CN103554537A - Membrane and preparation method thereof - Google Patents
Membrane and preparation method thereof Download PDFInfo
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- CN103554537A CN103554537A CN201310530700.7A CN201310530700A CN103554537A CN 103554537 A CN103554537 A CN 103554537A CN 201310530700 A CN201310530700 A CN 201310530700A CN 103554537 A CN103554537 A CN 103554537A
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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
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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
- 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 provides a membrane and a preparation method thereof. The preparation method comprises the following steps: mixing CsHSO4 and mesoporous Al2O3 to obtain a mixture; mixing the mixture and a polyvinylidene fluoride solution to obtain mixed liquid; and making the mixed liquid into a membrane by a coating technology. By adopting the method to prepare a membrane, the cost is low, and the membrane is easy to form; when the film is used as a proton exchange membrane, the membrane has high conductivity at 100-200 DEG C, the conductivity is increased to 10<-3>S.cm<-1>, the proton conductivity can reach 2.5*10<-3>S.cm<-1>, and the alcohol resistance rate is about 3 magnitude orders higher than Nafion.
Description
Technical field
The present invention relates to a kind of film, in particular to a kind of inorganic-organic proton exchange membrane and preparation method thereof.
Background technology
Various films have been developed up to now, for example, reverse osmosis membrane (0.0001～0.005 μ m), nanofiltration membrane (0.001～0.005 μ m), ultra-filtration membrane (0.001～0.1 μ m), microfiltration membrane (0.1～1 μ m), electrodialytic membranes, Pervaporation membrane, liquid membrane, gas separation membrane, electrode film, proton exchange membrane etc.The separating mechanism that they are corresponding different, different equipment, has different applications.Film itself can be made by polymkeric substance, inorganic materials or liquid, its structure can be homogeneous or heterogeneous, porous or atresia, solid or liquid, charged or neutral.The thickness of film can be as thin as several microns, thick in several millimeters.Different films has different microtextures and function, need to prepare with diverse ways.Film-forming method is the core technology that the core research topic ，Ye Shige company in film field holds in close confidence always.Wherein, proton exchange membrane (Proton Exchange Membrane Fuel, PEM) is the core component of PEMFC, and the barrier film using in PEM and general chemical power source is had any different.Proton Exchange Membrane Fuel Cells has become the most competitive cleaning of gasoline internal combustion mechanomotive force and has replaced propulsion source.
As everyone knows, energy problem receives global concern always, taps a new source of energy and becomes a major portion of every country development.Fuel cell is owing to having the advantages such as effciency of energy transfer is high, environmental pollution is little and be subject to the generally attention of countries in the world.Fuel cell has many types, Proton Exchange Membrane Fuel Cells (Polymer Exchange Membrane Fuel Cell wherein, PEMFC) have that started quickly at low temperature, specific energy are high, noiselessness, the plurality of advantages such as pollution-free, be used as the desirable energy of electromobile and movable small power supply system, the uninterruptible power supply of electronics, decentralized power station, space flight and military equipment power supply, public place emergency source of electric power etc., its wide application prospect is just becoming one of study hotspot of countries in the world.On the basis of PEMFC, the methyl alcohol of usining replaces pure hydrogen directly as fuel, simplified system greatly, and this fuel cell is called direct methanol fuel cell (Direct Methanol Fuel Cell, DMFC).The advantages such as DMFC has that volume is little, lightweight, fuel source is abundant, low price, storage are easy to carry are desirable car power sources.
Proton exchange membrane (Proton exchange membrane, PEM) be Proton Exchange Membrane Fuel Cells (Proton exchange membrane fuel cell, PEMFC) and one of the core component of direct alcohol fuel cell (comprising DMFC and DEFC), its effect is: (1) separates anode and negative electrode, stops fuel and air (oxygen) directly to mix chemical reaction occurs; (2) proton conducting, proton conductivity is higher, and the internal resistance of film is less, and the efficiency of fuel cell is higher; (3) electrical insulator, stops electronics to conduct in film, and electronics by outside line road direction cathode flow, produces foreign current for people to use by anode.Conventionally, fuel cell must meet following requirement with PEM material: (1) low cost; (2) high proton conductivity; (3) good mechanical strength (anti-swelling) and dimensional stability; (4) excellent chemical stability and electrochemical stability; (5) very low gas or methanol permeability; (6) mate with catalyst layer; (7) life-time service is stable.The performance of proton exchange membrane will directly affect battery performance, effciency of energy transfer and the work-ing life of PEMFC and DMFC.
At present, using maximum proton exchange membrane is the Nafion film that du pont company produces, and has advantages of that low temperature proton conductivity is high and chemical stability is good.But it still exists some shortcomings: 1) to rely on consumingly water be transmission medium to this film, when working temperature surpasses 100 ℃, because moisture evaporation in film causes proton conduction property sharply to decline, can only below low temperature (80 ℃), more than high humidity (40%RH), use.At present, assembling PEMFC and DMFC extensively adopt Nafion film, therefore need additional huge humidifying equipment to reduce battery temperature; 2) while working at the temperature below 80 ℃, there is the poison problem of serious CO to catalyzer, and for DMFC, selection trafficability characteristic to first alcohol and water is poor, alcohol-rejecting ability is poor, more than 40% methyl alcohol can see through this film in use, this has just reduced battery performance and fuel availability, be not suitable for use in direct methanol fuel cell (Directmethanol fuel cell, DMFC) PEM, methyl alcohol is the subject matter that restriction DMFC develops by the caused anode performance decay of infiltration of Nafion film simultaneously.Therefore it is imperative that this serial difficult problem, being caused by Nafion enables for the development research of comparatively high temps (T>100 ℃), novel proton exchange membranes that resistance alcohol rate is high.
Summary of the invention
For the film using in fuel cell in prior art lower problem of proton conductivity in the situation that working temperature surpasses 100 ℃, the invention provides and a kind ofly under middle low temperature, there is film of high conductivity and preparation method thereof.
According to an aspect of the present invention, provide a kind of preparation method who prepares film, the method comprises the following steps:
A) by CsHSO
4with mesoporous Al
2o
3be mixed to get mixture;
B) mixture is become to mixed solution with polyvinylidene difluoride (PVDF) solution mixing system; And
C) use coating process that mixed solution is prepared to film forming.
In step a), by CsHSO
4with mesoporous Al
2o
3the step for preparing mixture further comprises: by CsHSO
4with mesoporous Al
2o
3mix and obtain mixture; Mixture is heated to 250 ℃ and constant temperature 12 hours, is cooled to room temperature; And grinding mixture 5 minutes; Wherein, CsHSO
4with mesoporous Al
2o
3mass ratio between 0.75 and 5.81.
In step b), become the step of mixed solution further to comprise with polyvinylidene difluoride (PVDF) solution mixing system in mixture: under 50 ℃-70 ℃ heating and/or agitation condition, by polyvinylidene difluoride (PVDF) and N, N-N,N-DIMETHYLACETAMIDE mixes, be prepared into polyvinylidene difluoride (PVDF) solution, the time of wherein stirring is until form the polyvinylidene difluoride (PVDF) solution of clarification; And under stirring and/or ultra-sonic oscillation condition, preferably stir and condition that ultra-sonic oscillation are used alternatingly continuously under, mixture and polyvinylidene difluoride (PVDF) solution are mixed to get to mixed solution, and wherein, the mass ratio of mixture and polyvinylidene difluoride (PVDF) is between 0.34 and 2.22; And the time of stirring is 20-30 minute, and the time of ultra-sonic oscillation is 20-30 minute.
In this step, by adopting PVDF as the film forming material (substrate) of film, because PVDF has good thermoplasticity, the mechanical property of composite membrane is improved, can also improve the resistance alcohol rate of composite membrane simultaneously; And PVDF's is cheap, can directly reduce the price of film.
In addition,, by mixture is become to mixed solution with polyvinylidene difluoride (PVDF) solution mixing system, make CsHSO
4with mesoporous Al
2o
3be dispersed in uniformly in polyvinylidene difluoride (PVDF) solution.When low temperature (below 100 ℃), mesoporous Al
2o
3the water molecules of mesoporous absorption as proton conduction body, make film there is higher low-temperature conductivity.At mesophilic range (100 ℃-200 ℃), solid acid CsHSO
4as proton conductor, can make film there is middle temperature electroconductibility.
In step c), the step of using coating process that mixed solution is prepared to film forming further comprises: utilize coating instrument that mixed solution is coated on substrate, dry mixed liquid is with produced film; And peel off described film from substrate.
At above-mentioned steps c) in, in baking oven, implement the step of dry mixed liquid, wherein, dry temperature is 50 ℃-70 ℃, the dry time is 3-5 hour; Coating instrument is adjustable spreader, spin coater, automatic coating machine, coating machine; And substrate can be sheet glass.
Before step a), can also comprise the mesoporous Al of preparation
2o
3step, this step comprises: six hydration lanthanum trichlorides are dissolved in deionized water, make the second solution, take solvent hexanaphthene and tensio-active agent, make the 3rd solution, mix the second solution and the 3rd solution, generate the first white gels, add aluminium secondary butylate, obtain the second white gels; The second white gels is transferred in constant temperature oscillator, under 60 ℃, 180rpm/ minute, vibrates 24 hours; Described the second white gels after vibration is transferred in filter flask and carries out suction filtration, and suction filtration after product is dry at 100 ℃, obtains mesoporous aluminium mixture powder; And the method roasting with temperature programming by mesoporous aluminium mixture powder, the program of roasting is: from 25 ℃ of intensifications 4 hours to 500 ℃, at 500 ℃, be incubated 4 hours, from 500 ℃, lower the temperature 2 hours to 25, wherein, thus the speed of cooling is 1.98 ℃/min obtains mesoporous Al
2o
3; Wherein, described tensio-active agent is Span80, Span85 or X114.
The film of preparing by above-mentioned steps can be used as proton exchange membrane.
According to a second aspect of the invention, also provide a kind of basis film prepared by above method, by weight percentage, the composition of described film comprises:
CsHSO
4 17.16%-47.37%
Mesoporous Al
2o
38.16%-22.84%;
Polyvinylidene difluoride (PVDF) 31.58%-73.47%;
Film provided by the invention can be used as proton exchange membrane.
In sum, the present invention adopts polyvinylidene difluoride (PVDF) (PVDF) as substrate, then by solid peracid CsHSO
4meso-porous alumina (the Al of doping
2o
3) be doped in polyvinylidene difluoride (PVDF), by this method the film of preparation not only cost low, be easy to film forming, and there is high conductivity 100-200 ℃ of scope, specific conductivity is increased to 10
-3scm-1, its proton conductivity can reach 2.5 * 10 at 200 ℃
-3scm-1, resistance alcohol rate is than high approximately 3 orders of magnitude of Nafion.
Accompanying drawing explanation
Fig. 1 is according to the photo of the film of embodiments of the invention 1;
Fig. 2 is at 25 ℃-200 ℃ temperature variant graphic representations of temperature range inner proton electric conductivity according to the film of embodiments of the invention 1; And
Fig. 3 is according to the correlation curve figure of the methanol permeability of the film of embodiments of the invention 2 and Nafion film.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, the every other embodiment that those of ordinary skills obtain, belongs to the scope of protection of the invention.
The preparation of embodiment 1 film S1
Get 37.3670g C
6h
12with 6.2021g X-114(4-(C
8h
17) C
6h
4(OCH
2cH
2)
n-OH) mix and blend generates solution I for 15 minutes; Get 0.660g LaCL
36H
2o and 7.992g distilled water mixing and stirring, generate solution II; Solution I and solution II mixing and stirring, generate white gels I; Get 21.893g Al (C
4h
9o)
3join in white gels I, stir, obtain white gels II; White gels II is put into water bath with thermostatic control vibration case, 60 ℃ of constant temperature, 180rpm/ minute vibration 24h; By the white gels II after vibration, with Büchner funnel suction filtration 1.5h, the white powder obtaining is put into baking oven, and 100 ℃ of constant temperature dry 1440 minutes to remove moisture; Sample after drying is put into chamber type electric resistance furnace roasting, obtain mesoporous Al
2o
3powdered sample.Calcination procedure is: from 25 ℃ of intensifications 4 hours to 500 ℃, at 500 ℃, be incubated 4 hours, from 500 ℃ of coolings 2 hours to 25 ℃.
Get 2.303gCsHSO
4with the mesoporous Al of 3.065g
2o
3powder mixes, and mixture is heated to 250 ℃ and constant temperature 12 hours, is cooled to room temperature.Grind 5 minutes, obtain mix powder sample.
Get 3g PVDF(polyvinylidene difluoride (PVDF)) join 25g DMAC(N, N-N,N-DIMETHYLACETAMIDE) in, be heated to 50 ℃, and use magnetic agitation, until solution clarification prepares PVDF-DMFC solution.
Get 2g mix powder and add PVDF-DMFC solution, magnetic agitation is used alternatingly with ultra-sonic oscillation for 30 minutes for 30 minutes continuously, until mesoporous Al
2o
3uniform particles is dispersed in the middle of solution, the solution glue that is white in color.Then, this mixed uniformly white colloidal solution is slowly poured on smooth surface, clean sheet glass, with adjustable painting step instrument, be coated onto on sheet glass, then put into baking oven, 50 ℃ of constant temperature are dried 3h; Finally take out sheet glass, with blade, scrape film, obtain film, the picture of film is with reference to figure 1, and wherein, in this film, by weight percentage, the composition of film comprises: CsHSO
417.16%; Mesoporous Al
2o
322.84%; Polyvinylidene difluoride (PVDF) 60%.This film can be used as the proton exchange membrane in fuel cell.
The preparation of embodiment 2 film S2
Get 37.3670g C
6h
12with 6.2021g X-114(4-(C
8h
17) C
6h
4(OCH
2cH
2)
n-OH) mix and blend generates solution I for 15 minutes; Get 0.660g LaCL
36H
2o and 7.992g distilled water mixing and stirring, generate solution II; Solution I and solution II mixing and stirring, generate white gels I; Get 21.893g Al (C
4h
9o)
3join in white gels I, stir, obtain white gels II; White gels II is put into water bath with thermostatic control vibration case, 60 ℃ of constant temperature, 180rpm/ minute vibration 24h; By the white gels II after vibration, with Büchner funnel suction filtration 1.5h, the white powder obtaining is put into baking oven, and 100 ℃ of constant temperature dry 1440 minutes to remove moisture; Sample after drying is put into chamber type electric resistance furnace roasting, obtain mesoporous Al
2o
3powdered sample.Calcination procedure is: from 25 ℃ of intensifications 4 hours to 500 ℃, at 500 ℃, be incubated 4 hours, from 500 ℃ of coolings 2 hours to 25 ℃.
Get 4.504gCsHSO
4with the mesoporous Al of 2.012g
2o
3powder mixes, and mixture is heated to 250 ℃ and constant temperature 12 hours, is cooled to room temperature.Grind 5 minutes, obtain mix powder sample.
Get 1.003g PVDF(polyvinylidene difluoride (PVDF)) join 25g DMAC(N, N-N,N-DIMETHYLACETAMIDE) in, be heated to 70 ℃, and use magnetic agitation, until solution clarification prepares PVDF-DMFC solution.
Get 0.3611g mix powder and add PVDF-DMFC solution, magnetic agitation is used alternatingly with ultra-sonic oscillation for 25 minutes for 25 minutes continuously, until mesoporous Al
2o
3uniform particles is dispersed in the middle of solution, the solution glue that is white in color.Then, this mixed uniformly white colloidal solution is slowly poured on smooth surface, clean sheet glass, with adjustable painting step instrument, be coated onto on sheet glass, then put into baking oven, 70 ℃ of constant temperature are dried 3h; Finally take out sheet glass, with blade, scrape film, obtain film, the picture of film is with reference to figure 1, and wherein, in this film, by weight percentage, the composition of film comprises: CsHSO
418.37%; Mesoporous Al
2o
38.16%; Polyvinylidene difluoride (PVDF) 73.47%.This film can be used as the proton exchange membrane in fuel cell.
The preparation of embodiment 3 film S3
Get 37.3670g C
6h
12with 6.2021g X-114(4-(C
8h
17) C
6h
4(OCH
2cH
2)
n-OH) mix and blend generates solution I for 15 minutes; Get 0.660g LaCL
36H
2o and 7.992g distilled water mixing and stirring, generate solution II; Solution I and solution II mixing and stirring, generate white gels I; Get 21.893g Al (C
4h
9o)
3join in white gels I, stir, obtain white gels II; White gels II is put into water bath with thermostatic control vibration case, 60 ℃ of constant temperature, 180rpm/ minute vibration 24h; By the white gels II after vibration, with Büchner funnel suction filtration 1.5h, the white powder obtaining is put into baking oven, and 100 ℃ of constant temperature dry 1440 minutes to remove moisture; Sample after drying is put into chamber type electric resistance furnace roasting, obtain mesoporous Al
2o
3powdered sample.Calcination procedure is: from 25 ℃ of intensifications 4 hours to 500 ℃, at 500 ℃, be incubated 4 hours, from 500 ℃ of coolings 2 hours to 25 ℃.
Get 4.504gCsHSO
4with the mesoporous Al of 2.012g
2o
3powder mixes, and mixture is heated to 250 ℃ and constant temperature 12 hours, is cooled to room temperature.Grind 5 minutes, obtain mix powder sample.
Get 1.003g PVDF(polyvinylidene difluoride (PVDF)) join 25g DMAC(N, N-N,N-DIMETHYLACETAMIDE) in, be heated to 70 ℃, and use magnetic agitation, until solution clarification prepares PVDF-DMFC solution.
Get 2.1667g mix powder and add PVDF-DMFC solution, magnetic agitation is used alternatingly with ultra-sonic oscillation for 20 minutes for 20 minutes continuously, until mesoporous Al
2o
3uniform particles is dispersed in the middle of solution, the solution glue that is white in color.Then, this mixed uniformly white colloidal solution is slowly poured on smooth surface, clean sheet glass, with adjustable painting step instrument, be coated onto on sheet glass, then put into baking oven, 70 ℃ of constant temperature are dried 2h; Finally take out sheet glass, with blade, scrape film, obtain film, the picture of film is with reference to figure 1, and wherein, in this film, by weight percentage, the composition of film comprises: CsHSO
447.37%; Mesoporous Al
2o
321.05%; Polyvinylidene difluoride (PVDF) 31.58%.This film can be used as the proton exchange membrane in fuel cell.
The mensuration of the proton conductivity of the film under embodiment 4 differing tempss
As shown in Figure 2, the S1 film preparing in embodiment 1, recording its film thickness is 100 μ m, the proton conductivity that is recorded 25 ℃-100 ℃ by electric impedance analyzer can reach 10
-4scm
-1; At 100-200 ℃, proton conductivity is increased to 10
-3scm
-1, in the time of 200 ℃, its proton conductivity can reach 2.5 * 10
-3scm
-1.
The comparison of the resistance alcohol rate of embodiment 5 film of the present invention and Nafion film
Because direct methanol fuel cell (DMFC) can only be used at the temperature lower than methyl alcohol boiling point, therefore, the present invention has measured the resistance alcohol rate of the film S2 preparing in embodiment 2 at 25 ℃ of-70 ℃ of temperature, as shown in Figure 3, measurement result shows under the temperature range of 25 ℃-70 ℃, the resistance alcohol rate of film is than high 3 orders of magnitude of Nafion film, thereby is more suitable for for direct methanol fuel cell.
Above-described embodiment shows that the proton conductivity of film provided by the invention is 10 in the time of 25 ℃-100 ℃
-4scm
-1; In the time of 100-200 ℃, proton conductivity is increased to 10
-3scm
-1, in the time of 200 ℃, its proton conductivity can reach 2.5 * 10
-3scm
-1.As can be seen here, the specific conductivity of film provided by the invention is higher, not only can below low temperature (100 ℃), use, simultaneously can also be at the lower use of middle temperature (100-200 ℃), Applicable temperature a wider range.In addition, because the resistance alcohol rate of film provided by the invention is higher, than high 3 orders of magnitude of Nafion film, thereby be more suitable for for direct methanol fuel cell.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a preparation method for film, comprises the following steps:
By CsHSO
4with mesoporous Al
2o
3be mixed to get mixture;
Described mixture is become to mixed solution with polyvinylidene difluoride (PVDF) solution mixing system; And
Use coating process that described mixed solution is prepared to film forming.
2. preparation method according to claim 1, is characterized in that, described by CsHSO
4with mesoporous Al
2o
3the step that is mixed to get mixture further comprises:
By described CsHSO
4with described mesoporous Al
2o
3mix and obtain mixture;
Described mixture is heated to 250 ℃ and constant temperature 12 hours, is cooled to room temperature; And
Grind described mixture 5 minutes;
Wherein, described CsHSO
4with described mesoporous Al
2o
3mass ratio between 0.75 and 5.81.
3. preparation method according to claim 1 and 2, is characterized in that, becomes the step of mixed solution further to comprise in described mixture with described polyvinylidene difluoride (PVDF) solution mixing system:
Polyvinylidene difluoride (PVDF) is mixed with N,N-dimethylacetamide, be prepared into described polyvinylidene difluoride (PVDF) solution; And
Described mixture and described polyvinylidene difluoride (PVDF) solution are mixed to get to described mixed solution, and wherein, the mass ratio of described mixture and described polyvinylidene difluoride (PVDF) is between 0.34 and 2.22.
4. preparation method according to claim 3, it is characterized in that, under 50 ℃-70 ℃ heating and/or agitation condition, implement the step that described polyvinylidene difluoride (PVDF) is mixed with described N,N-dimethylacetamide, wherein, the time of described stirring is until form the described polyvinylidene difluoride (PVDF) solution of clarification;
Under stirring and/or ultra-sonic oscillation condition, enforcement mixes described mixture step with described polyvinylidene difluoride (PVDF) solution, wherein, the time of described stirring is 20-30 minute, the time of described ultra-sonic oscillation is 20-30 minute.
5. preparation method according to claim 1, is characterized in that, the step that described use coating process is prepared film forming by described mixed solution further comprises:
Utilize coating instrument that described mixed solution is coated on substrate, dry described mixed solution is to generate described film; And
From described substrate, peel off described film.
6. preparation method according to claim 5, is characterized in that, implements the step of dry described mixed solution in baking oven, and wherein, described dry temperature is 50 ℃-70 ℃, and the described dry time is 3-5 hour;
Described coating instrument is adjustable spreader, spin coater, automatic coating machine, coating machine; And
Described substrate is sheet glass.
7. according to the preparation method described in any one in claim 1-6, it is characterized in that, described film is proton exchange membrane.
8. a film of preparing according to the preparation method described in any one in claim 1-7, is characterized in that, by weight percentage, the composition of described film comprises:
CsHSO
4 17.16%-47.37%
Mesoporous Al
2o
38.16%-22.84%;
Polyvinylidene difluoride (PVDF) 31.58%-73.47%.
9. film according to claim 8, is characterized in that, described film is proton exchange membrane.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105140545A (en) * | 2015-08-04 | 2015-12-09 | 中国计量学院 | Preparation technology of composite proton exchange membrane |
| CN105355937A (en) * | 2015-12-08 | 2016-02-24 | 中国计量学院 | Preparation process of membrane electrode assembly for proton exchange membrane fuel cell |
| CN107240705A (en) * | 2017-05-10 | 2017-10-10 | 上海交通大学 | A kind of middle temperature melting proton conductor dielectric film and its production and use |
| CN107331883A (en) * | 2017-05-10 | 2017-11-07 | 上海交通大学 | A kind of middle temperature proton exchange film and preparation method thereof |
| CN113410496A (en) * | 2021-06-16 | 2021-09-17 | 东北大学秦皇岛分校 | All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof |
| CN113839074A (en) * | 2021-09-24 | 2021-12-24 | 上海交通大学 | Preparation method of solid acid proton conduction membrane |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140545A (en) * | 2015-08-04 | 2015-12-09 | 中国计量学院 | Preparation technology of composite proton exchange membrane |
| CN105355937A (en) * | 2015-12-08 | 2016-02-24 | 中国计量学院 | Preparation process of membrane electrode assembly for proton exchange membrane fuel cell |
| CN107240705A (en) * | 2017-05-10 | 2017-10-10 | 上海交通大学 | A kind of middle temperature melting proton conductor dielectric film and its production and use |
| CN107331883A (en) * | 2017-05-10 | 2017-11-07 | 上海交通大学 | A kind of middle temperature proton exchange film and preparation method thereof |
| CN107331883B (en) * | 2017-05-10 | 2020-07-14 | 上海交通大学 | Intermediate-temperature proton exchange membrane and preparation method thereof |
| CN107240705B (en) * | 2017-05-10 | 2020-08-04 | 上海交通大学 | Medium-temperature molten proton conductor electrolyte membrane and application |
| CN113410496A (en) * | 2021-06-16 | 2021-09-17 | 东北大学秦皇岛分校 | All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof |
| CN113410496B (en) * | 2021-06-16 | 2023-02-14 | 东北大学秦皇岛分校 | All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof |
| CN113839074A (en) * | 2021-09-24 | 2021-12-24 | 上海交通大学 | Preparation method of solid acid proton conduction membrane |
| CN113839074B (en) * | 2021-09-24 | 2023-10-20 | 上海交通大学 | Preparation method of solid acid proton conducting membrane |
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| CN103554537B (en) | 2016-10-19 |
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