CN103715438B - A kind of nanometer composite proton exchange membrane and its preparation method and application - Google Patents
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Abstract
The invention belongs to Proton Exchange Membrane Fuel Cells technical field, particularly a kind of nanometer composite proton exchange membrane for high-temperature anhydrous condition Proton Exchange Membrane Fuel Cells and its preparation method and application.Described nanometer composite proton exchange membrane is the stannic oxide/graphene nano compound proton exchange membrane that sulfonated polyether-ether-ketone and poly-dopamine are modified.A kind of nanometer composite proton exchange membrane provided by the invention shows higher than pure polymeric membrane and more excellent battery performance, uses under being particluarly suitable for high-temperature anhydrous condition.<b/>
Description
Technical field
The invention belongs to Proton Exchange Membrane Fuel Cells technical field, particularly a kind of nanometer composite proton exchange membrane for high-temperature anhydrous condition Proton Exchange Membrane Fuel Cells and its preparation method and application.
Background technology
Proton exchange membrane (PEM) is the core component of Proton Exchange Membrane Fuel Cells (PEMFC), and PEMFC is regarded as a kind of clean energy resource switch technology of most prospect, has potential great market.Proton exchange membrane (PEM) is one of critical component restricting Proton Exchange Membrane Fuel Cells (PEMFC) commercial applications at present, is the focus of current fuel cell technology research.The PEMFCs mainly low-temperature fuel cell of current Application and Development, uses the Nafion of perfluorinated sulfonic acid polymer such as DuPont E.I.Du Pont Company as PEM.But these fuel cell systems have a series of problem, the efficiency as battery is low.Improve one's methods and normally operating condition is changed into high temperature (>100 DEG C) low humidity (anhydrous).But most PEMs, comprises Nafion, unstable under high temperature low humidity conditions.The drain evaporation of moisture under this condition, causes film proton conduction property and battery performance sharp-decay.Therefore, under exploitation high-temperature anhydrous (low humidity) condition, the PEM of high conductance has become a common-denominator target of fuel cell technology.
In order to realize this target, researcher has carried out a large amount of work, as (1) replaces water with other proton solvent (as nitrogen-containing heterocycle compound and ionic liquid); (2) anhydrous proton-conducting material (as Inorganic-Organic Hybrid Material and soda acid composite material) is developed.Wherein soda acid composite material gets the attention due to the proton conduction mode of its uniqueness.In soda acid composite material, proton donor (acid groups) and acceptor (base groups) compact siro spinning technology, proton can in anhydrous conditions, directly transmit between donor and acceptor with Hopping mechanism, but prepare the stable soda acid composite material of stuctures and properties still need explore.
Summary of the invention
The object of this invention is to provide a kind of nanometer composite proton exchange membrane and its preparation method and application, described film proton conductivity is high, thermal stability, good mechanical stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of nanometer composite proton exchange membrane, described nanometer composite proton exchange membrane is the stannic oxide/graphene nano compound proton exchange membrane that sulfonated polyether-ether-ketone and poly-dopamine are modified.
In film, the mass ratio of the graphene oxide that sulfonated polyether-ether-ketone and poly-dopamine are modified is 100:2.5-10, and the sulfonation degree of sulfonated polyether-ether-ketone is 60%-68%.When sulfonated polyether-ether-ketone sulfonation degree is too small, proton conductivity is low, and time excessive, film degree of swelling is larger.
The thickness of described nanometer composite proton exchange membrane is 60-70 μm.
Present invention also offers a kind of preparation method of described nanometer composite proton exchange membrane, graphene oxide is modified through poly-dopamine, then blendedly with sulfonated polyether-ether-ketone prepares nanometer composite proton exchange membrane.
The process that graphene oxide is modified through poly-dopamine is: graphene oxide being added pH value is in the aqueous dopamine solution of 7.5-9.5, is fully separated the dry graphene oxide obtaining poly-dopamine and modify after mixing.
Concrete, by the amount controlling trishydroxymethylaminomethane (Tris) and NaOH, pH value is adjusted.
The concentration of aqueous dopamine solution is 2.0-8.0 mg/mL, and 1 g graphene oxide joins in the aqueous dopamine solution of 20-40 mL.
Further, the dimethyl formamide of the graphene oxide (DGO) that the poly-dopamine of preparation is modified or dimethylacetamide solution, after add sulfonated polyether-ether-ketone (SPEEK) and fully mixing obtains casting solution, the mass ratio of the graphene oxide that sulfonated polyether-ether-ketone and poly-dopamine are modified is 100:2.5-10; The mass ratio of sulfonated polyether-ether-ketone and dimethyl formamide or dimethylacetylamide is 1:8-10.
In the process for preparation of nano composite membrane casting solution, after preferably first DGO powder being dispersed in DMF solvent, then SPEEK is added wherein, and continue to stir to reach the homodisperse effect of nanoscale.
Casting solution adopts the tape casting to prepare nanometer composite proton exchange membrane: casting solution curtain coating on a glass, dry 8-12h at first 50-70 DEG C, after be warming up to 80-120 DEG C at continue dry 8-12 h and obtain described nanometer composite proton exchange membrane.
Concrete, the preparation method of described nanometer composite proton exchange membrane, step is as follows:
1) graphene oxide being added pH value is in the aqueous dopamine solution of 8.5, after stirring at room temperature 4 h, the graphene oxide that centrifugal, deionized water washs, 60 DEG C of dryings obtain the modification of poly-dopamine, aqueous dopamine solution concentration is 2.0 mg/mL, and 1 g graphene oxide adds in 20 mL aqueous dopamine solution;
2) graphene oxide that poly-dopamine is modified is added in DMF, at room temperature ultrasonic process 1 h stir 8 h; Again sulfonated polyether-ether-ketone is joined in above-mentioned DMF solution, continue stirring 12 h and obtain casting solution; The mass ratio of the graphene oxide that sulfonated polyether-ether-ketone and poly-dopamine are modified is 100:2.5-10; The mass ratio of sulfonated polyether-ether-ketone and DMF is 1:8-10.
3) casting solution curtain coating is on a glass, first dried overnight at 60 DEG C, after be warming up to 80 DEG C and continue dry 12 h and obtain nanometer composite proton exchange membrane.
Gained film can called after SPEEK/DGO-X, wherein X=2.5, and 5,7.5,10, represent that filler gathers graphene oxide DGO that dopamine the modifies mass percent relative to sulfonated polyether-ether-ketone SPEEK.
Described graphene oxide GO is prepared according to existing method, as can according to but be not limited to be prepared according to laxative remedy: 4.5 g graphite flakes and 27.0 g KMnO
4slowly join with vigorous stirring (the 540 mL concentrated sulfuric acids and 60 mL phosphoric acid) in the nitration mixture of 600 mL.20 h are stirred, subsequently by the cooling of gained solution and down to 1200 mL water and 30 mL H at reactant liquor being heated to 50 DEG C
2o
2in mixed liquor.After ultrasonic process 1 h under 800 rpm centrifugal 5 min, rpm is centrifugal for gained supernatant 10000, is suspended by gained solid in the HCL aqueous solution of 30%.Gained powder dispersion is stirred 12 h, centrifugal, CH in the HCL of 300 mL 10%
3oH washing, vacuumize also grinding obtain GO.
Described nanometer composite proton exchange membrane has good application in high-temperature anhydrous condition Proton Exchange Membrane Fuel Cells.
Graphene oxide (GO), one is typically rich in the two-dimensional structure of multiple oxy radical (as hydroxy, epoxy radicals, carbonyl), and its polymolecularity and long continuity all make GO become a kind of well polymer compound film packing material.Its large specific area and high proton-conducting make GO become good PEMs nano-composite material.GO has been applied to PEM film under water condition, but the proton conduction of its nano composite membrane formed in anhydrous conditions and battery performance still lack further investigation.In ocean, bonding Mussels secretion binding proteins makes himself to stick to rock surface.Dopamine is a kind of micromolecular bionical binding proteins, and it has amino, the imino group of functional catechol and alkalescence.Catechol structure enables dopamine monomer be oxidized to adjacent benzene diquinone, and auto polymerization subsequently forms homogeneous poly-dopamine (PDA) nano thin-layer.PDA thin layer by strong physics or chemical interaction stick to securely nearly all inorganic, organic material is surperficial.By this plain mode, material surface is by Hydrophilic modification and introduce a large amount of amino and imino group.
The present invention, in mechanism, is subject to bioadhesive effect and inspires, and utilizes dopamine auto polymerization to form one deck on graphene oxide (GO) surface and is rich in poly-DOPA amine layer that is amino and imino group, obtain the graphene oxide (DGO) that poly-dopamine is modified; Be doped to by DGO in sulfonated polyether-ether-ketone (SPEEK) matrix, on DGO surface alkalinty group and SPEEK chain, sulfonic acid group forms acid-base pair, conducts fast, thus construct continuous anhydrous proton transfer passage for proton in anhydrous mode (Hopping mechanism).
This nano composite membrane shows the thermal stability higher than pure polymeric membrane, mechanical stability, proton conductivity and more excellent battery performance, uses under being particluarly suitable for high-temperature anhydrous condition.
Compared with prior art, tool has the following advantages in the present invention:
A kind of nanometer composite proton exchange membrane provided by the invention shows higher than pure polymeric membrane and more excellent battery performance, uses under being particluarly suitable for high-temperature anhydrous condition.
Accompanying drawing explanation
Fig. 1 is the photo of graphene oxide (GO);
Fig. 2 is the photo of the graphene oxide (DGO) that poly-dopamine is modified;
The photo of SPEEK/DGO-5 film that Fig. 3 is followed successively by sulfonated polyether-ether-ketone (SPEEK) film from left to right, SPEEK/GO-5 film, embodiment 2 obtain;
Fig. 4 is the electromicroscopic photograph of SPEEK/GO-5 film;
Fig. 5 is the glue connection part stereoscan photograph of the SPEEK/DGO-5 film that embodiment 2 obtains;
Fig. 6 is DGO preparation and structure, nano composite membrane, proton schematic diagram of Hopping mechanism between the acid-base pair of DGO-SPEEK surface;
In the preparation of described SPEEK/GO-5 film, save GO is modified to DGO step with poly-dopamine, other are identical with embodiment 2.
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1-4 SPEEK sulfonation degree used is 60.2%.
Embodiment 1
4.5 g graphite flakes and 27.0 g KMnO
4slowly join with vigorous stirring (the 540 mL concentrated sulfuric acids and 60 mL phosphoric acid) in the nitration mixture of 600 mL.20 h are stirred, subsequently by the cooling of gained solution and down to 1200 mL water and 30 mL H at reactant liquor being heated to 50 DEG C
2o
2in mixed liquor.After ultrasonic process 1 h under 800 rpm centrifugal 5 min, gained supernatant is centrifugal with 10000 rpm, suspended in the HCL aqueous solution of 30wt% by gained solid, after supernatant centrifugation, gained powder dispersion stirs 12 h, centrifugal, CH in the HCL of 300 mL 10wt%
3oH washing, vacuumize also grinding obtain GO.
5.0 g GO are added 100 mL 2.0 mg mL
-1aqueous dopamine solution in (pH 8.5), after stirring at room temperature 4 h, the washing of centrifugal, deionized water, 60 DEG C of dryings obtain DGO.
0.01875 g DGO is added in 6.0 g DMF, at room temperature ultrasonic process 1 h stir 8 h.Subsequently, the SPEEK of 0.75 g joins in above-mentioned DMF solution, continues stirring 12 h.By gained casting solution curtain coating on a glass, first dry 12 h at 60 DEG C, after at 80 DEG C dry 12 h obtain nano composite membrane.Gained film is named as SPEEK/DGO-2.5, represents that DGO filler is 2.5% relative to the mass percent of SPEEK; The thickness of prepared dry film is 65 μm.
Its thermodynamic property is tested in thermogravimetric analysis (TGA), and recording its initial degradation temperature is 308.5 DEG C.It is 896.1 MPa that stretching records film Young's modulus, and hot strength is 57.5 MPa.Under 30 DEG C and 100% relative humidity, the proton conductivity of film is 15.9 mS cm
-1, under 120 DEG C and anhydrous condition, the proton conductivity of film is 2.60 mS cm
-1.
Embodiment 2
4.5 g graphite flakes and 27.0 g KMnO
4slowly join with vigorous stirring (the 540 mL concentrated sulfuric acids and 60 mL phosphoric acid) in the nitration mixture of 600 mL.20 h are stirred, subsequently by the cooling of gained solution and down to 1200 mL water and 30 mL H at reactant liquor being heated to 50 DEG C
2o
2in mixed liquor.After ultrasonic process 1 h under 800 rpm centrifugal 5 min, gained supernatant is centrifugal with 10000 rpm, is suspended by gained solid in the HCL aqueous solution of 30%, and after supernatant centrifugation, gained powder dispersion stirs 12 h, centrifugal, CH in the HCL of 300 mL 10%
3oH washing, vacuumize also grinding obtain GO.
5.0 g GO are added 100 mL 2.0 mg mL
-1aqueous dopamine solution in (pH 8.5), after stirring at room temperature 4 h, the washing of centrifugal, deionized water, 60 DEG C of dryings obtain DGO.
0.0375 g DGO is added in 7.5 g DMF, at room temperature ultrasonic process 1 h stir 8 h.Subsequently, the SPEEK of 0.75 g joins in above-mentioned DMF solution, continues stirring 12 h.By gained casting solution curtain coating on a glass, first dry 12 h at 60 DEG C, after at 80 DEG C dry 12 h obtain nano composite membrane.Gained film is named as SPEEK/DGO-5, represents that DGO filler is 5% relative to the mass percent of SPEEK; The thickness of prepared dry film is 65 μm.
Its thermodynamic property is tested in thermogravimetric analysis (TGA), and recording its initial degradation temperature is 309.4 DEG C.It is 940.7 MPa that stretching records film Young's modulus, and hot strength is 65.9 MPa.Under 30 DEG C and 100% relative humidity, the proton conductivity of film is 18.3 mS cm
-1, under 120 DEG C and anhydrous condition, the proton conductivity of film is 2.91 mS cm
-1.This film is assembled into membrane electrode and tests its H
2/ O
2fuel battery performance, records maximum current density and reaches 698.6 mA cm
-2, maximum power density is 192.1 mW cm
-2.
Embodiment 3
4.5 g graphite flakes and 27.0 g KMnO
4slowly join with vigorous stirring (the 540 mL concentrated sulfuric acids and 60 mL phosphoric acid) in the nitration mixture of 600 mL.20 h are stirred, subsequently by the cooling of gained solution and down to 1200 mL water and 30 mL H at reactant liquor being heated to 50 DEG C
2o
2in mixed liquor.After ultrasonic process 1 h under 800 rpm centrifugal 5 min, gained supernatant is centrifugal with 10000 rpm, is suspended by gained solid in the HCL aqueous solution of 30%, and after supernatant centrifugation, gained powder dispersion stirs 12 h, centrifugal, CH in the HCL of 300 mL 10%
3oH washing, vacuumize also grinding obtain GO.
5.0 g GO are added 100 mL 2.0 mg mL
-1aqueous dopamine solution in (pH 8.5), after stirring at room temperature 4 h, the washing of centrifugal, deionized water, 60 DEG C of dryings obtain DGO.
0.05625 g DGO is added in 7.5g DMF, at room temperature ultrasonic process 1 h stir 8 h.Subsequently, the SPEEK of 0.75 g joins in above-mentioned DMF solution, continues stirring 12 h.By gained casting solution curtain coating on a glass, first dry 12 h at 60 DEG C, after at 80 DEG C dry 12 h obtain nano composite membrane.Gained film is named as SPEEK/DGO-7.5, represents that DGO filler is 7.5% relative to the mass percent of SPEEK.The thickness of prepared dry film is 68 μm.
Its thermodynamic property is tested in thermogravimetric analysis (TGA), and recording its initial degradation temperature is 314.1 DEG C.It is 832.8 MPa that stretching records film Young's modulus, and hot strength is 62.4 MPa.Under 30 DEG C and 100% relative humidity, the proton conductivity of film is 22.7 mS cm
-1, under 120 DEG C and anhydrous condition, the proton conductivity of film is 3.72 mS cm
-1.
Embodiment 4
4.5 g graphite flakes and 27.0 g KMnO
4slowly join with vigorous stirring (the 540 mL concentrated sulfuric acids and 60 mL phosphoric acid) in the nitration mixture of 600 mL.20 h are stirred, subsequently by the cooling of gained solution and down to 1200 mL water and 30 mL H at reactant liquor being heated to 50 DEG C
2o
2in mixed liquor.After ultrasonic process 1 h under 800 rpm centrifugal 5 min, gained supernatant is centrifugal with 10000 rpm, is suspended by gained solid in the HCL aqueous solution of 30%, after supernatant centrifugation, gained powder dispersion is stirred 12 h, centrifugal, CH in the HCL of 300 mL 10%
3oH washing, vacuumize also grinding obtain GO.
5.0 g GO are added 100 mL 2.0 mg mL
-1aqueous dopamine solution in (pH 8.5), after stirring at room temperature 4 h, the washing of centrifugal, deionized water, 60 DEG C of dryings obtain DGO.
0.075 g DGO is added in 6.0 g DMF, at room temperature ultrasonic process 1 h stir 8 h.Subsequently, the SPEEK of 0.75 g joins in above-mentioned DMF solution, continues stirring 12 h.By gained casting solution curtain coating on a glass, first dry 12 h at 60 DEG C, after at 80 DEG C dry 12 h obtain nano composite membrane.Gained film is named as SPEEK/DGO-10, represents that DGO filler is 10% relative to the mass percent of SPEEK.The thickness of prepared dry film is 63 μm.
Its thermodynamic property is tested in thermogravimetric analysis (TGA), and recording its initial degradation temperature is 311.5 DEG C.It is 841.2 MPa that stretching records film Young's modulus, and hot strength is 58.0 MPa.Under 30 DEG C and 100% relative humidity, the proton conductivity of film is 26.4 mS cm
-1, under 120 DEG C and anhydrous condition, the proton conductivity of film is 4.08 mS cm
-1.
Embodiment 5
The pH value of aqueous dopamine solution is 7.5, and other are with embodiment 1, and testing result is with embodiment 1.
Embodiment 6
Aqueous dopamine solution concentration is 6mg mL
-1, other are with embodiment 2, and result is identical with embodiment 2.
Embodiment 7
The preparation method of GO is as follows: in the beaker of drying, add the concentrated sulfuric acid of appropriate 98%, be cooled to 0 DEG C with low-temperature cooling fluid circulating pump, add a certain amount of natural flake graphite, NaNO in stirring
3and KMnO
4, control reacting liquid temperature at 10 ~ 15 DEG C, stirring reaction certain hour, this stage is low-temp reaction.Then beaker is placed in the water bath with thermostatic control of about 35 DEG C, when question response liquid temp rises to about 35 DEG C, continues stirring 30 min, namely complete the reaction of middle temperature.Finally carry out pyroreaction, namely in stirring, add a certain amount of deionized water, control reacting liquid temperature within 100 DEG C, continue to stir 30min.Add again after reactant liquor being diluted to 800 mL with deionized water to fit and put 5%H
2o
2, filter while hot, fully wash until without SO in filtrate with 5%HCl and deionized water
4 2-, then dry 48h in the baking oven of 50 DEG C, after grinding is sieved, is placed in drier and preserves standby survey.Other are with embodiment 3.
Its thermodynamic property is tested in thermogravimetric analysis (TGA), and recording its initial degradation temperature is 314.1 DEG C.It is 831.8 MPa that stretching records film Young's modulus, and hot strength is 62.5 MPa.Under 30 DEG C and 100% relative humidity, the proton conductivity of film is 22.8 mS cm
-1, under 120 DEG C and anhydrous condition, the proton conductivity of film is 3.73 mS cm
-1.
Comparative example:
The SPEEK of 0.75 g is joined in 7.5g DMF solution, vigorous stirring 12 h.Gained casting solution curtain coating on a glass, first dry 12 h at 60 DEG C, after at 80 DEG C dry 12 h.The thickness of prepared SPEEK dry film is 66 μm.
Its thermodynamic property is tested in thermogravimetric analysis (TGA), and recording its initial degradation temperature is 298.2 DEG C.It is 716.1 MPa that stretching records film Young's modulus, and hot strength is 52.5 MPa.Under 30 DEG C and 100% relative humidity, the proton conductivity of film is 15.1 mS cm
-1, under 120 DEG C and anhydrous condition, the proton conductivity of film is 1.17 mS cm
-1.
Claims (8)
1. a nanometer composite proton exchange membrane, is characterized in that, described nanometer composite proton exchange membrane is the stannic oxide/graphene nano compound proton exchange membrane that sulfonated polyether-ether-ketone and poly-dopamine are modified.
2. nanometer composite proton exchange membrane as claimed in claim 1, it is characterized in that, in film, the mass ratio of the graphene oxide that sulfonated polyether-ether-ketone and poly-dopamine are modified is 100:2.5-10, and the sulfonation degree of sulfonated polyether-ether-ketone is 60-68%.
3. nanometer composite proton exchange membrane as claimed in claim 1 or 2, it is characterized in that, the thickness of described nanometer composite proton exchange membrane is 60-70 μm.
4. prepare the method for nanometer composite proton exchange membrane described in claim 1, it is characterized in that, graphene oxide is modified through poly-dopamine, then blendedly with sulfonated polyether-ether-ketone prepares nanometer composite proton exchange membrane.
5. prepare the method for nanometer composite proton exchange membrane as claimed in claim 4, it is characterized in that, the process that graphene oxide is modified through poly-dopamine is: graphene oxide being added pH value is in the aqueous dopamine solution of 7.5-9.5, is fully separated the dry graphene oxide obtaining poly-dopamine and modify after mixing.
6. prepare the method for nanometer composite proton exchange membrane as claimed in claim 5, it is characterized in that, the concentration of aqueous dopamine solution is 2.0-8.0 mg/mL, and 1 g graphene oxide joins in the aqueous dopamine solution of 20-40 mL.
7. prepare the method for nanometer composite proton exchange membrane as claimed in claim 4, it is characterized in that, the dimethyl formamide of the graphene oxide that the poly-dopamine of preparation is modified or dimethylacetamide solution, after add sulfonated polyether-ether-ketone and fully mixing obtains casting solution, the mass ratio of the graphene oxide that sulfonated polyether-ether-ketone and poly-dopamine are modified is 100:2.5-10; The mass ratio of sulfonated polyether-ether-ketone and dimethyl formamide or dimethylacetylamide is 1:8-10.
8. prepare the method for nanometer composite proton exchange membrane as claimed in claim 4, it is characterized in that, step is as follows:
1) graphene oxide being added pH value is in the aqueous dopamine solution of 8.5, after room temperature fully stirs, the graphene oxide that centrifugal, deionized water washs, 60 DEG C of dryings obtain the modification of poly-dopamine, aqueous dopamine solution concentration is 2.0 mg/mL, and 1 g graphene oxide adds in 20 mL aqueous dopamine solution;
2) add in dimethyl formamide by the graphene oxide that poly-dopamine is modified, at room temperature ultrasonic process 1 h also fully stirs; Again sulfonated polyether-ether-ketone is joined in above-mentioned dimethyl formamide solution, continue stirring and obtain casting solution; The mass ratio of the graphene oxide that sulfonated polyether-ether-ketone and poly-dopamine are modified is 100:2.5-10; The mass ratio of sulfonated polyether-ether-ketone and dimethyl formamide is 1:8-10;
3) casting solution curtain coating is on a glass, first dry 12h at 60 DEG C, after be warming up to 80 DEG C and continue dry 12 h and obtain nanometer composite proton exchange membrane.
9. the arbitrary described nanometer composite proton exchange membrane of claim 1-3 is applied in high-temperature anhydrous condition Proton Exchange Membrane Fuel Cells.
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| CN104017209B (en) * | 2014-06-17 | 2017-01-25 | 北京航空航天大学 | Method for preparing tough integrated biomimetic layered graphene composite material |
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| CN105742677B (en) * | 2016-02-23 | 2019-03-22 | 天津大学 | Nafion/ phosphorylation graphene oxide hybridized film and preparation and application |
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| CN106977753B (en) * | 2017-03-28 | 2019-08-06 | 天津大学 | Bionical ultrathin membrane of a kind of high intensity solid electrolyte and preparation method thereof |
| EP3810686B1 (en) * | 2018-06-22 | 2024-05-08 | Luxembourg Institute of Science and Technology (LIST) | Nanoparticles of polydopamine and s-paek (sulfonated-polyaryletherketone) derivatives and water-based process for preparing thereof |
| CN109755613B (en) * | 2018-12-19 | 2021-09-24 | 湖北工程学院 | Three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane and preparation method thereof |
| CN109818024B (en) * | 2019-01-30 | 2020-12-08 | 湖北工程学院 | Composite proton exchange membrane and preparation method thereof |
| CN110010941B (en) * | 2019-04-16 | 2022-03-22 | 河北工业大学 | Preparation method of acid-base double-layer core-shell nanotube/SPEEK composite proton exchange membrane |
| CA3141780A1 (en) * | 2019-05-27 | 2020-12-03 | Council Of Scientific & Industrial Research | A composition for fuel cell membranes and a process for the preparation thereof |
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| CN111193054B (en) * | 2020-01-09 | 2022-08-02 | 安徽师范大学 | Preparation method of proton exchange membrane |
| CN114447383A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Organic-inorganic composite proton exchange membrane and preparation method thereof |
| CN112687927B (en) * | 2020-12-25 | 2022-06-21 | 南京大学 | High-durability fuel cell composite proton exchange membrane and preparation method and application thereof |
| CN113078344B (en) * | 2021-03-30 | 2022-04-01 | 江苏科润膜材料有限公司 | Method for modifying perfluorinated sulfonic acid proton exchange membrane by gel extrusion casting |
| CN113078345B (en) * | 2021-03-30 | 2022-03-08 | 江苏科润膜材料有限公司 | Method for preparing modified perfluorinated sulfonic acid proton exchange membrane by steel band tape casting method |
| CN113346116B (en) * | 2021-05-20 | 2022-11-01 | 华中科技大学 | Polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof |
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| CN103337649B (en) * | 2013-06-27 | 2016-08-10 | 暨南大学 | A kind of modified graphene/sulfonated poly (phenylene oxide) PEM and preparation method thereof |
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