CN102983344B - Method for preparing porous silicon-based proton exchange membrane - Google Patents
Method for preparing porous silicon-based proton exchange membrane Download PDFInfo
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- CN102983344B CN102983344B CN201210484580.7A CN201210484580A CN102983344B CN 102983344 B CN102983344 B CN 102983344B CN 201210484580 A CN201210484580 A CN 201210484580A CN 102983344 B CN102983344 B CN 102983344B
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- porous silicon
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- silicon film
- silane coupler
- exchange membrane
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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 discloses a method for preparing a porous silicon-based proton exchange membrane. The method comprises the following three steps: (1) hydrophilization of a porous silicon membrane: treating the porous silicon membrane by using sulfuric acid and hydrogen peroxide so that enough hydroxyls are grafted to the sidewall of the porous silicon membrane; (2) grafting of a silane coupling agent: grafting the silane coupling agent to the sidewall of porous silicon by using condensation reaction so as to form a skeleton for sulfonic groups; and (3) sulfonation: oxidizing sulfhydryls at the tail end of the silane coupling agent by using nitric acid so that the sulfhydryls are oxidized into the sulfonic groups.
Description
Technical field
The invention belongs to micro-energy field, be specifically related to a kind of method of porous silicon-base proton exchange membrane.
Background technology
Along with portable type electronic product, the development of radio sensing network and other micro-systems, more and more higher to the requirement of micro-energy.Silicon based minisize direct carbinol fuel cell (DMFC) based on MEMS technology becomes the candidate power supply of following portable set and micro-system with advantages such as its high-energy utilance, low pollution, low costs.But at present the proton exchange membrane of direct methanol fuel cell large multiplex be Nafion film, it is the copolymer membrane of a kind of polytetrafluoroethylene (PTFE) and sulfonic acid, its proton exchange membrane as micro fuel cell has following problem: 1) incompatible with bulk silicon process, this makes the integrated difficulty that becomes of fuel cell and micro-system; 2) thickness of Nafion film is conventionally in 100um left and right, and this can increase internal resistance of fuel cell and volume; 3) shape of Nafion film can change along with the variation of water content, thereby causes catalyst to come off, the problems such as cell package leakage.How addressing these problems, preparing high performance proton exchange membrane is the challenge that micro fuel cell faces.
T. the people such as Pichonat utilizes micro-processing and anodised method to prepare porous silicon, and physics is filled Nafion solution therein, and solvent evaporated, makes the proton exchange membrane material of Nafion/ porous silicon composite membrane as micro fuel cell.The manufacture method of this proton exchange membrane material is to utilize the skeleton of porous silicon as Nafion, it can improve Nafion and micro fabrication is incompatible and shape changes with change of moisture content problem, but because porous silicon has occupied the position of part Nafion film, cause the proton on-state rate of this composite membrane in theory can not exceed the proton on-state rate of Nafion film itself.In follow-up research, utilize again method a kind of salt in porous silicon surface grafting of chemical grafting, N-(3-methoxy propyl is a silica-based) ethylenediamine triacetic acid sodium, then utilize hydrogen ion in sulfuric acid solution to replace the sodium ion of salt end, thereby realize the function of proton conducting, its functional group that is used for carrying out proton conducting is the acetate of end, this is a kind of acid of weak hydrolysis, itself has stronger combination to hydrogen proton, thus cause grafting the proton on-state rate of porous silicon-base proton exchange membrane of this material neither be very high.S. the people such as Oleksandrov utilizes the method for chemical grafting to realize solid-state proton exchange membrane equally, they are sulfonic groups in grafting on porous anodic aluminium oxide, because sulfonic acid itself is a kind of strong acid, its conducting proton very capable is the anodic oxidation aluminum matrix proton exchange of 2 times of commercial Nafion films so obtained proton on-state rate.But in this method, backing material used is porous anodic aluminium oxide, and it is still incompatible with bulk silicon process, this can cause the integrated difficulty that becomes of fuel cell and micro-system.So, how to prepare high proton on-state rate and with the proton exchange membrane of bulk silicon process compatibility be the problem that the research of current silicon-base miniature fuel exists.
Summary of the invention
The present invention has realized a kind of method of utilizing chemical grafting to prepare porous silicon-base proton exchange membrane.It is characterized in that: by method grafting sulfonic group (SO on the sidewall of the hole of porous silicon of chemical grafting
3h), this sulfonic group can conducting proton, just can utilize this with sulfonic porous silicon the proton exchange membrane as fuel cell, and this method can with silicon micromachining technology compatibility.
Utilize chemical grafting to be divided into three steps in the sulfonic process of porous silicon pores sidewall grafting: to be first the hydrophiling of porous silicon film, to utilize sulfuric acid and hydrogen peroxide to process porous silicon film, make the abundant hydroxyl of its sidewall grafting (OH); Next is the grafting of silane coupler, utilize condensation reaction silane coupler grafting the sidewall at porous silicon, as sulfonic skeleton; Be finally sulfonation, utilize the sulfydryl (SH) of nitric acid oxidation end of silane, make it be oxidized into sulfonic group.
The technical problem to be solved in the present invention is to provide a kind of method of utilizing chemical grafting to prepare porous silicon-base proton exchange membrane.
Brief description of the drawings
Fig. 1 leaves standstill the contact angle on porous silicon film surface after 1 week through hydrophilicity-imparting treatment and in air
The Fourier transform infrared spectroscopy figure in Fig. 2 porous silicon film cross section after silane coupler grafting
The Fourier transform infrared spectroscopy figure in Fig. 3 porous silicon film cross section after oversulfonate
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is described.
The present invention is directed to the problem of silica-based fuel battery proton exchange film, design has realized a kind of method of utilizing chemical grafting to prepare porous silicon-base proton exchange membrane.The method comprises three steps: be first hydrophiling, utilize sulfuric acid and hydrogen peroxide to process porous silicon film, make the abundant hydroxyl of grafting on its sidewall; Next is silane coupler grafting, utilize condensation reaction silane coupler grafting the sidewall at porous silicon, as sulfonic skeleton; Be finally sulfonation, utilize the sulfydryl of nitric acid oxidation end of silane, make it be oxidized into sulfonic group.
1, the hydrophiling of porous silicon film:
A) porous silicon film: for the follow-up needs of preparing fuel cell, need to require the parameter of porous silicon film as follows: thickness is 40um-60um, aperture is 5nm-30nm, and porosity is 60%-80%.Thickness is the mechanical strength in order to ensure porous silicon and limits its resistance; Aperture is the material infiltration in order to ensure its proton on-state rate and restriction proton exchange membrane; Porosity is the mechanical strength in order to ensure its proton on-state rate and porous silicon.
B) hydrophiling: utilize 60%-80% sulfuric acid that volume ratio is 3:1 and the hydrogen peroxide mixed solution of 60%-80% to boil porous silicon film 10min-20min, until hydrogen peroxide boiling makes the enough hydroxyls of porous silicon film surface graft epipodium.
After hydrophiling, the contact angle of porous silicon and water is substantially close to 0, be difficult to observe, Fig. 1 is the contact angle that leaves standstill porous silicon surface after 1 week through hydrophilicity-imparting treatment and in air, can see after long-time leaving standstill, the contact angle of porous silicon and water only has 8.57 °, on this presentation of results porous silicon grafting abundant hydroxyl, and after long-time leaving standstill, still retain the effect of hydrophiling.
2, the grafting of silane coupler:
A) silane coupler: HS (CH
2)
3si (OCH
3)
3, select the reason of this silane coupler to be mainly two aspects: 1) in this material-Si-O-CH
3group can issue unboiled water solution in the effect of a small amount of water, generation-Si-OH group, and-Si-OH group can with porous silicon on-there is at normal temperatures dehydration condensation, make silane coupler grafting easily on porous silicon sidewall in Si-OH group; 2) this end of silane is with sulfydryl, and it is easy to be oxidized into sulfonic group, thereby realizes proton conducting function.
B) concrete technology condition: the porous silicon film of just process hydrophiling is put into the HS (CH that mass ratio is 40%-60%
2)
3si (OCH
3)
3: in the mixed liquor of benzene, soak at normal temperatures 24-48 hour.
After silane coupler grafting, the Fourier transform infrared spectroscopy figure in porous silicon film cross section, as Fig. 2, can see at 2550cm in figure
-1place occur an absworption peak, what this peak was corresponding is the absworption peak of end of silane sulfydryl, this explanation silane coupler be grafted on porous silicon sidewall.
3, sulfonation
The main purpose of sulfonation is sulfhydryl oxidase on silane coupler skeleton to become the sulfonic group that can carry out proton conducting.Concrete process conditions are: the aqueous solution of nitric acid of putting into 25%-30% through the porous silicon film of silane coupler grafting is soaked to 3-5 hour.
Fig. 3 shows the Fourier transform infrared spectroscopy figure in porous silicon film cross section after oversulfonate, can see at 2550cm
-1the absworption peak of local sulfydryl has disappeared, and this explanation sulfydryl has been oxidized into sulfonic group.
Claims (5)
1. prepare a method for porous silicon-base proton exchange membrane, it is characterized in that described method comprises three steps:
1) first, the hydrophiling of porous silicon film, utilizes sulfuric acid and hydrogen peroxide to process porous silicon film, makes the abundant hydroxyl of grafting on its sidewall;
2) secondly, the grafting of silane coupler, utilize condensation reaction silane coupler grafting in step 1) in the sidewall of the porous silicon film through hydrophiling, as sulfonic skeleton;
3) last, sulfonation, utilizes nitric acid oxidation step 2) in the sulfydryl of the end of silane of grafting on porous silicon film sidewall, make it be oxidized into sulfonic group;
The silane coupler using in the grafting step of described silane coupler, its molecular formula is HS (CH
2)
3si (OCH
3)
3.
2. prepare according to claim 1 the method for porous silicon-base proton exchange membrane, it is characterized in that the thickness of porous silicon film in the hydrophiling step of described porous silicon film is 40um-60um, aperture is 5nm-30nm, and porosity is 60%-80%.
3. prepare according to claim 1 the method for porous silicon-base proton exchange membrane, it is characterized in that utilizing in the hydrophiling step of described porous silicon film 60%-80% sulfuric acid that volume ratio is 3:1 and the hydrogen peroxide mixed solution of 60%-80% to boil porous silicon film 10min-20min, until hydrogen peroxide boiling.
4. prepare according to claim 1 the method for porous silicon-base proton exchange membrane, it is characterized in that, in the grafting step of described silane coupler, the mixed liquor of putting into silane coupler and benzene through the porous silicon film of hydrophiling is soaked to 24-48 hour at normal temperatures, the mass ratio of described silane coupler and benzene is 40%-60%.
5. prepare according to claim 1 the method for porous silicon-base proton exchange membrane, it is characterized in that, in described sulfonation procedure, the aqueous solution of nitric acid of putting into 25%-30% through the porous silicon film of silane coupler grafting is soaked to 3-5 hour.
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| SG11202112837WA (en) * | 2019-06-04 | 2021-12-30 | Membrion Inc | Ceramic cation exchange materials |
| CN110783611B (en) * | 2019-11-04 | 2020-09-25 | 郑州轻工业学院 | Perfluorosulfonic acid hybrid ion exchange membrane and preparation method and application thereof |
| CN114432847A (en) * | 2022-03-15 | 2022-05-06 | 辽宁石油化工大学 | Gas deep dehumidification film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6541149B1 (en) * | 2000-02-29 | 2003-04-01 | Lucent Technologies Inc. | Article comprising micro fuel cell |
| US6949616B2 (en) * | 2001-12-21 | 2005-09-27 | Jacob Stephane | Proton-conductive membranes and layers and methods for their production |
| CN1897338A (en) * | 2006-06-22 | 2007-01-17 | 厦门大学 | Modified alcohol-barrier proton exchange film based on hydrophilic area surface and its production |
| CN102626617A (en) * | 2012-03-20 | 2012-08-08 | 清华大学 | Preparation method of porous silicon supported three-dimensional platinum nanometer catalyst |
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2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6541149B1 (en) * | 2000-02-29 | 2003-04-01 | Lucent Technologies Inc. | Article comprising micro fuel cell |
| US6949616B2 (en) * | 2001-12-21 | 2005-09-27 | Jacob Stephane | Proton-conductive membranes and layers and methods for their production |
| CN1897338A (en) * | 2006-06-22 | 2007-01-17 | 厦门大学 | Modified alcohol-barrier proton exchange film based on hydrophilic area surface and its production |
| CN102626617A (en) * | 2012-03-20 | 2012-08-08 | 清华大学 | Preparation method of porous silicon supported three-dimensional platinum nanometer catalyst |
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