CN103022530A - Porous membrane and preparation method as well as application thereof in fuel battery - Google Patents
Porous membrane and preparation method as well as application thereof in fuel battery Download PDFInfo
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- CN103022530A CN103022530A CN2012105419597A CN201210541959A CN103022530A CN 103022530 A CN103022530 A CN 103022530A CN 2012105419597 A CN2012105419597 A CN 2012105419597A CN 201210541959 A CN201210541959 A CN 201210541959A CN 103022530 A CN103022530 A CN 103022530A
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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 relates to a porous membrane which is prepared by taking an organic polymer resin as a raw material and comprises skin layers in different shapes and supporting layers. A preparation method of the porous membrane comprises the following steps of: dissolving the organic polymer resin in DMSO, DMAC, NMP or DMF solvent, and fully stirring at 20-100 DEG C for 0.5-10 hours to obtain a blended solution, wherein the concentration of the organic polymer resin in the blended solution is 5-70wt%, and the concentration of a volatile solvent in a blended solvent is 0-50wt%; pouring out the blended solution prepared in the step one on a non-woven fabric base or directly pouring out the blended solution on a glass plate or stainless steel plate to volatile, and then steeping the non-woven fabric base or the glass plate or stainless steel plate in a poor solvent of the resin at minus 2-100 DEG C for 5-600 seconds to prepare the porous membrane. The ion permeability of the membrane is maintained in the application of the porous membrane in a fuel cell, the function of the ion exchange membrane in the fuel cell is realized, and the reduction of oxidation stability of the polymer is avoided. The preparation method is simple, controllable in bore diameters and low in cost.
Description
Technical field
The present invention relates to preparation method and the application thereof, particularly a kind of porous septum and preparation method thereof of a kind of barrier film, this barrier film and the application in fuel cell.
Background technology
Direct methanol fuel cell is at first to realize business-like fuel cell, and it not only can be widely used in fuel cell electric vehicle, and exceeds 5～10 times energy density than general battery, 20～50 ℃ of lower work, and can be at any time, postcombustion easily.
At present exploitation and the fuel cell barrier film that uses, be amberplex, be that membrane material is comprised of the polymer that contains ion-exchange group, mainly be divided into exchange membrane containing fluorine and non-fluorine ion exchange membrane, because fluoropolymer membrane is expensive, the problems such as ion selectivity is poor, the researcher has carried out a large amount of research-and-development activitys for non-fluorine ion exchange membrane material, and common non-fluorinated polymer is the materials such as the poly aryl ketone, polyarylsulfone (PAS), polyarylether, polyimides of sulfonation or season ammonification.Wherein ion-exchange group plays a part the transmission ion, and main polymer chain guarantees the mechanical performance of film.But to the non-fluorine ion exchange membrane of the overwhelming majority, the introducing of ion-exchange group greatly reduces the oxidation stability of film, has limited the useful life of film in fuel cell.
The operation principle of fuel cell is found: the Main Function that film plays at inside battery is to intercept fuel (such as methyl alcohol, sodium borohydride), conducting ion and isolated electronics.For most resins, isolated electronics is easy to accomplish that difficult is conducting ion and isolated fuel.Further research direct methanol fuel cell and direct sodium borohydride fuel cell are found, the inside of battery is the mixed system of fuel and water, and ion can transmit by the aqueous solution.From this 3 point, consider with the act as a fuel barrier film of battery of the perforated membrane that does not contain ion-exchange group.The application principle of such perforated membrane is, the pore size of controlling diaphragm utilizes the affine difference of resin material and methyl alcohol, boron hydrogen radical ion and water, realizes the effective obstruct to fuel.Can realize that this purpose resin comprises polyvinyl alcohol, shitosan, cross linked polyacrylate, polysulfones, polyimides, polyether-ether-ketone, Kynoar, polybenzimidazoles, polybenzoxazoles, polypropylene, polyethylene, polybutadiene or cellulose acetate etc.
Summary of the invention
The object of the invention is to the deficiency that in fuel cell, exists for present amberplex, a kind of good, simple porous septum of preparation method of long service life, barriering effect and preparation method thereof and application in fuel cell in fuel cell is provided.
Porous septum of the present invention is to be prepared from as raw material take one or two or more kinds organic polymer resin, described organic polymer resin is polyvinyl alcohol, polysulfones, polyketone, polyimides, polybenzimidazoles, Kynoar, polyvinyl pyridine, polyacrylonitrile, polypropylene, polyethylene, polybutadiene or cellulose acetate, and described organic polymer resin more than two kinds is any proportioning or equivalent proportioning.
Described porous septum is comprised of the cortex that comes in every shape and supporting layer, and described skin thickness is 0.1-50um, and aperture size is 0.05～50nm, and porosity is 6～90%; Described supporting layer thickness is 50～500mm, and aperture size is 0.05～10 um.
The preparation method of porous septum of the present invention, step is as follows:
1) described organic polymer resin being dissolved in one or two or more kinds the solvent among DMSO, DMAC, NMP, the DMF or being dissolved in one or two or more kinds the solvent and the mixed solvent of effumability solvent among DMSO, DMAC, NMP, the DMF, is that 20～100 ℃ of lower 0.5～10h that fully stir make blend solution in temperature; Wherein the concentration of organic polymer resin in blend solution is 5～70wt%, and the concentration of effumability solvent in mixed solvent is 0～50wt%;
Described solvent more than two kinds is any proportioning or equivalent proportioning, and described effumability solvent is oxolane or cyclohexane or chloroform;
2) blend solution that step (1) is prepared is poured at the bottom of the nonwoven fabric base or is poured directly on glass plate or the corrosion resistant plate, solvent flashing 0～60 second, then it is impregnated into 5～600s in the poor solvent of resin, under-20～100 ℃ of temperature, be prepared into porous septum, or be placed in the steam atmosphere of poor solvent of resin, under-20～100 ℃, be prepared into perforated membrane; Described poor solvent is water or methyl alcohol or ethanol or acetone.
Described fuel cell is direct methyl alcohol types of fuel cells or direct ethanol types of fuel cells or direct sodium borohydride fuel cell.
The application of porous septum of the present invention in fuel cell; Described fuel cell is direct methyl alcohol types of fuel cells or direct ethanol types of fuel cells or direct sodium borohydride fuel cell.
Useful result of the present invention is as follows:
1, the present invention is prepared into porous septum and is applied in the fuel cell, realize separating of water and fuel (alcohol, sodium borohydride) by the control pore size, the ion permeability that has kept film, do not need to introduce any ion-exchange group, can realize the function of amberplex in fuel cell, avoid the reduction of the polymer oxidation stability that the introducing owing to conventional film intermediate ion cation exchange groups causes.
2, such membrane material preparation method is simple, and the aperture is controlled, and low, the easy realization of cost is produced in enormous quantities.
3, the present invention has widened kind and the scope of application of fuel cell with membrane material.
Description of drawings
Fig. 1 is the sectional view of the porous septum of embodiment 1 preparation;
The sectional view of the porous septum of Fig. 2 present embodiment 7 preparations;
Fig. 3 is the operating condition figure of perforated membrane in direct sodium borohydride fuel cell of embodiment 10 preparations;
Fig. 4 is the operating condition figure of Comparative Examples Nafion212 film in direct sodium borohydride fuel cell.
Embodiment
Porous septum of the present invention is to be prepared from as raw material take one or two or more kinds organic polymer resin, wherein organic polymer resin is polyvinyl alcohol, polysulfones, polyketone, polyimides, polybenzimidazoles, Kynoar, polyvinyl pyridine, polyacrylonitrile, polypropylene, polyethylene, polybutadiene or cellulose acetate, organic polymer resin more than two kinds is any proportioning, comprises the equivalent proportioning.
Porous septum of the present invention is comprised of the cortex that comes in every shape and supporting layer, wherein skin thickness is 0.1 um or 1 um or 5 um or 10 um or 15 um or 20 um or 30 um or 40 um or 50 um, namely between 0.1-50um, all can, aperture size is 0.05 nm or 0.1 nm or 1 nm or 10 nm or 20 nm or 30 nm or 40 nm or 50 nm nm, namely between 0.05～50nm, all can, porosity is 6% or 15% or 25% or 35% or 45% or 55% or 65% or 75% or 85% or 90%, namely all can between 6～90%.Supporting layer thickness is 50mm or 100mm or 200mm or 300mm or 400mm or 500mm, namely between 50～500mm all can, aperture size is 0.05um or 1um or 2um or 4um or 6um or 8um or 10um, namely all can between 0.05～10 um.
The preparation method of porous septum of the present invention, step is as follows:
1) with above-mentioned organic polymer resin (polyvinyl alcohol, polysulfones, polyketone, polyimides, polybenzimidazoles, Kynoar, polyvinyl pyridine, polyacrylonitrile, polypropylene, polyethylene, polybutadiene or cellulose acetate) a kind of or any proportioning or equivalent proportioning be dissolved in DMSO more than two kinds, DMAC, NMP, in the solvent of one or two or more kinds among the DMF or be dissolved in DMSO, DMAC, NMP, in the mixed solvent of the solvent of one or two or more kinds among the DMF and effumability solvent, be fully to stir 0.5h or 1h or 3h or 6h or 10h under the condition of 20 ℃ or 40 ℃ or 80 ℃ or 100 ℃ in temperature, make blend solution.Wherein the concentration of organic polymer resin in blend solution is 5 wt% or 10 wt% or 20 wt% or 40 wt% or 60 wt% or 70 wt%, namely between 5～70wt%, all can, the concentration of effumability solvent in mixed solvent is 0 wt% or 10 wt% or 20 wt% or 30 wt% or 40 wt% or 50 wt%, namely all can between 0～50wt%.
The above-mentioned solvent more than two kinds is any proportioning, comprises the equivalent proportioning.Above-mentioned effumability solvent is oxolane or cyclohexane or chloroform;
2) blend solution that step (1) is prepared is poured at the bottom of the nonwoven fabric base or is poured directly on glass plate or the corrosion resistant plate, volatilization solvent wherein 0～60 second, then it is impregnated into 5s or 50s or 100s or 300s or 600s in the poor solvent of resin, namely between 5～600s, all can, under-20 ℃ or-10 ℃ or 0 ℃ or 20 ℃ or 50 ℃ or 80 ℃ or 100 ℃ of temperature, be prepared into porous septum, or be placed in the steam atmosphere of poor solvent of resin, under-20 ℃ or-10 ℃ or 0 ℃ or 20 ℃ or 50 ℃ or 80 ℃ or 100 ℃ of temperature, be prepared into porous septum; Above-mentioned poor solvent is water or methyl alcohol or ethanol or acetone.
The application of porous septum of the present invention in fuel cell, wherein fuel cell is direct methyl alcohol types of fuel cells or direct ethanol types of fuel cells or direct sodium borohydride fuel cell.
Specific embodiments of the invention are as follows:
7.5 the gram polyimides is dissolved among the DMAC, stirs 5 hours, the polymer solution of formation is tiled in glass plate, then immerses rapidly in the 5L acetone, solidifies 5 minutes, forms porous septum.
Perforated membrane of the present invention is after testing: methanol permeability is: 2.7*10
-7Cm
2/ s, proton conductivity are 3.9*10
-2S/cm.
5 gram polyimides are dissolved among the DMF, stir 5 hours, and the polymer solution of formation is tiled in glass plate, among the volatilization 10s, then immerse rapidly in the 5L water, 10 minutes curing times, form porous septum.
Perforated membrane of the present invention is after testing: methanol permeability is: 2.8*10
-7Cm
2/ s, proton conductivity are 3.8*10
-2S/cm.
Embodiment 3
5 gram polyimides are dissolved among the 30mlDMSO+10mlTHF, stir 5 hours, and the polymer solution of formation is tiled in glass plate, among the volatilization 20s, then immerse rapidly in the 5L water, 10 minutes curing times, form porous septum.
Perforated membrane of the present invention is after testing: methanol permeability is: 2.0*10
-7Cm
2/ s, proton conductivity are 3.0*10
-2S/cm.
Embodiment 4
8 gram polyimides are dissolved among the 30mlDMSO+10mlTHF, stir 5 hours, and the polymer solution of formation is tiled in glass plate, among the volatilization 20s, then immerse rapidly in the 5L water, 10 minutes curing times, form porous septum.
Perforated membrane of the present invention is after testing: methanol permeability is: 1.5*10
-7Cm
2/ s, proton conductivity are 3.0*10
-2S/cm.
Find out relatively that by embodiment 1-3 methanol crossover performance along with reducing of membrane aperture, the methanol permeability of film significantly reduces, proton conductivity almost remains unchanged.Illustrate suitably to reduce the aperture that it is very favorable improving for the performance of film.
Embodiment 5
With embodiment 1, change polymer into polysulfones, solvent changes NMP into, preparation polysulfones porous septum.
Embodiment 6
With embodiment 1, change polymer into polyketone, solvent changes NMP into, preparation polyimides porous septum.
Embodiment 7
7.5 the gram polyacrylonitrile is dissolved among the 50mlDMSO, stirs the polymer solution of formation 5 hours, be tiled in glass plate, then immerse rapidly in the 5L water, solidify, form porous septum, Fig. 2 provides the section S EM picture of prepared membrane material, shows the pore structure of rule.
Embodiment 8
With embodiment 1, change polymer into shitosan, solvent changes NMP into, prepares chitosan multi-porous barrier film.
Embodiment 9
9 gram Kynoar are dissolved among the 50mlDMF, stir 5 hours, and the polymer solution of formation is tiled in glass pane surface, then immerses rapidly in the 5L water, solidifies, and forms porous septum.This perforated membrane be impregnated in the 10M potassium hydroxide-ethanol solution 10 hours, carry out hydrophilic modification.
Perforated membrane of the present invention is after testing: methanol permeability is: 2.5*10
-7Cm
2/ s, proton conductivity are 3.5*10
-2S/cm.
With embodiment 1, change polymer into polybenzimidazoles, solvent is DMAC, the preparation perforated membrane.And directly carrying out on-line testing in the sodium borohydride battery.This perforated membrane shows the performance than the Nafion212 excellence in direct sodium borohydride battery, the peak power of unit are battery reaches 200mW, sees Fig. 3.
Comparative Examples 1
Compare with Nafion212 film and embodiment 10 film of doing, find the poor-performing of Nafion212 film in direct sodium borohydride fuel cell, peak cell power is seen Fig. 4 less than 50mW.
Claims (5)
1. porous septum, it is characterized in that: described porous septum is to be prepared from as raw material take one or two or more kinds organic polymer resin, described organic polymer resin is polyvinyl alcohol, polysulfones, polyketone, polyimides, polybenzimidazoles, Kynoar, polyvinyl pyridine, polyacrylonitrile, polypropylene, polyethylene, polybutadiene or cellulose acetate, and described organic polymer resin more than two kinds is any proportioning or equivalent proportioning.
2. porous septum according to claim 1, it is characterized in that: described porous septum is comprised of the cortex that comes in every shape and supporting layer, and described skin thickness is 0.1-50um, and aperture size is 0.05～50nm, and porosity is 6～90%; Described supporting layer thickness is 50～500mm, and aperture size is 0.05～10 um.
3. the preparation method of a porous septum as claimed in claim 1 or 2, it is characterized in that: step is as follows:
1) described organic polymer resin being dissolved in one or two or more kinds the solvent among DMSO, DMAC, NMP, the DMF or being dissolved in one or two or more kinds the solvent and the mixed solvent of effumability solvent among DMSO, DMAC, NMP, the DMF, is that 20～100 ℃ of lower 0.5～10h that fully stir make blend solution in temperature; Wherein the concentration of organic polymer resin in blend solution is 5～70wt%, and the concentration of effumability solvent in mixed solvent is 0～50wt%;
Described solvent more than two kinds is any proportioning or equivalent proportioning, and described effumability solvent is oxolane or cyclohexane or chloroform;
2) blend solution that step (1) is prepared is poured at the bottom of the nonwoven fabric base or is poured directly on glass plate or the corrosion resistant plate, solvent flashing 0～60 second, then it is impregnated into 5～600s in the poor solvent of resin, under-20～100 ℃ of temperature, be prepared into porous septum, or be placed in the steam atmosphere of poor solvent of resin, under-20～100 ℃, be prepared into perforated membrane; Described poor solvent is water or methyl alcohol or ethanol or acetone.
4. the application of porous septum as claimed in claim 1 or 2 in fuel cell; Described fuel cell is direct methyl alcohol types of fuel cells or direct ethanol types of fuel cells or direct sodium borohydride fuel cell.
5. the application of porous septum as claimed in claim 3 in fuel cell; Described fuel cell is direct methyl alcohol types of fuel cells or direct ethanol types of fuel cells or direct sodium borohydride fuel cell.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106941145A (en) * | 2017-02-21 | 2017-07-11 | 上海奥威科技开发有限公司 | With high temperature resistant, the barrier film of flame-retarding characteristic and preparation method |
| CN108075091A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院金属研究所 | A kind of preparation method of functional porous polyvinylidene fluoride film used for all-vanadium redox flow battery |
| CN108134107A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of perforated membrane is in the application of Alkaline Zinc iron liquid galvanic battery |
| CN109867805A (en) * | 2019-01-28 | 2019-06-11 | 青岛九维华盾科技研究院有限公司 | A kind of preparation method with infrared stealth film material with function |
| CN110943237A (en) * | 2018-09-21 | 2020-03-31 | 中国科学院大连化学物理研究所 | Application of ion-conducting membrane in flow battery |
| CN112143019A (en) * | 2020-09-01 | 2020-12-29 | 中国科学院山西煤炭化学研究所 | Method for preparing polybenzimidazole-based porous polymer ion exchange membrane by adopting non-solvent induced phase inversion method and application thereof |
| CN112886133A (en) * | 2021-01-05 | 2021-06-01 | 中材锂膜有限公司 | Coating diaphragm for eliminating proton hydrogen and preparation method thereof |
| CN112993205A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | Elastic electrode constructed by CNT array and preparation and application thereof |
| CN113067095A (en) * | 2019-12-14 | 2021-07-02 | 中国科学院大连化学物理研究所 | Three-dimensional porous elastic diaphragm and preparation and application thereof |
| CN113698660A (en) * | 2021-09-08 | 2021-11-26 | 郑州新世纪材料基因组工程研究院有限公司 | Polymer porous material and preparation method thereof, porous anionic polymer material and preparation method and application thereof |
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Cited By (14)
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| CN108075091A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院金属研究所 | A kind of preparation method of functional porous polyvinylidene fluoride film used for all-vanadium redox flow battery |
| CN108075091B (en) * | 2016-11-18 | 2019-10-22 | 中国科学院金属研究所 | A kind of preparation method of functional porous polyvinylidene fluoride film used for all-vanadium redox flow battery |
| CN108134107A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of perforated membrane is in the application of Alkaline Zinc iron liquid galvanic battery |
| CN106941145A (en) * | 2017-02-21 | 2017-07-11 | 上海奥威科技开发有限公司 | With high temperature resistant, the barrier film of flame-retarding characteristic and preparation method |
| CN110943237A (en) * | 2018-09-21 | 2020-03-31 | 中国科学院大连化学物理研究所 | Application of ion-conducting membrane in flow battery |
| CN109867805A (en) * | 2019-01-28 | 2019-06-11 | 青岛九维华盾科技研究院有限公司 | A kind of preparation method with infrared stealth film material with function |
| CN109867805B (en) * | 2019-01-28 | 2022-03-15 | 青岛九维华盾科技研究院有限公司 | Preparation method of film material with infrared stealth function |
| CN113067095A (en) * | 2019-12-14 | 2021-07-02 | 中国科学院大连化学物理研究所 | Three-dimensional porous elastic diaphragm and preparation and application thereof |
| CN112993205A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | Elastic electrode constructed by CNT array and preparation and application thereof |
| CN112993205B (en) * | 2019-12-14 | 2022-03-08 | 中国科学院大连化学物理研究所 | Elastic electrode constructed by CNT array and preparation and application thereof |
| CN113067095B (en) * | 2019-12-14 | 2022-05-10 | 中国科学院大连化学物理研究所 | Three-dimensional porous elastic diaphragm and preparation and application thereof |
| CN112143019A (en) * | 2020-09-01 | 2020-12-29 | 中国科学院山西煤炭化学研究所 | Method for preparing polybenzimidazole-based porous polymer ion exchange membrane by adopting non-solvent induced phase inversion method and application thereof |
| CN112886133A (en) * | 2021-01-05 | 2021-06-01 | 中材锂膜有限公司 | Coating diaphragm for eliminating proton hydrogen and preparation method thereof |
| CN113698660A (en) * | 2021-09-08 | 2021-11-26 | 郑州新世纪材料基因组工程研究院有限公司 | Polymer porous material and preparation method thereof, porous anionic polymer material and preparation method and application thereof |
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Application publication date: 20130403 |