CN103715438A - Nano-composite proton exchange membrane as well as preparation method and application thereof - Google Patents
Nano-composite proton exchange membrane as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of a proton exchange membrane fuel cell, and particularly relates to a nano-composite proton exchange membrane for the proton exchange membrane fuel cell under a high-temperature anhydrous condition as well as a preparation method and an application thereof. The nano-composite proton exchange membrane is a graphene oxide nano-composite proton exchange membrane which is modified by sulfonated poly(ether ether ketone) and polydopamine. Compared with a pure polymeric membrane, the nano-composite proton exchange membrane provided by the invention has more excellent battery performance and is particularly suitable to be applied under the high-temperature anhydrous condition.
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 tool prospect, has potential great market.Proton exchange membrane (PEM) is one of critical component restricting at present Proton Exchange Membrane Fuel Cells (PEMFC) commercial applications, is the focus of current fuel cell technology research.At present the PEMFCs of Application and Development is mainly low-temperature fuel cell, use perfluorinated sulfonic acid polymer for example the Nafion of DuPont E.I.Du Pont Company as PEM.Yet these fuel cell systems have a series of problem, as low in the efficiency of battery.Improve one's methods and normally operating condition is changed into high temperature (>100 ℃) low humidity (anhydrous).Yet most PEMs, comprises Nafion, unstable under high temperature low humidity condition.The drain evaporation dividing at this Water Under, 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) develop anhydrous proton-conducting material (as Inorganic-Organic Hybrid Material and soda acid composite material).Wherein soda acid composite material is because its unique proton conduction mode gets the attention.In soda acid composite material, proton donor (acid groups) is closely connected with acceptor (base groups), proton can directly transmit between donor and acceptor with Hopping mechanism under anhydrous condition, but the soda acid composite material of preparation structure and stable performance still needs to be explored.
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 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.
The mass ratio of the graphene oxide that in film, 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 when excessive, film degree of swelling is larger.
The thickness of described nanometer composite proton exchange membrane is 60-70 μ m.
The present invention also provides a kind of preparation method of described nanometer composite proton exchange membrane, and graphene oxide is modified through poly-dopamine, then prepares nanometer composite proton exchange membrane with sulfonated polyether-ether-ketone blend.
The process that graphene oxide is modified through poly-dopamine is: graphene oxide is added in the dopamine aqueous solution of pH value for 7.5-9.5 to the separated dry graphene oxide that poly-dopamine is modified that obtains after fully mixing.
Concrete, can pH value be adjusted by controlling the amount of trishydroxymethylaminomethane (Tris) and NaOH.
The concentration of the dopamine aqueous solution is 2.0-8.0 mg/mL, and 1 g graphene oxide joins in the dopamine aqueous solution of 20-40 mL.
Further, dimethyl formamide or the dimethylacetamide solution of the graphene oxide (DGO) that the poly-dopamine of preparation is modified, after add sulfonated polyether-ether-ketone (SPEEK) and fully mix and obtain casting solution, sulfonated polyether-ether-ketone is 100:2.5-10 with the mass ratio of the graphene oxide of poly-dopamine modification; 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 glass plate, dry 8-12h at first 50-70 ℃, after be warming up to and at 80-120 ℃, 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 to pH value is in 8.5 the dopamine aqueous solution, after stirring at room 4 h, centrifugal, deionized water washs, 60 ℃ of dry graphene oxides that obtain poly-dopamine modification, dopamine concentration of aqueous solution is 2.0 mg/mL, and 1 g graphene oxide adds in the 20 mL dopamine aqueous solution;
2) graphene oxide of poly-dopamine being modified adds in DMF, at room temperature ultrasonic processing 1 h stir 8 h; Again sulfonated polyether-ether-ketone is joined in above-mentioned DMF solution, continue to stir 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 glass plate, first dried overnight at 60 ℃, after be warming up to 80 ℃ and continue dry 12 h and obtain nanometer composite proton exchange membrane.
Gained film can called after SPEEK/DGO-X, X=2.5 wherein, and 5,7.5,10, represent that graphene oxide DGO that the poly-dopamine of filler modifies is with respect to the mass percent of 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
4under vigorous stirring, slowly join in the nitration mixture of 600 mL (the 540 mL concentrated sulfuric acids and 60 mL phosphoric acid).Reactant liquor is heated to and at 50 ℃, stirs 20 h, subsequently gained solution is cooling and to 1200 mL water and 30 mL H
2o
2in mixed liquor.After ultrasonic processing 1 h under 800 rpm centrifugal 5 min, 10000 rpm are centrifugal for gained supernatant, and gained solid is suspended in 30% the HCL aqueous solution.Gained powder is distributed in the HCL of 300 mL 10% and stirs 12 h, centrifugal, CH
3oH washing, vacuumize 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), a kind of two-dimensional structure that is typically rich in multiple oxy radical (as hydroxy, epoxy radicals, carbonyl), its polymolecularity and long continuity all make GO become a kind of good polymer compound film packing material.The specific area that it is large and high proton-conducting make GO become good PEMs nano-composite material.GO has been applied to PEM film under water condition, yet the proton conduction of its nano composite membrane forming under anhydrous condition 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 functional catechol and alkaline amino, imino group.Catechol structure makes dopamine monomer can be oxidized to adjacent benzene diquinone, and auto polymerization subsequently forms poly-dopamine (PDA) nano thin-layer of homogeneous.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 on graphene oxide (GO) surface the poly-dopamine layer that one deck is rich in amino and imino group, obtains the graphene oxide (DGO) that poly-dopamine is modified; DGO is doped in sulfonated polyether-ether-ketone (SPEEK) matrix, and on DGO surface alkalinty group and SPEEK chain, sulfonic acid group forms acid-base pair, conducts fast, thereby 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 better battery performance, is particluarly suitable for using under 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 than the higher and better battery performance of pure polymeric membrane, is particluarly suitable for using under 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) of poly-dopamine modification;
Fig. 3 is followed successively by the photo of the SPEEK/DGO-5 film of sulfonated polyether-ether-ketone (SPEEK) film, SPEEK/GO-5 film, embodiment 2 acquisitions from left to right;
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 of embodiment 2 acquisitions;
Fig. 6 is the schematic diagram of DGO preparation and structure, nano composite membrane, proton Hopping mechanism between the acid-base pair of DGO-SPEEK surface;
In the preparation of described SPEEK/GO-5 film, save GO and with poly-dopamine, be modified to the step of DGO, 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 to this:
Embodiment 1-4 SPEEK sulfonation degree used is 60.2%.
Embodiment 1
4.5 g graphite flakes and 27.0 g KMnO
4under vigorous stirring, slowly join in the nitration mixture of 600 mL (the 540 mL concentrated sulfuric acids and 60 mL phosphoric acid).Reactant liquor is heated to and at 50 ℃, stirs 20 h, subsequently gained solution is cooling and to 1200 mL water and 30 mL H
2o
2in mixed liquor.After ultrasonic processing 1 h under 800 rpm centrifugal 5 min, gained supernatant is centrifugal with 10000 rpm, gained solid is suspended in the HCL of the 30wt% aqueous solution, and after supernatant centrifugation, gained powder is distributed in the HCL of 300 mL 10wt% and stirs 12 h, centrifugal, CH
3oH washing, vacuumize grinding obtain GO.
5.0 g GO are added to 100 mL 2.0 mg mL
-1the dopamine aqueous solution in (pH 8.5), after stirring at room 4 h, the washing of centrifugal, deionized water, 60 ℃ of dry DGO that obtain.
0.01875 g DGO is added in 6.0 g DMF, at room temperature ultrasonic processing 1 h stir 8 h.Subsequently, the SPEEK of 0.75 g joins in above-mentioned DMF solution, continues to stir 12 h.By gained casting solution curtain coating on glass plate, first dry 12 h at 60 ℃, after at 80 ℃ dry 12 h obtain nano composite membrane.Gained film is named as SPEEK/DGO-2.5, represents that DGO filler is 2.5% with respect to the mass percent of SPEEK; The thickness of prepared dry film is 65 μ m.
Its thermodynamic property is tested in thermogravimetric analysis (TGA), and recording its initial degradation temperature is 308.5 ℃.It is 896.1 MPa that stretching records film Young's modulus, and hot strength is 57.5 MPa.Under 30 ℃ and 100% relative humidity, the proton conductivity of film is 15.9 mS cm
-1, under 120 ℃ 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
4under vigorous stirring, slowly join in the nitration mixture of 600 mL (the 540 mL concentrated sulfuric acids and 60 mL phosphoric acid).Reactant liquor is heated to and at 50 ℃, stirs 20 h, subsequently gained solution is cooling and to 1200 mL water and 30 mL H
2o
2in mixed liquor.After ultrasonic processing 1 h under 800 rpm centrifugal 5 min, gained supernatant is centrifugal with 10000 rpm, and gained solid is suspended in 30% the HCL aqueous solution, after supernatant centrifugation, gained powder is distributed in the HCL of 300 mL 10% and stirs 12 h, centrifugal, CH
3oH washing, vacuumize grinding obtain GO.
5.0 g GO are added to 100 mL 2.0 mg mL
-1the dopamine aqueous solution in (pH 8.5), after stirring at room 4 h, the washing of centrifugal, deionized water, 60 ℃ of dry DGO that obtain.
0.0375 g DGO is added in 7.5 g DMF, at room temperature ultrasonic processing 1 h stir 8 h.Subsequently, the SPEEK of 0.75 g joins in above-mentioned DMF solution, continues to stir 12 h.By gained casting solution curtain coating on glass plate, first dry 12 h at 60 ℃, after at 80 ℃ dry 12 h obtain nano composite membrane.Gained film is named as SPEEK/DGO-5, represents that DGO filler is 5% with respect to the mass percent of SPEEK; The thickness of prepared dry film is 65 μ m.
Its thermodynamic property is tested in thermogravimetric analysis (TGA), and recording its initial degradation temperature is 309.4 ℃.It is 940.7 MPa that stretching records film Young's modulus, and hot strength is 65.9 MPa.Under 30 ℃ and 100% relative humidity, the proton conductivity of film is 18.3 mS cm
-1, under 120 ℃ 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
4under vigorous stirring, slowly join in the nitration mixture of 600 mL (the 540 mL concentrated sulfuric acids and 60 mL phosphoric acid).Reactant liquor is heated to and at 50 ℃, stirs 20 h, subsequently gained solution is cooling and to 1200 mL water and 30 mL H
2o
2in mixed liquor.After ultrasonic processing 1 h under 800 rpm centrifugal 5 min, gained supernatant is centrifugal with 10000 rpm, and gained solid is suspended in 30% the HCL aqueous solution, after supernatant centrifugation, gained powder is distributed in the HCL of 300 mL 10% and stirs 12 h, centrifugal, CH
3oH washing, vacuumize grinding obtain GO.
5.0 g GO are added to 100 mL 2.0 mg mL
-1the dopamine aqueous solution in (pH 8.5), after stirring at room 4 h, the washing of centrifugal, deionized water, 60 ℃ of dry DGO that obtain.
0.05625 g DGO is added in 7.5g DMF, at room temperature ultrasonic processing 1 h stir 8 h.Subsequently, the SPEEK of 0.75 g joins in above-mentioned DMF solution, continues to stir 12 h.By gained casting solution curtain coating on glass plate, first dry 12 h at 60 ℃, after at 80 ℃ dry 12 h obtain nano composite membrane.Gained film is named as SPEEK/DGO-7.5, represents that DGO filler is 7.5% with respect to the mass percent of SPEEK.The thickness of prepared dry film is 68 μ m.
Its thermodynamic property is tested in thermogravimetric analysis (TGA), and recording its initial degradation temperature is 314.1 ℃.It is 832.8 MPa that stretching records film Young's modulus, and hot strength is 62.4 MPa.Under 30 ℃ and 100% relative humidity, the proton conductivity of film is 22.7 mS cm
-1, under 120 ℃ 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
4under vigorous stirring, slowly join in the nitration mixture of 600 mL (the 540 mL concentrated sulfuric acids and 60 mL phosphoric acid).Reactant liquor is heated to and at 50 ℃, stirs 20 h, subsequently gained solution is cooling and to 1200 mL water and 30 mL H
2o
2in mixed liquor.After ultrasonic processing 1 h under 800 rpm centrifugal 5 min, gained supernatant is centrifugal with 10000 rpm, and gained solid is suspended in 30% the HCL aqueous solution, after supernatant centrifugation, gained powder is distributed in the HCL of 300 mL 10% and stirs 12 h, centrifugal, CH
3oH washing, vacuumize grinding obtain GO.
5.0 g GO are added to 100 mL 2.0 mg mL
-1the dopamine aqueous solution in (pH 8.5), after stirring at room 4 h, the washing of centrifugal, deionized water, 60 ℃ of dry DGO that obtain.
0.075 g DGO is added in 6.0 g DMF, at room temperature ultrasonic processing 1 h stir 8 h.Subsequently, the SPEEK of 0.75 g joins in above-mentioned DMF solution, continues to stir 12 h.By gained casting solution curtain coating on glass plate, first dry 12 h at 60 ℃, after at 80 ℃ dry 12 h obtain nano composite membrane.Gained film is named as SPEEK/DGO-10, represents that DGO filler is 10% with respect to the mass percent of SPEEK.The thickness of prepared dry film is 63 μ m.
Its thermodynamic property is tested in thermogravimetric analysis (TGA), and recording its initial degradation temperature is 311.5 ℃.It is 841.2 MPa that stretching records film Young's modulus, and hot strength is 58.0 MPa.Under 30 ℃ and 100% relative humidity, the proton conductivity of film is 26.4 mS cm
-1, under 120 ℃ and anhydrous condition, the proton conductivity of film is 4.08 mS cm
-1.
The pH value of the dopamine aqueous solution is 7.5, and other are with embodiment 1, and testing result is with embodiment 1.
Embodiment 6
Dopamine concentration of aqueous solution 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 dry beaker, add appropriate 98% the concentrated sulfuric acid, with low-temperature cooling fluid circulating pump, be cooled to 0 ℃, add a certain amount of natural flake graphite, NaNO in stirring
3and KMnO
4, control reacting liquid temperature at 10 ~ 15 ℃, stirring reaction certain hour, this stage is low-temp reaction.Then beaker is placed in to the water bath with thermostatic control of 35 ℃ of left and right, when question response liquid temp rises to 35 ℃ of left and right, continues to stir 30 min, completed middle temperature reaction.Finally carry out pyroreaction, in stirring, add a certain amount of deionized water, control reacting liquid temperature in 100 ℃, continue to stir 30min.After reactant liquor being diluted to 800 mL with deionized water, add again the suitable 5%H that puts
2o
2, filter while hot, with 5%HCl and deionized water fully wash until in filtrate without SO
4 2-, then dry 48h in the baking oven of 50 ℃, 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 ℃.It is 831.8 MPa that stretching records film Young's modulus, and hot strength is 62.5 MPa.Under 30 ℃ and 100% relative humidity, the proton conductivity of film is 22.8 mS cm
-1, under 120 ℃ 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 to vigorous stirring 12 h.Gained casting solution curtain coating on glass plate, first dry 12 h at 60 ℃, after at 80 ℃ dry 12 h.The thickness of prepared SPEEK dry film is 66 μ m.
Its thermodynamic property is tested in thermogravimetric analysis (TGA), and recording its initial degradation temperature is 298.2 ℃.It is 716.1 MPa that stretching records film Young's modulus, and hot strength is 52.5 MPa.Under 30 ℃ and 100% relative humidity, the proton conductivity of film is 15.1 mS cm
-1, under 120 ℃ and anhydrous condition, the proton conductivity of film is 1.17 mS cm
-1.
Claims (9)
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, is characterized in that, the mass ratio of the graphene oxide that in film, 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, is characterized in that, the thickness of described nanometer composite proton exchange membrane is 60-70 μ m.
4. the preparation method of nanometer composite proton exchange membrane described in claim 1, is characterized in that, graphene oxide is modified through poly-dopamine, then prepares nanometer composite proton exchange membrane with sulfonated polyether-ether-ketone blend.
5. the preparation method of 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 is added in the dopamine aqueous solution of pH value for 7.5-9.5 to the separated dry graphene oxide that poly-dopamine is modified that obtains after fully mixing.
6. the preparation method of nanometer composite proton exchange membrane as claimed in claim 5, is characterized in that, the concentration of the dopamine aqueous solution is 2.0-8.0 mg/mL, and 1 g graphene oxide joins in the dopamine aqueous solution of 20-40 mL.
7. the preparation method of nanometer composite proton exchange membrane as claimed in claim 4, it is characterized in that, dimethyl formamide or the dimethylacetamide solution of the graphene oxide that the poly-dopamine of preparation is modified, after add sulfonated polyether-ether-ketone and fully mix and obtain casting solution, sulfonated polyether-ether-ketone is 100:2.5-10 with the mass ratio of the graphene oxide of poly-dopamine modification; The mass ratio of sulfonated polyether-ether-ketone and dimethyl formamide or dimethylacetylamide is 1:8-10.
8. the preparation method of nanometer composite proton exchange membrane as claimed in claim 4, is characterized in that, step is as follows:
1) graphene oxide being added to pH value is in 8.5 the dopamine aqueous solution, after room temperature fully stirs, centrifugal, deionized water washs, 60 ℃ of dry graphene oxides that obtain poly-dopamine modification, dopamine concentration of aqueous solution is 2.0 mg/mL, and 1 g graphene oxide adds in the 20 mL dopamine aqueous solution;
2) graphene oxide of poly-dopamine being modified adds in dimethyl formamide, at room temperature ultrasonic processing 1 h fully stirring; 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 glass plate, first dry 12h at 60 ℃, after be warming up to 80 ℃ and continue dry 12 h and obtain nanometer composite proton exchange membrane.
9. described in claim 1-3, nanometer composite proton exchange membrane is applied in high-temperature anhydrous condition Proton Exchange Membrane Fuel Cells.
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|---|---|---|---|
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| CN104017209A (en) * | 2014-06-17 | 2014-09-03 | 北京航空航天大学 | Method for preparing tough integrated biomimetic layered graphene composite material |
| CN104779400A (en) * | 2015-03-31 | 2015-07-15 | 华北电力大学 | Preparation method of modified carbon nanotubes for proton exchange membrane |
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| CN109755613A (en) * | 2018-12-19 | 2019-05-14 | 湖北工程学院 | A kind of three-dimensional framework and aromatic sulfonated polymer compound proton exchange membrane and preparation method thereof |
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| CN110311143A (en) * | 2019-06-25 | 2019-10-08 | 一汽解放汽车有限公司 | A kind of preparation method from humidification membrane electrode of fuel batter with proton exchange film |
| CN111193054A (en) * | 2020-01-09 | 2020-05-22 | 安徽师范大学 | Preparation method of proton exchange membrane |
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| 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 |
| CN112687927A (en) * | 2020-12-25 | 2021-04-20 | 南京大学 | High-durability fuel cell composite proton exchange membrane and preparation method and application thereof |
| 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 |
| CN113078344A (en) * | 2021-03-30 | 2021-07-06 | 江苏科润膜材料有限公司 | Method for modifying perfluorinated sulfonic acid proton exchange membrane by gel extrusion casting |
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| 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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