CN1803921A - Intermediate temperature proton electro-conductive film material based on sulphonated polystyrene resin hollow nano-microsphere - Google Patents
Intermediate temperature proton electro-conductive film material based on sulphonated polystyrene resin hollow nano-microsphere Download PDFInfo
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- CN1803921A CN1803921A CN 200510112402 CN200510112402A CN1803921A CN 1803921 A CN1803921 A CN 1803921A CN 200510112402 CN200510112402 CN 200510112402 CN 200510112402 A CN200510112402 A CN 200510112402A CN 1803921 A CN1803921 A CN 1803921A
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Abstract
The invention relates to a mesothermal proton conductive material is composed with sulfonated polystyrene nano hollow bead that can improves system proton-holding capacity both on chemical composition and space structure, basic or acidic polymer and protonation agent; has well proton conductivity even above the water boiling point, and can be used as the proton exchange membrane and electrode for mesothermal fuel cell.
Description
Technical field
The invention belongs to macromolecular material and technical field of electrochemistry, be specifically related to a kind of polymer proton conductive film material that is applicable to electrochemical devices such as intermediate temperature fuel cell and preparation method thereof.
Background technology
In temperature (100-200 ℃) polymer dielectric film fuel cell (PEMFC) compare with normal temperature PEMFC at present commonly used and have the following advantages, (1) eelctro-catalyst active and the permissible concentration height of impurity such as CO; (2) might significantly reduce the consumption of noble metal electrocatalysts such as Pt; (3) the electrode kinetics characteristic improves, fuel availability and energy capacity of battery density height; (4) saved the humidification system of battery; (5) saved the cooling system of battery.But middle temperature PEMFC also has higher requirement to materials such as ionogen, require proton exchange membrane (PEM) under 100-200 ℃ working temperature, to still have enough proton conductives and transport capacity, and this is a difficult problem for hydration shells such as Nafion perfluoro sulfonic acid membranes, because water makes the film dehydration and loses the proton conductive ability in easy evaporation more than 100 ℃.
The exploitation non-aqueous proton conducting material is a direction, and the middle temperature PEMFC of open report has much with the preparation method of non-aqueous proton conducting material in the document, and more representational method has, and (1) will be with the polymkeric substance and the H of alkalescence
3PO
4Compound Deng mineral acid, to the protonation of acidic components or form hydrogen bond and make the acid disassociation, make polymkeric substance and sour mixture can show a kind of proton conductive behavior between pure acid and acid solution by basic group.With the polybenzimidazole is that the polymkeric substance that contains nitrogen heterocyclic structures such as imidazoles of representative and the compound system of derivative and phosphoric acid thereof are system (Pu H.T., MeyerW.H., the Wegner G. that studies at most, J.Polym.Sci., Part B.Polym.Phys., 2002,40 (7): 663).But the phosphoric acid in this type of film is hydrophilic small molecules, contacts for a long time with negative electrode, still might partly run off with the water vapour of its generation.(2) inorganic proton conductor is as based on SrCeO
3The anhydrous proton conductor, also can obtain preferably the anhydrous proton conductivity (Steel B.C.H., Heinze A., Nature, 2001,414:345), but the most film forming difficulty of inorganic materials, the mechanical property and the barrier property of film are poor.(3) Nafion/ imidazoles compound system is at 160-180 ℃ of specific conductivity (Yang C., Costamagn P., the Srinivas S. that can reach 0.1S/cm, Benziger J., Bocarsly A.B., J.Power Sources, 2001,103:1), but imidazoles also is a soluble small molecular.(4) oligopolymer and the CF of band imidazole group
3SO
3Can obtain anhydrous proton conductivity (Schuster M.F.H., Meyer W.H., Schuster M., Kreuer K.D. preferably after H is compound, Chem.Mater., 2004,16 (2): 329), but the oligomer molecule amount is low, the film forming difficulty, and mechanical property and barrier property are poor.
Summary of the invention
The objective of the invention is to develop warm proton-conducting membrane material and preparation method thereof in a kind of new polymers that is suitable for electrochemical devices such as intermediate temperature fuel cell.
Middle temperature (100-200 ℃) proton-conducting membrane material that the present invention proposes, by the compound system that acid or alkaline polymkeric substance of sulfonated polystyrene hollow Nano microsphere and protonated auxiliary agent are formed, each component is as follows by the mole number proportioning:
100 parts in alkalescence or tart polymkeric substance (repeating unit mole number)
Sulfonated polystyrene hollow Nano microsphere 20-40 part (mole number)
Protonated auxiliary agent 0-50 part (mole number)
Described alkalescence or acidic polymer, can be for containing the polymkeric substance of lewis acidity or lewis base property group, as polybenzimidazole, polyimide, polyvinyl alcohol, polyvinyl azole polymkeric substance, sulfonated polyphenyl and imidazoles, sulfonated polyimide or sulfonic fluoropolymer film etc., but be not limited only to this.
Described sulfonated polystyrene (PSSA) hollow Nano microsphere, its microballoon skin is partly sulfonated polystyrene, and internal layer is a hollow structure, and particle diameter is 80-120nm, and acidity (mole number of the sulfonic acid group that contains among every gram PSSA) is 1-100mmol/g.It is template that nano SiO 2 particle (about particle diameter 50-70nm) is adopted in its preparation, both can adopt sulfonated phenylethylene and styrene copolymerized synthetic PSSA Nano microsphere, again the silicon-dioxide etching is got the PSSA hollow microsphere; Also can first synthetic polystyrene microballoon, then with the silicon-dioxide etching, again the sulfonation of polystyrene hollow microsphere is got the PSSA hollow microsphere.
Described protonated auxiliary agent can as water, imidazoles, pyridine, benzoglyoxaline etc., but be not limited only to this for being easy to protonated micromolecular compound.
The preparation method of warm proton-conducting membrane material is as follows in described: PSSA hollow Nano microsphere is dispersed in the solvent (being generally water), join in the alkalescence or acidic polymer solution that weight concentration is 4-7wt% in the mole number ratio, add protonated auxiliary agent again, fully stir.Mixed solution is poured on the polyfluortetraethylene plate, and behind the levelling, most of solvent is removed in evaporation under infrared lamp automatically, puts into the vacuum drying oven oven dry again, can obtain film sample.
The present invention adopts wetting ability proton auxiliary agents such as sulfonated polystyrene (PSSA) hollow nano-hydrophilic microballoon Bao Nashui, imidazoles to help to reduce it in evaporation under the middle temperature environment or the extent of migration in middle heated steam environment, thereby guarantees that it still has enough proton conductive performances under middle temperature operational temperature conditions.
The present invention has studied the water retention property of sulfonated polystyrene hollow microsphere, finds to reach 52.6% at 120 ℃ of its water ratio.With sulfonated polyphenyl and imidazoles/sulfonated polystyrene hollow microsphere/moisture film is example, and its proton conductivity can all be better than corresponding sulfonated polyphenyl and imidazoles/moisture film at aspects such as water retention property, specific conductivity and accessible working temperatures near 10-3S/cm at 120 ℃.
Description of drawings
The transmission electron microscope picture of Fig. 1 sulfonated polystyrene hollow Nano microsphere.
The water-intake rate of Fig. 2 sulfonated polystyrene hollow Nano microsphere and the relation of temperature.
Fig. 3 sulfonated polyphenyl and imidazoles/sulfonated polystyrene hollow microsphere composite membrane hydration shell specific conductivity is with variation of temperature figure.
The alternating-current impedance figure of Fig. 4 polyvinyl alcohol (Mn=17200)/sulfonated polystyrene hollow microsphere/imidazoles composite membrane
Fig. 5 polyvinyl alcohol (Mn=17200)/sulfonated polystyrene hollow microsphere/imidazoles composite membrane specific conductivity is with variation of temperature figure
Specific implementation method
Following examples are only for further specifying the present invention, are not violating under the purport of the present invention, and the present invention should be not limited to the content that following experimental example is specifically expressed.
Used starting material are as follows:
Polyvinyl alcohol (PVA), Aldrich, molecular weight 17200
Sulfonated polystyrene hollow Nano microsphere, prepared in laboratory, particle diameter 90nm, acidity 4.2mmol/g, its microballoon skin is partly sulfonated polystyrene, internal layer is a hollow structure.It is template that nano SiO 2 particle (about particle diameter 50-70nm) is adopted in its preparation, both can adopt sulfonated phenylethylene and styrene copolymerized synthetic PSSA Nano microsphere, again the silicon-dioxide etching is got the PSSA hollow microsphere; Also can first synthetic polystyrene microballoon, then with the silicon-dioxide etching, again the sulfonation of polystyrene hollow microsphere is got the PSSA hollow microsphere.
Sulfonated polyphenyl and imidazoles are according to document preparation (Appleby A., J Fuel Cell System[M], New York, Plenum Press, 1993).
Imidazoles, Shanghai moisten prompt chemical reagent company limited.
Raw materials used proportioning is as follows:
1 part of sulfonated polyphenyl and imidazoles (repeating unit mole number)
0.35 part of sulfonated polystyrene hollow microsphere (mole number)
Water is an amount of
The preparation method of composite membrane: sulfonated polyphenyl and imidazoles are dissolved in the 1-methyl-2-pyrrolidone, make the solution of 5wt%.The sulfonated phenylethylene hollow microsphere is in solvent, and ultra-sonic dispersion adds in the aforementioned solution, fully stirs; Then solution is poured on the polyfluortetraethylene plate, behind the levelling, puts into the vacuum drying oven oven dry and can obtain the dry composite film automatically, composite membrane is immersed in the water again, after 24 hours, the moisture on surface that flips obtains the composite membrane sample.
The pattern of sulfonated polystyrene hollow microsphere and the test of water retention property:
The pattern of sulfonated polystyrene hollow microsphere proves its hollow structure, as shown in Figure 1 by transmission electron microscope (H-800, Hitachi Co.) test.
The test of sulfonated polystyrene hollow microsphere water retention property: earlier the hollow microsphere sample is immersed in the water, after 24 hours, the surface-moisture that flips places container, put it into the regular hour (being set at 20 minutes) in the climatic chamber of design temperature and humidity, W again weighs
a, elevated temperature, repetitive operation after temperature is elevated to a certain degree, continues elevated temperature to 150 ℃, and the quality of sulfonation hollow microsphere also no longer changes, and this moment, the quality of sample was the dry weight W of sulfonated polystyrene
Dry, (W then
a-W
Dry)/W
DryBe the water-intake rate of this sulfonated polystyrene.Water-intake rate-temperature curve as shown in Figure 2, water-intake rate reaches 52.6% in the time of 120 ℃.
The mensuration of composite membrane proton conductive performance:
With alternating current impedance instrument (EG ﹠amp with 273 type potentiostat/galvanostats and 5210 type lock-in amplifiers; G PrincetonApplied Research Co.) composite impedance of mensuration composite membrane changes into the direct current proton conductivity by calculating again.The proton conductive performance of composite membrane as shown in Figure 3.
Embodiment 2
Raw materials used proportioning is as follows:
1 part of polyvinyl alcohol (molecular weight 17200) (repeating unit mole number)
0.25 part of sulfonated polystyrene hollow microsphere (mole number)
Imidazoles 0.25-0.5 part (mole number)
The preparation of composite membrane:
PVA is dissolved in hot water, makes the solution of 6wt%, add the solution and the imidazoles of sulfonated polystyrene hollow microsphere respectively by proportioning, fully stir, make homogeneous phase solution.Solution is poured on the polyfluortetraethylene plate, behind the levelling, puts into the vacuum drying oven oven dry and can obtain the composite membrane sample automatically.
The mensuration of composite membrane proton conductive performance is similar to Example 1, and its proton conductive performance as shown in Figure 4 and Figure 5.
Embodiment 3
Raw materials used proportioning is as follows:
1 part of polyvinyl alcohol (molecular weight 6000-7000) (repeating unit mole number)
0.25 part of sulfonated polystyrene hollow microsphere (mole number)
Imidazoles 0.25-0.5 part (mole number)
The mensuration of the preparation method of composite membrane and proton conductive performance is similar to Example 2, and its proton conductive performance is similar as shown in Figure 4 and Figure 5.
Embodiment 4
Raw materials used proportioning is as follows:
1 part of polyvinyl alcohol (molecular weight 17200) (repeating unit mole number)
0.5 part in sulfuric acid (mole number)
0.20 part of sulfonated polystyrene hollow microsphere (mole number)
0.5 part of imidazoles (mole number)
The mensuration of the preparation method of composite membrane and proton conductive performance is similar to Example 1, its proton conductive performance and Fig. 4 and shown in Figure 5 similar.
In the foregoing description, the parameter of each component raw material and consumption and preparation process only is the representative of choosing in order to describe invention.In fact a large amount of experiments show, in summary of the invention part institute restricted portion, all can obtain the similar proton exchange membrane of the foregoing description.
Claims (5)
1, a kind of middle temperature proton-conducting membrane material based on sulfonated polystyrene hollow Nano microsphere is characterized in that composition comprises:
100 parts in alkalescence or tart polymkeric substance, in the repeating unit mole number,
Sulfonated polystyrene hollow Nano microsphere 20-40 part, in mole number,
Protonated auxiliary agent 0-50 part, in mole number,
Here alkalescence or acidic polymer are the polymkeric substance that contains lewis acidity or lewis base property group.
2, warm proton-conducting membrane material in according to claim 1 is characterized in that described polymkeric substance is polybenzimidazole, polyimide, polyvinyl alcohol, polyvinyl azole polymkeric substance, sulfonated polyphenyl and imidazoles, sulfonated polyimide or sulfonic fluoropolymer film.
3, warm proton-conducting membrane material in according to claim 1 is characterized in that described sulfonated polystyrene hollow Nano microsphere, and its skin is partly sulfonated polystyrene, and internal layer is a hollow structure, and particle diameter is 80-120nm, and acidity is 1-100mmol/g.
4, warm proton-conducting membrane material in according to claim 1 is characterized in that described protonated auxiliary agent is water, imidazoles, pyridine or benzoglyoxaline.
5, a kind of as claimed in claim 1 in the preparation method of warm proton-conducting membrane material, it is characterized in that concrete steps are as follows: sulfonated polystyrene hollow Nano microsphere is dispersed in the solvent, joining weight concentration in proportion is in the alkalescence or acidic polymer solution of 4-7wt%, add protonated auxiliary agent again, fully stir; Mixed solution is poured on the polyfluortetraethylene plate, and automatically behind the levelling, most of solvent is removed in evaporation under infrared lamp, puts into the vacuum drying oven oven dry again, get final product required mould material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100586997C (en) * | 2008-04-03 | 2010-02-03 | 同济大学 | Intermediate-temperature proton-conducting membrane material based on silicon dioxide hollow micro-sphere and preparation method thereof |
| CN101250310B (en) * | 2008-04-03 | 2010-06-09 | 同济大学 | Organic-inorganic composite intermediate-temperature proton-conducting membrane material and preparation method thereof |
| CN101431157B (en) * | 2007-11-07 | 2011-12-21 | 国立大学法人静冈大学 | Electrolyte membrane for fuel cell |
| CN116913576A (en) * | 2023-07-10 | 2023-10-20 | 乐凯胶片股份有限公司 | Conductive paste and heterojunction solar cell |
-
2005
- 2005-12-30 CN CN 200510112402 patent/CN1803921A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101431157B (en) * | 2007-11-07 | 2011-12-21 | 国立大学法人静冈大学 | Electrolyte membrane for fuel cell |
| CN100586997C (en) * | 2008-04-03 | 2010-02-03 | 同济大学 | Intermediate-temperature proton-conducting membrane material based on silicon dioxide hollow micro-sphere and preparation method thereof |
| CN101250310B (en) * | 2008-04-03 | 2010-06-09 | 同济大学 | Organic-inorganic composite intermediate-temperature proton-conducting membrane material and preparation method thereof |
| CN116913576A (en) * | 2023-07-10 | 2023-10-20 | 乐凯胶片股份有限公司 | Conductive paste and heterojunction solar cell |
| CN116913576B (en) * | 2023-07-10 | 2024-05-28 | 乐凯胶片股份有限公司 | Conductive paste and heterojunction solar cell |
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