CN100570936C - The preparation method of Nafion/ mesoporous silicon dioxide composite proton exchange film - Google Patents
The preparation method of Nafion/ mesoporous silicon dioxide composite proton exchange film Download PDFInfo
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- CN100570936C CN100570936C CNB2008100509853A CN200810050985A CN100570936C CN 100570936 C CN100570936 C CN 100570936C CN B2008100509853 A CNB2008100509853 A CN B2008100509853A CN 200810050985 A CN200810050985 A CN 200810050985A CN 100570936 C CN100570936 C CN 100570936C
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Abstract
The invention provides the preparation method of Nafion/ mesoporous silicon dioxide composite proton exchange film.Utilize the method for original position dip-coating, the silicon source colloidal sol that will contain surfactant is coated in Nafion film surface by the method that lifts, and obtains the Nafion/ mesoporous silicon dioxide composite proton exchange film.By the kind of change surfactant, surfactant concentrations, speed that dip-coating lifts and number of times, repeatedly dip-coating lifts alcohol-rejecting ability and the proton conductive performance that interlude is controlled hybridized film.Resulting composite membrane surface has the network configuration of nano level mesoporous silicon oxide, can stop methyl alcohol penetrate effectively, owing to the hydrophilicity of mesoporous silicon oxide network, it is suitable even higher than Nafion film with the Nafion film that the proton conductivity of composite membrane still keeps simultaneously.It is very wide that These characteristics makes that composite membrane is applied to the prospect of direct methanol fuel cell.
Description
Technical field
The present invention relates to the preparation method of Nafion/ mesoporous silicon dioxide composite proton exchange film.
Background technology
The energy is one of necessary condition of the human society survival and development, and fossil energy faces exhaustion, is that the clean energy resource epoch of representative arrive with the Hydrogen Energy.The notion of clean energy resource mainly is to be based upon on the basis of fuel cell technology.Direct methanol fuel cell (DirectMethanol Fuel Cells, DMFC) directly utilize methanol in water to act as a fuel, utilize oxygen or air as oxidant, generally in 20 ℃ of-80 ℃ of scopes, work, have that efficient, safety, relative volume are less, a noiselessness, advantage such as pollution-free.These characteristics makes direct methanol fuel cell be subjected to extensive concern.The core part of direct methanol fuel cell is that (Proton Exchange Membrane PEM), is also referred to as dielectric film to solid proton exchange membrane.It is not only a kind of diaphragm material, or the substrate of electrolyte and electrode active material, and the character of film is directly determining fuel cell performance.Therefore become the focus of various countries scientist research.Generally require proton exchange membrane to have higher ion activity and good proton electricity to lead, higher hydratability is arranged, enough thermal stabilitys and long useful life.Studies show that perfluorinated sulfonic acid type film is present commercial best dielectric film.For example: the Nafion series membranes of U.S. DuPont company, as Nafion117.The advantage of this class film be thickness generally at 50-175 μ m, proton conductivity height (water content is bigger), and at strong acid, highly basic, in the strong redox, the chemical property of film, mechanical performance are all more stable.But the shortcoming of this class film is also very outstanding.Because the proton conduction of such film depends on water, when the working temperature of fuel cell approaches 80 ℃ or when higher, the water evaporates rate improves in the film, causes proton conductivity to descend, thereby cause film resistance to raise and the internal resistance of cell raises, battery efficiency reduces.In addition, the methanol permeability of this class film is very high, and is particularly outstanding when temperature is higher.And methanol crossover can cause cathod catalyst to be poisoned.These shortcomings all can reduce the performance of direct methanol fuel cell.Therefore people need develop the novel proton exchange membranes that electric conductivity is good, methanol permeability is low.
One of focus of research carries out modification to existing Nafion film exactly at present.Jia etc. generate a strata 1-methylpyrrole at Nafion film surface aggregate, can reduce by 90% methanol crossover, but obviously reduced proton conductivity (the Jia N. of dielectric film simultaneously, et al.Modification of Nafion proton exchange membranes to reducemethanol crossover in PEM fuel cells, Electrochem.andSolid-State Lette., 2000,3 (12): 529-531).Uchida etc. are impregnated into the platinum ammonium complex compound in the Nafion film, and nano level platinum particles is dispersed in the Nafion film through reduction, can play certain resistance alcohol effect (Uchida H., et al.Suppression of methanol crossover and distribution of ohmicresistance in Pt-dispersed PEMs under DMFC operation, J.Electrochem.Soc, 2002,149 (6): A682-A687).But platinum is noble metal, and it significantly improves the cost of Modified Membrane.And methanol crossover is still relatively more serious when methanol concentration is higher.Studies show that silicon dioxide (SiO
2) can play the effect of good modification Nafion.Miyake etc. adopt doping SiO
2Method strengthened the water absorbing capacity of Nafion film.Work as SiO
2When content is about 20% (quality percentage composition), methanol crossover speed obviously reduces (Miyake N., et al.Evaluation of a sol-gel derived Nafion/silica hybrid membrane for polymer electrolyte membrane fuelcell applications (II) .Methanol uptake and methanolpermeability, J Electrochem Soc, 2001,148 (8): A905-A909).Pereira etc. adopt the ethanolic solution blend of organosilicon source gel and Nafion112 to form the Nafion-organic silicon solution of hydridization, and the method for double teeming notes obtains containing mesoporous SiO then
2The Nafion112 film.They think that the film of this hydridization is adapted at using in the high-temperature fuel cell than the Nafion112 film of commodity more.(F.Pereira，et?al.Advancedmesostructured?hybrid?silica-nafion?membranes?forhigh-performance?PEM?fuel?cell，Chem.Mater.20(2008)1710-1718)。
Up to the present, the multiple hybridized film of utilizing the method preparation of nano-silicon dioxide modified Nafion series membranes, nano particle all is to be deposited in the proton exchange membrane, rather than on purpose intercepts in the methyl alcohol passage.The proton exchange membrane that these methods are handled is difficult to make methanol permeability to descend above 50%, but also can significantly reduce the conductivity of film.And adopt simple original position dip coating to form the network configuration of nano level mesoporous silicon oxide on Nafion film surface, can effectively stop methyl alcohol penetrate, owing to the hydrophilicity of mesoporous silicon oxide network, it is suitable even higher than Nafion film with the Nafion film that the proton conductivity of composite membrane still keeps simultaneously.Investigate from angle of practical application, the original position dip coating more helps the application of composite membrane in direct methanol fuel cell that obtain.
Summary of the invention
In order to solve the methanol crossover height of commodity Nafion proton exchange membrane, and when temperature range was 20 ℃-80 ℃, proton conductivity was lower, and the method complexity of traditional modification Nafion film, the shortcoming that modified effect is not good.The preparation method who the purpose of this invention is to provide the Nafion/ mesoporous silicon dioxide composite proton exchange film.
The present invention utilizes the advantage of original position dip-coating, and the prepared silicon source colloidal sol that contains surfactant is coated in Nafion film surface by the method that lifts.In air, after normal temperature ageing 2-6 hour, clean composite membrane 3 times with ethanol, to remove surfactant.Obtain the Nafion/ mesoporous silicon dioxide composite proton exchange film.By the kind of change surfactant, surfactant concentrations, the speed that dip-coating lifts, the number of times that dip-coating lifts (being the number of plies of mesoporous silicon oxide), repeatedly dip-coating lifts the performance that interlude is controlled hybridized film.
Step of the inventive method and condition are:
Surfactant is joined in the ethanolic solution of tetraethoxysilane of 0.5mol/L, regulating the pH value is 2-3, and sonic oscillation is 30 minutes then, obtains silicon source colloidal sol; The surfactant that adopts is: Pluronic P123, Pluronic F127, Pluronic L121, Brij-56, Brij-58 or softex kw (CTAB); The mol ratio of surfactant and tetraethoxysilane is from 10-1 to 1-100;
The Nafion film immerses in the colloidal sol of above-mentioned silicon source with constant speed, the scope of described constant speed is 30mm/s-120mm/s, pull out silicon source colloidal sol with this speed then, this moment, silicon source colloidal sol promptly was adsorbed in Nafion film surface, the Nafion film of silicon source colloidal sol to be coated in air 10 ℃-30 ℃ after ageing 2-6 hour, clean composite membrane with ethanol, remove surfactant, obtain the Nafion/ mesoporous silicon dioxide composite proton exchange film; The speed range that the dip-coating of Nafion film lifts is 30mm/s-120mm/s, and the number of times that dip-coating lifts is 1 time-5 times, (being that mesoporous silicon oxide is 1 layer-5 layers), and repeatedly to lift interlude be 0 minute-60 minutes in dip-coating; The Nafion film kind that adopts is Nafion117, Nafion115 or Nafion112.
Beneficial effect: the method that the present invention prepares the Nafion/ mesoporous silicon dioxide composite proton exchange film has the reaction condition gentleness, the characteristics that method is simple, and manufacturing cycle is short, thereby be easy to amplify preparation.Resulting composite membrane surface has the network configuration of nano level mesoporous silicon oxide, can stop methyl alcohol penetrate effectively, owing to the hydrophilicity of mesoporous silicon oxide network, it is suitable even higher than Nafion film with the Nafion film that the proton conductivity of composite membrane still keeps simultaneously.It is very wide that These characteristics makes that composite membrane is applied to the prospect of direct methanol fuel cell.
Embodiment
Embodiment 1: the Pluronic P123 of 0.5mol is joined in the ethanolic solution of tetraethoxysilane of 100ml, the concentration of tetraethoxysilane is 0.5mol/L, and regulating the pH value is 2, ultrasonic then 30 minutes.Nafion 117 films immerse in the colloidal sol of above-mentioned silicon source with the speed of 30mm/s, pull out silicon source colloidal sol with this speed then.This moment, silicon source colloidal sol promptly was adsorbed in Nafion 117 film surfaces.The film of silicon source colloidal sol to be coated after ageing 2-6 hour, cleans composite membrane 3 times with ethanol 10 ℃ of conditions in the air, removes surfactant.Obtain the Nafion/ mesoporous silicon dioxide composite proton exchange film.Resulting composite membrane surface has the network configuration of the nano level mesoporous silicon oxide of one deck.Can effectively stop methyl alcohol penetrate.The proton conductivity of composite membrane still keep with the Nafion film at the same order of magnitude.
Embodiment 2: the Pluronic F127 of 0.005mol is joined in the ethanolic solution of tetraethoxysilane of 1000ml, the concentration of tetraethoxysilane is 0.5mol/L, and regulating the pH value is 2, ultrasonic then 30 minutes.Nafion 115 films immerse in the colloidal sol of above-mentioned silicon source with the speed of 100mm/s, pull out silicon source colloidal sol with this speed then.This moment, silicon source colloidal sol promptly was adsorbed in Nafion 112 film surfaces.After this repeat above-mentioned immersion after 5 minutes at interval respectively and lift process, repeat altogether 4 times.The film of silicon source colloidal sol to be coated is 15 ℃ of conditions, in the air after normal temperature ageing 2-6 hour, cleans composite membrane 3 times with ethanol in the air, removes surfactant.Obtain the Nafion/ mesoporous silicon dioxide composite proton exchange film.Resulting composite membrane surface has the network configuration of five layers of nano level mesoporous silicon oxide.The methyl alcohol penetrate of composite membrane is than through low 10 times of the methyl alcohol penetrate of the film of modification, and proton conductivity still keep with the Nafion film at the same order of magnitude.
Embodiment 3 joins the CTAB of 0.01mol in the ethanolic solution of tetraethoxysilane of 200ml, and the concentration of tetraethoxysilane is 0.5mol/L, and regulating the pH value is 3, ultrasonic then 30 minutes.Nafion 112 films immerse in the colloidal sol of above-mentioned silicon source with the speed of 120mm/s, pull out silicon source colloidal sol with this speed then.This moment, silicon source colloidal sol promptly was adsorbed in Nafion 112 film surfaces.After this repeat above-mentioned immersion after 60 minutes at interval respectively and lift process, repeat altogether 2 times.The film of silicon source colloidal sol to be coated in air 25 ℃ after ageing 2-6 hour cleans composite membrane 3 times with ethanol, removes surfactant.Obtain the Nafion/ mesoporous silicon dioxide composite proton exchange film.Resulting composite membrane surface has the network configuration of three layers of nano level mesoporous silicon oxide.The methyl alcohol penetrate ratio of the composite membrane not methyl alcohol penetrate of the film of process modification hangs down 2 times, and proton conductivity still keeps suitable with the Nafion film.
Embodiment 4: the Pluronic L121 of 0.01mol is joined in the ethanolic solution of tetraethoxysilane of 130ml, the concentration of tetraethoxysilane is 0.5mol/L, and regulating the pH value is 3, ultrasonic then 30 minutes.Nafion 117 films immerse in the colloidal sol of above-mentioned silicon source with the speed of 60mm/s, pull out silicon source colloidal sol with this speed then.This moment, silicon source colloidal sol promptly was adsorbed in Nafion 117 film surfaces.After this repeat above-mentioned immersion after 35 minutes at interval and lift process 1 time.The film of silicon source colloidal sol to be coated after 30 ℃ of ageing ageings 2-6 hour, cleans composite membrane 3 times with ethanol in air, remove surfactant.Obtain the Nafion/ mesoporous silicon dioxide composite proton exchange film.Resulting composite membrane surface has the network configuration of two layers of nano level mesoporous silicon oxide.The methyl alcohol penetrate of composite membrane is than through low 3 times of the methyl alcohol penetrate of the film of modification, and proton conductivity still keep with the Nafion film at the same order of magnitude.
Embodiment 5: the Pluronic P123 of 0.01mol is joined in the ethanolic solution of tetraethoxysilane of 80ml, the concentration of tetraethoxysilane is 0.5mol/L, and regulating pH value is 3, ultrasonic then 30 minutes.Nafion 112 films immerse in the colloidal sol of above-mentioned silicon source with the speed of 90mm/s, pull out silicon source colloidal sol with this speed then.This moment, silicon source colloidal sol promptly was adsorbed in Nafion 117 film surfaces.After this repeat above-mentioned immersion after 25 minutes at interval and lift process 2 times.The film of silicon source colloidal sol to be coated after 20 ℃ of ageing ageings 2-6 hour, cleans composite membrane 3 times with ethanol in air, remove surfactant.Obtain the Nafion/ mesoporous silicon dioxide composite proton exchange film.Resulting composite membrane surface has the network configuration of three layers of nano level mesoporous silicon oxide.The methyl alcohol penetrate of composite membrane is than through low 5 times of the methyl alcohol penetrate of the film of modification, and proton conductivity still keep with the Nafion film at the same order of magnitude.
Embodiment 6: the Brij-56 of 0.001mol is joined in the ethanolic solution of tetraethoxysilane of 600ml, the concentration of tetraethoxysilane is 0.5mol/L, and regulating pH value is 3, ultrasonic then 30 minutes.Nafion 112 films immerse in the colloidal sol of above-mentioned silicon source with the speed of 120mm/s, pull out silicon source colloidal sol with this speed then.This moment, silicon source colloidal sol promptly was adsorbed in Nafion 112 film surfaces.After this repeat above-mentioned immersion after 55 minutes at interval and lift process 3 times.The film of silicon source colloidal sol to be coated in air 23 ℃ after ageing 2-6 hour cleans composite membrane 3 times with ethanol, removes surfactant.Obtain the Nafion/ mesoporous silicon dioxide composite proton exchange film.Resulting composite membrane surface has the network configuration of four layers of nano level mesoporous silicon oxide.The methyl alcohol penetrate of composite membrane is than through low 4 times of the methyl alcohol penetrate of the film of modification, and proton conductivity still keep with the Nafion film at the same order of magnitude.
Embodiment 7: the Brij-58 of 0.03mol is joined in the ethanolic solution of tetraethoxysilane of 100ml, the concentration of tetraethoxysilane is 0.5mol/L, and regulating pH value is 2, ultrasonic then 30 minutes.Nafion 115 films immerse in the colloidal sol of above-mentioned silicon source with the speed of 90mm/s, pull out silicon source colloidal sol with this speed then.This moment, silicon source colloidal sol promptly was adsorbed in Nafion 115 film surfaces.After this repeat above-mentioned immersion after 35 minutes at interval and lift process 2 times.The film of silicon source colloidal sol to be coated in air 26 ℃ after ageing 2-6 hour cleans composite membrane 3 times with ethanol, removes surfactant.Obtain the Nafion/ mesoporous silicon dioxide composite proton exchange film.Resulting composite membrane surface has the network configuration of three layers of nano level mesoporous silicon oxide.The methyl alcohol penetrate of composite membrane is than through low 3 times of the methyl alcohol penetrate of the film of modification, and proton conductivity still keep with the Nafion film at the same order of magnitude.
Claims (1)
1.Nafion/ the preparation method of mesoporous silicon dioxide composite proton exchange film is characterized in that its step and condition are:
Surfactant is joined in the ethanolic solution of tetraethoxysilane of 0.5mol/L, regulating the pH value is 2-3, and sonic oscillation is 30 minutes then, obtains silicon source colloidal sol; The surfactant that adopts is: Pluronic P123, Pluronic F127, Pluronic L121, Brij-56, Brij-58 or softex kw (CTAB); The mol ratio of surfactant and tetraethoxysilane is from 10-1 to 1-100;
The Nafion film immerses in the colloidal sol of above-mentioned silicon source with constant speed, the scope of described constant speed is 30mm/s-120mm/s, pull out silicon source colloidal sol with this speed then, this moment, silicon source colloidal sol promptly was adsorbed in Nafion film surface, the Nafion film of silicon source colloidal sol to be coated in air 10 ℃-30 ℃ after ageing 2-6 hour, clean composite membrane with ethanol, remove surfactant, obtain the Nafion/ mesoporous silicon dioxide composite proton exchange film; The speed range that the dip-coating of Nafion film lifts is 30mm/s-120mm/s, and the number of times that dip-coating lifts is 1 time-5 times, (being that mesoporous silicon oxide is 1 layer-5 layers), and repeatedly to lift interlude be 0 minute-60 minutes in dip-coating; The Nafion film kind that adopts is Nafion117, Nafion115 or Nafion112.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102188913B (en) * | 2011-03-15 | 2013-06-12 | 北京科技大学 | Method for preparing high-conductivity proton exchange membrane for direct methanol fuel cells |
| CN102263270B (en) * | 2011-06-09 | 2014-04-30 | 西北师范大学 | Palygorskite methanol fuel cell carrier, and preparation and application thereof |
| CN104448638B (en) * | 2014-12-02 | 2016-12-07 | 天津大学 | The amino acid modified hollow mesoporous silicon hybridized film of Nafion/ and preparation and application |
| CN108183189A (en) * | 2017-12-07 | 2018-06-19 | 常州市沃兰特电子有限公司 | A kind of preparation method of high temp resistance lithium ion cell diaphragm |
| CN110571392B (en) * | 2018-06-29 | 2020-12-08 | 华中科技大学 | Functional interlayer material of lithium-sulfur battery and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156184A (en) * | 1997-12-10 | 2000-12-05 | De Nora S.P.A. | Polymeric membrane electrochemical cell operating at temperatures above 100° C. |
| US20050227135A1 (en) * | 2004-04-12 | 2005-10-13 | Elena Chalkova | Composite membrane for fuel cell and fuel cells incorporating said membranes |
| CN1725536A (en) * | 2005-06-08 | 2006-01-25 | 广州市培源燃料电池有限公司 | Self-moist proton exchange film and its preparation method |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156184A (en) * | 1997-12-10 | 2000-12-05 | De Nora S.P.A. | Polymeric membrane electrochemical cell operating at temperatures above 100° C. |
| US20050227135A1 (en) * | 2004-04-12 | 2005-10-13 | Elena Chalkova | Composite membrane for fuel cell and fuel cells incorporating said membranes |
| CN1725536A (en) * | 2005-06-08 | 2006-01-25 | 广州市培源燃料电池有限公司 | Self-moist proton exchange film and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| Fabrication and characterization of self-assembledNafion-SiO2-ePTFE composite membrane of PEM fuel cell. Zhu Jie, Tang Haolin et al.Journal of Membrane Science,Vol.312. 2007 * |
| Nafion/SiO2 hybrid membrane for vanadium redox flowbattery. Jingyu Xi, Zenghua Wu et al.Journal of Power Sources,Vol.166. 2007 * |
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