CN1897338A - Modified alcohol-barrier proton exchange film based on hydrophilic area surface and its production - Google Patents
Modified alcohol-barrier proton exchange film based on hydrophilic area surface and its production Download PDFInfo
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- CN1897338A CN1897338A CNA2006100919863A CN200610091986A CN1897338A CN 1897338 A CN1897338 A CN 1897338A CN A2006100919863 A CNA2006100919863 A CN A2006100919863A CN 200610091986 A CN200610091986 A CN 200610091986A CN 1897338 A CN1897338 A CN 1897338A
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Abstract
An hydrophile area surface modified methanol concentration proton exchange film and the preparation method, involves a proton exchange film fuel battery, provides methanol concentration proton exchange compound film and the preparation method using for the direct mellow fuel battery with the better methanol concentration and proton conducting capability and based on hydrophile area surface modified. It is nanometer inorganic organic compound film with the framework of polyperfluorocarboxylic acid, the quality content is 79%~97%; the chemistry compound surface in the ion cluster hydrophile area is with different nanometer silicon oxide with functionalization group, the quality content is 3%~21%. The method is: put the polyperfluorocarboxylic acid film into the H2O2, H2SO4 and water in turn when processing preparation, takes out and put into the methanol water-solution for hydration after drying, gets the ready polyperfluorocarboxylic acid film to be used; mixes the mixing solution by the silance resin acceptor and the organic solvent, immerges the ready polyperfluorocarboxylic acid film into the mixing solution, drying after dipping, gets the methanol concentration proton exchange compound film based on the hydrophile area surface modified.
Description
Technical field
The present invention relates to a proton exchanging film fuel battery, especially relate to a kind of preparation method of the resistance alcohol proton exchange composite membrane based on the hydrophilic area surface modification.
Background technology
Fuel cell is the device that directly chemical energy of fuel is converted into electric energy, and because of it does not have complicated combustion process, it is few to emit heat energy, and the energy transformation ratio of fuel is improved greatly; And system environments close friend.With methyl alcohol is the direct methanol fuel cell (DMFC) of fuel, because of methyl alcohol normal temperature is liquid down, with H
2Compare safety and reliability, and easily store, transport, fuel supplement is convenient.Methyl alcohol can directly be obtained by the plant fermentation process, belongs to biological renewable resource, and cheap.Because of its Direct Electrochemistry oxidation methyl alcohol, system is comparatively simple, more easy of integrationization, miniaturization.Comprehensive above-mentioned advantage, DMFC is best small-sized, a mobile model fuel cell of present commercialization prospect.
As the proton exchange membrane of one of DMFC key components, extensive use at present be the perfluorinated sulfonic acid polymer film, Nafion film and the similar products (as the Dow film of Dow company production) produced as Dupont company.This polymer, for example the molecule of Nafion can be divided into three parts: hydrophobic fully perfluocarbon skeleton, the fluorinated ether side chain that plays interconnect function and hydrophilic especially ionization sulfonic acid group.Because of carbon-fluorine bond bond energy height, the perfluorocarbon structure makes Nafion film acid and alkali resistance corrosion and high temperature resistant, has good chemistry and thermal stability.When polymer contains the water of capacity, sulfonic acid group-SO
3The H hydration forms the ion cluster hydrophilic area, can discharge and proton conducting, makes the Nafion film have high proton conductivity.But because of methanol molecules little, polarity is strong, with water sizable affinity is arranged, can permeate to negative electrode by anode by the ion cluster hydrophilic area in the perfluoro sulfonic acid membrane, permeability can reach 40%, also can the Poisoning cathode catalyst when methyl alcohol that sees through makes negative electrode produce mixed potential, battery performance is declined to a great extent and cause the waste of fuel, therefore become one of two hang-ups that hinder the DMFC development.
The problems referred to above at perfluoro sulfonic acid membrane, present research mainly concentrates on two aspects: the one, seek or the synthetic new material system that substitutes perfluoro sulfonic acid membrane, as polybenzimidazoles (PBI), polyether-ether-ketone (PEEK) and polysulfones (PS) etc. and the doping that these polymer are carried out, connect and prop up the compound system (U.S. Pat 6 that forms with copolymerization, 946,211), these polymeric acceptors tie up to resistance alcohol and significant improvement (100 ℃ of Approaches and RecentDevelopment of Polymer Electrolyte Membranes for Fuel Cells Operating above have been compared in high temperature resistant aspect with perfluoro sulfonic acid membrane, Chemistry of Materials, 2005,15:4896-4915), for making it to have good proton conductivity with realistic application, general Direct Sulfonation method (the Development of new proton exchange membrane electrolytes forwater electrolysis at higher temperatures that adopts, International Journal of Hydrogen Energy1998,23:525-529) or inorganic/organic acid doped method (Proton-conducting polymer electrolytes based onphosphoric acid, Solid State Ionics, 1999,125:255-233), but the too high meeting of sulfonation degree causes film to become fragile and the mechanical performance variation, and the composite membrane that acid is mixed is difficult to avoid the acid in the battery operation to be run off, and the electrical conductivity problems that therefore how to solve the new material system preferably also needs further research.
The 2nd, existing perfluoro sulfonic acid membrane is improved, comprise with inorganic organic material compoundly, film is carried out metal deposition, carry out copolymerization, blend with polymer monomer and connect a modification etc.Shichun Mu etc. find that positively charged nano-metal particles such as Au can be at the electronegative SO of perfluoro sulfonic acid membrane
3-On carry out self assembly and form the single layer structure of resistance alcohol, make methanol crossover nearly 80% (Au nanoparticles self-assembled onto Nafion membranes for use asmethanol-blocking barriers that descended, Electrochemistry Communications, 2005,7:1143-1147).ChangHoun Rhee etc. cast film altogether with the montmorillonite and the Nafion of surperficial organic sulfonic acidization, the composite membrane of comparing formation with the Nafion-115 film makes methanol crossover reduce nearly 90% (Nafion/Sulfonated montmorillonite composite:A New ConceptElectrolyte Membrane for Direct Methanol Fuel Cells, Chemistry of Materials, 2005,17:1691-1697).Maurit etc. with commercial perfluoro sulfonic acid membrane (as Nafion) thus sol gel reaction take place under acid catalysis formed nanoporous SiO2 in Nafion film inside with the positive silane of tetraethoxy, thereby reduced methanol permeation, the method of modifying of its simple controllable is also extensively used for reference (Microstructural evolution of a silicon oxide phase in aperfluorosulfonic acid ionomer by an in situ sol-gel reaction, Journal of Applied PolymerScience, 1995,55:181-190).
From present research situation, though new membrane material synthetic obtained very big progress, but new material still is difficult to surmount perfluoro sulfonic acid membrane at aspects such as proton conductivity, chemical stability, thermal stability and mechanical performances comprehensively and replaces the latter, and the large-scale industrial production of new material also has quite long road to walk, and therefore improving to reduce its methanol crossover to existing perfluorinated sulfonic acid film system is to realize commercial more quick, the feasible method of direct methanol fuel cell as early as possible.
Summary of the invention
The objective of the invention is at present commercial perfluoro sulfonic acid membrane methanol crossover important disadvantages, a kind of direct alcohol fuel battery that is applied to is provided, compare with commodity Nafion film, methanol permeability declines to a great extent when having particular surface functionalization group, proton conductivity slightly reduces, mechanical performances etc. do not have the composite membrane of significant change, promptly have the pure and mild proton conductivity of good resistance based on the resistance of hydrophilic area surface modification alcohol proton exchange composite membrane and preparation method thereof.
Resistance alcohol proton exchange composite membrane based on the hydrophilic area surface modification of the present invention is the nano inorganic organic hybrid films, is skeleton with the perfluorinated sulfonic acid, and mass content is 79%～97%; Chemically composited surface has the nano-silicon oxide of difference in functionality group in the ion cluster hydrophilic area, and mass content is 3%～21%.
Preparation of the present invention based on the technical scheme of the resistance alcohol proton exchange composite membrane of hydrophilic area surface modification is: commercial perfluoro sulfonic acid membrane and the organo silane coupling agent with different surfaces organic group are reacted, at the methanol permeation passage---the ion cluster hydrophilic area of perfluoro sulfonic acid membrane carries out modification, obtained the nano silicon oxide composite membrane of a series of modification different surfaces functionalization groups, its step is as follows:
1) perfluoro sulfonic acid membrane is placed on H successively
2O
2, H
2SO
4In water, the oven dry back is taken out and is inserted hydration in the methanol aqueous solution, and the perfluoro sulfonic acid membrane that obtains handling well is stand-by;
2) be made into mixed solution with silane coupler and organic solvent, the perfluoro sulfonic acid membrane of handling well is immersed in the mixed solution, the dry resistance alcohol proton exchange composite membrane that obtains based on the hydrophilic area surface modification is taken out in the dipping back.
In step 1), described perfluoro sulfonic acid membrane is the Nafion117 film; H
2O
2Concentration be 3%～10%, be preferably 5%; H
2SO
4Concentration be 0.5～2mol/l, be preferably 1mol/l; The temperature of handling is 60～100 ℃, is preferably 80 ℃; Bake out temperature is 60～100 ℃, is preferably 80 ℃; The methyl alcohol of described methanol aqueous solution and the mixed proportion of water are (0～10) by volume: 1.
In step 2) in, silane coupler is the positive silane of tetraethoxy, vinyl trichlorosilane, the 3-mercaptopropyl trimethoxysilane, 3-(2-aminoethyl)-aminopropyl trimethoxysilane, methacryloxypropyl trimethoxy silane, a kind of in the 3-urea groups propyl-triethoxysilicane etc., the mixed proportion of described silane coupler and organic solvent is 1 by volume: (6～1), described organic solvent are methyl alcohol, ethanol, acetone, a kind of in the acetonitrile etc., described dip time is 1～10min, is preferably 3～8min.
Described drying can be transferred to the perfluoro sulfonic acid membrane behind the dipping 80 ℃ of also dryings that react completely in the vacuum drying chamber.
Outstanding feature of the present invention is on the basis of commercialization perfluoro sulfonic acid membrane, the organo silane coupling agent that utilization has the different surfaces organic group reacts with it, difference because of surface-functionalized group, performance has very big difference between the inorganic organic hybrid films of response characteristic mechanism and preparation, when using specific surface-functionalized group compound when a certain amount of, methyl alcohol permeates hardly under the room temperature, and the composite membrane proton conductivity of most of preparation is about former perfluoro sulfonic acid membrane half (seeing accompanying drawing and subordinate list).Be the present invention can effectively reduce film under proton exchange membrane proton conductivity reduction situation seldom methanol crossover, the amount that contains surface-functionalized Si oxide in the composite membrane that obtains is about 3%～21%.And preparation technology is simple, and is quick, need not specific complex instrument equipment, is easy to industrialization.Be expected to and be widely used in direct alcohol fuel battery as alcohol-barrier proton exchange film, and obtain battery performance preferably.
Description of drawings
Fig. 1 is the methyl alcohol in time contrast of penetration curve of composite membrane under room temperature (25 ℃) of Nafion117 film and the embodiment of the invention 1～4 preparation.In Fig. 1, abscissa is time t/min, ordinate is infiltration back II chamber methanol concentration Methanolpermeated concentration (mol/l), the curve mark is followed successively by Nafion117 from top to bottom, embodiment: 1 (sample 1), 2 (sample 2), 3 (sample 3), 4 (sample 4).
Fig. 2 is the methyl alcohol in time contrast of penetration curve of composite membrane under room temperature (25 ℃) of Nafion117 film and the embodiment of the invention 5 and 6 preparations.In Fig. 2, abscissa is time t/min, and ordinate is infiltration back II chamber methanol concentration Methanolpermeated concentration (mol/l), and the curve mark is followed successively by Nafion117 from top to bottom, embodiment: 5 (sample 5), 6 (sample 6).
Fig. 3 is the contrast that the reflective infrared of the composite membrane of Nafion117 film and the embodiment of the invention 4 preparations is composed.In Fig. 3, abscissa is wave number Wavenumbers (cm
-1), ordinate is absorptance Absorbance.
Fig. 4 is the contrast that the reflective infrared of the composite membrane of Nafion117 film and the embodiment of the invention 5 preparations is composed.In Fig. 4, abscissa is wave number Wavenumbers (cm
-1), ordinate is absorptance Absorbance.
Fig. 5 is methanol crossover is lower in the embodiment 7 methanol permeabilities tests the methyl alcohol of 6# composite membrane under 60 a ℃ penetration curve in time, and contrasts with the Nafion117 film.In Fig. 5, abscissa is time t/min, and ordinate is infiltration back II chamber methanol concentration Methanol permeated concentration (mol/l).
Embodiment
1) with 4cm * 4cm Nafion-117 film successively at 3%H
2O
2, 0.5mol/lH
2SO
4, in the deionized water 60 ℃ handle 1h, weigh behind 60 ℃ of oven dry 24h in the vacuum drying chamber, insert after the taking-up in the deionized water fully more than the dipping hydration 24h.
2) the positive silane of tetraethoxy and methyl alcohol are made into 1: 6 mixed solution, take out after the Nafion117 film of the abundant hydration of step 1) inserted in the organosilan solution dipping 1min, remove the solution of silane of film remained on surface with methanol wash, film is transferred in the vacuum drying chamber 80 ℃ to react completely and dries more than the 24h and weigh, obtaining surface-functionalized group is hydroxyl, inorganic composite is the netted structure of nano silicone oxide, and the amount of Si oxide is 4.0% composite membrane.
Embodiment 2
1) with 4cm * 4cm Nafion-117 film successively at 4%H
2O
2, 0.8mol/l H
2SO
4, in the deionized water 70 ℃ handle 1h, weigh behind 70 ℃ of oven dry 24h in the vacuum drying chamber, methyl alcohol and deionized water are made into 1: 1 mixed solution, insert in this mixed solution after will film taking out and fully flood more than the hydration 24h.
2) vinyl trichlorosilane and ethanol are made into 1: 5 mixed solution, take out after the Nafion117 film of the abundant hydration of step 1) inserted in the organosilan solution dipping 10min, remove the solution of silane of film remained on surface with methanol wash, film is transferred in the vacuum drying chamber 80 ℃ to react completely and dries more than the 24h and weigh, obtaining surface-functionalized group is hydroxyl, inorganic composite is the netted structure of nano silicone oxide, and the amount of Si oxide is 10.14% composite membrane.
Embodiment 3
1) with 4cm * 4cm Nafion-117 film successively at 5%H
2O
2, 1.0mol/l H
2SO
4, in the deionized water 80 ℃ handle 1h, weigh behind 80 ℃ of oven dry 24h in the vacuum drying chamber, methyl alcohol and deionized water are made into 2: 1 mixed solution, insert in this mixed solution after will film taking out and fully flood more than the hydration 24h.
2) 3-mercaptopropyl trimethoxysilane and acetone are made into 1: 4 mixed solution, take out after the Nafon117 film of the abundant hydration of step 1) inserted in the organosilan solution dipping 5min, remove the solution of silane of film remained on surface with methanol wash, film is transferred in the vacuum drying chamber 80 ℃ to react completely and dries more than the 24h and weigh, obtaining surface-functionalized group is 3-mercapto propyl group, inorganic composite is the netted structure of nano silicone oxide, and the amount of Si oxide is 3.6% composite membrane.
1) with 4cm * 4cm Nafion-117 film successively at 6%H
2O
2, 1.2mol/l H
2SO
4, in the deionized water 90 ℃ handle 1h, weigh behind 90 ℃ of oven dry 24h in the vacuum drying chamber, methyl alcohol and deionized water are made into 3: 1 mixed solution, insert in this mixed solution after will film taking out and fully flood more than the hydration 24h.
2) methacryloxypropyl trimethoxy silane and acetonitrile are made into 1: 3 mixed solution, take out after the Nafion117 film of the abundant hydration of step 1) inserted in the organosilan solution dipping 5min, remove the solution of silane of film remained on surface with methanol wash, film is transferred in the vacuum drying chamber 80 ℃ to react completely and dries more than the 24h and weigh, obtaining surface-functionalized group is hydroxyl, inorganic composite is the netted structure of nano silicone oxide, and the amount of Si oxide is 3.4% composite membrane.
Embodiment 5
1) with 4cm * 4cm Nafion-117 film successively at 8%H
2O
2, 1.5mol/l H
2SO
4, in the deionized water 100 ℃ handle 1h, weigh behind 100 ℃ of oven dry 24h in the vacuum drying chamber, methyl alcohol and deionized water are made into 4: 1 mixed solution, insert in this mixed solution after will film taking out and fully flood more than the hydration 24h.
2) 3-(2-aminoethyl)-aminopropyl trimethoxysilane and methyl alcohol are made into 1: 2 mixed solution, take out after the Nafion117 film of the abundant hydration of step 1) inserted in the organosilan solution dipping 8min, remove the solution of silane of film remained on surface with methanol wash, film is transferred in the vacuum drying chamber 80 ℃ to react completely and dries more than the 24h and weigh, obtaining surface-functionalized group is 3-(2-aminoethyl)-aminopropyl, inorganic composite is the netted structure of nano silicone oxide, and the amount of Si oxide is 3.8% composite membrane.
Embodiment 6
1) with 4cm * 4cm Nafion-117 film successively at 10%H
2O
2, 2mol/l H
2SO
4, in the deionized water 80 ℃ handle 1h, weigh behind 120 ℃ of oven dry 24h in the vacuum drying chamber, methyl alcohol and deionized water are made into 5: 1 mixed solution, insert in this mixed solution after will film taking out and fully flood more than the hydration 24h.
2) 3-urea groups propyl-triethoxysilicane and acetone are made into 1: 1 mixed solution, take out after the Nafion117 film of the abundant hydration of step 1) inserted in the organosilan solution dipping 10min, remove the solution of silane of film remained on surface with methanol wash, film is transferred in the vacuum drying chamber 80 ℃ to react completely and dries more than the 24h and weigh, obtaining surface-functionalized group is 3-urea groups propyl group, inorganic composite is the netted structure of nano silicone oxide, and the amount of Si oxide is 3.2% composite membrane.
Embodiment 7
With the composite membrane of Nafion117 film and embodiment 1～6 preparation is that barrier film is packed in the barrier film diffusion cell, and its septation diffusion cell I chamber is the methanol solution of 1M and the H of 0.5M
2SO
4Solution, II chamber are the H of 0.5M
2SO
4Solution obtains the methanol crossover behavior in the 120min down of Nafon117 and each composite membrane room temperature (25 ℃) with timing current limitation electric current or gas-chromatography eluting peak area and methanol concentration relation.Sulfuric acid solution with 0.5M is an electrolyte solution, with four electrode method (A ComparativeInvestigation of Proton and Methanol Transport in Fluorinated Ionomeric Membranes, Journal ofThe Electrochemical Society, 2000,147:1286-1290) measure the proton conductivity of each composite membrane.Test environment is room temperature～25 ℃.Test result is shown in Fig. 1 and table 1.Table 1 is room temperature (25 ℃) the proton conductivity numerical value of the composite membrane of preparation among Nafion117 and the embodiment 1～6.
Table 1
| Sample film | Nafion117 | | Embodiment 2 | Embodiment 3 | |
| σ(s/cm) | 0.01639 | 9.217E-3 | 1.4041E-4 | 2.085E-3 | |
| | Embodiment | 4 | Embodiment 5 | Embodiment 6 | |
| σ(s/cm) | 8.059E-3 | 1.837E-7 | 8.219E-3 |
With the composite membrane of Nafion117 film and embodiment 1～6 preparation is that barrier film is packed in the barrier film diffusion cell, and its septation diffusion cell I chamber is the methanol solution of 2M and the H of 1M
2SO
4Solution, II chamber are the H of 1M
2SO
4Solution obtains the methanol crossover behavior in the 120min down of Nafion117 and each composite membrane room temperature (25 ℃) with timing current limitation electric current or gas-chromatography eluting peak area and methanol concentration relation.Sulfuric acid solution with 1M is an electrolyte solution, measures the proton conductivity of each composite membrane with four electrode method.
Embodiment 9
With the composite membrane of Nafion117 film and embodiment 1～6 preparation is that barrier film is packed in the barrier film diffusion cell, and its septation diffusion cell I chamber is the methanol solution of 3M and the H of 1.5M
2SO
4Solution, II chamber are the H of 1.5M
2SO
4Solution obtains the methanol crossover behavior in the 120min down of Nafion117 and each composite membrane room temperature (25 ℃) with timing current limitation electric current or gas-chromatography eluting peak area and methanol concentration relation.Sulfuric acid solution with 1.5M is an electrolyte solution, measures the proton conductivity of each composite membrane with four electrode method.
Embodiment 10
Characterize with the composite membrane of reflection absorption ftir spectroscopy (DRFTIR) Nafion117 film and embodiment 1～6 preparation, whether successful with checking modification experiment.Composite membrane with embodiment 4 and 5 is an example, and test result as shown in Figures 3 and 4.Among Fig. 3 and Fig. 4, wave number～1238cm
-1And～1150cm
-1CF for carbon fluorine skeleton
2Asymmetric and symmetrical stretching vibration absworption peak, wave number 1058cm
-1Be SO
3 -The symmetrical stretching vibration absworption peak of the hydrogen bond that group and hydrone form, wave number～980cm
-1Vibration absorption peak (Nanostructure of Nafion for C-O-C
Membranes at different states of hydration:An IR and Raman study, Vibrational Spectroscopy, 2001,26:215～225).And the synthetic composite membranes of embodiment 4 are compared with the Nafion117 film and wave number 1731.4cm also occurred
-1Absworption peak, be-CH through pointing out
2-COO-CH
2-C=O stretching vibration peak (reference 10), prove that the modification experiment of embodiment 4 is successful; Embodiment 5 synthetic composite membranes are compared with the Nafion117 film and wave number 2277.21cm also occurred
-1And 1915.16cm
-1Absworption peak, be respectively NH through pointing out
2 +And NH
3 +Vibration absorption peak (reference 10), prove that the modification experiment of embodiment 5 is successful.Therefore illustrate that also the inventive method is effective for the improvement of perfluoro sulfonic acid membrane.
Embodiment 11
With lower 6# composite membrane of methanol crossover in the embodiment 7 methanol permeabilities tests and Nafion117 is that barrier film is packed in the barrier film diffusion cell, and its septation diffusion cell I chamber is the methanol solution of 1M and the H of 0.5M
2SO
4Solution, II chamber are the H of 0.5M
2SO
4Solution obtains methanol crossover behavior in both 60 ℃ of following 120min with timing current limitation electric current and methanol concentration relation.Test result as shown in Figure 5.
Embodiment 12
With lower 6# composite membrane of methanol crossover in the embodiment 7 methanol permeabilities tests and Nafion117 is that barrier film is packed in the barrier film diffusion cell, and its septation diffusion cell I chamber is the methanol solution of 2M and the H of 1M
2SO
4Solution, II chamber are the H of 1M
2SO
4Solution obtains methanol crossover behavior in both 60 ℃ of following 120min with timing current limitation electric current and methanol concentration relation.
Claims (10)
1. based on the resistance alcohol proton exchange composite membrane of hydrophilic area surface modification, it is characterized in that being the nano inorganic organic hybrid films, is skeleton with the perfluorinated sulfonic acid, and mass content is 79%～97%; Chemically composited surface has the nano-silicon oxide of difference in functionality group in the ion cluster hydrophilic area, and mass content is 3%～21%.
2. the preparation method of the resistance alcohol proton exchange composite membrane based on the hydrophilic area surface modification as claimed in claim 1 is characterized in that its step is as follows:
1) perfluoro sulfonic acid membrane is placed on H successively
2O
2, H
2SO
4In water, the oven dry back is taken out and is inserted hydration in the methanol aqueous solution, and the perfluoro sulfonic acid membrane that obtains handling well is stand-by;
2) be made into mixed solution with silane coupler and organic solvent, the perfluoro sulfonic acid membrane of handling well is immersed in the mixed solution, the dry resistance alcohol proton exchange composite membrane that obtains based on the hydrophilic area surface modification is taken out in the dipping back.
3. the preparation method of the resistance alcohol proton exchange composite membrane based on the hydrophilic area surface modification as claimed in claim 2 is characterized in that in step 1) described perfluoro sulfonic acid membrane is the Nafion117 film.
4. the preparation method of the resistance alcohol proton exchange composite membrane based on the hydrophilic area surface modification as claimed in claim 2 is characterized in that in step 1) H
2O
2Concentration be 3%～10%, H
2SO
4Concentration be 0.5～2mol/l, the temperature of processing is 60～100 ℃, bake out temperature is 60～100 ℃.
5. the preparation method of the resistance alcohol proton exchange composite membrane based on the hydrophilic area surface modification as claimed in claim 4 is characterized in that in step 1) H
2O
2Concentration be 5%, H
2SO
4Concentration be 1mol/l, the temperature of processing is 80 ℃, bake out temperature is 80 ℃.
6. the preparation method of the resistance alcohol proton exchange composite membrane based on the hydrophilic area surface modification as claimed in claim 2 is characterized in that in step 1) the methyl alcohol of described methanol aqueous solution and the mixed proportion of water are 0～10: 1 by volume.
7. the preparation method of the resistance alcohol proton exchange composite membrane based on the hydrophilic area surface modification as claimed in claim 2, it is characterized in that in step 2) in, silane coupler is the positive silane of tetraethoxy, vinyl trichlorosilane, the 3-mercaptopropyl trimethoxysilane, 3-(2-aminoethyl)-aminopropyl trimethoxysilane, methacryloxypropyl trimethoxy silane, a kind of in the 3-urea groups propyl-triethoxysilicane.
8. the preparation method of the resistance alcohol proton exchange composite membrane based on the hydrophilic area surface modification as claimed in claim 2 is characterized in that in step 2) in, the mixed proportion of described silane coupler and organic solvent is 1: 6～1 by mass ratio.
9. the preparation method of the resistance alcohol proton exchange composite membrane based on the hydrophilic area surface modification as claimed in claim 2 is characterized in that in step 2) in, described organic solvent is a kind of in methyl alcohol, ethanol, acetone, the acetonitrile.
10. the preparation method of the resistance alcohol proton exchange composite membrane based on the hydrophilic area surface modification as claimed in claim 2 is characterized in that in step 2) in, described dip time is 1～10min.
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| CN102432903A (en) * | 2011-11-23 | 2012-05-02 | 中国科学院长春应用化学研究所 | Proton exchanging composite film and preparation method thereof |
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| WO2001018894A2 (en) * | 1999-09-09 | 2001-03-15 | Danish Power Systems Aps | Polymer electrolyte membrane fuel cells |
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| CN101254416B (en) * | 2007-12-07 | 2010-05-19 | 厦门大学 | Preparation of gelatine- aminosilane- -anode alumina compound film with affinity |
| CN102432903A (en) * | 2011-11-23 | 2012-05-02 | 中国科学院长春应用化学研究所 | Proton exchanging composite film and preparation method thereof |
| CN102432903B (en) * | 2011-11-23 | 2013-06-12 | 中国科学院长春应用化学研究所 | Proton exchanging composite film and preparation method thereof |
| CN102983344A (en) * | 2012-11-23 | 2013-03-20 | 清华大学 | Method for preparing porous silicon-based proton exchange membrane |
| CN102983344B (en) * | 2012-11-23 | 2014-11-26 | 清华大学 | Method for preparing porous silicon-based proton exchange membrane |
| CN111082113A (en) * | 2019-12-24 | 2020-04-28 | 中国科学院青岛生物能源与过程研究所 | Arginine modified proton exchange membrane and preparation method thereof |
| CN111082113B (en) * | 2019-12-24 | 2021-06-18 | 中国科学院青岛生物能源与过程研究所 | Arginine modified proton exchange membrane and preparation method thereof |
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