CN103474688A - Nano cerium oxide-modified sulfonated polyphenylene sulfide proton exchange membrane and preparation method thereof - Google Patents

Nano cerium oxide-modified sulfonated polyphenylene sulfide proton exchange membrane and preparation method thereof Download PDF

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CN103474688A
CN103474688A CN2013104399637A CN201310439963A CN103474688A CN 103474688 A CN103474688 A CN 103474688A CN 2013104399637 A CN2013104399637 A CN 2013104399637A CN 201310439963 A CN201310439963 A CN 201310439963A CN 103474688 A CN103474688 A CN 103474688A
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exchange membrane
proton exchange
spps
polyphenylene sulfide
nano
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郭强
李夏
钱君质
张天骄
毕宸洋
陈新新
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University of Shanghai for Science and Technology
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a nano cerium oxide-modified sulfonated polyphenylene sulfide proton exchange membrane and a preparation method thereof. The proton exchange membrane comprises the following components by mass percent: 82.5-99.9% of stable protein plasma solution (SPPS) of which the sulfonation degree is 57-80%, and 0.1-17.5% of nano CeO2 powder. The method disclosed by the invention comprises the following steps: with the SPPS as a base body and rare-earth metal oxide nano CeO2 as a filling phase, preparing an evenly mixed membrane casting solution, and then adopting a curtain coating or pressing and film-forming method to prepare an inorganic-organic composite film in a drying manner. The proton exchange membrane is low in preparation cost; the prepared SPPS/CeO2 proton exchange membrane is high in conductivity, and excellent in methanol permeability; the conductivity at 40-110 DEG C is 8.0*10<-3>-1.8*10<-2> S/cm; the alcohol resistance coefficient reaches 1.1*10<-8>-6.6*10<-7>cm<2>/s; the water absorption is 22.49-70.12%.

Description

Nano-cerium oxide modification sulphonation polyphenylene sulfide proton exchange membrane and preparation method thereof
Technical field
The present invention relates to a kind of Sulfonated Polyphenylene Sulfide proton exchange membrane and preparation method thereof, particularly a kind of nano-cerium oxide modification sulphonation polyphenylene sulfide proton exchange membrane and preparation method thereof.
Background technology
Proton exchange membrane (PEM) is as the core of the focus direct methanol fuel cell (DMFC) of energy field research and development at present, and its material must have good proton-conducting, suitable methanol permeability and good water resistant swellability is that proton conductivity at least should reach 10 -2s/cm, methanol permeability is lower than 10 -6cm 2/ s.Proton exchange membrane is had than the long life in DMFC.
At present most widely used is to take the perfluoro sulfonic acid membrane that the business-like Nafion film of U.S. DuPont company is representative, this fluoride meeting of long-term use serious environment pollution, when serviceability temperature surpasses 80 ° of C, proton conductivity obviously descends, and has limited the further application of perfluoro sulfonic acid membrane in fuel cell.The proton exchange membrane that for this reason, need further prepare excellent combination property.
Sulfonated Polyphenylene Sulfide (SPPS) material is because of the thermal stability with high mechanical properties, excellence and the primary study material that chemical stability becomes proton exchange membrane used for direct methanol fuel cell.With the sulfonation of concentrated sulfuric acid p-poly-phenyl thioether, sulfonic acid group is incorporated on the main chain of polyphenylene sulfide, existence due to the hydrophobic phase such as phenyl ring, carbon-sulfur bond on sulfonic group aqueous favoring and polymer backbone, can make polyphenyl thioether material there is certain proton conductivity, and the polyphenylene sulfide preparation cost is lower, heat-resistant stability is excellent can meet the requirement of fuel cell to proton exchange membrane material.But, the sulfonation degree of this material (DS) can directly affect the performance of proton exchange membrane, so to select the suitable sulfonation degree masking of being adulterated.On the conceptual design of Sulfonated Polyphenylene Sulfide proton exchange membrane, usually need to the method for Sulfonated Polyphenylene Sulfide sulfonation degree and modification be considered, obtain best proton exchange membrane.
Summary of the invention
One of purpose of the present invention is to provide a kind of nano-cerium oxide (CeO 2) modification sulphonation polyphenylene sulfide proton exchange membrane.
Two of purpose of the present invention is to provide the preparation method of this proton exchange membrane.
For achieving the above object, the present invention adopts following technical scheme:
A kind of nano-cerium oxide modification sulphonation polyphenylene sulfide proton exchange membrane is characterized in that the composition of this exchange membrane and quality percentage composition thereof are:
Sulfonated Polyphenylene Sulfide SPPS 82.5% ~ 99.9%;
Nano Ce O 2powder 0.1%～17.5%;
The structural formula of described Sulfonated Polyphenylene Sulfide SPPS is:
Figure 2013104399637100002DEST_PATH_IMAGE002
；
Described CeO 2the powder particle particle diameter is 25 ~ 30 nm.
The sulfonation degree of above-mentioned Sulfonated Polyphenylene Sulfide is 57%～80%.
A kind of method for preparing above-mentioned nano-cerium oxide modification sulphonation polyphenylene sulfide proton exchange membrane is characterized in that the concrete steps of the method are:
(1). Sulfonated Polyphenylene Sulfide is dissolved in the masking solvent, is mixed with the preparation liquid that mass percent concentration is 10%～50%;
(2). in the preparation liquid of above-mentioned steps (1) gained, add nano Ce O 2powder, under 20 ° of C～80 ° C, stir and make nano Ce O 2powder is uniformly dispersed in preparation liquid, obtains mixing preparation liquid;
(3). step (2) gained mixing preparation liquid is made to film, and then solvent flashing under 20 ° of C～90 ° C, obtain wet film;
(4). by step (3) gained wet film freeze-day with constant temperature 1 h ~ 24 h under 50 ° of C～180 ° C; Perhaps first dry 2 h ~ 24 h under 40 ° of C～110 ° C, then be warming up to dry 1 h of 120 ° of C～180 ° C ~ 7 h, obtain nano-cerium oxide modification sulphonation polyphenylene sulfide proton exchange membrane.
The preparation method of highly sulfonated Sulfonated Polyphenylene Sulfide proton exchange membrane in above-mentioned modification, is characterized in that masking solvent used is: N, N-dimethyl sulfoxide (DMSO) DMSO or DMA DMAC.
Sulfonation degree refers to the contained sulfonic acid group number of every 100 repetitives in SPPS.
Embodiment
Embodiment mono-:
1.SPPS the preparation of preparation liquid: adopt DMSO as preparation liquid, the SPPS material dissolves that is 70.2% by the sulfonation degree of grinding, in the masking solvent, is mixed with the preparation liquid that the SPPS mass percent is 10%.
2.SPPS/ nano Ce O 2the preparation of preparation liquid: in the SPPS of step 1 gained preparation liquid, be that 6% dosage adds nano Ce O by mass percentage 2powder, its grain diameter is 25 nm.With magnetic stirrer 4 h, stir 6 h under 75 ° of C under 30 ° of C, make nano Ce O 2powder is uniformly dispersed in preparation liquid, obtains SPPS/ nano Ce O 2preparation liquid.
3.SPPS/ nano Ce O 2the preparation of proton exchange membrane: pour the mixing preparation liquid of step 2 gained in clean flat plate mold casting film-forming.Mixing preparation liquid in mould is solvent flashing under 50 ° of C, obtains SPPS/ CeO 2wet film.Wet film is dry 2 h under 60 ° of C first, then are warming up to dry 2 h of 120 ° of C, obtain SPPS/ CeO 2dry film.
To the prepared SPPS/ CeO of above-described embodiment 2proton exchange membrane is applied to experiment, and its process and result are as described below:
1.SPPS/ CeO 2the test of proton exchange membrane conductivity:
On the basis that exchanges two-probe method, improved, designed, designed has also been set up a set of simple and easy reliable film resistance testing apparatus.Detected temperatures is 40 ° of C～110 ° C.SPPS/CeO 2conductivity during 40 ° of C of film is 8.0 * 10 -3s/cm, conductivity during 110 ° of C is 9.0 * 10 -3s/cm.
2.SPPS/ CeO 2the test of proton exchange membrane alcohol-rejecting ability:
Adopt the alcohol-rejecting ability of barrier film diffusion cell evaluated for film.Before test, the film sample is soaked one day in deionization, and tested after stablizing more than 2 h under probe temperature.Film is sandwiched in the middle of the two halves chamber, injects the 5 mol/L methanol solutions of 80 ml in a side, the pure water that opposite side injects suitable volume makes its liquid level equal with the liquid level of methyl alcohol.Adopt gas chromatography to measure in pure water methanol concentration situation over time.Have Fick diffusion second law can obtain methanol permeability:
Figure 2013104399637100002DEST_PATH_IMAGE004
S: methanol concentration temporal evolution slope of a curve
V 2: the volume of pure water
L: wet-film thickness
A: membrane area
C: methanol solution initial concentration
By test, under reaction condition as mentioned above, SPPS/ CeO 2the resistance alcohol coefficient of film is 1.1 * 10 -8cm 2/ s.
3.SPPS/ CeO 2the test of proton exchange membrane water absorption rate:
First, by SPPS film dry 24 h under 110 ° of C, claim to obtain desciccator diaphragm weight (M d), then film being immersed in deionized water, soaking at room temperature 24 h make its abundant swelling.Take out wet film, suck surperficial moisture content, claim to obtain (M in wet film w), the water absorption rate S of film wfor:
Figure 2013104399637100002DEST_PATH_IMAGE006
By test, under reaction condition as mentioned above, SPPS/ CeO 2the water absorption rate of proton exchange membrane is 70.12%.
Embodiment bis-:
1.SPPS the preparation of preparation liquid: adopt DMSO as preparation liquid, the SPPS material dissolves that is 72.1% by the sulfonation degree of grinding, in the masking solvent, is mixed with the preparation liquid that the SPPS mass percent is 10%.
2.SPPS/ nano Ce O 2the preparation of preparation liquid: in the SPPS of step 1 gained preparation liquid, be that 10% dosage adds nano Ce O by mass percentage 2powder, its grain diameter is 25 nm.With magnetic stirrer 4 h, stir 6 h under 75 ° of C under 30 ° of C, make nano Ce O 2powder is uniformly dispersed in preparation liquid, obtains SPPS/ nano Ce O 2preparation liquid.
3.SPPS/ nano Ce O 2the preparation of proton exchange membrane: pour the mixing preparation liquid of step 2 gained in clean flat plate mold casting film-forming.Mixing preparation liquid in mould is solvent flashing under 50 ° of C, obtains SPPS/ CeO 2wet film.Wet film is dry 2 h under 60 ° of C first, then are warming up to dry 2 h of 120 ° of C, obtain SPPS/ CeO 2dry film.
To the prepared SPPS/ CeO of above-described embodiment 2the proton exchange membrane application experiment, its process and result are as described below:
1.SPPS/ CeO 2the test of proton exchange membrane conductivity:
Method of testing as described in Example 1.SPPS/ CeO 2conductivity during 40 ° of C of film is 8.1 * 10 -3s/cm, conductivity during 110 ° of C is 1.1 * 10 -2s/cm.
2.SPPS/ CeO 2the test of proton exchange membrane alcohol-rejecting ability:
Method of testing as described in Example 1.SPPS/ CeO 2the resistance alcohol coefficient of film is 4.2 * 10 -7cm 2/ s.
3.SPPS/ CeO 2the test of proton exchange membrane water absorption rate:
Method of testing as described in Example 1.SPPS/ CeO 2the water absorption rate of proton exchange membrane is 48.69%
Embodiment tri-:
1.SPPS the preparation of preparation liquid: adopt DMAc as preparation liquid, the SPPS material dissolves that is 74.8% by the sulfonation degree of grinding, in the masking solvent, is mixed with the preparation liquid that the SPPS mass percent is 20%.
2.SPPS/ nano Ce O 2the preparation of preparation liquid: in the SPPS of step 1 gained preparation liquid, be that 14.5% dosage adds nano Ce O by mass percentage 2powder, its grain diameter is 30 nm.With magnetic stirrer 4 h, stir 6 h under 75 ° of C under 30 ° of C, make nano Ce O 2powder is uniformly dispersed in preparation liquid, obtains SPPS/ nano Ce O 2preparation liquid.
3.SPPS/ nano Ce O 2the preparation of proton exchange membrane: pour the mixing preparation liquid of step 2 gained in clean flat plate mold casting film-forming.Mixing preparation liquid in mould is solvent flashing under 50 ° of C, obtains SPPS/ CeO 2wet film.Wet film is dry 2 h under 60 ° of C first, then are warming up to dry 2 h of 120 ° of C, obtain SPPS/ CeO 2dry film.
To the prepared SPPS/ CeO of above-described embodiment 2the proton exchange membrane application experiment, its process and result are as described below:
1.SPPS/ CeO 2the test of proton exchange membrane conductivity:
Method of testing as described in Example 1.SPPS/CeO 2conductivity during 40 ° of C of film is 8.5 * 10 -3s/cm, conductivity during 110 ° of C is 1.5 * 10 -2s/cm.
2.SPPS/ CeO 2the test of proton exchange membrane alcohol-rejecting ability:
Method of testing as described in Example 1.SPPS/ CeO 2the resistance alcohol coefficient of film is 1.9 * 10 -8cm 2/ s.
3.SPPS/ CeO 2the test of proton exchange membrane water absorption rate:
Method of testing as described in Example 1.SPPS/ CeO 2the water absorption rate of proton exchange membrane is 34.31%
Embodiment tetra-:
1.SPPS the preparation of preparation liquid: adopt DMAc as preparation liquid, the SPPS material dissolves that is 76.7% by the sulfonation degree of grinding, in the masking solvent, is mixed with the preparation liquid that the SPPS mass percent is 20%.
2.SPPS/ nano Ce O 2the preparation of preparation liquid: in the SPPS of step 1 gained preparation liquid, be that 17.1% dosage adds nano Ce O by mass percentage 2powder, its grain diameter is 30 nm.With magnetic stirrer 4 h, stir 6 h under 75 ° of C under 30 ° of C, make nano Ce O 2powder is uniformly dispersed in preparation liquid, obtains SPPS/ nano Ce O 2preparation liquid.
3.SPPS/ nano Ce O 2the preparation of proton exchange membrane: pour the mixing preparation liquid of step 2 gained in clean flat plate mold casting film-forming.Mixing preparation liquid in mould is solvent flashing under 50 ° of C, obtains SPPS/ CeO 2wet film.Wet film is dry 2 h under 60 ° of C first, then are warming up to dry 2 h of 120 ° of C, obtain SPPS/ CeO 2dry film.
To the prepared SPPS/ CeO of above-described embodiment 2the proton exchange membrane application experiment, its process and result are as described below:
1.SPPS/ CeO 2the test of proton exchange membrane conductivity:
Method of testing as described in Example 1.SPPS/ CeO 2conductivity during 40 ° of C of film is 8.9 * 10 -3s/cm, conductivity during 110 ° of C is 1.7 * 10 -2s/cm.
2.SPPS/ CeO 2the test of proton exchange membrane alcohol-rejecting ability:
Method of testing as described in Example 1.SPPS/ CeO 2the resistance alcohol coefficient of film is 1.2 * 10 -8cm 2/ s.
3.SPPS/ CeO 2the test of proton exchange membrane water absorption rate:
Method of testing as described in Example 1.SPPS/ CeO 2the water absorption rate of proton exchange membrane is 24.98%.

Claims (4)

1. a nano-cerium oxide modification sulphonation polyphenylene sulfide proton exchange membrane is characterized in that the composition of this exchange membrane and quality percentage composition thereof are:
Sulfonated Polyphenylene Sulfide SPPS 82.5% ~ 99.9%;
Nano Ce O 2powder 0.1%～17.5%;
The structural formula of described Sulfonated Polyphenylene Sulfide SPPS is:
Figure 2013104399637100001DEST_PATH_IMAGE002
；
Described CeO 2the powder particle particle diameter is 25 ~ 30 nm.
2. nano-cerium oxide modification sulphonation polyphenylene sulfide proton exchange membrane according to claim 1, the sulfonation degree that it is characterized in that described Sulfonated Polyphenylene Sulfide is 57%～80%.
3. a method for preparing nano-cerium oxide modification sulphonation polyphenylene sulfide proton exchange membrane according to claim 1 and 2 is characterized in that the concrete steps of the method are:
(1). Sulfonated Polyphenylene Sulfide is dissolved in the masking solvent, is mixed with the preparation liquid that mass percent concentration is 10%～50%;
(2). in the preparation liquid of above-mentioned steps (1) gained, add nano Ce O 2powder, under 20 ° of C～80 ° C, stir and make nano Ce O 2powder is uniformly dispersed in preparation liquid, obtains mixing preparation liquid;
(3). step (2) gained mixing preparation liquid is made to film, and then solvent flashing under 20 ° of C～90 ° C, obtain wet film;
(4). by step (3) gained wet film freeze-day with constant temperature 1 h ~ 24 h under 50 ° of C～180 ° C; Perhaps first dry 2 h ~ 24 h under 40 ° of C～110 ° C, then be warming up to dry 1 h of 120 ° of C～180 ° C ~ 7 h, obtain nano-cerium oxide modification sulphonation polyphenylene sulfide proton exchange membrane.
4. the preparation method of highly sulfonated Sulfonated Polyphenylene Sulfide proton exchange membrane in modification according to claim 3, is characterized in that masking solvent used is: N, N-dimethyl sulfoxide (DMSO) DMSO or DMA DMAC.
CN2013104399637A 2013-09-22 2013-09-22 Nano cerium oxide-modified sulfonated polyphenylene sulfide proton exchange membrane and preparation method thereof Pending CN103474688A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105694455A (en) * 2016-04-13 2016-06-22 武汉纺织大学 Polyphenylene sulfide modified material preparation method
CN108878993A (en) * 2017-05-12 2018-11-23 中国科学院大连化学物理研究所 A method of slowing down proton exchange membrane electrochemical degradation
CN112930603A (en) * 2018-10-31 2021-06-08 德克萨斯大学***董事会 Composite membranes and methods of making and using the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101225181A (en) * 2007-12-06 2008-07-23 上海大学 Y2O3 modified sulfonated polyetheretherketone proton exchange membrane and preparation method thereof
CN101719553A (en) * 2009-11-03 2010-06-02 上海大学 Binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and preparation method thereof
CN101908632A (en) * 2010-07-15 2010-12-08 上海大学 Ternary doping modified SPEEK proton exchange membrane and preparation method
CN103236553A (en) * 2013-04-10 2013-08-07 清华大学深圳研究生院 A composite ion-exchange membrane and a preparation method thereof, and a redox flow battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101225181A (en) * 2007-12-06 2008-07-23 上海大学 Y2O3 modified sulfonated polyetheretherketone proton exchange membrane and preparation method thereof
CN101719553A (en) * 2009-11-03 2010-06-02 上海大学 Binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and preparation method thereof
CN101908632A (en) * 2010-07-15 2010-12-08 上海大学 Ternary doping modified SPEEK proton exchange membrane and preparation method
CN103236553A (en) * 2013-04-10 2013-08-07 清华大学深圳研究生院 A composite ion-exchange membrane and a preparation method thereof, and a redox flow battery

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105694455A (en) * 2016-04-13 2016-06-22 武汉纺织大学 Polyphenylene sulfide modified material preparation method
CN105694455B (en) * 2016-04-13 2017-12-29 武汉纺织大学 A kind of material modified preparation method of polyphenylene sulfide
CN108878993A (en) * 2017-05-12 2018-11-23 中国科学院大连化学物理研究所 A method of slowing down proton exchange membrane electrochemical degradation
CN112930603A (en) * 2018-10-31 2021-06-08 德克萨斯大学***董事会 Composite membranes and methods of making and using the same

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Application publication date: 20131225