CN101525432B - Polyarylether for preparing proton exchange membrane of fuel cell as well as preparation method and application thereof - Google Patents
Polyarylether for preparing proton exchange membrane of fuel cell as well as preparation method and application thereof Download PDFInfo
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- CN101525432B CN101525432B CN2009100384176A CN200910038417A CN101525432B CN 101525432 B CN101525432 B CN 101525432B CN 2009100384176 A CN2009100384176 A CN 2009100384176A CN 200910038417 A CN200910038417 A CN 200910038417A CN 101525432 B CN101525432 B CN 101525432B
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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
Abstract
The invention provides a polyarylether for preparing a proton exchange membrane of a fuel cell as well as a preparation method and an application thereof. The polyarylether comprises a molecular structure of a long sequence hydrophilic segment; the molecular structure comprising the long sequence hydrophilic segment in the polyarylether has long sequences with regular arrangement and is polymerized by a bis (phthalazinone) bisphenol-like monomer, a dihalo-monomer and a sulfonated dihalo-monomer by a two-step method. The invention also provides the application of the polyarylether used for preparing the proton exchange membrane of the fuel cell. The invention solves the technical problems that the proton conductivity is poor if the chemical stability is high and the chemical stability is poor and the water absorption rate is overlarge if the proton conductivity is high when the prior polyarylether is used in the fuel cell, and has high practical value.
Description
Technical field
The present invention relates to polyarylether of a kind of proton exchange membrane for the preparation of fuel cell and its preparation method and application, belong to fuel cell field.
Background technology
Fuel cell has effciency of energy transfer high (40～60%), environmental friendliness, and cleaning, pollution-free, the advantage that noiselessness etc. are outstanding is considered to the cleaning of 21 century first-selection, the energy of efficient, safe novel energy.Proton Exchange Membrane Fuel Cells (PEMFC) starts fast but also have room temperature except the advantage that possesses general fuel cell, and without electrolyte loss, water is easily discharged, and the life-span is long, the outstanding features such as specific power and specific energy height.Developing rapidly of Proton Exchange Membrane Fuel Cells (PEMFC) demonstrates good commercial promise and huge market potential.Proton exchange membrane is the core component of PEMFC, no matter the exploitation of ionic exchange film for fuel cell is in the membrane science technology, or all be of great significance at aspects such as national defence, science and technology, the energy, environment, the performance of proton exchange membrane is directly connected to the overall performance of whole fuel cell.At present general proton exchange membrane is perfluorinated sulfonic acid type proton exchange membrane in the world, wherein the most representative is the Nafion series perfluorinated sulfonic acid type proton exchange membrane that du pont company is produced, but there is complex synthetic route in this film, preparation cost is high, and the serious and temperature of the infiltration of methyl alcohol is higher than 100 and sharply descends the degradation problem owing to dehydration causes proton conductivity when spending when using in direct methanol fuel cell.Now, the research staff of various countries is devoted to seek the Nafion film substitute of high comprehensive performance.Novel material must meet following requirement: (1) is with low cost; (2) can keep good proton conductivity at high temperature (greater than 100 degree) low humidity (being lower than 60%); (3) chemical stability is good.
Polyarylether is an analog thermoplastic high performance engineering plastics, not only has good thermostability, also have concurrently anti-oxidant, resistant to hydrolysis and good mechanical property, behind the polyarylether sulfonic group, namely can be used as proton exchange membrane uses, but general sulfonated polyether needs very low EW value (equivalent weight, EW, Equivalent weight, it is the quality of the resin of every molar equivalent sulfonic acid group, unit is g/mequi.), could obtain preferably specific conductivity, but the too low bad stability that often causes again film of EW value even water-soluble, therefore occurred leading the proton rate when high electrochemical stability poor, and the carbinol-resisting infiltration is poor, or electrochemical stability leads again low disadvantage of proton rate when good, thus the over-all properties wretched insufficiency in the application of fuel cell.
Summary of the invention
The object of the invention is to overcome the deficiency that exists on the above-mentioned prior art, a kind of polyarylether of the proton exchange membrane for the preparation of fuel cell is provided, the proton exchange membrane proton conductivity of using polyarylether preparation of the present invention is high, and chemical stability is high, and the carbinol-resisting infiltration is high.
Another object of the present invention provides the simple efficiently preparation method of above-mentioned polyarylether.
A further object of the invention provides the application of above-mentioned polyarylether.
The present invention realizes above-mentioned purpose by the following technical solutions:
A kind of polyarylether of the proton exchange membrane for the preparation of fuel cell comprises the molecular structure of long sequence hydrophilic segment in its molecular structure, the molecular structure of described long sequence hydrophilic chain is suc as formula shown in the I:
N is 6～12 integer among the formula I; The molecular weight of hydrophilic segment is 6000～14500; Y is-CO-or-SO
2-; Among the formula I:
The molecular structure of the long sequence hydrophilic segment that comprises in the polyarylether of the present invention.It is the long sequence that has rule to arrange.Described polyarylether is to be polymerized through two-step approach by bis-phthalazinyl ketone biphenol monomer, dihalo-monomer and sulfonation dihalo-monomer, and its preparation method comprises the steps:
(1) with bis-phthalazinyl ketone biphenol monomer, sulfonation dihalo-monomer as reactant, add catalyzer, solvent and band aqua, reacting by heating refluxes, and then removes the band aqua, continues reacting by heating, then with the reaction mixture cool to room temperature again;
(2) in the reaction mixture of the cool to room temperature of step (1), add bis-phthalazinyl ketone biphenol monomer and dihalo-monomer, and catalyzer, solvent and band aqua reacting by heating, reflux, remove the band aqua, continue again reacting by heating, with pouring in the mixed solution of ethanol and water after the reaction mixture cooling, obtain polymkeric substance at last.
The preferred version of the mol ratio of each reactant is in the preparation process: the bis-phthalazinyl ketone biphenol monomer in the whole reaction process: the mol ratio of sulfonation dihalo-monomer and dihalo-monomer total amount is 1: 1; The dihalo-monomer: the mol ratio of sulfonation dihalo-monomer is 1: 9～7: 3; The repeating unit number of formed hydrophilic segment is 6～12 in the step (1).
Contain the bis-phthalazinyl-ketone that bis-phthalazinyl ketone biphenol monomer preferably contains '-biphenyl diphenol in the above-mentioned steps (1), the preferred sulfonation difluoro of sulfonation dihalo-monomer ketone, preferred 7: 6 of the mol ratio of the two, 9: 8,11: 10.
" add catalyzer, solvent and band aqua, reacting by heating, backflow " preferably at 150 ℃ described in the above-mentioned steps (1), preferred 3～5h of time; The preferred 175 ℃ of reaction 15～20h of " continuation reacting by heating " temperature.
Ethanol in the mixed solution of second alcohol and water described in the above-mentioned steps (2): the volume ratio of water is 1: 1.
150 ℃ of " adding bis-phthalazinyl ketone biphenol monomer and dihalo-monomer, and catalyzer, solvent and band aqua reacting by heating reflux " described in the above-mentioned steps (2) preferred temperature, time 3～5h; 175 ℃ of " continuation reacting by heating " preferred temperature, time 15～20h.
Catalyzer described in above-mentioned steps (1), (2) is preferred Anhydrous potassium carbonate all.
The aqua of band described in above-mentioned steps (1), (2) is preferred toluene all.
Solvent described in above-mentioned steps (1), (2) is preferred dimethyl sulfoxide (DMSO), N,N-dimethylacetamide or N-Methyl pyrrolidone all.
The present invention also provides the application of above-mentioned polyarylether, is the proton exchange membrane that is applied to for the preparation of fuel cell, specifically: be poured on the flat board after the polyarylether that makes is dissolved in solvent, leave standstill film forming under the heating condition, be cooled to the room temperature rear demoulding; Soak polymeric film with sulphuric acid soln, remove unnecessary sulfuric acid with deionized water or distilled water eccysis again, obtain proton exchange membrane.
The preferred dimethyl sulfoxide (DMSO) of described solvent, N,N-dimethylacetamide or N-Methyl pyrrolidone.
Described dull and stereotyped preferred glass plate.
Preferred 80 ℃ of the described temperature that leaves standstill film forming.
The sulphuric acid soln of preferred 1 mol/L of the concentration of described sulphuric acid soln; Soak time 24 hours.
Poor chemical stability when the proton rate of leading that has occurred when the present invention has overcome existing sulfonated polyether material and uses in fuel cell is high, lead proton rate again deficiency and the excessive problem of water-intake rate when chemical stability is high, reach the problem that existing perfluorinated sulfonic acid type proton exchange membrane can't at high temperature be worked, have following useful effect:
(1) the present invention contains that the proton exchange membrane of polyarylether preparation of long sequence hydrophilic segment is water insoluble, methyl alcohol, dissolve in N, N-N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone, be easy to be dissolved in casting film-forming in the solvent, have good thermostability, oxidative stability, mechanical property and proton conductivity, dimensional stability and high-temperature battery performance.
(2) preparation method provided by the invention is by one pot of two step synthesis, and hydrophilic segment forms when the first step polymerization, and hydrophilic segment forms the block type superpolymer of ordered arrangement again with bis-phthalazinyl ketone biphenol monomer, dihalo-monomer copolymerization.Owing to having formed effective aqueous favoring, film not only under high humidity proton conductivity greatly improve, even in very low humidity environment, the transmission situation of proton is compared with random copolymers of the same type, also is greatly improved.
(3) because the existence of sulfonation segment, it forms the aqueous favoring of reuniting in film, the non-proton transmission segment of film has formed the skeleton of polymkeric substance, and this structure has been resisted the attack of electronics in the environment effectively, so the oxidation-resistance of such film has had obvious improvement.
(4) proton exchange membrane preparation method technique provided by the invention is simple, and the prices of raw and semifnished materials are low, and working condition is gentle, is applied to prepare the production cost that fuel cell can significantly reduce fuel cell, has very wide application prospect.
The present invention is by the chemical structure to the Nafion film, especially to the research of transmission performance, the Microphase Structure of finding material has a great impact performance, researcher has been carried out extensive work in this regard, control the synthetic specific micromorphologic polymkeric substance that has, break through the technical bottleneck of synthetic novel material.Synthetic ionic polymer and the synthetic belt length side chain type ionic polymer that comprises long sequential polymerization thing is two thinkings of the polymkeric substance of synthetic Microphase Separation structure, and the former implementation method is simple, the polymerization route that improves existing monomer can be prepared the product of new capability, for the latter, then can be to the sulfonic long-chain branch of polymer graft band, the monomer direct polymerization that perhaps synthesizes the sulfonate form of belt length side chain, this is the synthetic purification process that reaches of a very complicated monomer.
Embodiment
Specific embodiment is by feeding intake shown in the table 1, and by the following method preparation:
(1) in the there-necked flask that agitator, airway, water trap and prolong are housed, add the bis-phthalazinyl-ketone, the sulfonation 4 that contain '-biphenyl diphenol, 4 '-difluorobenzene ketone adds Anhydrous potassium carbonate as catalyzer as reactant, adds N again, the N-N,N-DIMETHYLACETAMIDE is as solvent, toluene at 150 ℃ of band water 3h, steams toluene as the band aqua, be warmed up to 175 ℃ of reaction 17h, then with the reaction mixture cool to room temperature;
(2) bis-phthalazinyl-ketone that contains '-biphenyl diphenol, 4 that drops in the above-mentioned cooled reaction mixture, 4 '-difluorobenzene ketone, and Anhydrous potassium carbonate, N, N-N,N-DIMETHYLACETAMIDE and toluene, at 150 ℃ of backflow 3h, remove the band aqua, be warming up to again 175 ℃ of reaction 17h, then reaction mixture cooling is poured into ethanol and water volume ratio and be in 1: 1 the mixture, obtain polymkeric substance;
(3) polymkeric substance is dissolved in the solvent, after be poured on the sheet glass, leave standstill film forming at 80 ℃, be cooled to the room temperature rear demoulding;
(4) sulfuric acid with 1 mol/L soaked polymeric film 24 hours, repeatedly washed with deionized water and removed unnecessary sulfuric acid, namely obtained proton exchange membrane.
Table 1 proton exchange membrane is synthesized the magnitude relation of using of desired raw material
The proton exchange membrane that contains long sequence hydrophilic segment of above embodiment 1～3 gained is designated as respectively 1a-1,1a-2, and 1a-3, as a comparison, the random copolymers that the method that Comparative Examples adopts a step to feed intake makes is designated as 1b.
The proton exchange membrane 1a-1 of above embodiment 1～3 gained, 1a-2, the proton conductivity test result of 1a-3 under 100% relative humidity differing temps is as shown in table 2, and they all raise along with the rising of temperature; Under same temperature, in block polymer, the increase of the length of hydrophilic segment, specific conductivity increases, and in polymkeric substance 1a-1, hydrophilic segment is the shortest, and specific conductivity is minimum, and in polymkeric substance 1a-3, hydrophilic segment is the longest, and specific conductivity is the highest.They exceed 10～15 times than the feed intake proton conductivity of the random copolymers that makes of same amount one step.
Table 2 proton conductivity test result
The film that makes, with 80 Fenton reagent (3% hydrogen peroxide and the 2ppm ferrous sulfate mixing solutions) oxidations of spending 1 hour, the reduction per-cent of the quality that records, loading capacity was shown in Table 3.
Table 3 oxidation-resistance test result
| Embodiment | Proton exchange membrane | Quality reduces (%) | IEC reduces (%) |
| 1 | 1a-1 | 0 | 4.7 |
| 2 | 1a-2 | 0 | 5.6 |
| 3 | 1a-3 | 0 | 4.1 |
| Comparative Examples | 1b | 15 | 7.6 |
Claims (8)
1. the polyarylether for the preparation of the proton exchange membrane of fuel cell is a kind of block polymer, it is characterized in that comprising in its molecular structure the molecular structure of long sequence hydrophilic segment, and the molecular structure of described long sequence hydrophilic segment is suc as formula I:
N is 6～12 integer among the formula I; The molecular weight of hydrophilic segment is 6000～14500; Y is-CO-or-SO
2-;
Among the formula I:
Above-mentioned polyarylether adopts " one pot of two-step approach " preparation, it is characterized in that comprising the steps:
(1) with bis-phthalazinyl ketone biphenol monomer, sulfonation dihalo-monomer as reactant, add catalyzer, solvent and band aqua, reacting by heating refluxes, and then removes the band aqua, continues reacting by heating, then with the reaction mixture cool to room temperature again;
(2) in the reaction mixture of the cool to room temperature of step (1), add bis-phthalazinyl ketone biphenol monomer and dihalo-monomer, and catalyzer, solvent and band aqua reacting by heating, reflux, remove the band aqua, continue again reacting by heating, with pouring in the mixed solution of ethanol and water after the reaction mixture cooling, obtain polymkeric substance at last.
2. polyarylether as claimed in claim 1, it is characterized in that bis-phthalazinyl ketone biphenol monomer total amount in the described polyarylether preparation: the mol ratio of sulfonation dihalo-monomer and dihalo-monomer total amount is 1: 1; The dihalo-monomer: the mol ratio of sulfonation dihalo-monomer is 1: 9～7: 3.
3. polyarylether as claimed in claim 1 is characterized in that the catalyzer described in step (1), (2) is Anhydrous potassium carbonate; Described band aqua is toluene; Described solvent is dimethyl sulfoxide (DMSO), N,N-dimethylacetamide or N-Methyl pyrrolidone.
4. polyarylether as claimed in claim 1 is characterized in that adding described in the step (1) catalyzer, solvent and is 150 ℃ with the temperature of aqua reacting by heating and backflow, and the time is 3～5h; The temperature of described continuation reacting by heating is 175 ℃, and the time is 15～20h.
5. polyarylether as claimed in claim 1 is characterized in that adding bis-phthalazinyl ketone biphenol monomer and dihalo-monomer described in the step (2), and catalyzer, solvent and be 150 ℃ with the temperature of aqua reacting by heating and backflow, and the time is 3～5h; The temperature of described continuation reacting by heating is 175 ℃, and the time is 15～20h; Ethanol in the mixed solution of described second alcohol and water: the volume ratio of water is 1: 1.
6. the application of the described polyarylether of claim 1 is the proton exchange membrane that is applied to for the preparation of fuel cell.
7. application as claimed in claim 6 is characterized in that the method for described proton exchange membrane for the preparation of fuel cell is: be poured on the flat board after the polyarylether that makes is dissolved in solvent, leave standstill film forming under the heating condition, be cooled to the room temperature rear demoulding; Soak polymeric film with sulphuric acid soln, remove unnecessary sulfuric acid with deionized water or distilled water eccysis again, obtain proton exchange membrane.
8. application as claimed in claim 7 is characterized in that described solvent is dimethyl sulfoxide (DMSO), N,N-dimethylacetamide or N-Methyl pyrrolidone; Described flat board is sheet glass; The described temperature that leaves standstill film forming is 80 ℃; The concentration of described sulphuric acid soln is 1 mol/L; Soak time is 24 hours.
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| CN102516556A (en) * | 2011-12-01 | 2012-06-27 | 华南理工大学 | Polyarylene ether ionomer material having microphase separation structure and preparation method and application thereof |
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| CN1624022A (en) * | 2004-10-19 | 2005-06-08 | 中山大学 | Atactic sulfonated high polymer containing dual diaza naphthone and synthesis and application thereof |
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| CN1624022A (en) * | 2004-10-19 | 2005-06-08 | 中山大学 | Atactic sulfonated high polymer containing dual diaza naphthone and synthesis and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Yu-lin Chen et al.Poly(phthalazinone ether ketone) Ionomers Synthesized via N-C Coupling Reaction for Fuel Cell Applications.《Macromolecules》.2005,第38卷(第24期),第10007-10013页. * |
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