CN103601906A - Preparation method of SiO2-doped perfluorinated sulfonic acid proton exchange membrane - Google Patents
Preparation method of SiO2-doped perfluorinated sulfonic acid proton exchange membrane Download PDFInfo
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Abstract
The invention provides a preparation method of a SiO2-doped perfluorinated sulfonic acid proton exchange membrane. The preparation method comprises the following steps: (1), reacting a silicon dioxide precursor, water and acid in a molar ratio of 1: (0.2-15):(0.001-0.1) for 30 minutes-60 minutes at a temperature of 0 DEG C-50 DEG C to obtain SiO2 sol; (2), placing a perfluorinated sulfonic acid proton exchange membrane into the SiO2 sol to soak for 2 minutes-14 minutes, so that the SiO2 sol is adsorbed into the perfluorinated sulfonic acid proton exchange membrane; (3), removing sol on the surface of the SiO2 sol-adsorbed perfluorinated sulfonic acid proton exchange membrane, and carrying out thermal treatment for 0.5 hour-8 hours under the condition with temperature of 40 DEG C-100 DEG C to prepare the SiO2-doped perfluorinated sulfonic acid proton exchange membrane. The preparation method disclosed by the invention has the advantages of being simple in process, high in production efficiency, safe and environment-friendly and good in product performance.
Description
Technical field
The present invention relates to the preparation method of organic/inorganic composite proton exchanging membrane, be specifically related to a kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC), because of its feature with high-specific-power, high-energy conversion efficiency, has cold-starting, corrosion-free, zero pollution, eco-friendly advantage, becomes the desirable energy of electromobile, submarine and various movable equipments.Proton exchange membrane, as one of important integral part of PEMFC, plays key effect to its performance.
At present domestic and international application the most widely proton exchange membrane be consist of tetrafluoroethylene monomer and with the Nafion film of multipolymer ，Ru Dupont company of sulfonic perfluorovinyl sulfide ether monomer, the Dow film of the Aciplex Mo, Dow company of Asahi Chemical company etc.Be characterized in that carbon fluorine superpolymer main chain has good thermostability and chemical stability, can guarantee the work-ing life of proton membrane.And hydrophilic sulfonic acid group can be it as the medium of planar water higher electric conductivity is provided.But there is following problem in existing proton exchange membrane in actual use:
(1) if proton exchange membrane will keep higher proton conductivity must make it be placed in lesser temps (60-80
oc) and under higher ambient moisture, thereby need to be equipped with complicated temperature management system and moisture management system, thereby increased cost and the energy consumption of fuel cell system.
(2) under the Working environment of low temperature, CO is comparatively remarkable to the poisoning effect of fuel-cell catalyst Pt, higher to the purity requirement of geseous fuel, increases the running cost of fuel cell.
(3) though improve PEMFC service temperature, can reduce the adsorption effect of CO on Pt catalyzer, improve the performance of the anti-CO of battery.But when temperature surpasses 100 ℃, moisture excessive vaporization in Nafion film, causes proton conduction speed sharply to decline, and then affects battery performance.
Therefore, preparing the proton exchange membrane under high temperature low-humidity environment with excellent proton conduction property, is the inexorable trend of following fuel cell field development.In proton membrane, add hydrophilic inorganic material SiO
2it is one of poor important means of high temperature proton membrane conductive performance in solving.First, silicon-dioxide presoma contains the groups such as more wetting ability silanol and silicon hydroxyl, the water-absorbent of reinforcing membrane.Secondly, the silicon oxide that hydrolysis the obtains formation inierpeneirating network structure that is cross-linked with each other in film, the water-retentivity of reinforcing membrane, thereby the object that while reaching middle high temperature, proton conductivity improves.
Since the eighties in 20th century, through the development of nearly 30 years, people were to perfluorinated sulfonic resin/SiO
2the structure properties of compound proton exchange membrane, preparation method and battery performance etc. have carried out large quantity research, and have obtained certain achievement.Wherein, double teeming method and sol-gel method are to prepare perfluorinated sulfonic resin/SiO
2two kinds of methods that composite membrane is conventional.
Double teeming method is in perfluor sulfoacid resin solution, to add nanometer SiO
2particle or the silicon oxide water-sol having prepared, then film forming.(the Solid State Ionics such as Antonucci P L, 1999,125:431-437), (the J Electrochem Society such as Masahiro Watanabe, 1996,143 (2): 3847-3852), (the J Electrochem Society such as Adjemian K T, 2002,149 (3): A256-A261), (Polymer such as Zoppi R A, 1997, V39 (6-7): 1309-1315), and the equal report to some extent in succession of European patent EP 0926754, US Patent No. 5523181, US Patent No. 6515190.Sol-gel method is that one is immersed in the mixing solutions of alcohol and water through pretreated film in advance, alcohol and water is entered in film, then add the mixing solutions of silicon-dioxide presoma and alcohol, makes it to occur sol gel reaction in film, finally film is dried.As (Journal of Power Sources such as M.Amjadi, 2012,210:350-357), (the Journal of Membrane Science such as Ruichun Jiang, 2006,272:116 – 124), (the Journal of Applied Polymer Science such as K.A.MAURITZ, 1995,55:181-190), (Chem.Mater.1995 such as Phoebe L.Shao, 7:192-200), (the Journal of The Electrochemical Society such as N.Miyake, 2001,148 (8): report A898-A904).
But double teeming method and sol-gel method are being prepared perfluorinated sulfonic resin/SiO
2during composite membrane, there is following problem:
(1) double teeming method technique is simple, process is easily controlled, but SiO after film forming
2the particle size range of particle and degree of scatter be difficult to accomplish evenly, thereby affect the performance of PEMFC.
(2), although sol-gel method has solved uniform particles problem in composite membrane, current reported film-forming process is comparatively complicated, all needs through proton membrane being carried out to this intermediate steps of pre-treatment (as solvent soaking), then carries out sol gel reaction.
(3) all used organic solvent as alcohol, environment has been caused to corresponding pollution.
Even existing technique is within the longer reaction times, silicon doping amount is still less, and proton conductivity is poor.This will be extremely disadvantageous take in the large-scale commercial production that benefit is prerequisite.
Summary of the invention
The object of the invention is in order to overcome the defect of prior art, provide that a kind of technique is simple, production efficiency is high, the SiO of safety and environmental protection, good product performance
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: a kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film, comprises the following steps:
(1) silicon-dioxide presoma, water, acid are reacted 30～60 minutes 1:0.2～15:0.001～0.1 in molar ratio at 0～50 ℃, obtain SiO
2colloidal sol;
(2) perfluorosulfonic acid proton exchange film is put into above-mentioned SiO
2in colloidal sol, soak 2～14min, make SiO
2colloidal sol is adsorbed onto in perfluorosulfonic acid proton exchange film;
(3) will adsorb SiO
2the colloidal sol on the perfluorosulfonic acid proton exchange film surface after colloidal sol is removed, and under 40～100 ℃ of conditions, heat-treats 0.5～8h, makes SiO
2adulterated full fluorin sulfonic acid proton exchange film.
Further:
The mol ratio of described silicon-dioxide presoma, water and acid is preferably 1:2～6:0.002～0.01.
Described perfluorosulfonic acid proton exchange film main component is preferably tetrafluoroethylene monomer and with the multipolymer of sulfonic perfluorovinyl sulfide ether monomer.
Described silicon-dioxide presoma is preferably a kind of in methyl silicate, tetraethoxy, positive isopropyl silicate, methyltrimethoxy silane and diethyl diethoxy silane.
Described acid is preferably a kind of in hydrochloric acid, nitric acid, sulfuric acid, acetic acid and boric acid.
The present invention, not with an organic solvent in the situation that, obtains high SiO at short notice
2the perfluorosulfonic acid proton exchange film of doping, has that technique is simple, production efficiency is high, the advantage of safety and environmental protection, good product performance.
Silicon-dioxide presoma of the present invention can adopt the compound of silicon alkoxide or silicon alkoxide, and its general molecular formula is:
(R
1)
xSi(OR
2)
4-x
X=0,1 or 2, R wherein
1, R
2represent respectively the alkyl of H, C1-C4.The object lesson of silicon-dioxide presoma is as: methyl silicate, tetraethoxy, positive isopropyl silicate, methyltrimethoxy silane and diethyl diethoxy silane etc., is preferably a kind of in methyl silicate, tetraethoxy, positive isopropyl silicate, methyltrimethoxy silane and diethyl diethoxy silane.
Acid of the present invention is optional is all hydrionic compound with the positively charged ion that when ionization generates, example hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, formic acid, acetic acid, boric acid etc., and described acid is preferably a kind of in hydrochloric acid, nitric acid, sulfuric acid, acetic acid and boric acid.
Perfluorosulfonic acid proton exchange film of the present invention is prepared by perfluorinated sulfonic resin, perfluorinated sulfonic resin consists of tetrafluoroethylene monomer and with the multipolymer of sulfonic perfluorovinyl sulfide ether monomer, in perfluorosulfonic acid proton exchange film, the chemical structural formula of perfluorinated sulfonic resin can represent with following general formula:
Perfluorosulfonic acid proton exchange film of the present invention can adopt Dupont company
the Dow films of the Aciplex Mo, Dow company of film, Asahi Chemical company etc., above perfluorosulfonic acid proton exchange film all can commercially availablely be obtained.
Compared with prior art, the present invention has the following advantages:
1, technique is simple, production efficiency is high, without proton membrane being carried out to pre-treatment (as solvent soaking);
2, safety and environmental protection, preparation process is without with an organic solvent;
3, good product performance, the perfluorosulfonic acid proton exchange film SiO making
2doping is high, SiO
2doping mass percent reaches as high as 39.7%, has excellent proton conduction property under high temperature low-humidity environment.
Embodiment
Below embodiments of the invention are elaborated.The present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.
The perfluorosulfonic acid proton exchange film using in embodiment is prepared by perfluorinated sulfonic resin, perfluorinated sulfonic resin consists of tetrafluoroethylene monomer and with the multipolymer of sulfonic perfluorovinyl sulfide ether monomer, in perfluorosulfonic acid proton exchange film, the chemical structural formula of perfluorinated sulfonic resin can represent with following general formula:
Wherein:
Aciplex film: the perfluorosulfonic acid proton exchange film of commercial Asahi Chemical company.
Dow film: the perfluorosulfonic acid proton exchange film of commercial Dow company.
Embodiment 1
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by methyl silicate, water and hydrochloric acid 1:2:2 * 10 in molar ratio
-3at 8 ℃, stir 30 minutes, form SiO
2colloidal sol.Then by perfluorosulfonic acid proton exchange film
film) put into above-mentioned SiO
2in colloidal sol, soak 5min, make
in film, adsorb a certain amount of SiO
2colloidal sol.Finally, will
film takes out from colloidal sol, by the colloidal sol wiped clean on film surface, under 50 ℃ of conditions, heat-treats 1h, obtains SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 39.7%.
Embodiment 2
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by tetraethoxy, water and nitric acid 1:4:1 * 10 in molar ratio
-3at 10 ℃, stir 50 minutes, form SiO
2colloidal sol.Then perfluorosulfonic acid proton exchange film (Aciplex film) is put into above-mentioned SiO
2in colloidal sol, soak 4min, make to adsorb in Aciplex film a certain amount of SiO
2colloidal sol.Finally, Aciplex film is taken out from colloidal sol, by the colloidal sol wiped clean on film surface, under 80 ℃ of conditions, heat-treat 4h, obtain SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 29.7%.
Embodiment 3
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by positive isopropyl silicate, water and hydrochloric acid 1:4:1 * 10 in molar ratio
-3at 20 ℃, stir 40 minutes, form SiO
2colloidal sol.Then perfluorosulfonic acid proton exchange film (Dow film) is put into above-mentioned SiO
2in colloidal sol, soak 7min, make to adsorb in Dow film a certain amount of SiO
2colloidal sol.Finally, Dow film is taken out from colloidal sol, by the colloidal sol wiped clean on film surface, under 80 ℃ of conditions, heat-treat 4h, obtain SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 29.2%.
Embodiment 4
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by positive isopropyl silicate, water and acetic acid 1:10:4 * 10 in molar ratio
-2at 0 ℃, stir 60 minutes, form SiO
2colloidal sol.Then by perfluorosulfonic acid proton exchange film
film) put into above-mentioned SiO
2in colloidal sol, soak 9min, make
in film, adsorb a certain amount of SiO
2colloidal sol.Finally, will
film takes out from colloidal sol, by the colloidal sol wiped clean on film surface, under 40 ℃ of conditions, heat-treats 8h, obtains SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 34.2%.
Embodiment 5
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by methyltrimethoxy silane, water and boric acid 1:15:8 * 10 in molar ratio
-2at 10 ℃, stir 50 minutes, form SiO
2colloidal sol.Then perfluorosulfonic acid proton exchange film (Dow film) is put into above-mentioned SiO
2in colloidal sol, soak 14min, make to adsorb in Dow film a certain amount of SiO
2colloidal sol.Finally, Dow film is taken out from colloidal sol, by the colloidal sol wiped clean on film surface, under 40 ℃ of conditions, heat-treat 8h, obtain SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 25.7%.
Embodiment 6
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by tetraethoxy, water and hydrochloric acid 1:0.2:1 * 10 in molar ratio
-3at 20 ℃, stir 40 minutes, form SiO
2colloidal sol.Then by perfluorosulfonic acid proton exchange film
film) put into above-mentioned SiO
2in colloidal sol, soak 14min, make
in film, adsorb a certain amount of SiO
2colloidal sol.Finally, will
film takes out from colloidal sol, by the colloidal sol wiped clean on film surface, under 40 ℃ of conditions, heat-treats 8h, obtains SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 35.6%.
Embodiment 7
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by methyltrimethoxy silane, water and sulfuric acid 1:0.5:6 * 10 in molar ratio
-3at 50 ℃, high-speed stirring is 30 minutes, forms SiO
2colloidal sol.Then by perfluorosulfonic acid proton exchange film (
film) put into above-mentioned SiO
2in colloidal sol, soak 4min, make
in film, adsorb a certain amount of SiO
2colloidal sol.Finally, will
film takes out from colloidal sol, by the colloidal sol wiped clean on film surface, under 80 ℃ of conditions, heat-treats 4h, obtains SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 28.6%.
Embodiment 8
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by diethyl diethoxy silane, water and acetic acid 1:0.8:8 * 10 in molar ratio
-3at 0 ℃, stir 60 minutes, form SiO
2colloidal sol.Then perfluorosulfonic acid proton exchange film (Aciplex film) is put into above-mentioned SiO
2in colloidal sol, soak 9min, make to adsorb in Aciplex film a certain amount of SiO
2colloidal sol.Finally, Aciplex film is taken out from colloidal sol, by the colloidal sol wiped clean on film surface, under 40 ℃ of conditions, heat-treat 8h, obtain SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 33.4%.
Embodiment 9
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by tetraethoxy, water and hydrochloric acid 1:4:6 * 10 in molar ratio
-3at 5 ℃, stir 40 minutes, form SiO
2colloidal sol.Then perfluorosulfonic acid proton exchange film (Dow film) is put into above-mentioned SiO
2in colloidal sol, soak 8min, make to adsorb in Dow film a certain amount of SiO
2colloidal sol.Finally, Dow film is taken out from colloidal sol, by the colloidal sol wiped clean on film surface, under 60 ℃ of conditions, heat-treat 4h, obtain SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 38.7%.
Embodiment 10
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by positive isopropyl silicate, water and nitric acid 1:6:1 * 10 in molar ratio
-2at 10 ℃, stir 45 minutes, form SiO
2colloidal sol.Then by perfluorosulfonic acid proton exchange film (
film) put into above-mentioned SiO
2in colloidal sol, soak 10min, make
in film, adsorb a certain amount of SiO
2colloidal sol.Finally, will
film takes out from colloidal sol, by the colloidal sol wiped clean on film surface, under 70 ℃ of conditions, heat-treats 2.5h, obtains SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 38.6%.
Embodiment 11
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by methyltrimethoxy silane, water and hydrochloric acid 1:4:4 * 10 in molar ratio
-3at 20 ℃, stir 40 minutes, form SiO
2colloidal sol.Then by perfluorosulfonic acid proton exchange film (
film) put into above-mentioned SiO
2in colloidal sol, soak 2min, make
in film, adsorb a certain amount of SiO
2colloidal sol.Finally, will
film takes out from colloidal sol, by the colloidal sol wiped clean on film surface, under 100 ℃ of conditions, heat-treats 0.5h, obtains SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 24.36%.
Embodiment 12
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by methyl silicate, water and hydrochloric acid in molar ratio 1:4:0.1 at 20 ℃, stir 40 minutes, form SiO
2colloidal sol.Then by perfluorosulfonic acid proton exchange film (
film) put into above-mentioned SiO
2in colloidal sol, soak 4min, make
in film, adsorb a certain amount of SiO
2colloidal sol.Finally, will
film takes out from colloidal sol, by the colloidal sol wiped clean on film surface, under 80 ℃ of conditions, heat-treats 4h, obtains SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 28.36%.
Embodiment 13
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by tetraethoxy, water and hydrochloric acid in molar ratio 1:4:0.1 at 0 ℃, stir 60 minutes, form SiO
2colloidal sol.Then perfluorosulfonic acid proton exchange film (Aciplex film) is put into above-mentioned SiO
2in colloidal sol, soak 7min, make to adsorb in Aciplex film a certain amount of SiO
2colloidal sol.Finally, Aciplex film is taken out from colloidal sol, by the colloidal sol wiped clean on film surface, under 80 ℃ of conditions, heat-treat 4h, obtain SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 28.76%.
Embodiment 14
A kind of SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film: first by positive isopropyl silicate, water and hydrochloric acid in molar ratio 1:8:0.1 at 0 ℃, stir 60 minutes, form SiO
2colloidal sol.Then by perfluorosulfonic acid proton exchange film (
film) put into above-mentioned SiO
2in colloidal sol, soak 9min, make
in film, adsorb a certain amount of SiO
2colloidal sol.Finally, will
film takes out from colloidal sol, by the colloidal sol wiped clean on film surface, under 80 ℃ of conditions, heat-treats 4h, obtains SiO
2adulterated full fluorin sulfonic acid proton exchange film, SiO
2doping mass percent is 35.1%.
Claims (5)
1. a SiO
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film, is characterized in that comprising the following steps:
(1) silicon-dioxide presoma, water, acid are reacted 30～60 minutes 1:0.2～15:0.001～0.1 in molar ratio at 0～50 ℃, obtain SiO
2colloidal sol;
(2) perfluorosulfonic acid proton exchange film is put into above-mentioned SiO
2in colloidal sol, soak 2～14min, make SiO
2colloidal sol is adsorbed onto in perfluorosulfonic acid proton exchange film;
(3) will adsorb SiO
2the colloidal sol on the perfluorosulfonic acid proton exchange film surface after colloidal sol is removed, and under 40～100 ℃ of conditions, heat-treats 0.5～8h, makes SiO
2adulterated full fluorin sulfonic acid proton exchange film.
2. SiO according to claim 1
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film, is characterized in that the mol ratio of described silicon-dioxide presoma, water and acid is 1:2～6:0.002～0.01.
3. SiO according to claim 1
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film, is characterized in that described perfluorosulfonic acid proton exchange film main component is tetrafluoroethylene monomer and with the multipolymer of sulfonic perfluorovinyl sulfide ether monomer.
4. SiO according to claim 1
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film, is characterized in that described silicon-dioxide presoma is a kind of in methyl silicate, tetraethoxy, positive isopropyl silicate, methyltrimethoxy silane and diethyl diethoxy silane.
5. SiO according to claim 1
2the preparation method of adulterated full fluorin sulfonic acid proton exchange film, is characterized in that described acid is a kind of in hydrochloric acid, nitric acid, sulfuric acid, acetic acid and boric acid.
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| CN104078691A (en) * | 2014-05-21 | 2014-10-01 | 巨化集团技术中心 | Preparation method of superabsorbent proton exchange membrane |
| CN106229533A (en) * | 2016-08-24 | 2016-12-14 | 上海交通大学 | Compound Multilayer Film Electrode of hydrophilic/hydrophobic and preparation method thereof |
| CN108598538A (en) * | 2018-04-10 | 2018-09-28 | 中国地质大学（武汉） | A kind of lossless method of modifying in the original position of Nafion membrane |
| CN110112447A (en) * | 2019-05-09 | 2019-08-09 | 朝阳华鼎储能技术有限公司 | Multilayer composite proton exchange membrane and preparation method thereof containing perfluorinated sulfonic resin |
| CN117186476A (en) * | 2023-11-07 | 2023-12-08 | 华中科技大学 | Preparation method of ion-doped filling modified polymer ionic membrane |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104078691A (en) * | 2014-05-21 | 2014-10-01 | 巨化集团技术中心 | Preparation method of superabsorbent proton exchange membrane |
| CN106229533A (en) * | 2016-08-24 | 2016-12-14 | 上海交通大学 | Compound Multilayer Film Electrode of hydrophilic/hydrophobic and preparation method thereof |
| CN106229533B (en) * | 2016-08-24 | 2019-10-18 | 上海唐锋能源科技有限公司 | Compound Multilayer Film Electrode of hydrophilic/hydrophobic and preparation method thereof |
| CN108598538A (en) * | 2018-04-10 | 2018-09-28 | 中国地质大学（武汉） | A kind of lossless method of modifying in the original position of Nafion membrane |
| CN108598538B (en) * | 2018-04-10 | 2020-08-25 | 中国地质大学（武汉） | In-situ nondestructive modification method of Nafion membrane |
| CN110112447A (en) * | 2019-05-09 | 2019-08-09 | 朝阳华鼎储能技术有限公司 | Multilayer composite proton exchange membrane and preparation method thereof containing perfluorinated sulfonic resin |
| CN110112447B (en) * | 2019-05-09 | 2022-08-02 | 朝阳华鼎储能技术有限公司 | Multi-layer composite proton exchange membrane containing perfluorinated sulfonic acid resin and preparation method thereof |
| CN117186476A (en) * | 2023-11-07 | 2023-12-08 | 华中科技大学 | Preparation method of ion-doped filling modified polymer ionic membrane |
| CN117186476B (en) * | 2023-11-07 | 2024-02-09 | 华中科技大学 | Preparation method of ion-doped filling modified polymer ionic membrane |
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