CN109390601A - A kind of preparation method of amberplex - Google Patents
A kind of preparation method of amberplex Download PDFInfo
- Publication number
- CN109390601A CN109390601A CN201710672219.XA CN201710672219A CN109390601A CN 109390601 A CN109390601 A CN 109390601A CN 201710672219 A CN201710672219 A CN 201710672219A CN 109390601 A CN109390601 A CN 109390601A
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- Prior art keywords
- amberplex
- preparation
- solution
- mass percent
- diaphragm
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
-
- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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 a kind of preparation methods of amberplex, specifically include the preparation of 1. film forming solutions；2. diaphragm forming；3. modification；Step 3 include: 1) prepare modified solution: modified solution be metabisulfite solution, potassium sulfate solution or both mixing；2) by the molding diaphragm infiltration of step 2 in modified solution, infiltrating time is 30~90 minutes；3) diaphragm after infiltration is placed in thermostatic drying chamber and is dried by；4) the diaphragm taking-up after drying is cooled to room temperature by, obtains final amberplex.The preparation method of amberplex provided by the present invention, preparation process is simple, easy to accomplish, and safety is good, low in cost, is suitable for batch production.Using amberplex made from this method, its mechanical performance is greatly improved, and the coulombic efficiency of battery and energy efficiency can be improved about 3% after assembly, and battery performance stability is good.
Description
Technical field
The present invention relates to a kind of preparation methods of amberplex, belong to polymeric material field.
Background technique
Electric energy is difficult to store and indispensable, its production of any moment will meet power demand, therefore people one
Not only economy but also feasible energy storage technology directly are being found, to solve the contradiction between supply and demand, so that the production of electric energy and demand break off relations.
In addition power storage is in sides such as electric energy management, power grid ancillary service, voltage control, utilization of regenerative energy, large-scale uninterruptible power supplies
Face important role can reduce power station peaking capacity, reduce cost of electricity-generating and reduce dirty if combining with large-scale thermal power
Dye.If combining with renewable energy power generations such as wind-force, tide energies, it can be achieved that the continuous and stable of electric energy supplies, meet user demand.
It is easily designed since flow battery has the characteristics that power is separated with capacity, it is easy to operate, it has been increasingly becoming most promising
One of the first choice of large and medium-sized scale electric power storage.Wherein, flow battery is by favor.
Flow cell pile mostly uses structure of pressing filter at present, is mainly handed over by bipolar plates, positive and negative electrode, electrode frame, ion
Film (also referred to as diaphragm), end plate, sealing material and fastener is changed to constitute.Wherein, electrode frame, electrode frame are equipped between two bipolar plates
For hollow structure, inside is respectively equipped with positive and negative electrode, is equipped with diaphragm between positive and negative electrode.Anolyte used in flow battery
Liquid and electrolyte liquid are stored respectively in positive and negative electrode electrolyte storage tank.
Amberplex is extremely important to flow battery, is one of most important component of flow battery system, is that decision is whole
The key of a flow battery performance quality.It while separating positive and negative anodes electrolyte, also permission charge carrier pass freely through with
Guarantee the charge balance of positive and negative polarities.That there are still stability is not high for existing amberplex, and swellbility is big, high production cost
It is high, the disadvantages of complex process, bad mechanical property.
Current way has: processing solution or electrolyte is utilized, before carrying out before amberplex is assembled in pile
Phase processing prevents from destroying electricity due to its metamorphosis to guarantee that its volume after assembling and being passed through electrolyte will not change
The leakproofness of heap.There are still following problems: the processing time of amberplex is long, and processing solution toxicity is compared with strong, safety is poor, place
Reason solution price is more expensive, increases cost；The battery performance of amberplex is lower after assembly processing, seriously constrains liquid stream electricity
The development in pond.
Summary of the invention
In order to solve the above technical problems, utilizing this object of the present invention is to provide a kind of preparation method of amberplex
Its mechanical performance of amberplex made from method is greatly improved, and the coulombic efficiency of battery and energy efficiency can be improved after assembly
About 3%, while the production cost of film can be greatly reduced.
A kind of preparation method of amberplex, specifically comprises the following steps:
Step 1: film forming solution preparation；
Step 2: diaphragm forming；
Step 3: modification:
1) prepares modified solution: modified solution is the mixing of metabisulfite solution, potassium sulfate solution or both, wherein sulphur
The mass percent of sour sodium is 1~8%, and the mass percent of potassium sulfate is 1~5%；
2) diaphragm for obtaining step 2 infiltrates in modified solution, and infiltrating time is 30~90 minutes；
3) diaphragm after infiltration is placed in thermostatic drying chamber and is dried by, and drying temperature is controlled at 80~120 DEG C, does
The dry time is 60~120 minutes；
4) the diaphragm taking-up after drying is cooled to room temperature by, obtains final amberplex.
Further, the step 1 are as follows: use n,N-Dimethylformamide as solvent, perfluorinated sulfonic resin or sulfonation
Polyether-ether-ketone prepares film forming solution as solute, and wherein the mass percent of perfluorinated sulfonic resin is 1%~20%, sulfonated polyether
The mass percent of ether ketone is 1%~20%；The mass percent of the perfluorinated sulfonic resin is more preferably 10%；Institute
The mass percent for the sulfonated polyether-ether-ketone stated is more preferably 12%.
Further, diaphragm forming described in step 2 are as follows: the solution cast film formation for being obtained step 1 using the tape casting.
Further, modified solution described in step 1) is metabisulfite solution, and mass percent is 4~6%, further excellent
It is selected as 5%.
Further, modified solution described in step 1) is potassium sulfate solution, mass percent 3%.
Further, modified solution described in step 1) is the mixed solution of sodium sulphate and potassium sulfate, the quality of sodium sulphate
Percentage is 3%, and the mass percent of potassium sulfate is 2%.
Further, infiltrating time described in step 2) is 60~90 minutes, further preferably 60 or 90 minutes.
Further, the control of drying temperature described in step 3) is at 80~100 DEG C, and further preferably 80 or 100 DEG C；
The drying time is 60~90 minutes；Further preferably 60 or 90 minutes.
The preparation method of amberplex of the invention, the first two steps can also be other types amberplex
Conventional film formation step, such as sulfonation polyvinylidene fluoride alkenes amberplex, sulfonated polysulfone class amberplex, sulfonated polyether sulfone class
Amberplex, sulfonated polyphenyl ethers amberplex, sulfonate polybenzimidazole class amberplex, sulfonated polyimide class from
Proton exchange etc..
So-called the tape casting is exactly to be evenly coated in the polymer solution of certain viscosity on smooth backing material, then makes it
The technique of drying and forming-film.The advantages of flowing court of a feudal ruler method is: (1) processing range is extensive；(2) isotropism of film properties；(3) it is easy real
The volume production of existing film；(4) composite material of specific function can be made with compound many kinds of substance.It therefore, can be relatively wide using stream court of a feudal ruler method
Isotropic amberplex is prepared in general processing range.
The invention has the benefit that the preparation method of amberplex provided by the present invention, preparation process is simple, holds
It easily realizes, safety is good, low in cost, is suitable for batch production.Utilize its mechanical performance of amberplex made from this method
It is greatly improved, the coulombic efficiency of battery and energy efficiency can be improved about 3% after assembly, and battery performance stability is good.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
A kind of preparation method of amberplex, comprising:
1. prepared by film forming solution: perfluorinated sulfonic resin is dissolved in n,N-Dimethylformamide, perfluorinated sulfonic resin
Mass percent is 10%；
2. diaphragm forming: using the tape casting by perfluor sulfoacid resin solution casting film-forming, film thickness is 50 μm；
3. modification: the following steps are included:
1) it prepares modified solution: preparing the metabisulfite solution that mass percent is 1%；
2) by diaphragm infiltration in modified solution, infiltrating time is 60 minutes；
3) diaphragm after infiltrating, which is placed in thermostatic drying chamber, to be dried, and drying temperature control is in 80 DEG C, drying time
60 minutes；
4) the diaphragm taking-up after drying is cooled to room temperature, and obtains final amberplex.
Comparative example 1
A kind of preparation method of amberplex, comprising:
1. prepared by film forming solution: perfluorinated sulfonic resin being dissolved in n,N-Dimethylformamide, the quality percentage of resin
Number is 10%；
2. diaphragm forming: using the tape casting by perfluor sulfoacid resin solution casting film-forming, film thickness is 50 μm.
Comparative example 2
A kind of preparation method of amberplex, comprising:
1. prepared by film forming solution: sulfonated polyether-ether-ketone resin being dissolved in n,N-Dimethylformamide, the quality of resin
Percentage is 12%；
2. diaphragm forming: using the tape casting by sulfonated polyether-ether-ketone resin solution casting film-forming, film thickness is 50 μm.
Embodiment 2-48, preparation method basic step is identical as embodiment, and only following preparation parameter and embodiment 1 are not
Together.
It is detailed in following table:
As can be seen from the table, the amberplex prepared using the method for this patent, the coulombic efficiency of battery after assembly
3% or so is improved with energy efficiency.
Claims (10)
1. a kind of preparation method of amberplex, includes the following steps:
Step 1: film forming solution preparation；
Step 2: diaphragm forming；
It is characterized in that, also carrying out step 3: modification:
1) prepares modified solution: modified solution is the mixing of metabisulfite solution, potassium sulfate solution or both, wherein sodium sulphate
Mass percent be 1~8%, the mass percent of potassium sulfate is 1~5%；
2) diaphragm for obtaining step 2 infiltrates in modified solution, and infiltrating time is 30~90 minutes；
3) diaphragm after infiltration is placed in thermostatic drying chamber and is dried by, and drying temperature is controlled at 80~120 DEG C, when dry
Between be 60~120 minutes；
4) the diaphragm taking-up after drying is cooled to room temperature by, obtains final amberplex.
2. the preparation method of amberplex as described in claim 1, which is characterized in that the step 1 are as follows: use N, N- bis-
Methylformamide prepares film forming solution as solute as solvent, perfluorinated sulfonic resin or sulfonated polyether-ether-ketone, wherein perfluor sulphur
The mass percent of acid resin is 1%~20%, and the mass percent of sulfonated polyether-ether-ketone is 1%~20%.
3. the preparation method of amberplex as claimed in claim 2, which is characterized in that perfluorinated sulfonic acid described in step 1
The mass percent of resin is 10%；The mass percent of the sulfonated polyether-ether-ketone is 12%.
4. the preparation method of amberplex as described in claim 1, which is characterized in that modified solution is in the step 1)
Metabisulfite solution, mass percent are 4~6%.
5. the preparation method of amberplex as described in claim 1, which is characterized in that modified solution is in the step 1)
Potassium sulfate solution, mass percent 3%.
6. the preparation method of amberplex as described in claim 1, which is characterized in that modified solution is in the step 1)
The mixed solution of sodium sulphate and potassium sulfate, the mass percent of sodium sulphate are 3%, and the mass percent of potassium sulfate is 2%.
7. the preparation method of amberplex as claimed in claim 4, which is characterized in that the quality hundred of the metabisulfite solution
Score is 5%.
8. the preparation method of the amberplex as described in any one of claim 4-7, which is characterized in that the step
2) infiltrating time in is 60~90 minutes.
9. the preparation method of the amberplex as described in any one of claim 4-7, which is characterized in that the step
3) for the drying temperature control at 80~100 DEG C, drying time is 60~90 minutes；Further, the drying temperature control
At 80 or 100 DEG C, the drying time is 60 or 90 minutes.
10. the preparation method of amberplex as claimed in claim 8, which is characterized in that the infiltrating time is 60 or 90
Minute.
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|---|---|---|---|
| CN201710672219.XA CN109390601B (en) | 2017-08-08 | 2017-08-08 | Preparation method of ion exchange membrane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710672219.XA CN109390601B (en) | 2017-08-08 | 2017-08-08 | Preparation method of ion exchange membrane |
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| CN109390601A true CN109390601A (en) | 2019-02-26 |
| CN109390601B CN109390601B (en) | 2021-11-26 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111162300A (en) * | 2019-12-04 | 2020-05-15 | 大连融科储能技术发展有限公司 | Cation exchange membrane with high ion exchange capacity and preparation method and application thereof |
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| CN102005554A (en) * | 2009-09-01 | 2011-04-06 | 比亚迪股份有限公司 | Diaphragm for full-vanadium ionic liquid flow battery, preparation method and battery comprising diaphragm |
| CN102956910A (en) * | 2012-12-07 | 2013-03-06 | 中国海洋大学 | Hydrogel-based medium-high temperature PEM (Proton Exchange Membrane), preparation method thereof and application of hydrogel-based medium-high temperature PEM |
| CN102969473A (en) * | 2012-12-04 | 2013-03-13 | 宁德时代新能源科技有限公司 | Organic/inorganic composite porous thin film and electrochemical energy storing device using same |
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2017
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Patent Citations (3)
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| CN102005554A (en) * | 2009-09-01 | 2011-04-06 | 比亚迪股份有限公司 | Diaphragm for full-vanadium ionic liquid flow battery, preparation method and battery comprising diaphragm |
| CN102969473A (en) * | 2012-12-04 | 2013-03-13 | 宁德时代新能源科技有限公司 | Organic/inorganic composite porous thin film and electrochemical energy storing device using same |
| CN102956910A (en) * | 2012-12-07 | 2013-03-06 | 中国海洋大学 | Hydrogel-based medium-high temperature PEM (Proton Exchange Membrane), preparation method thereof and application of hydrogel-based medium-high temperature PEM |
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| CN111162300A (en) * | 2019-12-04 | 2020-05-15 | 大连融科储能技术发展有限公司 | Cation exchange membrane with high ion exchange capacity and preparation method and application thereof |
| CN111162300B (en) * | 2019-12-04 | 2021-05-14 | 大连融科储能技术发展有限公司 | Cation exchange membrane with high ion exchange capacity and preparation method and application thereof |
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| CN109390601B (en) | 2021-11-26 |
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