CN103601906B - A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film - Google Patents
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film Download PDFInfo
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Abstract
The invention provides a kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film, comprises the following steps：（1）By silica precursor, water, acid in molar ratio 1：0.2~15：0.001~0.1 reacts 30~60 minutes at 0~50 DEG C, obtains SiO2Colloidal sol；（2）Perfluorosulfonic acid proton exchange film is put into above-mentioned SiO22~14min is soaked in colloidal sol, makes SiO2Colloidal sol is adsorbed onto in perfluorosulfonic acid proton exchange film；（3）SiO will be adsorbed2The colloidal sol on the perfluorosulfonic acid proton exchange film surface after colloidal sol is removed, and 0.5~8h of heat treatment is carried out under the conditions of 40~100 DEG C, and SiO is obtained2Adulterated full fluorin sulfonic acid proton exchange film.The present invention has the advantages that process is simple, production efficiency high, safety and environmental protection, good product performance.
Description
Technical field
The present invention relates to the preparation method of organic/inorganic composite proton exchanging membrane, and in particular to a kind of SiO2Adulterated full fluorin
The preparation method of sulfonic acid proton exchange film.
Background technology
Proton Exchange Membrane Fuel Cells（PEMFC）The characteristics of there is high-specific-power, high-energy conversion efficiency because of it, with low
Startup temperature, corrosion-free, no pollution, environment-friendly advantage, the preferable energy as electric automobile, submarine and various movable equipments
Source.PEM serves key as one of PEMFC important part to its performance.
The current widest PEM of domestic and international application is composition for tetrafluoroethylene monomer and with sulfonic complete
The copolymer of fluoride-based ether monomer, such as Nafion membrane of Dupont companies, the Aciplex films of Asahi Chemical companies,
Dow films of Dow companies etc..It is characterized in that carbon fluorine high polymer main chain has excellent heat endurance and chemical stability, can be true
Protect the service life of proton membrane.And hydrophilic sulfonic acid group can provide conductance higher as the medium of absorption water for it.
But there is problems with actual use in existing PEM：
(1) PEM must place it in lower temperature to holding proton conductivity higher（60-80oC）With
And under ambient humidity higher, thus complicated temperature management system and moisture management system need to be equipped with, so as to increased fuel electricity
The cost and energy consumption of cell system.
(2) under the working environment of low temperature, CO is more notable to the poisoning effect of fuel-cell catalyst Pt, to gaseous fuel
Purity requirement it is higher, increase fuel cell operating cost.
(3) though improving PEMFC operation temperatures can reduce adsorption effects of the CO on Pt catalyst, the property of the anti-CO of battery is improved
Energy.But when temperature is more than 100 DEG C, excessive water evaporation, causes proton conduction velocity drastically to decline, Jin Erying in Nafion membrane
Ring battery performance.
Therefore, the PEM with excellent proton conduction property under high temperature low-humidity environment is prepared, is future fuel
The inexorable trend of field of batteries development.To addition hydrophilic inorganic material SiO in proton membrane2It is to solve the conduction of high temperature proton membrane
One of important means of poor performance.First, silica precursor contains the groups such as more hydrophily silanol and silicone hydroxyl, increases
The water imbibition of strong film.Secondly, the silica that hydrolysis is obtained is cross-linked with each other to form inierpeneirating network structure in film, strengthens the water conservation of film
Property, so as to reach the purpose that proton conductivity is improved during high temperature.
Since the eighties in 20th century, by the development of nearly 30 years, people were to perfluorinated sulfonic resin/SiO2Composite proton is handed over
Changing structural behaviour, preparation method and battery performance of film etc. has carried out numerous studies, and achieves certain achievement.Wherein, weight
Casting and sol-gel process are to prepare perfluorinated sulfonic resin/SiO2The conventional two methods of composite membrane.
Double teeming method is that Nano-meter SiO_2 is added in perfluor sulfoacid resin solution2Particle or the silica for having prepared are water-soluble
Glue, then film forming.Antonucci P L etc.（Solid State Ionics,1999,125:431-437）、Masahiro
Watanabe etc.（J Electrochem Society,1996,143(2):3847-3852）, (the J such as Adjemian K T
Electrochem Society,2002,149(3):A256-A261), Zoppi R A etc.（Polymer,1997,V39(6-7):
1309-1315）, and European patent EP 0926754, United States Patent (USP) US5523181, United States Patent (USP) US6515190 have in succession
Reported.Sol-gel process is, by a film mixed solution of the immersion alcohol with water in advance by pretreatment, to enter alcohol and water
Enter in film, add the mixed solution of silica precursor and alcohol, be allowed to sol gel reaction in film, finally will
Film is dried.Such as M.Amjadi（Journal of Power Sources, 2012,210：350-357）、Ruichun Jiang
Deng（Journal of Membrane Science, 2006,272：116–124）, K.A.MAURITZ etc.（Journal of
Applied Polymer Science, 1995,55:181-190）, Phoebe L.Shao etc.（Chem.Mater.1995,7:
192-200）, (the Journal of The Electrochemical Society, 2001,148 (8) such as N.Miyake:A898-
A904）Report.
But double teeming method and sol-gel process are preparing perfluorinated sulfonic resin/SiO2There is problems with during composite membrane：
(1) double teeming method technique relatively simple, process is easily controlled, but SiO after film forming2The particle size range and degree of scatter of particle
It is difficult to uniformly, so as to influence the performance of PEMFC.
(2) although sol-gel process solves the problems, such as particle uniformity in composite membrane, but the film-forming process reported at present
It is complex, it is both needed to carry out pre-treatment by proton membrane（Such as solvent soaking）This intermediate steps, then to carry out sol-gel anti-
Should.
(3) organic solvent such as alcohol has been used, corresponding pollution has been caused to environment.
Even existing process is within the reaction time more long, silicon doping is still smaller, and proton conductivity is poor.This with
To be extremely disadvantageous in large-scale industrial production premised on benefit.
The content of the invention
Defect the invention aims to overcome prior art, there is provided a kind of process is simple, production efficiency are high, safety
Environmental protection, the SiO of good product performance2The preparation method of adulterated full fluorin sulfonic acid proton exchange film.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following technical solutions：A kind of SiO2Adulterated full fluorin
The preparation method of sulfonic acid proton exchange film, comprises the following steps：
（1）By silica precursor, water, acid in molar ratio 1：0.2~15：0.001~0.1 reacts at 0~50 DEG C
30~60 minutes, obtain SiO2Colloidal sol；
（2）Perfluorosulfonic acid proton exchange film is put into above-mentioned SiO22~14min is soaked in colloidal sol, makes SiO2Colloidal sol is adsorbed onto
In perfluorosulfonic acid proton exchange film；
（3）SiO will be adsorbed2The colloidal sol on the perfluorosulfonic acid proton exchange film surface after colloidal sol is removed, in 40~100 DEG C of conditions
Under carry out 0.5~8h of heat treatment, be obtained SiO2Adulterated full fluorin sulfonic acid proton exchange film.
Further：
The mol ratio of the silica precursor, water and acid is preferably 1：2~6：0.002~0.01.
The perfluorosulfonic acid proton exchange film main component is preferably tetrafluoroethylene monomer and with sulfonic perfluor second
The copolymer of alkenyl ether monomer.
The silica precursor is preferably methyl silicate, tetraethyl orthosilicate, positive isopropyl silicate, methyl trimethoxy oxygen
One kind in base silane and diethyldiethoxysilane.
Described acid is preferably the one kind in hydrochloric acid, nitric acid, sulfuric acid, acetic acid and boric acid.
The present invention obtains SiO high in a short time in the case where organic solvent is not used2The perfluorinated sulfonic acid matter of doping
Proton exchange, safety and environmental protection, the advantage of good product performance high with process is simple, production efficiency.
Silica precursor of the present invention can use the compound of silicon alkoxide or silicon alkoxide, and its general molecular formula be：
(R1)xSi(OR2)4-x
Wherein x=0,1 or 2, R1, R2The alkyl of H, C1-C4 is represented respectively.The specific example of silica precursor is such as：Just
Methyl silicate, tetraethyl orthosilicate, positive isopropyl silicate, MTMS and diethyldiethoxysilane etc., preferably
For in methyl silicate, tetraethyl orthosilicate, positive isopropyl silicate, MTMS and diethyldiethoxysilane
It is a kind of.
It is entirely hydrionic compound that acid of the present invention can select the cation generated during ionization, such as hydrochloric acid, phosphorus
Acid, nitric acid, sulfuric acid, formic acid, acetic acid, boric acid etc., described acid are preferably in hydrochloric acid, nitric acid, sulfuric acid, acetic acid and boric acid
Kind.
Perfluorosulfonic acid proton exchange film of the present invention is prepared by perfluorinated sulfonic resin, perfluorinated sulfonic resin
Constitute as tetrafluoroethylene monomer and the copolymer with sulfonic perfluorovinyl ether monomer, perfluorosulfonic acid proton exchange film
The chemical structural formula of middle perfluorinated sulfonic resin is represented by the formula：
Perfluorosulfonic acid proton exchange film of the present invention can be using Dupont companiesFilm, Asahi
The Aciplex films of Chemical companies, Dow films of Dow companies etc., the commercially available acquirement of above perfluorosulfonic acid proton exchange film.
Compared with prior art, the present invention has advantages below：
1st, process is simple, production efficiency are high, without carrying out pre-treatment to proton membrane（Such as solvent soaking）；
2nd, safety and environmental protection, preparation process is without using organic solvent；
3rd, good product performance, obtained perfluorosulfonic acid proton exchange film SiO2Doping is high, SiO2Doping mass percent is most
It is high by reachable 39.7%, there is excellent proton conduction property under high temperature low-humidity environment.
Specific embodiment
Embodiments of the invention are elaborated below.The present embodiment is lower real premised on technical solution of the present invention
Apply, give detailed implementation method and specific operating process, but protection scope of the present invention is not limited to following embodiments.
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 deformations and improvement, these belong to protection scope of the present invention.
The perfluorosulfonic acid proton exchange film used in embodiment is prepared by perfluorinated sulfonic resin, perfluorinated sulfonic acid tree
Fat composition is tetrafluoroethylene monomer and the copolymer with sulfonic perfluorovinyl ether monomer, perfluorosulfonic acid proton exchange film
The chemical structural formula of middle perfluorinated sulfonic resin is represented by the formula：
Wherein：
Film：The perfluorosulfonic acid proton exchange film of Dupont companies purchased in market.
Aciplex films：The perfluorosulfonic acid proton exchange film of Asahi Chemical companies purchased in market.
Dow films：The perfluorosulfonic acid proton exchange film of Dow companies purchased in market.
Embodiment 1
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：Methyl silicate, water and hydrochloric acid are pressed first
Mol ratio 1:2:2×10-3Stirred 30 minutes at 8 DEG C, form SiO2Colloidal sol.Then by perfluorosulfonic acid proton exchange filmFilm）It is put into above-mentioned SiO25min is soaked in colloidal sol, is madeA certain amount of SiO is adsorbed in film2Colloidal sol.Finally,
WillFilm takes out from colloidal sol, by the colloidal sol wiped clean on film surface, heat treatment 1h is carried out under the conditions of 50 DEG C, obtains final product
To SiO2Adulterated full fluorin sulfonic acid proton exchange film, SiO2Doping mass percent is 39.7%.
Embodiment 2
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：Tetraethyl orthosilicate, water and nitric acid are pressed first
Mol ratio 1:4:1×10-3Stirred 50 minutes at 10 DEG C, form SiO2Colloidal sol.Then by perfluorosulfonic acid proton exchange film
（Aciplex films）It is put into above-mentioned SiO24min is soaked in colloidal sol, makes to adsorb a certain amount of SiO in Aciplex films2Colloidal sol.Finally,
Aciplex films are taken out from colloidal sol, by the colloidal sol wiped clean on film surface, heat treatment 4h is carried out under the conditions of 80 DEG C, obtained final product
To SiO2Adulterated full fluorin sulfonic acid proton exchange film, SiO2Doping mass percent is 29.7%.
Embodiment 3
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：First by positive isopropyl silicate, water and hydrochloric acid
In molar ratio 1:4:1×10-3Stirred 40 minutes at 20 DEG C, form SiO2Colloidal sol.Then by perfluorosulfonic acid proton exchange film
（Dow films）It is put into above-mentioned SiO27min is soaked in colloidal sol, makes to adsorb a certain amount of SiO in Dow films2Colloidal sol.Finally, by Dow films from
Taken out in colloidal sol, by the colloidal sol wiped clean on film surface, heat treatment 4h is carried out under the conditions of 80 DEG C, that is, obtain SiO2Adulterated full fluorin
Sulfonic acid proton exchange film, SiO2Doping mass percent is 29.2%.
Embodiment 4
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：First by positive isopropyl silicate, water and acetic acid
In molar ratio 1:10:4×10-2Stirred 60 minutes at 0 DEG C, form SiO2Colloidal sol.Then by perfluorosulfonic acid proton exchange filmFilm）It is put into above-mentioned SiO29min is soaked in colloidal sol, is madeA certain amount of SiO is adsorbed in film2Colloidal sol.Finally,
WillFilm takes out from colloidal sol, by the colloidal sol wiped clean on film surface, heat treatment 8h is carried out under the conditions of 40 DEG C, obtains final product
To SiO2Adulterated full fluorin sulfonic acid proton exchange film, SiO2Doping mass percent is 34.2%.
Embodiment 5
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：First by MTMS, water and
Boric acid in molar ratio 1:15:8×10-2Stirred 50 minutes at 10 DEG C, form SiO2Colloidal sol.Then by perfluorinated sulfonic acid proton exchange
Film（Dow films）It is put into above-mentioned SiO214min is soaked in colloidal sol, makes to adsorb a certain amount of SiO in Dow films2Colloidal sol.Finally, by Dow
Film takes out from colloidal sol, by the colloidal sol wiped clean on film surface, heat treatment 8h is carried out under the conditions of 40 DEG C, that is, obtain SiO2Doping
Perfluorosulfonic acid proton exchange film, SiO2Doping mass percent is 25.7%.
Embodiment 6
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：Tetraethyl orthosilicate, water and hydrochloric acid are pressed first
Mol ratio 1:0.2:1×10-3Stirred 40 minutes at 20 DEG C, form SiO2Colloidal sol.Then by perfluorosulfonic acid proton exchange filmFilm）It is put into above-mentioned SiO214min is soaked in colloidal sol, is madeA certain amount of SiO is adsorbed in film2Colloidal sol.Finally,
WillFilm takes out from colloidal sol, by the colloidal sol wiped clean on film surface, heat treatment 8h is carried out under the conditions of 40 DEG C, obtains final product
To SiO2Adulterated full fluorin sulfonic acid proton exchange film, SiO2Doping mass percent is 35.6%.
Embodiment 7
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：First by MTMS, water and
Sulfuric acid in molar ratio 1:0.5:6×10-3High-speed stirred 30 minutes at 50 DEG C, form SiO2Colloidal sol.Then by perfluorinated sulfonic acid matter
Proton exchange（Film）It is put into above-mentioned SiO24min is soaked in colloidal sol, is madeA certain amount of SiO is adsorbed in film2It is molten
Glue.Finally, willFilm is taken out from colloidal sol, and the colloidal sol wiped clean on film surface is heat-treated under the conditions of 80 DEG C
4h, that is, obtain SiO2Adulterated full fluorin sulfonic acid proton exchange film, SiO2Doping mass percent is 28.6%.
Embodiment 8
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：First by diethyldiethoxysilane, water
With acetic acid in molar ratio 1:0.8:8×10-3Stirred 60 minutes at 0 DEG C, form SiO2Colloidal sol.Then perfluorinated sulfonic acid proton is handed over
Change film（Aciplex films）It is put into above-mentioned SiO29min is soaked in colloidal sol, makes to adsorb a certain amount of SiO in Aciplex films2Colloidal sol.Most
Afterwards, Aciplex films are taken out from colloidal sol, by the colloidal sol wiped clean on film surface, heat treatment 8h is carried out under the conditions of 40 DEG C, i.e.,
Obtain SiO2Adulterated full fluorin sulfonic acid proton exchange film, SiO2Doping mass percent is 33.4%.
Embodiment 9
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：Tetraethyl orthosilicate, water and hydrochloric acid are pressed first
Mol ratio 1:4:6×10-3Stirred 40 minutes at 5 DEG C, form SiO2Colloidal sol.Then by perfluorosulfonic acid proton exchange film（Dow
Film）It is put into above-mentioned SiO28min is soaked in colloidal sol, makes to adsorb a certain amount of SiO in Dow films2Colloidal sol.Finally, by Dow films from colloidal sol
Middle taking-up, by the colloidal sol wiped clean on film surface, carries out heat treatment 4h under the conditions of 60 DEG C, that is, obtain SiO2Adulterated full fluorin sulfonic acid
PEM, SiO2Doping mass percent is 38.7%.
Embodiment 10
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：First by positive isopropyl silicate, water and nitric acid
In molar ratio 1:6:1×10-2Stirred 45 minutes at 10 DEG C, form SiO2Colloidal sol.Then by perfluorosulfonic acid proton exchange film（Film）It is put into above-mentioned SiO210min is soaked in colloidal sol, is madeA certain amount of SiO is adsorbed in film2Colloidal sol.Finally,
WillFilm takes out from colloidal sol, by the colloidal sol wiped clean on film surface, heat treatment 2.5h is carried out under the conditions of 70 DEG C, i.e.,
Obtain SiO2Adulterated full fluorin sulfonic acid proton exchange film, SiO2Doping mass percent is 38.6%.
Embodiment 11
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：First by MTMS, water and
Hydrochloric acid in molar ratio 1:4:4×10-3Stirred 40 minutes at 20 DEG C, form SiO2Colloidal sol.Then by perfluorinated sulfonic acid proton exchange
Film（Film）It is put into above-mentioned SiO22min is soaked in colloidal sol, is madeA certain amount of SiO is adsorbed in film2Colloidal sol.Most
Afterwards, willFilm is taken out from colloidal sol, and the colloidal sol wiped clean on film surface is heat-treated under the conditions of 100 DEG C
0.5h, that is, obtain SiO2Adulterated full fluorin sulfonic acid proton exchange film, SiO2Doping mass percent is 24.36%.
Embodiment 12
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：Methyl silicate, water and hydrochloric acid are pressed first
Mol ratio 1:4:0.1 stirs 40 minutes at 20 DEG C, forms SiO2Colloidal sol.Then by perfluorosulfonic acid proton exchange film（
Film）It is put into above-mentioned SiO24min is soaked in colloidal sol, is madeA certain amount of SiO is adsorbed in film2Colloidal sol.Finally, willFilm takes out from colloidal sol, by the colloidal sol wiped clean on film surface, heat treatment 4h is carried out under the conditions of 80 DEG C, that is, obtain
SiO2Adulterated full fluorin sulfonic acid proton exchange film, SiO2Doping mass percent is 28.36%.
Embodiment 13
A kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film：Tetraethyl orthosilicate, water and hydrochloric acid are pressed first
Mol ratio 1:4:0.1 stirs 60 minutes at 0 DEG C, forms SiO2Colloidal sol.Then by perfluorosulfonic acid proton exchange film（Aciplex
Film）It is put into above-mentioned SiO27min is soaked in colloidal sol, makes to adsorb a certain amount of SiO in Aciplex films2Colloidal sol.Finally, by Aciplex
Film takes out from colloidal sol, by the colloidal sol wiped clean on film surface, heat treatment 4h is carried out under the conditions of 80 DEG C, that is, obtain SiO2Mix
Miscellaneous perfluorosulfonic acid proton exchange film, SiO2Doping mass percent is 28.76%.
Embodiment 14
A kind of SiO2The 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 stirs 60 minutes at 0 DEG C, forms SiO2Colloidal sol.Then by perfluorosulfonic acid proton exchange film（Film）It is put into above-mentioned SiO29min is soaked in colloidal sol, is madeA certain amount of SiO is adsorbed in film2Colloidal sol.Finally,
WillFilm takes out from colloidal sol, by the colloidal sol wiped clean on film surface, heat treatment 4h is carried out under the conditions of 80 DEG C, obtains final product
To SiO2Adulterated full fluorin sulfonic acid proton exchange film, SiO2Doping mass percent is 35.1%.
Claims (1)
1. a kind of SiO2The preparation method of adulterated full fluorin sulfonic acid proton exchange film, it is characterised in that comprise the following steps：
(1) by methyl silicate, water, hydrochloric acid in molar ratio 1：2:2×10-3Stirred 30 minutes at 8 DEG C, obtain SiO2Colloidal sol；
(2) perfluorosulfonic acid proton exchange film is put into above-mentioned SiO25min is soaked in colloidal sol, makes SiO2Colloidal sol is adsorbed onto perfluorinated sulfonic acid
In PEM, the perfluorosulfonic acid proton exchange film is Dupont companiesFilm；
(3) SiO will be adsorbed2Perfluorosulfonic acid proton exchange film after colloidal sol takes out from colloidal sol, the colloidal sol on surface is removed, 50
Heat treatment 1h is carried out under the conditions of DEG C, SiO is obtained2Adulterated full fluorin sulfonic acid proton exchange film.
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| CN104078691B (en) * | 2014-05-21 | 2016-05-18 | 巨化集团技术中心 | A kind of preparation method of high-hydroscopicity PEM |
| 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 |
| CN108598538B (en) * | 2018-04-10 | 2020-08-25 | 中国地质大学（武汉） | In-situ nondestructive modification method of Nafion membrane |
| 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 |
| 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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| CN101440167A (en) * | 2007-11-19 | 2009-05-27 | 中国石油大学(北京) | Preparation of SiO2/organic polymer composite proton exchange membrane |
| CN101798177A (en) * | 2010-03-30 | 2010-08-11 | 上海交通大学 | Proton conductive composite and hydro-thermal treatment preparation method thereof |
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| CN101440167A (en) * | 2007-11-19 | 2009-05-27 | 中国石油大学(北京) | Preparation of SiO2/organic polymer composite proton exchange membrane |
| CN101798177A (en) * | 2010-03-30 | 2010-08-11 | 上海交通大学 | Proton conductive composite and hydro-thermal treatment preparation method thereof |
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