CN104659395B - Organic-inorganic composite proton exchange membrane for proton exchange membrane fuel cell and preparation method thereof - Google Patents
Organic-inorganic composite proton exchange membrane for proton exchange membrane fuel cell and preparation method thereof Download PDFInfo
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- CN104659395B CN104659395B CN201310593705.4A CN201310593705A CN104659395B CN 104659395 B CN104659395 B CN 104659395B CN 201310593705 A CN201310593705 A CN 201310593705A CN 104659395 B CN104659395 B CN 104659395B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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
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Abstract
The invention discloses an organic-inorganic composite proton exchange membrane for a proton exchange membrane fuel cell and a preparation method thereof. The proton exchange membrane comprises a functional polymer (such as polyvinylpyrrolidone) of which the side chain contains N-heterocycle, heteropoly acid and skeleton polymers (such as polyvinylidene fluoride, polyethersulfone, polysulfone and polyethylene sulfone). The preparation method comprises adding the functional polymer, the skeleton polymers and the heteropoly acid into an organic solvent (such as N, N-dimethyl formamide, N, N-dimethyl acetamide and N-methyl-2-pyrrolidone), heating the mixture with stirring until complete dissolution so that a transparent and uniform proton exchange membrane solution is obtained, and carrying out solution casting or curtain coating to obtain the organic-inorganic composite proton exchange membrane. The organic-inorganic composite proton exchange membrane is uniform, transparent and compact, has excellent chemical stability, heat stability, mechanical properties and proton conductivity, and does not lost a proton conductor easily. The preparation method utilizes easily available and cheap raw materials, has simple processes, is suitable for large-scale production and can be widely used in fuel cells, flow cells, plumbic acid cells and a water-electrolyser.
Description
Technical field
The present invention relates to a kind of used in proton exchange membrane fuel cell organic-inorganic composite proton exchange membrane and its preparation side
Method, belongs to new material technology and technical field of new energies.
Background technology
Proton Exchange Membrane Fuel Cells（PEMFCs）Be a kind of by electrochemical reaction by the chemistry in fuel and oxidant
The TRT of electric energy can be converted into.Power density is big, energy conversion efficiency is high, battery structure is tight due to having for PEMFCs
Gather, toggle speed is fast, environmental pollution is little, can application extensively etc. many merits and become in all kinds of fuel cells and develop
Hurry up, a types of fuel cells that technology is the most ripe.
Existing it is widely used in Proton Exchange Membrane Fuel Cells（≤80℃）Perfluorosulfonic acid proton exchange film（As the U.S.
E.I.Du Pont Company producesSeries membranes）, its heat endurance, proton conductivity of phosphoric acid, mechanicalness are all very excellent, but its cost
Very high, and because methanol crossover is serious, be not suitable for being applied to direct alcohol fuel cell.Therefore high-performance, low price
The research and development of novel proton exchange membranes receive the extensive concern of people.
Heteropoly acid is as a kind of excellent proton conductor（As the electrical conductivity under phosphotungstic acid normal temperature can reach 0.18S cm-1）, it has been widely used in fuel cell.For example itself can be used as solid electrolyte use, more in the case of be and film base
Body material such as Nafion, SPEEK（Sulfonated polyether-ether-ketone）, PVA（Polyvinyl alcohol）, inorganic compounding matrix P2O5–SiO2, micropore
The doping and blending such as material, the organic or inorganic composite membrane being prepared possesses heteropoly acid and polyelectrolyte double properties, has relatively
Good Proton conducting ability, and the preparation process is simple of film.
However, in current heteropoly acid doping type composite membrane, because heteropoly acid has good water solubility, thus multiple
Close film and there is heteropoly acid loss by dissolution, especially in DMFC（DMFC）Under environment, more have very sufficient
Circulating water, and heteropoly acid, due to having extremely strong hydrophily, can gradually run off, and leads to electrical conductivity to decline, final battery performance
Also can significantly decay.
Content of the invention
For the problems referred to above, object of the present invention is to provide a kind of new high-performance organic-inorganic composite proton
Exchange membrane and preparation method thereof, prepared organic-inorganic composite proton exchange membrane is homogeneous, transparent, dense membrane, has
Excellent heat endurance, chemical stability, mechanical performance and excellent proton conductive and stability.
According to an aspect of the invention, it is provided a kind of used in proton exchange membrane fuel cell Organic-inorganic composite proton
Exchange membrane it is characterised in that：Described organic-inorganic composite proton exchange membrane carries the functional polymer of N- heterocycle by side chain（As
Polyvinylpyrrolidone, polyvinylpyridine etc.）, heteropoly acid（As phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid）And skeleton polymer（As
Polyether sulfone（PES）, polysulfones（PSF）, PPSU（PPSF）, Kynoar（PVDF）Deng）Composition；Described compound proton exchange membrane
The weight/mass percentage composition that middle side chain carries the polymer of azacyclo- is 20～80%, the weight/mass percentage composition of described skeleton polymer
For 10～50%, the weight/mass percentage composition of described heteropoly acid is 10-60%.
According to a further aspect of the present invention, above-mentioned organic-inorganic composite proton exchange membrane for fuel cell
It is characterised by：The polymer that described side chain carries azacyclo- is polyvinylpyrrolidone（PVP）.
According to a further aspect of the present invention, above-mentioned organic-inorganic composite proton exchange membrane for fuel cell
It is characterised by：Described heteropoly acid is phosphotungstic acid（PWA）, phosphomolybdic acid（PMA）, silico-tungstic acid（SWA）
According to a further aspect of the present invention, above-mentioned organic-inorganic composite proton exchange membrane for fuel cell
It is characterised by：There is the skeleton polymer polyether sulfone of chemical resistance and heat endurance（PES）, polysulfones（PSF）, PPSU
（PPSF）, Kynoar（PVDF）One of and/or in them two or more composition mixture.
According to another aspect of the present invention, there is provided a kind of preparation method of organic-inorganic composite proton exchange membrane, its
Be characterised by including：
A）Mix having the polymer with N heterocycle for the side chain according to certain mass ratio with skeleton polymer, dissolving
In suitable organic solvent, obtain the clear polymer solution that polymer concentration is 5～20wt%；
B）The heteropoly acid of certain mass is dissolved in the organic solvent of above-mentioned dissolving polymer, obtaining transparent heteropoly acid has
Machine solution, the concentration of heteropoly acid solution is 5-50wt%；
C）Under conditions of stirring, by above-mentioned steps B）Middle gained heteropoly acid solution is added to step according to certain ratio
B）In prepared polymer solution, continue stirring 5～12 hours, obtain transparent homogeneous PEM casting solution；
D）Preparation organic-inorganic composite proton exchange membrane.
According to a further aspect of the present invention, above-mentioned steps D）Middle had using solution-cast or the tape casting preparation
Machine-inorganic composite proton exchange membrane, wherein, becomes film process to be to be dried at a temperature of 50-120 DEG C and/or solvent flashing
Process, its film formation time is 10-24 hour；
According to a further aspect of the present invention, above-mentioned organic-inorganic composite proton exchange membrane for fuel cell
Preparation method is characterised by：Selected organic solvent is from by DMF（DMF）, N, N- dimethylacetamide
Amine（DMAc）, 1-METHYLPYRROLIDONE（NMP）, dimethyl sulfoxide (DMSO)（DMSO）The one kind or therein two selected in the group of composition
The mixed solvent planted.
According to a further aspect of the present invention, above-mentioned organic-inorganic composite proton exchange membrane for fuel cell
Preparation method is characterised by：The weight/mass percentage composition that described side chain carries the polymer of azacyclo- is 20～80%, described skeleton
The mass concentration of polymer is 10～50%, and the weight/mass percentage composition of described heteropoly acid is 10-60%.
Advantages of the present invention includes：
- described organic-inorganic composite proton exchange membrane raw material are easy to get, low price, suitable industry simple for process
Metaplasia is produced；
The film making solution of-described organic-inorganic composite proton exchange membrane is homogeneous phase transparent, and heteropoly acid is in organic solvent
Not with the effect such as PVP and generate the compound of indissoluble, but after organic solvent volatilization film forming, heteropoly acid carries azacyclo- with side chain
Polymer interacts, and generates water-fast compound it is ensured that under fuel cell operating condition, heteropoly acid does not flow
Lose.
- described organic-inorganic composite proton exchange membrane is homogeneous, transparent, fine and close, has excellent heat endurance, chemically-resistant
Corrosivity, high ionic conductivity, can reach 5 × 10-2S/cm, and show good stability；
- can be adjusted by simple regulation and control skeleton polymer and the weight ratio of functional polymer and the content of heteropoly acid
The mechanical performance of control organic-inorganic composite proton exchange membrane and proton conductivity, are easy to exploitation with series of products to meet difference
The demand of application.
Brief description
The Organic inorganic film obtaining in Fig. 1 one embodiment of the present of invention（PES33-PVP67-HPW67）As having
The battery of the diaphragm material assembling of machine-inorganic composite proton exchange membrane fuel cell is in the output performance of different temperatures.
Specific embodiment
Embodiment 1：
Weigh the PPSU of 1 unit of weight（PPSF）Polyvinylpyrrolidone with 1 unit of weight（PVP）It is dissolved in 18
The DMF of unit of weight（DMF）In, stirring is until dissolving is complete；
Weigh the phosphotungstic acid of 1 unit of weight, be dissolved in the DMF of 9 unit of weights（DMF）In, stirring
Until dissolving is completely；
Above two solution is mixed and stirs, after polymer solution is deaerated, cast in clean smooth consolidating
Body surface face（As glass plate）Surface drying and volatilizing solvent film forming at 50 DEG C.
Gained organic-inorganic composite proton exchange membrane has high mechanical performance and good pliability.Mechanical performance is surveyed
Pilot production GB GB13022-91 measures, and instrument is CMT6202, tensile strength=35MPa, and elongation at break reaches
40%.
Gained organic-inorganic composite proton exchange membrane has good proton conductive, when under room temperature, electrical conductivity=
0.02S/cm, this result is the electrical conductivity on film direction being recorded by ac impedance technology.
Embodiment 2：
Weigh the polysulfones of 1 unit of weight（PSF）Polyvinylpyrrolidone with 1.5 unit of weights（PVP）, it is dissolved in 10
The DMA of unit of weight（DMAc）In, stirring is until dissolving is complete；
Weigh the phosphotungstic acid of 1.5 unit of weights, be dissolved in the DMF of 8.5 unit of weights（DMF）In,
Stirring is until dissolving is complete；
Above two polymer solution is mixed and stirs, after polymer solution is deaerated adopt the tape casting in
Drying and volatilizing solvent film forming at 60 DEG C.
Gained organic-inorganic composite proton exchange membrane has high mechanical performance and good pliability.Mechanical performance is surveyed
Pilot production GB GB13022-91 measures, and instrument is CMT6202, tensile strength=32MPa, and elongation at break reaches
50%.
Gained organic-inorganic composite proton exchange membrane has good proton conductive, electrical conductivity=0.04S/ under room temperature
Cm, this result is the electrical conductivity on film direction being recorded by ac impedance technology.
Embodiment 3：
Weigh the polyether sulfone of 1 unit of weight（PES）Polyvinylpyrrolidone with 2 unit of weights（PVP）, it is dissolved in 11
The 1-METHYLPYRROLIDONE of unit of weight（NMP）In, stirring is until dissolving is complete；Above two polymer solution is blended in one
Rise and stir,
Weigh the phosphotungstic acid of 2 unit of weights, be dissolved in the DMF of 8 unit of weights（DMF）In, stirring
Until dissolving is completely；
Above two polymer solution is mixed and stirs, after polymer solution is deaerated adopt the tape casting in
Drying and volatilizing solvent film forming at 70 DEG C.
Gained organic-inorganic composite proton exchange membrane has high mechanical performance and good pliability.Mechanical performance is surveyed
Pilot production GB GB13022-91 measures, and instrument is CMT6202, tensile strength=28MPa, and elongation at break reaches
58%.
Gained organic-inorganic composite proton exchange membrane has excellent proton conductive, electrical conductivity=0.06S/ under room temperature
Cm, this result is the electrical conductivity on film direction being recorded by ac impedance technology.
Fig. 1 is the organic-inorganic composite proton exchange membrane obtained by the present embodiment（PES33-PVP67-HPW67）As having
The battery of the diaphragm material assembling of machine-inorganic composite proton exchange membrane fuel cell is in the output performance of different temperatures.From Fig. 1
Can see that the electric discharge behavior of organic-inorganic composite proton exchange membrane fuel cell is normal, show good chemical property
（Output power density highest can reach nearly 500mW/cm2）.Illustrate that the barrier film prepared by the present embodiment can meet have completely
The use requirement of machine-inorganic composite proton exchange membrane fuel cell.
Embodiment 4：
Weigh the Kynoar of 1 unit of weight（PVDF）, the polyvinylpyrrolidone of 3 unit of weights（PVP）, it is molten
DMA in 1,6 unit of weight（DMAc）And 1-METHYLPYRROLIDONE（NMP）（Volume ratio is 8/2）Mixing
In solvent, stirring is until dissolving is complete；
Weigh the phosphotungstic acid of 2 unit of weights, be dissolved in the DMA of 10 unit of weights（DMAc）And N-
Methyl pyrrolidone（NMP）（Volume ratio is 8/2）Mixed solvent in, stirring until dissolving completely；
Above two polymer solution is mixed and stirs, after polymer solution is deaerated, adopt solution-cast
Method drying and volatilizing solvent film forming at 80 DEG C.
Gained organic-inorganic composite proton exchange membrane has high mechanical performance and good pliability.Mechanical performance is surveyed
Pilot production GB GB13022-91 measures, and instrument is CMT6202, tensile strength=18MPa, and elongation at break reaches
75%.
Gained organic-inorganic composite proton exchange membrane has excellent proton conductive, electrical conductivity=0.08S/ under room temperature
Cm, this result is the electrical conductivity on film direction being recorded by ac impedance technology.
Embodiment 5：
Weigh the polyether sulfone of 1 unit of weight（PES）It is dissolved in 13 weight list with the polyvinylpyrrolidone of 1 unit of weight
The DMF of position（DMF）In, stirring is until dissolving is complete；
Weigh the phosphomolybdic acid of 2 unit of weights, be dissolved in the DMA of 8 unit of weights（DMAc）In, stir
Mix until dissolving is complete；
Above two polymer solution is mixed and stirs, cast in clean flat after polymer solution is deaerated
The whole surface of solids（As glass plate）Surface drying and volatilizing solvent film forming at 80 DEG C.
Gained organic-inorganic composite proton exchange membrane has high mechanical performance and good pliability.Mechanical performance is surveyed
Pilot production GB GB13022-91 measures, and instrument is CMT6202, tensile strength=32MPa, and elongation at break reaches
40%.
Gained organic-inorganic composite proton exchange membrane has excellent high temperature proton conductive, when 150 DEG C, electrical conductivity=
0.03S/cm, this result is the electrical conductivity on film direction being recorded by ac impedance technology.
Embodiment 6：
Weigh the polyether sulfone of 1 unit of weight（PES）Polyvinylpyrrolidone with 2 unit of weights（PVP）, it is dissolved in 11
The 1-METHYLPYRROLIDONE of unit of weight（NMP）In, stirring is until dissolving is complete；Above two polymer solution is blended in one
Rise and stir,
, it is dissolved in the DMA of 15 unit of weights（DMAc）In, stirring is until dissolving is complete；
Weigh the phosphomolybdic acid of 2 unit of weights, be dissolved in the 1-METHYLPYRROLIDONE of 15 unit of weights（NMP）In, stirring
Until dissolving is completely；
Above two polymer solution is mixed and stirs, after polymer solution is deaerated adopt the tape casting in
Drying and volatilizing solvent film forming at 80 DEG C.
Gained organic-inorganic composite proton exchange membrane has high mechanical performance and good pliability.Mechanical performance is surveyed
Pilot production GB GB13022-91 measures, and instrument is CMT6202, tensile strength=29MPa, and elongation at break reaches
40%.
Gained organic-inorganic composite proton exchange membrane has excellent proton conductive, conductance=0.045S/cm under room temperature,
This result is the electrical conductivity on film direction being recorded by ac impedance technology.
Embodiment 7：
Weigh the polysulfones of 1 unit of weight（PSF）With the polyvinylpyrrolidone of 1 unit of weight, it is dissolved in 14 weight list
The DMF of position（DMF）In, stirring is until dissolving is complete；
Weigh the silico-tungstic acid of 2 unit of weights, be dissolved in the 1-METHYLPYRROLIDONE of 15 unit of weights（NMP）In, stirring
Until dissolving is completely；
Above two polymer solution is mixed and stirs, after polymer solution is deaerated adopt the tape casting in
Drying and volatilizing solvent film forming at 100 DEG C.
Gained organic-inorganic composite proton exchange membrane has high mechanical performance and good pliability.Mechanical performance is surveyed
Pilot production GB GB13022-91 measures, and instrument is CMT6202, tensile strength=30MPa, and elongation at break reaches
40%.
Gained organic-inorganic composite proton exchange membrane has good proton conductive, electrical conductivity=0.024S/ under room temperature
Cm, this result is the electrical conductivity on film direction being recorded by ac impedance technology.
Embodiment 8：
Weigh the Kynoar of 1 unit of weight（PVDF）, the polyether sulfone of 1 unit of weight（PES）And, 2 unit of weights
Polyvinylpyrrolidone（PVP）It is dissolved in the DMA of 16 unit of weights（DMAc）In, stirring is until molten
Solution is completely；
Weigh the phosphotungstic acid of 3 unit of weights, be dissolved in the 1-METHYLPYRROLIDONE of 15 unit of weights（NMP）In, stirring
Until dissolving is completely；
Above two polymer solution is mixed and stirs, after polymer solution is deaerated adopt the tape casting in
Drying and volatilizing solvent film forming at 100 DEG C.
Gained organic-inorganic composite proton exchange membrane has high mechanical performance and good pliability.Mechanical performance is surveyed
Pilot production GB GB13022-91 measures, and instrument is CMT6202, tensile strength=28MPa, and elongation at break reaches
50%.
Gained organic-inorganic composite proton exchange membrane has excellent high temperature proton conductive, when 150 DEG C, electrical conductivity=
0.05S/cm, this result is the electrical conductivity on film direction being recorded by ac impedance technology.
Embodiment 9：
Weigh the polyether sulfone of 1 unit of weight（PES）With the polyvinylpyrrolidone of 0.75 unit of weight, it is dissolved in 15 weights
The DMF of amount unit（DMF）In, stirring is until dissolving is complete；
Weigh the phosphotungstic acid of 0.75 unit of weight, be dissolved in the DMF of 15 unit of weights（DMF）In,
Stirring is until dissolving is complete；
Above two polymer solution is mixed and stirs, after polymer solution is deaerated, adopt solution-cast
Method drying and volatilizing solvent film forming at 70 DEG C.
After demoulding, homogeneous for gained blend film being immersed in mass ratio is immersion treatment 48 hours in 40wt% phosphotungstic acid, takes out
Dry surface and float acid, that is, obtain high-performance organic-inorganic compound proton exchange membrane.
Gained organic-inorganic composite proton exchange membrane has high mechanical performance and good pliability.Mechanical performance is surveyed
Pilot production GB GB13022-91 measures, and instrument is CMT6202, tensile strength=33MPa, and elongation at break reaches
35%.
Gained organic-inorganic composite proton exchange membrane has good proton conductive, electrical conductivity=0.01S/ under room temperature
Cm, this result is the electrical conductivity on film direction being recorded by ac impedance technology.
It can be seen that, in the above-described embodiments, prepare the concentration of the polymer solution during homogeneous blend film not shadow in 5～20wt%
Ring chemical property and the mechanical performance of organic-inorganic composite proton exchange membrane.And in the above-described embodiments, all can be similar to
The organic-inorganic composite proton exchange membrane of property：
Described organic-inorganic composite proton exchange membrane also is used as the devices such as fuel cell, flow battery, lead-acid battery
Barrier film.
Claims (8)
1. a kind of preparation method of organic-inorganic composite proton exchange membrane for fuel cell it is characterised in that：
A) mix having the polymer with N heterocycle for the side chain according to certain mass ratio with skeleton polymer, be dissolved in suitable
When organic solvent in, obtain the clear polymer solution that polymer concentration is 5～20wt%；
B) heteropoly acid of certain mass is dissolved in the organic solvent of above-mentioned dissolving polymer, obtains transparent heteropoly acid organic molten
Liquid, the concentration of heteropoly acid solution is 5-50wt%；
C) stirring under conditions of, by above-mentioned steps B) in gained heteropoly acid solution according to make described heteropoly acid described organic-
Weight/mass percentage composition in inorganic composite proton exchange membrane be 10-60% ratio be added to step A) prepared by polymer molten
In liquid, continue stirring 5～12 hours, obtain transparent homogeneous PEM casting solution；
D) prepare described organic-inorganic composite proton exchange membrane for fuel cell with described PEM casting solution.
2. method according to claim 1 is it is characterised in that described step D) in come using the one kind selected from following method
Preparation organic-inorganic composite proton exchange membrane：
Solution-cast,
The tape casting.
3. the method according to claim 1 or 2, wherein said step D) include：
Be dried at a temperature of 50-120 DEG C and/or solvent flashing process, its film formation time be 10-24 hour.
4. the method according to claim 1 or 2 it is characterised in that：Described organic solvent is from by DMF
(DMF), select in the group that DMA (DMAc), 1-METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO) (DMSO) form
The mixture of a kind of or therein two kinds going out.
5. with a kind of used in proton exchange membrane fuel cell Organic-inorganic composite of the method preparation according to one of claim 1-4
PEM it is characterised in that：
Described organic-inorganic composite proton exchange membrane carries the functional polymer of azacyclo-, heteropoly acid and skeleton polymerization by side chain
Thing forms,
Percent mass in described organic-inorganic composite proton exchange membrane for the functional polymer with azacyclo- for the described side chain contains
Measure as 20～80%,
Described skeleton polymer in described organic-inorganic composite proton exchange membrane weight/mass percentage composition be 10～50%,
Weight/mass percentage composition in described organic-inorganic composite proton exchange membrane for the described heteropoly acid is 10-60%.
6. organic-inorganic composite proton exchange membrane for fuel cell according to claim 5 it is characterised in that：
The polymer that described side chain carries azacyclo- is polyvinylpyrrolidone (PVP).
7. organic-inorganic composite proton exchange membrane for fuel cell according to claim 5 it is characterised in that：
Described heteropoly acid be the one kind selected from the group being made up of phosphotungstic acid (PWA), phosphomolybdic acid (PMA), silico-tungstic acid (SWA) or
Multiple mixtures.
8. organic-inorganic composite proton exchange membrane for fuel cell according to claim 5 it is characterised in that：
Described skeleton polymer is from by polyether sulfone (PES), polysulfones (PSF), PPSU (PPSF), Kynoar (PVDF) group
The mixture that a kind of and/or in them the two or more selected in the group becoming forms.
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| CN106252696B (en) * | 2016-10-21 | 2019-02-01 | 长春工业大学 | Fuel cell inorganic-organic hybrid type proton exchange membrane and preparation method thereof |
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| CN113991140B (en) * | 2021-10-25 | 2023-02-03 | 吉林大学 | Organic covalent grafting-based heteropoly acid hybrid perfluorosulfonic acid membrane and preparation method and application thereof |
| CN115051004B (en) * | 2022-06-10 | 2023-09-08 | 四川大学 | Proton exchange membrane of fuel cell and preparation method thereof |
| CN116207313B (en) * | 2023-05-06 | 2023-07-11 | 苏州擎动动力科技有限公司 | Self-humidifying membrane electrode and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102376961A (en) * | 2010-08-18 | 2012-03-14 | 北京航空航天大学 | High temperature proton exchange membrane for fuel cell, and preparation method thereof |
-
2013
- 2013-11-20 CN CN201310593705.4A patent/CN104659395B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102376961A (en) * | 2010-08-18 | 2012-03-14 | 北京航空航天大学 | High temperature proton exchange membrane for fuel cell, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Proton Conducting Composite Membranes from Polysulfone and Heteropolyacid for Fuel Cell Applications.;B.Smitha et al.;《Journal of Polymer Science Part B: Polymer Physics》;20050429;第43卷(第12期);第1538-1547页 * |
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