CN103724643B - A kind of half interpenetrating network structure proton exchange membrane and preparation method thereof - Google Patents
A kind of half interpenetrating network structure proton exchange membrane and preparation method thereof Download PDFInfo
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- CN103724643B CN103724643B CN201310749996.1A CN201310749996A CN103724643B CN 103724643 B CN103724643 B CN 103724643B CN 201310749996 A CN201310749996 A CN 201310749996A CN 103724643 B CN103724643 B CN 103724643B
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- 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 belongs to field of membrane science, particularly a kind of half interpenetrating network structure proton exchange membrane and preparation method thereof.Sulfonic acid-based polymer, 2-acrylamide-2-methyl propane sulfonic, Ethylene glycol dimethacrylate, benzophenone are dissolved in polar solvent by the inventive method, obtained solution is heated at a certain temperature and makes solvent evaporates, when solvent residual amount reaches certain content, obtain the film with gel state, film gained with gel state irradiates certain hour under ultraviolet lamp, all residual solvents are removed again by the immersion of dilute sulphuric acid and water, and make whole sulfonate radical in the film of gained convert the form of acid to, obtain a kind of half interpenetrating network structure proton exchange membrane.The proton exchange membrane material of the inventive method gained has higher proton conductivity, lower methanol permeability and reliable dimensional stability, can be applicable to direct methanol fuel cell.
Description
Technical field
The invention belongs to field of membrane science, particularly a kind of half interpenetrating network structure proton exchange membrane and preparation method thereof.
Background technology
Proton exchange membrane is one of most critical parts of direct methanol fuel cell, the conduction not being only proton provides passage, also should stop the diffusion of methyl alcohol as much as possible, and play the effect of separate batteries anode and cathode, its performance quality directly affects the overall performance of fuel cell.The Nafion series product of DuPont are that current over-all properties is best, the commercialization proton exchange membrane be most widely used.Nafion series product have higher proton conductivity, excellent mechanical property, good chemistry and electrochemical stability and lasting work-ing life, but when it is applied to direct methanol fuel cell, there is following deficiency: a) methanol permeability is higher, cause mixed potential at negative electrode, cause battery efficiency lower; B) preparation technology's very complicated, expensive; C) fluorine in material will cause environmental pollution in fuel cell operation and removal process.Therefore, development cost cheap, one of preparation and recovery process is easy, the proton exchange membrane of excellent combination property is direct methanol fuel cell application aspect always core research direction.In recent years, non-fluorine hydro carbons sulfonic acid-based polymer, due to its low price, wide material sources, various structures, advantages of environment protection, is one of main direction of current proton exchange membrane research field.
But non-fluorine hydro carbons sulfonic acid-based polymer also also exists and problems in use, such as will reach high proton conductivity, must use the sulfonic acid-based polymer that sulfonation degree is high.Once the sulfonation degree of non-fluorine hydro carbons sulfonic acid-based polymer is too high, methanol permeability also rises thereupon, and higher water-intake rate also makes the easy swelling fracture of proton exchange membrane, affects structural stability and the work-ing life of film.
Summary of the invention
Not enough for prior art, the invention provides a kind of half interpenetrating network structure proton exchange membrane and preparation method thereof.
Sulfonic acid-based polymer, 2-acrylamide-2-methyl propane sulfonic (AMPS), Ethylene glycol dimethacrylate (EGDMA), benzophenone are dissolved in polar solvent by the present invention, AMPS autohemagglutination is made to obtain PAMPS, recycling burst of ultraviolel, using benzophenone as light trigger, EGDMA is as linking agent, PAMPS is cross-linked, obtains the proton exchange membrane for fuel cell.In this film, PAMPS has network structure, formation half interpenetrating network structure blended with sulfonic acid-based polymer molecule.Because AMPS self is with sulfonate radical, adding of it has very large lifting to the specific conductivity of proton exchange membrane.Simultaneously due to the existence of cross-linking system, the half interpenetrating network structure formed in film can reduce the diffusion of methyl alcohol, and the dimensional stability of film is increased, and effectively suppresses film to raise because of water-intake rate the overplumping caused, improves the work-ing life of film.In addition, the present invention not by complete for solvent evaporate to dryness, but removes all residual solvents by the immersion of dilute sulphuric acid and water when film forming.In the film process that this is special, polar solvent residual in film and water have good intermiscibility, in film process, water spreads in film, sulfonate radical is under the induction of water molecules, motion flocks together, facilitate being separated in film, be formed with the passage being beneficial to proton conduction, residual solvent spreads and makes to produce nanometer micropore in sulfonic acid-based polymer in water simultaneously.This structure effectively can increase the content of water in film, and promote proton transport, the proton conductivity of film is further enhanced.
A preparation method for half interpenetrating network structure proton exchange membrane, its concrete scheme is as follows:
Sulfonic acid-based polymer, 2-acrylamide-2-methyl propane sulfonic, Ethylene glycol dimethacrylate, benzophenone are dissolved in polar solvent, obtained solution is heated at a certain temperature and makes solvent evaporates, when solvent residual amount reaches certain content, obtain the film with gel state, film gained with gel state irradiates certain hour under ultraviolet lamp, all residual solvents are removed again by the immersion of dilute sulphuric acid and water, and make whole sulfonate radical in the film of gained convert the form of acid to, obtain a kind of half interpenetrating network structure proton exchange membrane.
A preparation method for half interpenetrating network structure proton exchange membrane, its concrete steps are as follows:
(1) sulfonic acid-based polymer, 2-acrylamide-2-methyl propane sulfonic, Ethylene glycol dimethacrylate, benzophenone are dissolved in polar solvent, after dissolving, gained solution is poured in culture dish, then dry 3 ~ 18 hours are inserted in baking oven, drying temperature is 60 DEG C ~ 120 DEG C, obtains the film with gel state;
(2) preparation-obtained for step (1) film with gel state is placed 10min ~ 30min in the UV-crosslinked instrument of dark box type, the power of crosslinked instrument is 10W ~ 100W, ultraviolet wavelength 254nm ~ 365nm;
(3) soak 24h by after step (2) process in the film product of the gained dilute sulphuric acid at 1mol/L, then wash residual sulfuric acid with water, obtain a kind of half interpenetrating network structure proton exchange membrane.
Described sulfonic acid-based polymer is the sulfonation non-fluorine hydrocarbon polymer with proton exchange function.
Described sulfonic acid-based polymer is one or more in sulfonated polyether sulfone, sulfonated poly (phenylene oxide), sulfonated phosphazene, sulfonated polyimide and sulfonated polyether-ether-ketone.
The sulfonation degree of described sulfonic acid-based polymer is 40% ~ 80%.
Described sulfonic acid-based polymer accounts for 50% ~ 90% of total raw material quality; Described 2-acrylamide-2-methyl propane sulfonic and Ethylene glycol dimethacrylate account for 5% ~ 45% of total raw material quality respectively, and benzophenone accounts for 3% of 2-acrylamide-2-methyl propane sulfonic and Ethylene glycol dimethacrylate total mass.
Described polar solvent is one or more in N,N-DIMETHYLACETAMIDE (DMAc), dimethyl formamide (DMF), N-Methyl pyrrolidone (NMP) and dimethyl sulfoxide (DMSO) (DMSO).
The described mass percent concentration being dissolved in gained solution in polar solvent is 5% ~ 15%.
The described film Semi-polarity solvent residual amount with gel state is 20% ~ 80% of the film total mass with gel state.
A kind of half interpenetrating network structure proton exchange membrane, described half interpenetrating network structure proton exchange membrane is prepared by aforesaid method, and the half interpenetrating network structure of described half interpenetrating network structure proton exchange membrane is by gathering the network cross-linked structure of 2-acrylamide-2-methyl propane sulfonic and sulfonic acid-based polymer molecule is blended is formed.
Beneficial effect of the present invention is:
The proton exchange membrane with half interpenetrating network structure obtained by the inventive method has higher proton conductivity, lower methanol permeability and reliable dimensional stability.Cross-linking modified in background technology is combined with blending and modifying by the present invention, introduce the autopolymer of the monomer with sulfonate radical structure simultaneously, while the proton conductivity improving film, utilize alcohol-resistant performance and the stability of crosslinking structure, make the methanol permeability of film and the expansion of size remain in suitable scope, successfully prepare the proton exchange membrane with high selective penetrated property and lasting work-ing life.The inventive method not by complete for solvent evaporate to dryness, but removes all residual solvents by the immersion of dilute sulphuric acid and water when film forming.In immersion process, polar solvent residual in film is replaced by water molecules gradually, sulfonate radical moves and flocks together under the induction of water molecules, is formed with the phase separation structure being beneficial to proton conduction, and residual solvent spreads and makes to produce nanometer micropore in sulfonic acid-based polymer in water simultaneously.This structure is conducive to the content increasing water in film, and promote proton transport, the proton conductivity of film is significantly improved.Proton exchange membrane prepared by the present invention is compared with the pure sulfonic acid-based polymer film prepared by general technology, and proton conductivity improves more than 2.5 times, and selective penetrated property improves about 20% ~ 50%, and the cubical expansivity of film in 60 DEG C of 1M methanol solutions does not change substantially.
Accompanying drawing explanation
Fig. 1 is the structural representation of half interpenetrating network structure proton exchange membrane of the present invention, and wherein solid line is the network cross-linked structure of PAMPS, and dotted line is the sulfonic acid-based polymer molecule Semi-IPN with PAMPS, and zero is the cross-linking set of PAMPS.
Embodiment
The invention provides a kind of half interpenetrating network structure proton exchange membrane and preparation method thereof, below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
The preparation of half interpenetrating network structure sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM):
Be that the sulfonated polyether-ether-ketone of 45%, AMPS, EGDMA, benzophenone are dissolved in NMP with the mass ratio of 150:90:10:3 and are made into the solution that total mass mark is 5% by sulfonation degree; Pour in culture dish by gained solution, be then placed in dry 5 hours of the baking oven of 100 DEG C, now gained has the film internal solvent residual mass mark of gel state is 60%; Film gained with gel state places 15min in the UV-crosslinked instrument of dark box type, soaks, washes, obtain half interpenetrating network structure sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) through dilute sulphuric acid.
Embodiment 2
The preparation of half interpenetrating network structure Sulfonated Polyethersulfone Proton Exchange Membrane:
Be that the sulfonated polyether sulfone of 55%, AMPS, EGDMA, benzophenone are dissolved in DMAc with the mass ratio of 200:70:30:3 and are made into the solution that total mass mark is 12% by sulfonation degree; Pour in culture dish by gained solution, be then placed in dry 10 hours of the baking oven of 80 DEG C, now gained has the film internal solvent residual mass mark of gel state is 30%; Film gained with gel state places 30min in the UV-crosslinked instrument of dark box type, soaks, washes, obtain half interpenetrating network structure Sulfonated Polyethersulfone Proton Exchange Membrane through dilute sulphuric acid.
Embodiment 3
The preparation of half interpenetrating network structure sulfonated poly (phenylene oxide) proton exchange membrane:
Be that the sulfonated poly (phenylene oxide) of 70%, AMPS, EGDMA, benzophenone are dissolved in NMP with the mass ratio of 250:90:10:3 and are made into the solution that total mass mark is 8% by sulfonation degree; Pour in culture dish by gained solution, be then placed in dry 4 hours of the baking oven of 120 DEG C, now gained has the film internal solvent residual quantity of gel state is 35%; Film gained with gel state places 20min in the UV-crosslinked instrument of dark box type, soaks, washes, obtain half interpenetrating network structure sulfonated poly (phenylene oxide) proton exchange membrane through dilute sulphuric acid.
Embodiment 4
The preparation of half interpenetrating network structure sulfonated phosphazene proton exchange membrane:
Be that the sulfonated phosphazene of 65%, AMPS, EGDMA, benzophenone are dissolved in DMAc with the mass ratio of 100:80:20:3 and are made into the solution that total mass mark is 15% by sulfonation degree; Pour in culture dish by gained solution, be then placed in dry 3 hours of the baking oven of 100 DEG C, now gained has the film internal solvent residual quantity of gel state is 80%; Film gained with gel state places 12min in the UV-crosslinked instrument of dark box type, soaks, washes, obtain half interpenetrating network structure sulfonated phosphazene proton exchange membrane through dilute sulphuric acid.
Embodiment 5
The preparation of half interpenetrating network structure sulfonated polyimide proton exchange membrane:
Be that the sulfonated polyimide of 50%, AMPS, EGDMA, benzophenone are dissolved in DMSO with the mass ratio of 150:75:25:3 and are made into the solution that total mass mark is 10% by sulfonation degree; Pour in culture dish by gained solution, be then placed in dry 18 hours of the baking oven of 60 DEG C, now gained has the film internal solvent residual quantity of gel state is 50%; Film gained with gel state places 18min in the UV-crosslinked instrument of dark box type, soaks, washes, obtain proton exchange membrane through dilute sulphuric acid.
Comparative example 1
By sulfonation degree be 45% sulfonated polyether-ether-ketone be dissolved in NMP and be made into the solution that massfraction is 5%; Pour in culture dish by gained solution, be then placed in dry 48 hours of the baking oven of 100 DEG C, now the solvent residual amount of gained film is very little; The film obtained is soaked through dilute sulphuric acid, washes, obtains proton exchange membrane.
Comparative example 2
By sulfonation degree be 55% sulfonated polyether-ether-ketone be dissolved in DMAc and be made into the solution that massfraction is 12%; Pour in culture dish by gained solution, be then placed in dry 72 hours of the baking oven of 80 DEG C, now the solvent residual amount of gained film is very little; The film obtained is soaked through dilute sulphuric acid, washes, obtains proton exchange membrane.
Comparative example 3
By sulfonation degree be 70% sulfonated phosphazene resin be dissolved in DMF and be made into the solution that massfraction is 8%; Pour in culture dish by gained solution, be then placed in dry 48 hours of the baking oven of 120 DEG C, now the solvent residual amount of gained film is very little; The film obtained is soaked through dilute sulphuric acid, washes, obtains proton exchange membrane.
Comparative example 4
By sulfonation degree be 65% sulfonated polyimide resin be dissolved in DMSO and be made into the solution that massfraction is 15%; Pour in culture dish by gained solution, be then placed in dry 48 hours of the baking oven of 100 DEG C, now the solvent residual amount of gained film is very little; The film obtained is soaked through dilute sulphuric acid, washes, obtains proton exchange membrane.
Comparative example 5
By sulfonation degree be 50% sulfonated polyether-ether-ketone resin be dissolved in NMP and be made into the solution that massfraction is 10%; Pour in culture dish by gained solution, be then placed in dry 72 hours of the baking oven of 60 DEG C, now the solvent residual amount of gained film is very little; The film obtained is soaked through dilute sulphuric acid, washes, obtains proton exchange membrane.
Table 1 illustrates the performance comparison of each embodiment and comparative example gained film.
The each embodiment of table 1 and comparative example gained film properties correlation data table
Claims (7)
1. a preparation method for half interpenetrating network structure proton exchange membrane, is characterized in that, concrete scheme is as follows:
Sulfonic acid-based polymer, 2-acrylamide-2-methyl propane sulfonic, Ethylene glycol dimethacrylate, benzophenone are dissolved in polar solvent, obtained solution is heated at a certain temperature and makes solvent evaporates, when solvent residual amount reaches certain content, obtain the film with gel state, film gained with gel state irradiates certain hour under ultraviolet lamp, all residual solvents are removed again by the immersion of dilute sulphuric acid and water, and make whole sulfonate radical in the film of gained convert the form of acid to, obtain a kind of half interpenetrating network structure proton exchange membrane;
Described sulfonic acid-based polymer is the sulfonation non-fluorine hydrocarbon polymer with proton exchange function, is one or more in sulfonated polyether sulfone, sulfonated poly (phenylene oxide), sulfonated phosphazene, sulfonated polyimide and sulfonated polyether-ether-ketone;
Described sulfonic acid-based polymer accounts for 50% ~ 90% of total raw material quality; Described 2-acrylamide-2-methyl propane sulfonic and Ethylene glycol dimethacrylate account for 5% ~ 45% of total raw material quality respectively, and benzophenone accounts for 3% of 2-acrylamide-2-methyl propane sulfonic and Ethylene glycol dimethacrylate total mass.
2. the preparation method of a kind of half interpenetrating network structure proton exchange membrane according to claim 1, it is characterized in that, concrete steps are as follows:
(1) sulfonic acid-based polymer, 2-acrylamide-2-methyl propane sulfonic, Ethylene glycol dimethacrylate, benzophenone are dissolved in polar solvent, after dissolving, gained solution is poured in culture dish, then dry 3 ~ 18 hours are inserted in baking oven, drying temperature is 60 ~ 120 DEG C, obtains the film with gel state;
(2) preparation-obtained for step (1) film with gel state is placed 10 ~ 30min in the UV-crosslinked instrument of dark box type, the power of crosslinked instrument is 10 ~ 100W, ultraviolet wavelength 254nm ~ 365nm;
(3) soak 24h by after step (2) process in the film product of the gained dilute sulphuric acid at 1mol/L, then wash residual sulfuric acid with water, obtain a kind of half interpenetrating network structure proton exchange membrane.
3. the preparation method of a kind of half interpenetrating network structure proton exchange membrane according to claim 1 and 2, is characterized in that: the sulfonation degree of described sulfonic acid-based polymer is 40% ~ 80%.
4. the preparation method of a kind of half interpenetrating network structure proton exchange membrane according to claim 1 and 2, is characterized in that: described polar solvent is one or more in N,N-DIMETHYLACETAMIDE, dimethyl formamide, N-Methyl pyrrolidone and dimethyl sulfoxide (DMSO).
5. the preparation method of a kind of half interpenetrating network structure proton exchange membrane according to claim 1 and 2, is characterized in that: described in be dissolved in gained solution in polar solvent mass percent concentration be 5% ~ 15%.
6. the preparation method of a kind of half interpenetrating network structure proton exchange membrane according to claim 1 and 2, is characterized in that: described in there is gel state film Semi-polarity solvent residual amount be 20% ~ 80% of the film total mass with gel state.
7. a half interpenetrating network structure proton exchange membrane, it is characterized in that: described half interpenetrating network structure proton exchange membrane is prepared by the method described in claim 1-6 any one claim, the half interpenetrating network structure of described half interpenetrating network structure proton exchange membrane is by gathering the network cross-linked structure of 2-acrylamide-2-methyl propane sulfonic and sulfonic acid-based polymer molecule is blended is formed.
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| CN107146902A (en) * | 2017-03-29 | 2017-09-08 | 同济大学 | A kind of half interpenetrating network structure enhancing Nafion compound proton exchange membranes and preparation method thereof |
| CN107540861A (en) * | 2017-08-29 | 2018-01-05 | 中国地质大学（武汉） | A kind of PEM with low swelling and high alcohol-rejecting ability and preparation method thereof |
| CN108520970A (en) * | 2018-04-19 | 2018-09-11 | 长春工业大学 | One kind is based on 2- acrylamide-2-methyl propane sulfonic proton exchange membrane and preparation method thereof |
| CN108598533B (en) * | 2018-04-25 | 2020-11-03 | 同济大学 | Coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane and preparation method thereof |
| CN111269449A (en) * | 2020-03-25 | 2020-06-12 | Tcl华星光电技术有限公司 | Optical film and preparation method and application thereof |
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| CN102775628A (en) * | 2012-01-09 | 2012-11-14 | 北京化工大学 | Preparation method of polymer matrix proton exchange membrane (PEM) with cross-linked structure |
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