CN100586997C - Intermediate-temperature proton-conducting membrane material based on silicon dioxide hollow micro-sphere and preparation method thereof - Google Patents

Intermediate-temperature proton-conducting membrane material based on silicon dioxide hollow micro-sphere and preparation method thereof Download PDF

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CN100586997C
CN100586997C CN200810035587A CN200810035587A CN100586997C CN 100586997 C CN100586997 C CN 100586997C CN 200810035587 A CN200810035587 A CN 200810035587A CN 200810035587 A CN200810035587 A CN 200810035587A CN 100586997 C CN100586997 C CN 100586997C
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proton
hss
dioxide hollow
hso
membrane material
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袁俊杰
浦鸿汀
周光斌
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Tongji University
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Abstract

The invention belongs to the organic inorganic composite material and electrochemical technical field, in particular to an intermediate temperature proton conductive film material based on the silicadioxide hollow microsphere and a preparation process thereof. The film material is prepared through introducing sulfonic group functional inorganic silica dioxide hollow micro-sphere (HSO3-HSS) in acidic or basic polymer, which can simultaneously increase the keeping ability of the system for proton auxiliary agent from the two aspects of chemical components and space structure. The proton conductive film material which is prepared still has excellent proton conductive property above the boiling point of water, and can be used on the proton exchanging film of intermediate temperature (100 DEGC to 200 DEG C) fuel cells and film polarity.

Description

Based on middle temperature proton-conducting membrane material of silicon-dioxide hollow microsphere and preparation method thereof
Technical field
The invention belongs to organic/inorganic composite material and technical field of electrochemistry, be specifically related to compound proton-conducting membrane material of organic-inorganic of electrochemical devices such as a kind of intermediate temperature fuel cell and preparation method thereof.
Background technology
In temperature (100-200 ℃) polymer fuel cell (PEMFC) and present conventional P EMFC (normal pressure maximum operating temperature≤70 ℃) compare, middle temperature PEMFC has the following advantages: the active height of (1) anode catalyst, to 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) thermal management of battery and water management system are simplified.But middle temperature PEMFC has also proposed requirements at the higher level to materials such as ionogen, require proton exchange membrane (PEM) that enough proton conductives and transport capacity are still arranged under 100-200 ℃, and this is a difficult problem for hydration shells such as perfluoro sulfonic acid membrane such as Nafion, makes the film dehydration and loses conductive capability because water evaporates on 100 ℃ easily.
Developing non-water electro-conductive 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, by basic group to the protonation of acidic components or form hydrogen bond and make the acid disassociation, make the mixture of polymkeric substance and acid can show a kind of proton conductive behavior (Pu H.T. between pure acid and acid solution, Liu Q.Z., Qiao L., Yang Z.L., Eur.Polym.J., 2005,41 (10): 2505).With polybenzimidazole (PBI) is that the polymkeric substance that contains nitrogen heterocyclic structures such as imidazoles of representative and the non-water compound system of phosphoric acid are system (Pu H.T., Meyer W.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, might be with the chronic loss of the water vapour of its generation.(2) inorganic proton conductor is as based on SrCeO 3The anhydrous proton conductor (Steel B.C.H., Heinze A., Nature, 2001,414:345), also can obtain anhydrous proton conductivity preferably, 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 (the Yang C. that can reach 0.1S/cm, Costamagn P., Srinivas S., Benziger J., Bocarsly A.B., J.Power Sources, 2001,103:1) but imidazoles also is a soluble small molecular, also can be with the chronic loss of water vapour, and the consistency of components such as imidazoles and Nafion, catalyzer and bad.(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 object of the present invention is to provide a kind of novel organic-inorganic that is suitable for electrochemical devices such as intermediate temperature fuel cell compound in warm proton-conducting membrane material and preparation method thereof.
Middle temperature (100-200 ℃) proton-conducting membrane material that the present invention proposes is the inorganic silicon dioxide hollow microsphere (HSO by the sulfonic acid group officialization 3-HSS), the compound system formed of acid or alkaline polymkeric substance and protonated auxiliary agent, each component proportioning by mass is as follows:
100 parts in acid or alkaline polymkeric substance;
HSO 3-HSS 0-15 part, preferred 1-15 part;
Protonated auxiliary agent 0-40 part, preferred 1-15 part.
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 polyimide, sulfonated polyphenyl and imidazoles or sulfonic fluoropolymer film etc., but be not limited thereto.
The silicon-dioxide hollow microsphere that described sulfonic acid group is functionalized, its surfaces externally and internally all has functional group of sulfonic acid, internal layer is a hollow structure, and particle diameter is 50-1000nm, and it is template that polystyrene microsphere (about 50-1000nm) is adopted in its preparation, adjust the pH value of solution value, add mercaptosilane coupling agents, this one type of silane coupling agent is through sol gel reaction, use hydrogen peroxide oxidation then, obtain sulfonic acid group functional silicon dioxide hollow microsphere at last.
Described protonated auxiliary agent can as water, imidazoles, pyridine, benzoglyoxaline etc., but be not limited thereto for being easy to protonated micromolecular compound.
The preparation method of warm proton-conducting membrane material is as follows in described: with the HSO that obtains 3-HSS dispersion liquid is directly pressed HSO 3The consumption mass ratio of-HSS joins in the alkalescence or acidic polymer solution that concentration is 4-7wt.%, adds protonated auxiliary agent again, fully stirs; Perhaps with HSO 3-HSS is dispersed in the solvent and (is generally water), joins in the alkalescence or acidic polymer solution that concentration is 4-7wt.% by certain mass ratio then, adds protonated auxiliary agent again, fully stirs.Mixed solution is poured on the polyfluortetraethylene plate, and behind the levelling, evaporation goes most of solvent to put into the vacuum drying oven oven dry again under infrared lamp, can obtain film sample automatically.
The present invention adopts HSO 3-HSS bag is received wetting ability proton auxiliary agents such as planar water, imidazoles and is helped 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 HSO 3The water retention property of-HSS is found to reach 83.4wt.% at 100 ℃ of its water ratio, is example with perfluoro sulfonic acid membrane (Nafion)/silicon-dioxide hollow microsphere/moisture film, its proton conductivity at 130 ℃ still 4.423 * 10 -2More than the S/cm, all be better than corresponding N afion moisture film aspect water retention property, electric conductivity and the accessible working temperature etc.
Description of drawings
The infrared spectrum of the silicon-dioxide hollow microsphere of Fig. 1 surfaces externally and internally band sulfonic acid group
The transmission electron microscope picture of the silicon-dioxide hollow microsphere of Fig. 2 surfaces externally and internally band sulfonic acid group.
The water-intake rate of the silicon-dioxide hollow microsphere/Nafion composite membrane of Fig. 3 surfaces externally and internally band sulfonic acid group and the relation (HSO of temperature 3The particle diameter of-HSS is 120nm).
The silicon-dioxide hollow microsphere composite membrane hydration shell specific conductivity of Fig. 4 Nafion/ surfaces externally and internally band sulfonic acid group is with variation of temperature figure (HSO 3The particle diameter of-HSS is 120nm).
Embodiment
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:
Perfluoro sulfonic acid membrane (Nafion), E.I.Du Pont Company.
Mercapto propyl silane coupling agent, GE.
The silicon-dioxide hollow microsphere of surfaces externally and internally band sulfonic acid group, according to patent (Yuan person of outstanding talent, period-luminosity is refined, letter spit of fland, Pu. a kind of preparation method of hollow microsphere of surfaces externally and internally band sulfydryl, application number: 200710047411.6) preparation promptly gets above-mentioned empty ball, particle diameter 50-1000nm through the hydrogen peroxide oxidation then, surfaces externally and internally all has sulfonic acid group, and internal layer is a hollow structure.It is template that polystyrene microsphere (about 100-1000nm) is adopted in its preparation, adjusts the pH value of solution value, adds mercaptosilane coupling agents, through sol gel reaction, obtains sulfonic acid group functional silicon dioxide hollow microsphere.
Embodiment 1
Raw materials used proportioning is as follows:
100 parts of Nafion films in mass;
HSO 33 parts of-HSS in mass;
Water is an amount of
The preparation method of composite membrane: the Nafion film is dissolved in N, and N '-dimethyl formamide (DMF) is made into the solution of 5wt.%.HSO 3-HSS dispersion liquid or with HSO 3-HSS pours in the Nafion solution after being distributed in the solvent, fully stirs; Then mixed 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.
HSO 3The test of-HSS structure and pattern and water retention property;
HSO 3The structure of-HSS and pattern prove that its surfaces externally and internally contains sulfonic acid group and inside is hollow structure, as depicted in figs. 1 and 2 by infrared spectra and transmission electron microscope (H-800, Hitachi Co.) test.
HSO 3The test of-HSS/Nafion film water retention property:
Earlier sample is immersed in the water, the surface-moisture that flips after 24 hours places container, puts it into the regular hour (being set at 20 minutes) in the climatic chamber of design temperature and humidity, and W again weighs a, elevated temperature, repetitive operation after temperature is elevated to a certain degree, continues elevated temperature to 100 ℃, and the quality of silicon-dioxide hollow microsphere also no longer changes, and this moment, the quality of sample was the dry weight W of silicon-dioxide hollow microsphere Dry, (W then a-W Dry)/W DryBe the water-intake rate of this composite membrane.Water-intake rate-temperature curve as shown in Figure 3,100 ℃ water-intake rate reaches 55.2wt.%.
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 4.
Embodiment 2
Raw materials used proportioning is as follows:
100 parts of Nafion films in mass;
HSO 35 parts of-HSS in mass;
Water is an amount of
The preparation method of composite membrane: the Nafion film is dissolved in N, and N '-dimethyl formamide (DMF) is made into the solution of 5wt.%.HSO 3-HSS dispersion liquid or with HSO 3-HSS pours in the Nafion solution after being distributed in the solvent, fully stirs; Then mixed 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 mensuration of composite membrane proton conductive performance is similar to Example 1, and its proton conductive performance as shown in Figure 4.
Embodiment 3
Raw materials used proportioning is as follows:
100 parts of Nafion films in mass;
HSO 310 parts of-HSS in mass;
Water is an amount of
The preparation method of composite membrane: the Nafion film is dissolved in N, and N '-dimethyl formamide (DMF) is made into the solution of 5wt.%.HSO 3-HSS dispersion liquid or with HSO 3-HSS pours in the Nafion solution after being distributed in the solvent, fully stirs; Then mixed 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 mensuration of composite membrane proton conductive performance is similar to Example 1, and its proton conductive performance as shown in Figure 4.
Embodiment 4
Raw materials used proportioning is as follows:
100 parts of Nafion films in mass;
HSO 315 parts of-HSS in mass;
Water is an amount of
The preparation method of composite membrane: the Nafion film is dissolved in N, and N '-dimethyl formamide (DMF) is made into the solution of 5wt.%.HSO 3-HSS dispersion liquid or with HSO 3-HSS pours in the Nafion solution after being distributed in the solvent, fully stirs; Then mixed 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 mensuration of composite membrane proton conductive performance is similar to Example 1, and its proton conductive performance as shown in Figure 4.
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, not in the branch restricted portion, all can obtain the similar proton exchange membrane of above-mentioned example at summary of the invention.

Claims (3)

1, a kind of middle temperature proton-conducting membrane material based on the silicon-dioxide hollow microsphere is characterized in that moiety proportioning by mass is as follows:
100 parts in acid or alkaline polymkeric substance;
Sulfonic acid group functional silicon dioxide hollow microsphere is designated as HS03-HSS 1-15 part;
Protonated auxiliary agent 1-15 part;
Wherein, the polymkeric substance of described acidity or alkalescence is polybenzimidazole, polyimide, polyvinyl alcohol, polyvinyl imidazol base polymer, sulfonated polyimide, sulfonated polyphenyl and imidazoles or sulfonic fluoropolymer film; The functionalized inorganic silicon dioxide hollow microsphere of described sulfonic acid group, its surfaces externally and internally all has sulfonic acid group, and inside is hollow structure, and particle diameter is between the 50-1000nm.
2, warm proton-conducting membrane material in according to claim 1 is characterized in that described protonated auxiliary agent is water, imidazoles, pyridine or benzoglyoxaline.
3, a kind of as claimed in claim 1 in the preparation method of warm proton-conducting membrane material, it is as follows to it is characterized by concrete steps: with HSO 3-HSS dispersion liquid or HSO 3-HSS is distributed in the solvent, joins in the alkalescence or acidic polymer solution that concentration is 4-7wt.% by the consumption quality proportioning of component, adds protonated auxiliary agent again, fully stirs; Mixed solution is poured on the polyfluortetraethylene plate, and levelling steams most of solvent under infrared lamp automatically, promptly obtains required thin-film material.
CN200810035587A 2008-04-03 2008-04-03 Intermediate-temperature proton-conducting membrane material based on silicon dioxide hollow micro-sphere and preparation method thereof Expired - Fee Related CN100586997C (en)

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CN103474680A (en) * 2013-08-09 2013-12-25 上海交通大学 Super absorbent proton exchange membrane and preparation method thereof
CN103724630B (en) * 2013-12-06 2015-11-25 同济大学 The synthetic method of block type sulfonated polyimide-polybenzimidazole proton exchange membrane material
CN104966845B (en) * 2015-04-28 2017-04-12 大连理工大学 Semi-hyper branched semi-cross-linking type sulfonated polyimide composite proton exchange membrane and preparation method thereof

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CN1803921A (en) * 2005-12-30 2006-07-19 同济大学 Intermediate temperature proton electro-conductive film material based on sulphonated polystyrene resin hollow nano-microsphere
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CN1793205A (en) * 2005-12-30 2006-06-28 中国科学院广州化学研究所 Precess for preparing non-fluorine proton exchanging membrane mixed with silicon dioxide
CN1803921A (en) * 2005-12-30 2006-07-19 同济大学 Intermediate temperature proton electro-conductive film material based on sulphonated polystyrene resin hollow nano-microsphere

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