CN110148770A - A kind of structure regulating method of perfluorosulfonic acid proton exchange film - Google Patents
A kind of structure regulating method of perfluorosulfonic acid proton exchange film Download PDFInfo
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- CN110148770A CN110148770A CN201910384569.5A CN201910384569A CN110148770A CN 110148770 A CN110148770 A CN 110148770A CN 201910384569 A CN201910384569 A CN 201910384569A CN 110148770 A CN110148770 A CN 110148770A
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- Prior art keywords
- film
- proton exchange
- perfluorosulfonic acid
- regulating method
- acid proton
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to amberplex field, in particular to the structure regulating method of a kind of perfluorosulfonic acid proton exchange film.Perfluorinated sulfonic resin is dissolved in coordinative solvent, form certain density preparation solution, a certain proportion of functional material can be added as needed, striking forms a film under certain temperature and atmosphere, electric field or magnetic field are applied to wet film to regulate and control the micro-structure of film, final acquisition has the proton exchange membrane of specific structure and performance.By applying energy field in film forming procedure, the microstructure of effective Modulated Films significantly improves the ion transport performance of film, improves the ion selectivity of film the present invention.Proton exchange film properties produced by the present invention are better than commercial product, while preparation process is simple, is of great significance for the broader applications of amberplex.
Description
Technical field
The present invention relates to amberplex field, in particular to a kind of structure regulating side of perfluorosulfonic acid proton exchange film
Method.
Background technique
The important channel that renewable energy is response environment pollution and greenhouse effects is greatly developed, is current energy development
Trend, wherein the renewable energy power generation based on wind energy and solar energy will gradually quickly become main energy form.
However, the intermittence of output, discontinuity feature are to restrict the main problem of these renewable energy forms application developments, need
Overcome by developing corresponding energy storage technology.Flow battery (especially all-vanadium flow battery) and fuel cell are as big
The first choice of scale electrochemical energy storage obtains extensive concern and application in world wide.
Proton exchange membrane is the core component of vanadium flow battery and fuel cell, plays isolation battery the two poles of the earth and proton conducting
Effect, directly affect the performance, economy and service life of battery.Currently, perfluorosulfonic acid proton exchange film is widely used,
It has the advantages that proton conductivity is high, chemical stability is good, and the most commonly used is the Nafion membranes of DuPont Corporation.But
There is the disadvantages of making difficult, at high cost, easy swelling, low humidity conductivity is poor in Nafion membrane.
In recent years, researcher develops inclined fluorine, non-fluorine-type proton exchange membrane, although film cost is remarkably decreased, film
The index of perfluoro sulfonic acid membrane is also not achieved in performance and used life.
Therefore, proton exchange membrane of the exploitation based on perfluorinated sulfonic resin film is an effective way, as long as by having
The breakthrough of film properties can be realized in the Design of Membrane Structure of effect and regulation.
Summary of the invention
The object of the present invention is to provide a kind of structure regulating method of perfluorosulfonic acid proton exchange film, can solve it is existing every
The problems such as membrane structure existing defects, poor ion transport performance.
The technical scheme is that
A kind of structure regulating method of perfluorosulfonic acid proton exchange film, preparation and preparation process including proton exchange membrane
In film micro-structure regulation and film ion transport performance regulate and control；
Proton exchange membrane is prepared as with perfluorinated sulfonic resin as main resin raw material, addition threadiness or graininess function
Material, by being configured at film liquid, knifing and wet film curing process prepare proton exchange membrane；
The regulation of film micro-structure refers to by applying energy field to wet film, makes into microcosmic point of some materials in film liquid or wet film
Son, group or macroscopic material align, and then show ordered structure；
The regulation of ion transport performance, which refers to, realizes ion sieve component selections using the characteristic ordered structure of film, i.e. hydrogen ion passes
Speed maximization is passed, other heteroions obstruct completely.
The structure regulating method of the perfluorosulfonic acid proton exchange film, functional material include: graphene, graphite oxide
One of alkene, Carbon fibe, carbon nanotube, titanium oxide whisker, silica, iron oxide or more than one, functional material is perfluor
The 1~10% of sulfonate resin weight.
The structure regulating method of the perfluorosulfonic acid proton exchange film, can field include electric field or magnetic field, wherein electric-field strength
20~500N/C of range is spent, magnetic field strength range is 5~300A/M.
The structure regulating method of the perfluorosulfonic acid proton exchange film, the preparation of perfluorosulfonic acid proton exchange film is according to such as
Lower step carries out:
(1) it is configured to film liquid, in a solvent by perfluorinated sulfonic resin dissolution, perfluor sulfoacid resin solution is formed, according to need
Functional material is added, is futher stirred uniformly；
(2) striking wet film controls temperature and atmosphere, according to design thickness, the striking wet film in clean plane；
(3) membrane structure regulates and controls, and applies energy field to wet film, adjusts the micro-structure of film, and it is molten in wet film to cooperate Elevated Temperature Conditions to make
Agent volatilization, and then it is solidified into dry film.
The structure regulating method of the perfluorosulfonic acid proton exchange film, the solvent for configuring perfluor sulfoacid resin solution is N,
One of dinethylformamide, methanol, water, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, N- base pyrrolidones are a kind of
More than, the mass concentration of perfluor sulfoacid resin solution is 5~20%.
The structure regulating method of the perfluorosulfonic acid proton exchange film, the wet-film thickness model of perfluorosulfonic acid proton exchange film
Enclosing is 20~400 μm, and the dry film thickness range of perfluorosulfonic acid proton exchange film is 10~120 μm.
The structure regulating method of the perfluorosulfonic acid proton exchange film, energy field applying mode is to be continuously applied, either
Pulsed applies.
The structure regulating method of the perfluorosulfonic acid proton exchange film, the main hydrogen for improving film of ion transport performance regulation
Ion transport rate is expressed as the ionic conductivity of film, reduces the vanadium ion delivery rate of film.
The proton exchange membrane of the structure regulating method of the perfluorosulfonic acid proton exchange film, this method preparation is used for high property
Energy vanadium flow battery, or adjusted and controlled amberplex is needed for fuel cell and other types.
Design philosophy of the invention is:
Perfluorinated sulfonic resin is to the effect that dissolved in coordinative solvent by the present invention, forms certain density preparation solution, root
According to needing to be added a certain proportion of functional material, striking forms a film under certain temperature and atmosphere, applies electric field or magnetic field to wet film
It is final to obtain the proton exchange membrane with specific structure and performance to regulate and control the micro-structure of film.Proton exchange produced by the present invention
Film properties are better than commercial product, while preparation process is simple, is of great significance for the broader applications of amberplex.
The invention has the advantages and beneficial effects that:
1, the present invention carries out space structure to the segmented structure of perfluorinated sulfonic resin, ion-exchange group using different energy fields
Type regulation, optimizes the micro-structure of proton exchange membrane.
2, the hydrogen ion delivery rate of proton exchange membrane prepared by the present invention can regulate and control in a big way, and to vanadium ion
Effectively stopped etc. non-conductive ion, improves vanadium flow battery efficiency.
3, proton exchange membrane structure regulating method and process of the present invention is simple and convenient to operate, and is conducive to promote.
4, perfluorinated sulfonic resin is dissolved in coordinative solvent by the present invention, forms certain density preparation solution, can be as needed
A certain proportion of functional material is added, striking forms a film under certain temperature and atmosphere, applies electric field or magnetic field to wet film to regulate and control
The micro-structure of film, it is final to obtain the proton exchange membrane with specific structure and performance.The present invention is by applying energy in film forming procedure
, the microstructure of effective Modulated Films significantly improves the ion transport performance of film, improves the ion selectivity of film.
Specific embodiment
In the specific implementation process, the present invention is passed with optimizing proton exchange membrane microstructure, improving proton exchange membrane ion
For the purpose of passing performance, innovatively propose using it is different can field strength polymer segments, group align, and then improve film
Ion transport performance, preparation step specifically include that (1) film forming solution configure；(2) striking wet film；(3) membrane structure regulates and controls and consolidates
It is melted into film, finally obtains compound proton exchange membrane of the invention.
In the following, by embodiment, invention is further described in detail.
Embodiment 1
It in the present embodiment, weighs appropriate perfluorinated sulfonic resin and is dissolved in n,N-Dimethylformamide, obtain mass concentration
For 8% perfluor sulfoacid resin solution, the carbon nanotube for being 5wt% relative to perfluorinated sulfonic resin is wherein being added, further
It is handled 24 hours under 150 revs/min of mechanical stirring, obtains film forming solution.It, will in the environment of in room, epidemic disaster is 55%
In the striking of cleaned glass plate surface with a thickness of 60 μm of wet film, apply intensity to wet film upper and lower surfaces immediately is above-mentioned resin
50N/C uniform electric field continues 2 hours, while solidifying at a temperature of so that wet film is maintained at 120 DEG C, obtains dry film after 6 hours.
Using proton exchange membrane made from the present embodiment with a thickness of 32 μm, proton conductivity 0.15S/cm, hydrogen ion/vanadium from
Sub- selectivity factor is 34.
Embodiment 2
It in the present embodiment, weighs appropriate perfluorinated sulfonic resin and is dissolved in n,N-dimethylacetamide, obtain mass concentration
For 6% perfluor sulfoacid resin solution, the titanium oxide whisker for being 2wt% relative to perfluorinated sulfonic resin is wherein being added, into one
Step is handled 24 hours under 300 revs/min of mechanical stirring, obtains film forming solution.In the environment of in room, epidemic disaster is 85%,
By above-mentioned resin in the striking of cleaned glass plate surface with a thickness of 100 μm of wet film, applying intensity to wet film immediately is that 60A/M is uniform
Magnetic field, direction and wet film plane keeping parallelism, continue 4 hours, while solidifying at a temperature of so that wet film is maintained at 140 DEG C, and 8 hours
After obtain dry film.
Using proton exchange membrane made from the present embodiment with a thickness of 55 μm, proton conductivity 0.11S/cm, hydrogen ion/vanadium from
Sub- selectivity factor is 43.
Embodiment 3
It in the present embodiment, weighs appropriate perfluorinated sulfonic resin and is dissolved in N methyl pyrrolidone solvent, obtain mass concentration
It is 50nm's the partial size for being 3.5wt% relative to perfluorinated sulfonic resin is wherein added for 12% perfluor sulfoacid resin solution
Silicon oxide particle is further handled 24 hours under 200 revs/min of mechanical stirring, obtains film forming solution.In room epidemic disaster
In the environment of 90%, by above-mentioned resin in the striking of cleaned glass plate surface with a thickness of 150 μm of wet film, immediately on wet film,
It is 300N/C uniform electric field that lower surface, which applies intensity, and acts on pause after ten minutes and apply 300N/C uniform electric field again in 2 minutes, such as
This is kept for electric field 3 hours, and wet film solidifies at a temperature of being maintained at 120 DEG C, obtains dry film after 4 hours.
Using proton exchange membrane made from the present embodiment with a thickness of 85 μm, proton conductivity 0.10S/cm, hydrogen ion/vanadium from
Sub- selectivity factor is 68.
Embodiment 4
It in the present embodiment, weighs appropriate perfluorinated sulfonic resin and is dissolved in dimethyl sulfoxide solvent, obtaining mass concentration is
The oxygen that the partial size for being 1.5wt% relative to perfluorinated sulfonic resin is 200nm is wherein being added in 6% perfluor sulfoacid resin solution
Change iron particle, further handled 24 hours under 300 revs/min of mechanical stirring, obtains film forming solution.In room, epidemic disaster is
In the environment of 50%, by above-mentioned resin in the striking of cleaned glass plate surface with a thickness of 40 μm of wet film, immediately to the upper and lower table of wet film
It is 220A/M uniform magnetic field that face, which applies intensity, and acts on pause after twenty minutes and apply 220A/M uniform magnetic field again in 5 minutes, is so protected
Hold magnetic field 4 hours, wet film solidifies at a temperature of being maintained at 120 DEG C, obtains dry film after 6 hours.
Using proton exchange membrane made from the present embodiment with a thickness of 24 μm, proton conductivity 0.18S/cm, hydrogen ion/vanadium from
Sub- selectivity factor is 35.
Above-described embodiment the result shows that, a kind of structure regulating method of perfluorosulfonic acid proton exchange film proposed by the present invention,
It can solve existing membrane configuration existing defects, the problems such as ion transport performance is poor.Proton exchange film properties produced by the present invention
Better than commercial product, while preparation process is simple, is of great significance for the broader applications of amberplex.
Claims (9)
1. a kind of structure regulating method of perfluorosulfonic acid proton exchange film, which is characterized in that the preparation including proton exchange membrane with
And the ion transport performance of the regulation of film micro-structure and film in preparation process regulates and controls；
Proton exchange membrane is prepared as with perfluorinated sulfonic resin as main resin raw material, addition threadiness or graininess function material
Material, by being configured at film liquid, knifing and wet film curing process prepare proton exchange membrane；
The regulation of film micro-structure refers to by applying energy field to wet film, makes into the micro molecule, base of some materials in film liquid or wet film
Group or macroscopic material align, and then show ordered structure；
The regulation of ion transport performance, which refers to, realizes ion sieve component selections, i.e. hydrogen ion transmitting speed using the characteristic ordered structure of film
Degree maximizes, other heteroions obstruct completely.
2. the structure regulating method of perfluorosulfonic acid proton exchange film described in accordance with the claim 1, which is characterized in that functional material
It include: one of graphene, graphene oxide, Carbon fibe, carbon nanotube, titanium oxide whisker, silica, iron oxide or one kind
More than.
3. the structure regulating method of perfluorosulfonic acid proton exchange film described in accordance with the claim 1, which is characterized in that energy field includes
Electric field or magnetic field, wherein 20~500N/C of electric field strength range, magnetic field strength range are 5~300A/M.
4. the structure regulating method of perfluorosulfonic acid proton exchange film described in accordance with the claim 1, which is characterized in that perfluorinated sulfonic acid
The preparation of proton exchange membrane carries out in accordance with the following steps:
(1) it is configured to film liquid, in a solvent by perfluorinated sulfonic resin dissolution, perfluor sulfoacid resin solution is formed, adds as needed
Add functional material, futher stirs uniformly；
(2) striking wet film controls temperature and atmosphere, according to design thickness, the striking wet film in clean plane；
(3) membrane structure regulates and controls, and applies energy field to wet film, adjusts the micro-structure of film, and Elevated Temperature Conditions is cooperated to wave solvent in wet film
Hair, and then it is solidified into dry film.
5. the structure regulating method of perfluorosulfonic acid proton exchange film according to claim 4, which is characterized in that configuration perfluor
The solvent of sulfonate resin solution is N,N-dimethylformamide, methanol, water, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, N- base
One of pyrrolidones or more than one, the mass concentration of perfluor sulfoacid resin solution is 5~20%.
6. the structure regulating method of perfluorosulfonic acid proton exchange film according to claim 4, which is characterized in that perfluorinated sulfonic acid
The wet-film thickness range of proton exchange membrane is 20~400 μm, and the dry film thickness range of perfluorosulfonic acid proton exchange film is 10~120
μm。
7. according to the structure regulating method of perfluorosulfonic acid proton exchange film described in claim 1 or 4, which is characterized in that can field
Applying mode be continuously applied or pulsed apply.
8. the structure regulating method of perfluorosulfonic acid proton exchange film described in accordance with the claim 1, which is characterized in that ion transport
The main hydrogen ion delivery rate for improving film of performance regulation, is expressed as the ionic conductivity of film, reduces the vanadium ion transmitting speed of film
Rate.
9. the structure regulating method of perfluorosulfonic acid proton exchange film described in accordance with the claim 1, which is characterized in that party's legal system
Standby proton exchange membrane be used for high performance vanadium flow battery, or for fuel cell and other types need it is adjusted and controlled from
Proton exchange.
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| CN201910384569.5A CN110148770A (en) | 2019-05-09 | 2019-05-09 | A kind of structure regulating method of perfluorosulfonic acid proton exchange film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110957514A (en) * | 2019-12-04 | 2020-04-03 | 大连融科储能技术发展有限公司 | Strong hydrophobic ion exchange membrane and preparation method and application thereof |
| CN111370723A (en) * | 2020-03-19 | 2020-07-03 | 辽宁科京新材料科技有限公司 | Preparation method of perfluorosulfonic acid membrane with adjustable and controllable microstructure |
| CN111969232A (en) * | 2020-08-27 | 2020-11-20 | 盐城工学院 | Preparation method of fuel cell diaphragm material |
| KR102272937B1 (en) * | 2020-02-12 | 2021-07-06 | 한국과학기술원 | Ion-Conducting Layer and the Fabrication Method Thereof |
| CN114960207A (en) * | 2022-06-21 | 2022-08-30 | 浙江巨化新材料研究院有限公司 | Perfluorosulfonic acid carbon fiber composite material and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110957514A (en) * | 2019-12-04 | 2020-04-03 | 大连融科储能技术发展有限公司 | Strong hydrophobic ion exchange membrane and preparation method and application thereof |
| CN110957514B (en) * | 2019-12-04 | 2023-04-25 | 大连融科储能技术发展有限公司 | Strong-hydrophobicity ion exchange membrane and preparation method and application thereof |
| KR102272937B1 (en) * | 2020-02-12 | 2021-07-06 | 한국과학기술원 | Ion-Conducting Layer and the Fabrication Method Thereof |
| CN111370723A (en) * | 2020-03-19 | 2020-07-03 | 辽宁科京新材料科技有限公司 | Preparation method of perfluorosulfonic acid membrane with adjustable and controllable microstructure |
| CN111370723B (en) * | 2020-03-19 | 2021-04-09 | 辽宁科京新材料科技有限公司 | Preparation method of perfluorosulfonic acid membrane with adjustable and controllable microstructure |
| CN111969232A (en) * | 2020-08-27 | 2020-11-20 | 盐城工学院 | Preparation method of fuel cell diaphragm material |
| CN111969232B (en) * | 2020-08-27 | 2021-11-16 | 盐城工学院 | Preparation method of fuel cell diaphragm material |
| CN114960207A (en) * | 2022-06-21 | 2022-08-30 | 浙江巨化新材料研究院有限公司 | Perfluorosulfonic acid carbon fiber composite material and preparation method and application thereof |
| CN114960207B (en) * | 2022-06-21 | 2023-08-15 | 浙江巨化新材料研究院有限公司 | Perfluorosulfonic acid carbon fiber composite material and preparation method and application thereof |
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Application publication date: 20190820 |