CN1166723C - Polystyrene sulfonate film for low-temp. direct methanol fuel cell and preparation process thereof - Google Patents
Polystyrene sulfonate film for low-temp. direct methanol fuel cell and preparation process thereof Download PDFInfo
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- CN1166723C CN1166723C CNB021151857A CN02115185A CN1166723C CN 1166723 C CN1166723 C CN 1166723C CN B021151857 A CNB021151857 A CN B021151857A CN 02115185 A CN02115185 A CN 02115185A CN 1166723 C CN1166723 C CN 1166723C
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Abstract
The present invention relates to a technology for electrochemical fuel cells, particularly to a polystyrene sulfonic acid film for low temperature direct methanol fuel cells and a preparation method thereof. In the present invention, industrial polystyrene is used as a raw material and has sulfonation by using a complex compound of an acylating agent and concentrated sulphuric acid as a sulfonating agent under the protection of inert gas; a polystyrene sulfonic acid film with low sulfonation degree is prepared by a flow casting method or other film forming methods; the polystyrene sulfonic acid film is modified by controlling the sulfonation degree of the polystyrene sulfonic acid film and the distribution condition of sulfonic acid groups; the permeation rate of methanol in the film is reduced, and the methanol resistant performance of the film is improved under the precondition that the proton conduction performance of the film is unchanged. The polystyrene sulfonic acid film of the present invention basically solves the difficult problem of methanol permeation of a proton exchange film for a direct methanol fuel cell and has the advantages of simple preparation technology, low price of raw materials and low preparation cost. The polystyrene sulfonic acid film can be used as a new proton exchange film for a low temperature direct methanol fuel cell.
Description
Technical field
The present invention relates to electrochemical fuel cell technology, be meant low temperature direct methanol fuel cell polystyrene sulfonate film in more detail.The invention still further relates to its preparation method.
Background technology
Fuel cell is a kind of mechanism of new electrochemical power sources of high performance, environmentally safe.By today of pay attention to day by day, the research and development of fuel cell has caused the attention of many developed countries in environment protection.Developed country governments such as the U.S., Japan, Canada have formulated the development that the policy of being correlated with promotes national fuel cell.Proton Exchange Membrane Fuel Cells be the 5th generation the advanced fuel battery, except general characteristic with fuel cell as the restriction that is not subjected to carnot's working cycle, the energy conversion efficiency advantages of higher, but have also simultaneously that normal temperature starts fast, no electrolyte loss, life-span are long, specific power and the high outstanding advantage of specific energy.Classify according to its employed fuel, now the Proton Exchange Membrane Fuel Cells of research mainly contains two classes: a class is to be the hydrogen-oxygen fuel cell of fuel with pure hydrogen or reformer hydrogen; Another kind of is to be the direct methanol fuel cell (DMFC) of fuel with methyl alcohol directly.Though hydrogen is Proton Exchange Membrane Fuel Cells ideal fuel, when being fuel with the pure hydrogen, the storage of hydrogen, conveying etc. not only have certain danger, and the investment that will set up the supply shared device of hydrogen is very huge; Though reformer hydrogen can be avoided the service of newly-built fuel, need to increase the reformation scavenging process of a gas, this also will increase battery cost undoubtedly; Be the battery structure complexity of the hydrogen-oxygen fuel cell of fuel with hydrogen in addition, thereby influence and limited the scale operation and the application of hydrogen-oxygen fuel cell to a certain extent.And than hydrogen-oxygen fuel cell, the most outstanding advantage of direct methanol fuel cell is exactly that methyl alcohol source is rich and easy to get, and low price is easy to carry about with one and stores.Owing to adopt mode, thereby make the simple in structure of direct methanol fuel cell with liquid feeding, volume of battery and weight little (be about hydrogen-oxygen fuel cell 1/3), battery cost lower (be about hydrogen-oxygen fuel cell 1/2).Therefore, direct methanol fuel cell is suitable for the removable propulsion source as various uses especially.The nineties in 20th century, the research and development of direct methanol fuel cell more and more were subjected to the attention of basic science circle and industry member.
The methanol crossover problem of proton exchange membrane is the main difficult technical that direct methanol fuel cell exists at present.At present because the perfluoro sulfonic acid membrane such as the Nafion film that extensively adopt in hydrogen-oxygen fuel cell have higher methanol permeability, methyl alcohol can see through the reaction that proton exchange membrane does not directly produce electric current in negative electrode and oxygen generation, can make poisoning of catalyst on the one hand, reduce the utilization ratio of methyl alcohol, cause the loss of fuel; Also can cause the oxygen electrode polar to increase significantly on the other hand, thereby reduce the overall performance of battery, and make the work-ing life of DMFC system short.Therefore, reducing the rate of permeation of methyl alcohol by proton exchange membrane, prepare that the pure ability of resistance is good, high-performance, proton exchange membrane material cheaply, is the important topic of the high performance direct methanol fuel cell of exploitation.Current, countries in the world have all focused on this aspect about the emphasis of the research and development of ionic exchange film for fuel cell.Wherein, patent No. WO99/29763 themes as the preparation of the dielectric film that is used for fuel cell, and people such as T.Soczka.Guth discloses a kind of sulfonated polyether-ether-ketone (PEEK) proton exchange membrane and preparation technology thereof in the patent.It is compared with perfluoro sulfonic acid membrane, though have and hinder pure ability preferably, but still exist preparing raw material complex process, the more high defective of price production cost more expensive, film, thereby still restricting its large-scale application in the direct methanol fuel cell field.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, a kind of low temperature direct methanol fuel cell polystyrene sulfonate film and preparation method thereof is provided, promptly come p-poly-phenyl vinyl sulfonic acid film to carry out modification by the sulfonation degree of control polystyrene sulfonate film and the distribution situation of sulfonic acid group, under the prerequisite of the proton conduction performance that does not influence film, reduce the rate of permeation of methyl alcohol in film, improve the alcohol-rejecting ability of mould material.
Low temperature direct methanol fuel cell proton exchange membrane of the present invention is that the polystyrene with technical grade is a raw material; under protection of inert gas, make sulphonating agent with the complex compound of the acylating agent and the vitriol oil; carry out sulfonation, and the polystyrene sulfonate film for preparing by films such as casting method, rolling process, coating method or cement-dipping methods.
Low temperature direct methanol fuel cell of the present invention comprises following three steps with the preparation method of polystyrene sulfonate film:
(1) preparation of sulphonating agent-acyl group sulfuric acid complexing salt:
Acylating agent and 1, the 2-ethylene dichloride places test tube by 1: 0.5～3.5 mixed, is mixed with solution, and feeds rare gas element and protect, and this solution is freezing, then feeding under the protection of inert gas, add the vitriol oil again, and the cover lid sealing is standby;
(2) preparation of polystyrene sulfonate film material:
(1) granules of polystyrene is dissolved in 1, it is that the solution of 10 grams per liters～300 grams per liters places reflux that the 2-ethylene dichloride is mixed with the bulking value specific concentration, and feeds protection of inert gas;
(2) under the mobile inert gas environment, do not stop to stir, heat this solution to room temperature～85 ℃, previously prepared acyl group sulfuric acid complexing salt is injected solution in 10%～80% the ratio that is equivalent to the polystyrene molar weight, this temperature next time stream carried out sulfonation reaction 0.5～5 hour, the 2-propyl alcohol that adds 1～30ml at last, stopped reaction;
(3), after vacuum-evaporation concentrates, dropwise drip in 0.1L～4.5L distilled water concentrated solution complete until polymer precipitation with the cooling of resulting solution;
(4) filter polymer precipitation, place reflux to use distilled water wash 0.5～5 hour, filter once more.With final product under room temperature～85 ℃, 0.6 normal atmosphere～normal pressure dry 0.5～50 hour, promptly obtain the polystyrene sulfonate film material at last;
(3) preparation of film:
Adopt casting method, with above-mentioned resulting polystyrene sulfonate film material dissolves in the mixed solvent of toluene and butanols, the volume ratio of toluene and butanols is 7: 4～1, make macromolecular solution, this solution is tiled in curtain coating on the polytetrafluoroethyldisk disk, vacuum-drying at room temperature is complete to solvent evaporation, again in room temperature～60 ℃, and under 0.6 normal atmosphere～condition of normal pressure dry 10～120 minutes; Perhaps adopt rolling process, cement-dipping method or coating method prepared to obtain polystyrene sulfonate film;
Described acylating agent is meant acyl compounds, concrete acyl chlorides, acid anhydrides or the ester of being meant;
Described rare gas element is meant nitrogen, argon gas or helium.
The optimum condition of above-mentioned steps of the present invention is as follows:
(1) preparation of sulphonating agent-acyl group sulfuric acid complexing salt:
With acid anhydrides and 1, the 2-ethylene dichloride places test tube by 1: 1.0～3.0 mixed, is mixed with solution, and feeds nitrogen and protect, and this solution is freezing, then under logical nitrogen protection, add the vitriol oil again, and the cover lid sealing is standby;
(2) preparation of polystyrene sulfonate film material:
(1) granules of polystyrene is dissolved in 1, it is that the solution of 50 grams per liters～200 grams per liters places reflux that the 2-ethylene dichloride is mixed with the bulking value specific concentration, and logical nitrogen protection;
(2) under the flowing nitrogen environment, do not stop to stir, heat this solution to room temperature～85 ℃, previously prepared acyl group sulfate complex is injected solution in 15%～20% the ratio that is equivalent to the polystyrene molar weight, this temperature next time stream carried out sulfonation reaction 0.5～3 hour, add 2-propyl alcohol stopped reaction at last;
(3), after vacuum-evaporation concentrates, dropwise drip in distilled water until polymer precipitation complete with injection system concentrated solution with the cooling of resulting solution;
(4) filter polymer precipitation, place reflux, filter once more, with final product under room temperature～60 ℃, 0.6 normal atmosphere～normal pressure dry 10～50 hours, promptly obtain the polystyrene sulfonate film material at last with distilled water wash 0.5～3 hour;
(3) preparation of film:
With above-mentioned resulting polystyrene sulfonate film material dissolves in the mixed solvent of toluene and butanols, the volume ratio of toluene and butanols is 7: 3～1, make macromolecular solution, this solution is tiled on the polytetrafluoroethyldisk disk, vacuum-drying at room temperature is complete to solvent evaporation, again in room temperature～60 ℃, 0.6 normal atmosphere～normal pressure dry 0.5～2 hour down, perhaps adopting rolling process, cement-dipping method or coating method technology to prepare sulfonation degree is 15%～50% polystyrene sulfonate film.
The sulfonation degree of the prepared polystyrene sulfonate film material of the present invention calculates by chemistry titration, specific as follows: the 0.3g sulfonated polymer is dissolved in the mixed solvent of the toluene of 30ml and butanols, the volume ratio of toluene and butanols is 9: 1, the NaOH/ methyl alcohol standardized solution of 0.1N is used for the titration polymers soln with after 5 times of the methyl alcohol dilutions, selection phenolphthalein is indicator, utilize the acid-base neutralisation reaction principle, reddening with phenolphthalein is reaction end, the amount of NaOH by participating in reaction calculates the amount of sulfonate group, draws sulfonation degree.
The present invention compared with prior art has following advantage:
1. the proton exchange membrane that the polystyrene sulfonate film material that the preparation method who utilizes the present invention to propose makes is done has higher proton conduction performance and alcohol-rejecting ability preferably under low temperature (20-90 ℃) condition.Wherein sulfonation degree is that the φ value of 20% low sulfonated polystyrene sulfonate film is higher than the φ value of Nafion117 film, specifically sees table 1 for details.Because the proton conduction of sulfonated polymeric film is all relevant with the thickness of film with methanol crossover, the proton conductivity of the film of the different thickness that same material is done and methanol permeability all have difference.Therefore, for the performance of characterization of membrane more objectively, be used as weighing the standard of film properties in order to the ratio psi of proton conductivity and methanol permeability, the performance of the high more then film of φ value is good more.
2. sample 1 proton conductivity at room temperature that the preparation method who utilizes the present invention to propose makes reaches 6.7 * 10
-2Ω
-1Cm
-1, near the proton conductivity of Nafion117 film under this temperature, and its methanol permeability specifically sees table 1 for details well below the methanol permeability of Nafion117 film.
3. the sulfonation degree of utilizing the present invention to prepare is that the performance of 20% polystyrene sulfonate film obviously is better than Nafion117 film (this film is the perfluoro sulfonic acid membrane that is widely used at present in the direct methanol fuel cell) in being lower than 100 ℃ of temperature ranges.
4. the present invention has solved the methanol crossover difficult problem of proton exchange membrane substantially, and its production technique is simple relatively, and the prices of raw and semifnished materials are lower, and production cost is low relatively.Its application can promote the development of low temperature direct methanol fuel cell.
Embodiment
Embodiment 1
Preparation acyl group sulfuric acid complexing salt: with acetic anhydride and 1, the 2-ethylene dichloride places test tube by 1: 2.0 mixed, is mixed with solution, and feeding nitrogen is protected.This solution is freezing, then under logical nitrogen protection, add the vitriol oil again, and the cover lid sealing is standby.
The 20g polystyrene is dissolved in 1 of 200ml, forms macromolecular solution in the 2-ethylene dichloride and place reflux.Under protection of nitrogen gas, solution is heated to 60 ℃, in solution, inject 0.038mol ready-formed ethanoyl sulfuric acid complexing salt solution, and stirring and refluxing was carried out sulfonation reaction 2 hours under this temperature.The 2-propyl alcohol that adds 10ml at last, stopped reaction.With the cooling of resulting solution, vacuum-evaporation concentrates, and concentrated solution is dropwise dripped into precipitation polymers in the 1.5L distilled water with injection system.Again polymer precipitation is filtered, place reflux to use 1L distilled water wash 2 hours, filter once more.With final product under 60 ℃, 0.9 normal atmosphere dry 30 hours, promptly obtain the sulfonated polymers mould material at last.Get in the mixed solvent that sulfonated polymer 0.3g behind the drying and dehydrating is dissolved in the toluene of 30ml and butanols, the volume ratio of toluene and butanols is 9: 1, with the NaOH/ methyl alcohol standardized solution of 0.1N with titration polymers soln after 5 times of the methyl alcohol dilutions, selection phenolphthalein is indicator, and recording its sulfonation degree is 20%.
The above-mentioned mould material that makes is dissolved in the mixed solvent of toluene and butanols, and the volume ratio of toluene and butanols is 7: 3, makes macromolecular solution.This solution is tiled in curtain coating on the polytetrafluoroethyldisk disk, and vacuum-drying at room temperature is complete to solvent evaporation.Under 50 ℃ of conditions, 0.6 normal atmosphere dry 60 minutes again.Can obtain the polystyrene sulfonate film of low sulfonation degree, be sample 1.Should earlier film be immersed in the deionized water 3 hours before using under 80 ℃.
Embodiment 2
Preparation acyl group sulfuric acid complexing salt: with methyl propionate and 1, the 2-ethylene dichloride places test tube by 1: 2.5 mixed, is mixed with solution, and feeding nitrogen is protected.This solution is freezing, then under logical nitrogen protection, add the vitriol oil again, and the cover lid sealing is standby.
The 20g polystyrene is dissolved in 1 of 200ml, forms macromolecular solution in the 2-ethylene dichloride and place reflux.Under protection of nitrogen gas, solution is heated to 85 ℃, injection 0.034mol ready-formed propionyl sulfuric acid complexing salt solution in solution, and stirring and refluxing was carried out sulfonation reaction 3 hours under this temperature.The 2-propyl alcohol that adds 10ml at last, stopped reaction.With the cooling of resulting solution, vacuum-evaporation concentrates, and concentrated solution is dropwise dripped into precipitation polymers in the 1.5L distilled water with injection system.Again polymer precipitation is filtered, place reflux to use 1L distilled water wash 4 hours, filter once more.With final product under 60 ℃, normal pressure dry 48 hours, promptly obtain the sulfonated polymers mould material at last.Get in the mixed solvent that sulfonated polymer 0.3g behind the drying and dehydrating is dissolved in the toluene of 30ml and butanols, the volume ratio of toluene and butanols is 9: 1, with the NaOH/ methyl alcohol standardized solution of 0.1N with titration polymers soln after 5 times of the methyl alcohol dilutions, selection phenolphthalein is indicator, and recording its sulfonation degree is 18%.
The above-mentioned mould material that makes is dissolved in the mixed solvent of toluene and butanols, and the volume ratio of toluene and butanols is 7: 3, makes macromolecular solution.This solution is tiled in curtain coating on the polytetrafluoroethyldisk disk, and vacuum-drying at room temperature is complete to solvent evaporation.Under 50 ℃, 0.8 normal atmosphere dry 60 minutes again.Can obtain the polystyrene sulfonate film of low sulfonation degree, be sample 2.Should earlier film be immersed in the deionized water 3 hours before using under 80 ℃.
Embodiment 3
Preparation acyl group sulfuric acid complexing salt: with ethyl formate and 1, the 2-ethylene dichloride places test tube by 1: 0.5 mixed, is mixed with solution, and the feeding argon gas is protected.This solution is freezing, then under logical argon shield, add the vitriol oil again, and the cover lid sealing is standby.
The 2g polystyrene is dissolved in 1 of 200ml, forms macromolecular solution in the 2-ethylene dichloride and place reflux.Under the protection of argon gas, solution is heated to 85 ℃, injection 0.029mol acyl group sulfuric acid complexing salt solution in solution, and stirring and refluxing was carried out sulfonation reaction 0.5 hour under this temperature.The 2-propyl alcohol that adds 1ml at last, stopped reaction.With the cooling of resulting solution, vacuum-evaporation concentrates, and concentrated solution is dropwise dripped into precipitation polymers in the 0.1L distilled water with injection system.Again polymer precipitation is filtered, place reflux to use 1L distilled water wash 0.5 hour, filter once more.With final product under room temperature, 0.6 normal atmosphere dry 0.5 hour, promptly obtain the sulfonated polymers mould material at last.Get in the mixed solvent that sulfonated polymer 0.3g behind the drying and dehydrating is dissolved in the toluene of 30ml and butanols, the volume ratio of toluene and butanols is 9: 1, with titration polymers soln after 5 times of the methyl alcohol dilutions, selection phenolphthalein is indicator, measures its sulfonation degree with the NaOH/ methyl alcohol standardized solution of 0.1N.
The above-mentioned mould material that makes is dissolved in the mixed solvent of toluene and butanols, and the volume ratio of toluene and butanols is 7: 1, makes macromolecular solution.This solution is tiled in curtain coating on the polytetrafluoroethyldisk disk, and vacuum-drying at room temperature is complete to solvent evaporation.Under room temperature, 0.6 atmospheric pressure dry 10 minutes again.Can obtain the polystyrene sulfonate film of low sulfonation degree.Should earlier film be immersed in the deionized water 3 hours before using under 80 ℃.
Embodiment 4
Preparation acyl group sulfuric acid complexing salt: with acetate acyl chlorides and 1, the 2-ethylene dichloride places test tube by 1: 3.5 mixed, is mixed with solution, and the feeding helium is protected.This solution is freezing, then under the helium injection gas shiled, add the vitriol oil again, and the cover lid sealing is standby.
The 60g polystyrene is dissolved in 1 of 200ml, forms macromolecular solution in the 2-ethylene dichloride and place reflux.Under the protection of helium, solution is heated to room temperature, injection 0.032mol ready-formed acyl group sulfuric acid complexing salt solution in solution, and stirring and refluxing was carried out sulfonation reaction 5 hours under this temperature.The 2-propyl alcohol that adds 30ml at last, stopped reaction.The cooling of resulting solution, vacuum-evaporation concentrates, and concentrated solution is dropwise dripped into precipitation polymers in the 4.5L distilled water with injection system.Again polymer precipitation is filtered, place reflux to use 1L distilled water wash 5 hours, filter once more.With final product under 85 ℃, normal pressure dry 50 hours, promptly obtain the sulfonated polymers mould material at last.Get in the mixed solvent that sulfonated polymer 0.3g behind the drying and dehydrating is dissolved in the toluene of 30ml and butanols, the volume ratio of toluene and butanols is 9: 1, with titration polymers soln after 5 times of the methyl alcohol dilutions, selection phenolphthalein is indicator, measures its sulfonation degree with the NaOH/ methyl alcohol standardized solution of 0.1N.
The above-mentioned mould material that makes is dissolved in the mixed solvent of toluene and butanols, and the volume ratio of toluene and butanols is 7: 4, makes macromolecular solution.This solution is tiled in curtain coating on the polytetrafluoroethyldisk disk, and vacuum-drying at room temperature is complete to solvent evaporation.Under 60 ℃, normal pressure dry 120 minutes again.Can obtain the polystyrene sulfonate film of low sulfonation degree.Should earlier film be immersed in the deionized water 3 hours before using under 80 ℃.
Embodiment 5
Preparation acyl group sulfuric acid complexing salt: with formic anhydride and 1, the 2-ethylene dichloride places test tube by 1: 1.5 mixed, is mixed with solution, and the feeding argon gas is protected.This solution is freezing, then under logical argon shield, add the vitriol oil again, and the cover lid sealing is standby.
The 40g polystyrene is dissolved in 1 of 200ml, forms macromolecular solution in the 2-ethylene dichloride and place reflux.Under the nitrogen protection effect, solution is heated to 85 ℃, injection 0.112mol ready-formed acyl group sulfuric acid complexing salt solution in solution, and stirring and refluxing was carried out sulfonation reaction 3 hours under this temperature.The 2-propyl alcohol that adds 30ml at last, stopped reaction.The cooling of resulting solution, vacuum-evaporation concentrates, and concentrated solution is dropwise dripped into precipitation polymers in the 3L distilled water with injection system.Again polymer precipitation is filtered, place reflux to use 1L distilled water wash 4 hours, filter once more.At last with final product 60 ℃ of following vacuum-dryings 2 days, promptly obtain the sulfonated polymers mould material.Get in the mixed solvent that sulfonated polymer 0.3g behind the drying and dehydrating is dissolved in the toluene of 30ml and butanols, the volume ratio of toluene and butanols is 9: 1, with titration polymers soln after 5 times of the methyl alcohol dilutions, selection phenolphthalein is indicator, measures its sulfonation degree with the NaOH/ methyl alcohol standardized solution of 0.1N.
Adopt cement-dipping method, the thickness aqueous solution of preparation polyvinyl alcohol with the above-mentioned mould material powder uniform mixing pulp liquid that makes, after deaeration, is coated with it and scrapes on the polyvinyl screen cloth air-dry film forming.
Embodiment 6
Preparation acyl group sulfuric acid complexing salt: with formic anhydride and 1, the 2-ethylene dichloride places test tube by 1: 1.5 mixed, is mixed with solution, and the feeding argon gas is protected.This solution is freezing, then under logical argon shield, add the vitriol oil again, and the cover lid sealing is standby.
The 40g polystyrene is dissolved in 1 of 200ml, forms macromolecular solution in the 2-ethylene dichloride and place reflux.Under the nitrogen protection effect, solution is heated to 85 ℃, injection 0.112mol ready-formed acyl group sulfuric acid complexing salt solution in solution, and stirring and refluxing was carried out sulfonation reaction 3 hours under this temperature.The 2-propyl alcohol that adds 30ml at last, stopped reaction.The cooling of resulting solution, vacuum-evaporation concentrates, and concentrated solution is dropwise dripped into precipitation polymers in the 3L distilled water with injection system.Again polymer precipitation is filtered, place reflux to use 1L distilled water wash 4 hours, filter once more.At last with final product 60 ℃ of following vacuum-dryings 2 days, promptly obtain the sulfonated polymers mould material.Get in the mixed solvent that sulfonated polymer 0.3g behind the drying and dehydrating is dissolved in the toluene of 30ml and butanols, the volume ratio of toluene and butanols is 9: 1, with titration polymers soln after 5 times of the methyl alcohol dilutions, selection phenolphthalein is indicator, measures its sulfonation degree with the NaOH/ methyl alcohol standardized solution of 0.1N.
Adopt coating method, above-mentioned mould material is mixed with slurries, be poured on the steel plate of completing woven fiber glass in advance, promote film liquid with glass stick, cover polyester film, squeeze residul liquid-removing, press steel plate with pressure roller, heat tracing is cooled to room temperature at last, peels off polyester film and promptly obtains required proton exchange membrane.
Embodiment 7
Preparation acyl group sulfuric acid complexing salt: with formic anhydride and 1, the 2-ethylene dichloride places test tube by 1: 1.5 mixed, is mixed with solution, and the feeding argon gas is protected.This solution is freezing, then under logical argon shield, add the vitriol oil again, and the cover lid sealing is standby.
The 40g polystyrene is dissolved in 1 of 200ml, forms macromolecular solution in the 2-ethylene dichloride and place reflux.Under the nitrogen protection effect, solution is heated to 85 ℃, injection 0.112mol ready-formed acyl group sulfuric acid complexing salt solution in solution, and stirring and refluxing was carried out sulfonation reaction 3 hours under this temperature.The 2-propyl alcohol that adds 30ml at last, stopped reaction.The cooling of resulting solution, vacuum-evaporation concentrates, and concentrated solution is dropwise dripped into precipitation polymers in the 3L distilled water with injection system.Again polymer precipitation is filtered, place reflux to use 1L distilled water wash 4 hours, filter once more.At last with final product 60 ℃ of following vacuum-dryings 2 days, promptly obtain the sulfonated polymers mould material.Get in the mixed solvent that sulfonated polymer 0.3g behind the drying and dehydrating is dissolved in the toluene of 30ml and butanols, the volume ratio of toluene and butanols is 9: 1, with titration polymers soln after 5 times of the methyl alcohol dilutions, selection phenolphthalein is indicator, measures its sulfonation degree with the NaOH/ methyl alcohol standardized solution of 0.1N.
Adopt rolling process, the high-pressure polyethylene of using as tackiness agent is added hot milling in rolling press complete to plasticizing, add flexibilizing agent rubber immediately, homogeneous mixes the back and adds minor amounts of lubricants and the above-mentioned mould material powder that makes, mixing repeatedly, membrane, nylon net cloth on the film both sides cover, and through oil press hot pressing, the cooling film forming.
The comparison of table 1 polystyrene sulfonate film and Nafion film properties
| Kind | Sample 1 | Sample 2 | Nafion117 | |
| The thickness of film/μ m | 338 | 196 | 187 | |
| Proton conductivity Ω -1cm -1(10 -2) | 25℃ | 6.70 | 5.90 | 7.90 |
| 60℃ | 12.60 | 10.80 | 14.90 | |
| Methanol permeability | 25℃ | 5.20 | 5.20 | 14.10 |
| 60℃ | 11.90 | 10.80 | 34.40 | |
| φ value (10 5) Ω -1cm 3s -1 | 25℃ | 1.29 | 1.13 | 0.56 |
| 60℃ | 1.06 | 1.00 | 0.43 |
Claims (2)
1. low temperature direct methanol fuel cell low sulfonation degree polystyrene sulfonate film; it is characterized in that it being that polystyrene with technical grade is a raw material; under protection of inert gas, make sulphonating agent with the complex compound of the acylating agent and the vitriol oil; carry out sulfonation; come p-poly-phenyl vinyl sulfonic acid film to carry out modification by the sulfonation degree of control polystyrene sulfonate film and the distribution situation of sulfonic acid group, and prepare by films such as casting method, rolling process, coating method or cement-dipping methods.Its more specifically the preparation method comprise following three steps:
(1) preparation of sulphonating agent-acyl group sulfuric acid complexing salt:
Acylating agent and 1, the 2-ethylene dichloride places test tube by 1: 0.5～3.5 mixed, is mixed with solution, and feeds rare gas element and protect, and this solution is freezing, then under logical protection of inert gas, add the vitriol oil again, and the cover lid sealing is standby;
Described acylating agent is meant acyl compounds, concrete acyl chlorides, acid anhydrides or the ester of being meant; Described rare gas element is meant nitrogen, argon gas or helium;
(2) preparation of low sulfonation degree polystyrene sulfonate film material:
(1) granules of polystyrene is dissolved in 1, it is that the solution of 10 grams per liters～300 grams per liters places reflux that the 2-ethylene dichloride is mixed with the bulking value specific concentration, and feeds protection of inert gas;
(2) under the mobile inert gas environment, do not stop to stir, heat this solution to room temperature～85 ℃, previously prepared acyl group sulfate complex is injected solution in 10%～80% the ratio that is equivalent to the polystyrene molar weight, this temperature next time stream carried out sulfonation reaction 0.5～5 hour, add the 2-propyl alcohol at last, stopped reaction;
(3), after vacuum-evaporation concentrates, dropwise drip in distilled water until polymer precipitation complete with injection system concentrated solution with the cooling of resulting solution;
(4) filter polymer precipitation, place reflux to use distilled water wash 0.5～5 hour, filter once more, at last with final product in room temperature～85 ℃ following 0.6 normal atmosphere～constant pressure and dry 0.5～50 hour, promptly obtain the polystyrene sulfonate film material of low sulfonation degree;
(3) preparation of film:
Adopt casting method, with above-mentioned resulting polystyrene sulfonate film material dissolves in the mixed solvent of toluene and butanols, the volume ratio of toluene and butanols is 7: 4～1, make macromolecular solution, this solution is tiled in curtain coating on the polytetrafluoroethyldisk disk, vacuum-drying at room temperature is complete to solvent evaporation, again in room temperature～60 ℃, and under 0.6 normal atmosphere～condition of normal pressure dry 10～120 minutes; Perhaps adopt rolling process, cement-dipping method or coating method prepared to obtain polystyrene sulfonate film.
2. the low temperature direct methanol fuel cell according to claim 1 preparation method of polystyrene sulfonate film is characterized in that:
(1) preparation of sulphonating agent-acyl group sulfuric acid complexing salt:
With acid anhydrides and 1, the 2-ethylene dichloride places test tube by 1: 1.0～3.0 mixed, is mixed with solution, and feeds nitrogen and protect, and this solution is freezing, then under logical nitrogen protection, add the vitriol oil again, and the cover lid sealing is standby;
(2) preparation of polystyrene sulfonate film material:
(1) granules of polystyrene is dissolved in 1, it is that the solution of 50 grams per liters～200 grams per liters places reflux that the 2-ethylene dichloride is mixed with the bulking value specific concentration, and logical nitrogen protection;
(2) under the flowing nitrogen environment, do not stop to stir, heat this solution to room temperature～85 ℃, previously prepared acyl group sulfate complex is injected solution in the ratio that is equivalent to polystyrene molar weight 15%～20%, this temperature next time stream carried out sulfonation reaction 0.5～3 hour, add 2-propyl alcohol stopped reaction at last;
(3), after vacuum-evaporation concentrates, dropwise drip in distilled water until polymer precipitation complete with injection system concentrated solution with the cooling of resulting solution;
(4) filter polymer precipitation, place reflux, filter once more, with final product under room temperature～60 ℃, 0.6 normal atmosphere～normal pressure dry 10～50 hours, promptly obtain the polystyrene sulfonate film material at last with distilled water wash 0.5～3 hour;
(3) preparation of film:
With above-mentioned resulting polystyrene sulfonate film material dissolves in the mixed solvent of toluene and butanols, the volume ratio of toluene and butanols is 7: 3～1, make macromolecular solution, this solution is tiled on the polytetrafluoroethyldisk disk, vacuum-drying at room temperature is complete to solvent evaporation, under room temperature～60 ℃, 0.6 normal atmosphere～normal pressure dry 0.5～2 hour again, perhaps adopting rolling process, cement-dipping method or coating method technology to prepare sulfonation degree was 15%～50% polystyrene sulfonate film.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021151857A CN1166723C (en) | 2002-05-09 | 2002-05-09 | Polystyrene sulfonate film for low-temp. direct methanol fuel cell and preparation process thereof |
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| CNB021151857A CN1166723C (en) | 2002-05-09 | 2002-05-09 | Polystyrene sulfonate film for low-temp. direct methanol fuel cell and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100599677B1 (en) * | 2003-10-31 | 2006-07-13 | 삼성에스디아이 주식회사 | A method for preparing sulfonated polystyrene for polymer electrolyte of fuel cell |
| CN100412116C (en) * | 2005-02-07 | 2008-08-20 | 财团法人工业技术研究院 | Proton conducting membrane and production |
| KR100659130B1 (en) | 2005-12-30 | 2006-12-19 | 삼성에스디아이 주식회사 | Polymer electrolytic membrane, and fuel cell employing the same |
| CN103326043B (en) * | 2013-06-14 | 2015-07-08 | 江苏中靖新能源科技有限公司 | Composite ion exchange membrane and preparation method thereof |
| CN109999678A (en) * | 2019-04-25 | 2019-07-12 | 山东师范大学 | A kind of ion exchange membrane material and the preparation method and application thereof |
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