CN109390601B - Preparation method of ion exchange membrane - Google Patents
Preparation method of ion exchange membrane Download PDFInfo
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- CN109390601B CN109390601B CN201710672219.XA CN201710672219A CN109390601B CN 109390601 B CN109390601 B CN 109390601B CN 201710672219 A CN201710672219 A CN 201710672219A CN 109390601 B CN109390601 B CN 109390601B
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- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 16
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 16
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 13
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 53
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 8
- 229920002530 polyetherether ketone Polymers 0.000 claims description 8
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 10
- 238000005266 casting Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fuel Cell (AREA)
Abstract
本发明涉及一种离子交换膜的制备方法，具体包括1.成膜溶液制备；2.隔膜成型；3.改性处理；步骤3包括：1).配制改性溶液：改性溶液为硫酸钠溶液、硫酸钾溶液或者两者的混合；2)将步骤2成型的隔膜浸润在改性溶液中，浸润时间为30～90分钟；3).将浸润后的隔膜置于恒温干燥箱中进行干燥；4).将干燥后的隔膜取出冷却至室温，得到最终的离子交换膜。本发明所提供的离子交换膜的制备方法，制备工艺简单、容易实现，安全性好、成本低廉，适用于批量生产。利用该方法制得的离子交换膜其机械性能有很大改善，装配后电池的库仑效率和能量效率可提高约3％，电池性能稳定性好。The present invention relates to a method for preparing an ion exchange membrane, which specifically includes: 1. film-forming solution preparation; 2. diaphragm forming; 3. modification treatment; step 3 includes: 1). Preparation of modified solution: the modified solution is sodium sulfate solution, potassium sulfate solution or a mixture of the two; 2) infiltrate the diaphragm formed in step 2 in the modified solution, and the infiltration time is 30 to 90 minutes; 3). Place the infiltrated diaphragm in a constant temperature drying oven for drying 4). The dried membrane is taken out and cooled to room temperature to obtain the final ion exchange membrane. The preparation method of the ion exchange membrane provided by the invention has the advantages of simple preparation process, easy realization, good safety and low cost, and is suitable for mass production. The mechanical properties of the ion exchange membrane prepared by the method are greatly improved, the coulombic efficiency and the energy efficiency of the assembled battery can be increased by about 3%, and the battery performance is stable.
Description
Technical Field
The invention relates to a preparation method of an ion exchange membrane, belonging to the field of high polymer materials.
Background
Electric energy is difficult to store and indispensable, and the production of the electric energy at any time meets the power utilization requirement, so people always find an economical and feasible energy storage technology to solve the contradiction between supply and demand and unhook the production and the demand of the electric energy. In addition, the electric energy storage has important effects on the aspects of electric energy management, power grid auxiliary service, voltage control, renewable energy utilization, large uninterrupted power supply and the like, and if the electric energy storage is combined with large thermal power generation, the peak capacity of a power station can be reduced, the power generation cost can be reduced, and the pollution can be reduced. If the device is combined with renewable energy sources such as wind power, tidal power and the like for power generation, continuous and stable supply of electric energy can be realized, and the requirements of users are met. Since the flow battery has the characteristics of power and capacity separation, is easy to design and convenient to operate, and is gradually one of the most promising large and medium-scale power storage options. Among them, flow batteries are preferred.
At present, the flow battery galvanic pile mostly adopts a filter press structure and mainly comprises a bipolar plate, a positive electrode, a negative electrode, an electrode frame, an ion exchange membrane (also called a diaphragm), an end plate, a sealing material and a fastening piece. Wherein, an electrode frame is arranged between the two bipolar plates, the electrode frame is of a hollow structure, positive and negative electrodes are respectively arranged in the electrode frame, and a diaphragm is arranged between the positive and negative electrodes. The positive electrolyte and the negative electrolyte used in the flow battery are respectively stored in a positive electrolyte storage tank and a negative electrolyte storage tank.
The ion exchange membrane is very important for the flow battery, is one of the most important components of a flow battery system, and is the key for determining the performance of the whole flow battery. The device separates the positive electrolyte from the negative electrolyte, and allows charge carriers to freely pass through so as to ensure the charge balance of the positive electrolyte and the negative electrolyte. The existing ion exchange membrane still has the defects of low stability, high swelling degree, high production cost, complex process, poor mechanical property and the like.
The current methods are as follows: by utilizing the treatment solution or the electrolyte, the ion exchange membrane is subjected to pretreatment before being assembled in the galvanic pile so as to ensure that the volume of the ion exchange membrane is not changed after the ion exchange membrane is assembled and the electrolyte is introduced, and prevent the sealing property of the galvanic pile from being damaged due to the form change of the ion exchange membrane. The following problems still remain: the treatment time of the ion exchange membrane is long, the toxicity of the treatment solution is strong, the safety is poor, the price of the treatment solution is high, and the cost is increased; the battery performance of the ion exchange membrane after assembly treatment is low, and the development of the flow battery is severely restricted.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of an ion exchange membrane, the mechanical property of the ion exchange membrane prepared by the method is greatly improved, the coulomb efficiency and the energy efficiency of a battery after assembly can be improved by about 3%, and meanwhile, the production cost of the membrane can be greatly reduced.
A preparation method of an ion exchange membrane specifically comprises the following steps:
step 1: preparing a film forming solution;
step 2: forming a diaphragm;
and step 3: modification treatment:
1) preparing a modified solution: the modified solution is a sodium sulfate solution, a potassium sulfate solution or a mixture of the sodium sulfate solution and the potassium sulfate solution, wherein the mass percent of the sodium sulfate is 1-8%, and the mass percent of the potassium sulfate is 1-5%;
2) soaking the diaphragm obtained in the step 2 in a modified solution for 30-90 minutes;
3) drying the soaked diaphragm in a constant-temperature drying box, wherein the drying temperature is controlled to be 80-120 ℃, and the drying time is 60-120 minutes;
4) and taking out the dried diaphragm and cooling to room temperature to obtain the final ion exchange membrane.
Further, the step 1 is as follows: preparing a film-forming solution by using N, N-dimethylformamide as a solvent and perfluorosulfonic acid resin or sulfonated polyether ether ketone as a solute, wherein the mass percent of the perfluorosulfonic acid resin is 1-20%, and the mass percent of the sulfonated polyether ether ketone is 1-20%; the mass percentage of the perfluorosulfonic acid resin is more preferably 10%; the mass percentage of the sulfonated polyether ether ketone is more preferably 12%.
Further, the separator described in step 2 is formed into: and (3) casting the solution obtained in the step (1) into a film by using a casting method.
Further, the modification solution in the step 1) is a sodium sulfate solution, and the mass percentage is 4-6%, and more preferably 5%.
Further, the modified solution in the step 1) is a potassium sulfate solution, and the mass percentage is 3%.
Further, the modified solution in the step 1) is a mixed solution of sodium sulfate and potassium sulfate, wherein the mass percent of the sodium sulfate is 3%, and the mass percent of the potassium sulfate is 2%.
Further, the soaking time in the step 2) is 60-90 minutes, and further preferably 60 or 90 minutes.
Further, the drying temperature in the step 3) is controlled to be 80-100 ℃, and further preferably 80 or 100 ℃; the drying time is 60-90 minutes; further preferably 60 or 90 minutes.
The first two steps of the preparation method of the ion exchange membrane can also be conventional film forming steps of other types of ion exchange membranes, such as sulfonated polyvinylidene fluoride ion exchange membranes, sulfonated polysulfone ion exchange membranes, sulfonated polyether sulfone ion exchange membranes, sulfonated polyphenylene ether ion exchange membranes, sulfonated polybenzimidazole ion exchange membranes, sulfonated polyimide ion exchange membranes and the like.
The casting method is a process of uniformly coating a polymer solution having a certain viscosity on a flat support material and then drying it to form a film. The advantages of the fluid court method are that (1) the process range is wide; (2) isotropy of film properties; (3) mass production of the film is easy to realize; (4) a plurality of substances can be compounded to prepare the composite material with specific functions. Thus, isotropic ion exchange membranes can be prepared in a wide range of processes using the fluidly coupled process.
The invention has the beneficial effects that: the preparation method of the ion exchange membrane provided by the invention has the advantages of simple preparation process, easiness in realization, good safety and low cost, and is suitable for batch production. The mechanical property of the ion exchange membrane prepared by the method is greatly improved, the coulomb efficiency and the energy efficiency of the assembled battery can be improved by about 3 percent, and the stability of the battery performance is good.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A method of preparing an ion exchange membrane comprising:
1. preparing a film forming solution: dissolving perfluorinated sulfonic acid resin in N, N-dimethylformamide, wherein the mass percent of the perfluorinated sulfonic acid resin is 10%;
2. forming a diaphragm: casting the perfluorinated sulfonic acid resin solution into a film by using a casting method, wherein the thickness of the film is 50 mu m;
3. modification treatment: the method comprises the following steps:
1) preparing a modified solution: preparing a sodium sulfate solution with the mass percent of 1%;
2) soaking the diaphragm in the modified solution for 60 minutes;
3) drying the soaked diaphragm in a constant-temperature drying box at 80 ℃ for 60 minutes;
4) and taking out the dried diaphragm and cooling to room temperature to obtain the final ion exchange membrane.
Comparative example 1
A method of preparing an ion exchange membrane comprising:
1. preparing a film forming solution: dissolving perfluorinated sulfonic acid resin in N, N-dimethylformamide, wherein the mass percent of the resin is 10%;
2. forming a diaphragm: the perfluorosulfonic acid resin solution was cast into a film having a thickness of 50 μm by a casting method.
Comparative example 2
A method of preparing an ion exchange membrane comprising:
1. preparing a film forming solution: dissolving sulfonated polyether ether ketone resin in N, N-dimethylformamide, wherein the mass percent of the resin is 12%;
2. forming a diaphragm: the sulfonated polyether ether ketone resin solution is cast into a film by a casting method, and the film thickness is 50 mu m.
Examples 2 to 48, the preparation process was carried out in the same manner as in example 1 except that the following preparation parameters were different.
See the following table for details:
as can be seen from the table, the coulomb efficiency and the energy efficiency of the assembled battery of the ion exchange membrane prepared by the method are improved by about 3 percent.
Claims (10)
1. A preparation method of an ion exchange membrane, which is used for a flow battery, comprises the following steps:
step 1: preparing a film forming solution;
step 2: forming a diaphragm;
it is characterized in that the method also comprises the following steps: modification treatment:
1) preparing a modified solution: the modified solution is a sodium sulfate solution, a potassium sulfate solution or a mixture of the sodium sulfate solution and the potassium sulfate solution, wherein the mass fraction of the sodium sulfate solution is 1-8%, and the mass fraction of the potassium sulfate solution is 1-5%;
2) soaking the diaphragm obtained in the step 2 in a modified solution for 30-90 minutes;
3) drying the soaked diaphragm in a constant-temperature drying box, wherein the drying temperature is controlled to be 80-120 ℃; the drying time is 60-120 minutes;
4) and taking out the dried diaphragm and cooling to room temperature to obtain the final ion exchange membrane.
2. The method for preparing an ion exchange membrane according to claim 1, wherein the step 1 is: the method comprises the steps of preparing a film forming solution by using N, N-dimethylformamide as a solvent and perfluorosulfonic acid resin or sulfonated polyether ether ketone as a solute, wherein the mass fraction of the film forming solution formed by the perfluorosulfonic acid resin is 1-20%, and the mass fraction of the film forming solution formed by the sulfonated polyether ether ketone is 1-20%.
3. The method for preparing an ion exchange membrane according to claim 2, wherein the mass fraction of the membrane solution formed by the perfluorosulfonic acid resin in the step 1 is 10%; the mass fraction of the membrane solution formed by the sulfonated polyether ether ketone is 12 percent.
4. The preparation method of the ion exchange membrane according to claim 1, wherein the modification solution in the step 1) is a sodium sulfate solution, and the mass fraction of the sodium sulfate solution is 4-6%.
5. The method for preparing the ion exchange membrane according to claim 1, wherein the modified solution in the step 1) is potassium sulfate solution, and the mass fraction of the modified solution is 3%.
6. The method for preparing an ion exchange membrane according to claim 1, wherein the modified solution in the step 1) is a mixed solution of sodium sulfate and potassium sulfate, the mass fraction of the sodium sulfate solution is 3%, and the mass fraction of the potassium sulfate solution is 2%.
7. The method for preparing an ion-exchange membrane according to claim 4, wherein the mass fraction of the sodium sulfate solution is 5%.
8. The method for preparing an ion exchange membrane according to any one of claims 4 to 7, wherein the soaking time in the step 2) is 60 to 90 minutes.
9. The method for preparing an ion-exchange membrane according to any one of claims 4 to 7, wherein the drying temperature in the step 3) is controlled to be 80 to 100 ℃ and the drying time is 60 to 90 minutes.
10. The method of preparing an ion exchange membrane according to claim 8, wherein the soaking time is 60 or 90 minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
|---|---|---|---|
| CN201710672219.XA CN109390601B (en) | 2017-08-08 | 2017-08-08 | Preparation method of ion exchange membrane |
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| CN109390601A CN109390601A (en) | 2019-02-26 |
| CN109390601B true CN109390601B (en) | 2021-11-26 |
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| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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- 2017-08-08 CN CN201710672219.XA patent/CN109390601B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 金属离子对质子交换膜燃料电池性能的影响;王磊磊等;《电源技术》;20070320;第31卷(第3期);第205-208页 * |
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