises, perfluoro sulfonic acid membrane is improved: be used to strengthen electrical property, improve film water retaining function, improve use temperature, strengthen alcohol-rejecting ability or the like; Or thoroughly cast aside perfluorinated material, the proton exchange membrane of development of new, the method for taking have Direct Sulfonation method, direct polymerization method, doping method, radiation graft process, soda acid composite algorithm, covalent cross-linking method or the like.Compare with improving perfluoro sulfonic acid membrane, the development of new proton exchange membrane has become the main direction of research.
Although the electrical property at the SPPESK film of higher DS (for example 91%) can be approaching with Nafion, but the film of this moment is because excessive swelling, lost dimensional stability, be not suitable for secular fuel cells applications, and the electrical property of the good SPPESK film of dimensional stability is compared with Nafion and is still had certain gap.The ubiquitous problem of this reflection proton exchange membrane research field: the contradiction between the raising of sulfonated polymer mould material electrical property and physical strength descend.
For addressing this problem, can adopt following several means: the porous completion method, sulfonated protonically conductive polymer material is filled in the good porous-film of dimensional stability, guarantee to suppress as much as possible under the prerequisite of enough high electrical performances the swelling of proton-conducting material; Ionic cross-linking is prepared into the soda acid composite membrane with proton conduction sulfonated polymer (acidity) and alkaline polymer blend, suppresses excessive swelling by electrostatic interaction stronger between the acid and alkaline group and H key constraint sulfonation material; Covalent cross-linking method couples together the sulfonation material by covalent linkage and to form cross-linked network and reach the swollen effect that suppresses.Compare with ionic cross-linking with the porous completion method, the covalent cross-linking film has higher stability, because the bonding force of covalent linkage is better than the Van der Waals force of porous filling and the electrostatic force and the effect of H key of ionomer.
The preparation means of covalent cross-linking film mainly contains: form sulfonephthalein amine, metallization route by binary amine and sulfonic acid group dehydrating condensation, link to each other by alkyl; By hydroxyl Yu burn base condensation fatization; By hydroxyl Yu the condensation of burn base is acetal, hemiacetal; Form methods such as sulfonic acid fat by polyvalent alcohol and sulfonic acid group dehydration.
Polyvinyl alcohol (PVA) has better chemical stability, good film-forming properties, and is simultaneously also very cheap.PVA has been used for the polyelectrolyte field, the alkaline matter that for example mixes be used for alkaline cell, with the Nafion blend improve alcohol-rejecting ability, with the heteropolyacid blend, with burn base fatization prepare the covalent cross-linking film, with the aldehyde radical condensation be that acetal or hemiacetal prepare covalent cross-linking film or the like.
This patent utilizes PVA and SPPESK that condensation reaction takes place, and has than other small molecules polyvalent alcohols as the PVA of polymkeric substance to be more suitable for as linking agent.Prepare PVA and SPPESK covalent cross-linking film, can further improve electrical property, the enhancing dimensional stability of SPPESK film.
Summary of the invention:
Technological method to be solved by this invention: provide a kind of manufacture method of utilizing polyvinyl alcohol and sulfonated polyether sulphone ketone generation condensation reaction to make covalent cross-linked proton exchange membrane (PEM).
Main technical schemes of the present invention is may further comprise the steps:
(1) sulfonated polyether sulphone ketone is synthetic;
(2) polyvinyl alcohol is removed moisture;
(3) 4g sulfonated polyether sulphone ketone is dissolved in the 36ml deionized water, stirs and make the solution of 10wt.%, remove by filter impurity, sealing is preserved.4g PVA is added in the 36ml deionized water, soaked 24 hours, through slowly stirring intensification, sonic oscillation to dissolving fully, make the solution of 10wt%, sealing is preserved;
(4) according to mass ratio 0.05/0.95～0.50/0.50 scope, PVA solution and semi-annular jade pendant poly (aryl ether sulfone ketone) solution are mixed, sonic oscillation, mix after-filtration and remove impurity.Casting film on the smooth sheet glass of smooth surface solidified at 60 ℃, drying afterwards in following 2 days, obtained uncrosslinked PVA/ semi-annular jade pendant poly (aryl ether sulfone ketone) composite membrane.Under (120 ℃) temperature, keep heat-treating over about 2 days, obtain crosslinked film.
Sulfonated polyether sulphone ketone synthetic: Poly-s 179 ketone through 120 ℃ of vacuum-drying 24h after according to the ratio (5-20ml/g) of semi-annular jade pendant agent and Poly-s 179 ketone. under induction stirring, slowly join sulfonated reagent (oleum, the perhaps mixture of the sulfuric acid and the vitriol oil) in, uniform mixing, keep steady temperature (0-80 ℃), in the reaction times (0.25-3h), after separating, can obtain sulfonated polyether sulphone ketone.
Polyvinyl alcohol is removed moisture: at 80 ℃ of vacuum-drying 24h, remove moisture.
Main beneficial effect of the present invention is: can strengthen electrical property, improve dimensional stability, they extremely are hopeful to be applied to the PEM field.In addition, consider that PVA and sulfonated polyether sulphone ketone all have excellent resistance alcohol characteristic, their cross linking membrane also may be fit to direct methanol fuel cell.
Description of drawings:
Accompanying drawing is the crosslinked of polyvinyl alcohol of the present invention and semi-annular jade pendant poly (aryl ether sulfone ketone)
Embodiment:
As shown in the figure, main embodiment of the present invention is as follows
(1) the semi-annular jade pendant poly (aryl ether sulfone ketone) is synthetic
Poly (aryl ether sulfone ketone) through 120 ℃ of vacuum-drying 24h after, according to the certain proportion (5-20ml/g) of sulphonating agent and poly (aryl ether sulfone ketone).Slowly join under induction stirring in the sulfonated reagent (oleum, the perhaps mixture of the sulfuric acid and the vitriol oil), uniform mixing keeps steady temperature (0-80 ℃), in the reaction times (0.25-3h), can get the semi-annular jade pendant poly (aryl ether sulfone ketone) after separating.
(2) PVA removes moisture at 80 ℃ of vacuum-drying 24h.
(3) 4g semi-annular jade pendant poly (aryl ether sulfone ketone) is dissolved in the 36ml deionized water, stirs and make the solution of 10wt.%, remove by filter impurity, sealing is preserved.4g PVA is added in the 36ml deionized water, soaked 24 hours, through slowly stirring intensification, sonic oscillation to dissolving fully, make the solution of 10wt%, sealing is preserved.
(4) according to mass ratio 0.05/0.95～0.50/0.50 scope, PVA solution and semi-annular jade pendant poly (aryl ether sulfone ketone) solution are mixed, sonic oscillation, mix after-filtration and remove impurity.Casting film on the smooth sheet glass of smooth surface solidified at 60 ℃, drying afterwards in following 2 days, obtained uncrosslinked PVA/ semi-annular jade pendant poly (aryl ether sulfone ketone) composite membrane.Under (120 ℃) temperature, keep heat-treating over about 2 days, obtain crosslinked film.
Claims (3)
1. manufacture method that is used for the covalent cross-linked proton exchange membrane (PEM) of fuel cell is characterized in that may further comprise the steps:
(1) the semi-annular jade pendant poly (aryl ether sulfone ketone) is synthetic;
(2) polyvinyl alcohol is removed moisture;
(3) the semi-annular jade pendant poly (aryl ether sulfone ketone) is dissolved in the 36ml deionized water, stir and make the solution of 10wt.%, remove by filter impurity, sealing is preserved, 4g PVA is added in the 36ml deionized water, soaked 24 hours, through slowly stirring intensification, sonic oscillation to dissolving fully, make the solution of 10wt%, sealing is preserved;
(4) amount is than 0.05/0.95～0.50/0.50 scope, PVA solution and semi-annular jade pendant poly (aryl ether sulfone ketone) solution are mixed, sonic oscillation, mix after-filtration and remove impurity, casting film on the smooth sheet glass of smooth surface, solidified in following 2 days at 60 ℃ afterwards, drying, obtain uncrosslinked PVA/ semi-annular jade pendant poly (aryl ether sulfone ketone) composite membrane, under (120 ℃) temperature, keep heat-treating over about 2 days, obtain crosslinked film.
2. a kind of manufacture method that is used for the covalent cross-linked proton exchange membrane (PEM) of fuel cell according to claim 1 is characterized in that: through behind 120 ℃ of vacuum-drying 24h according to the ratio (5-20ml/g) of semi-annular jade pendant agent and Poly-s 179 ketone, under induction stirring, slowly join sulfonated reagent (oleum, the perhaps mixture of the sulfuric acid and the vitriol oil) in, uniform mixing, keep steady temperature (0-80 ℃), in the reaction times (0.25-3h), after separating, can obtain sulfonated polyether sulphone ketone.
3. a kind of manufacture method that is used for the covalent cross-linked proton exchange membrane (PEM) of fuel cell according to claim 1 is characterized in that: polyvinyl alcohol is removed moisture at 80 ℃ of vacuum-drying 24h.
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| CN201010143425A CN101864085A (en) | 2010-03-10 | 2010-03-10 | Method for manufacturing covalent cross-linked proton exchange membrane (PEM) for fuel cell |
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| CN201010143425A CN101864085A (en) | 2010-03-10 | 2010-03-10 | Method for manufacturing covalent cross-linked proton exchange membrane (PEM) for fuel cell |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105098214A (en) * | 2015-07-10 | 2015-11-25 | 同济大学 | Proton exchange membrane having self-repairing capability and preparation method thereof |
| CN107623138A (en) * | 2017-08-14 | 2018-01-23 | 四川大学 | A kind of compound proton exchange membrane and preparation method 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 |
-
2010
- 2010-03-10 CN CN201010143425A patent/CN101864085A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《中国博士学位论文全文数据库（电子期刊）工程科技I辑》 20080630 顾爽 磺化聚芳醚砜酮新型质子交换膜的制备与研究 第26页，第74-84页 1-3 , 2 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105098214A (en) * | 2015-07-10 | 2015-11-25 | 同济大学 | Proton exchange membrane having self-repairing capability and preparation method thereof |
| CN105098214B (en) * | 2015-07-10 | 2018-12-04 | 同济大学 | A kind of proton exchange membrane and preparation method thereof with self-reparing capability |
| CN107623138A (en) * | 2017-08-14 | 2018-01-23 | 四川大学 | A kind of compound proton exchange membrane and preparation method thereof |
| CN107623138B (en) * | 2017-08-14 | 2020-12-29 | 四川大学 | Composite proton exchange membrane and preparation method 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 |
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Application publication date: 20101020 |