CN110120532B - Preparation method of composite membrane - Google Patents
Preparation method of composite membrane Download PDFInfo
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- CN110120532B CN110120532B CN201810115398.1A CN201810115398A CN110120532B CN 110120532 B CN110120532 B CN 110120532B CN 201810115398 A CN201810115398 A CN 201810115398A CN 110120532 B CN110120532 B CN 110120532B
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- 239000012528 membrane Substances 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 31
- 238000005342 ion exchange Methods 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 238000005096 rolling process Methods 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- 150000003460 sulfonic acids Chemical class 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000004693 Polybenzimidazole Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 229920002480 polybenzimidazole Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910001456 vanadium ion Inorganic materials 0.000 abstract description 6
- 230000003247 decreasing effect Effects 0.000 abstract description 4
- 230000008961 swelling Effects 0.000 abstract description 3
- 230000010220 ion permeability Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
Images
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
- H01M8/023—Porous and characterised by the material
- H01M8/0239—Organic resins; Organic polymers
-
- 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 invention relates to a preparation method of a composite membrane, belonging to the field of ionic membrane preparation. Taking perfluorosulfonic acid resin with good chemical stability as a main body of a membrane material, mixing polymers with different functions, dissolving the resin by an organic solvent to obtain slurry, adding an additive, and uniformly mixing to obtain a gel material; putting the gel material into an extruder for extrusion molding, putting the molded membrane into different temperature section environments, sequentially decreasing the temperature sections from high to low, putting the membrane subjected to gradient heat treatment into an extracting agent for extraction, taking out the membrane, washing the membrane by deionized water, and rolling by hot rollers to obtain the porous ion exchange composite membrane. The continuous preparation process of the composite membrane is simple, the prepared membrane has low swelling, good dimensional stability, high mechanical strength, low vanadium ion permeability, good chemical and thermal stability, is suitable for all-vanadium redox flow batteries, is simple to operate, and has low requirements on equipment and operators.
Description
Technical Field
The invention relates to the field of porous composite ionic membranes for all-vanadium redox flow batteries (VRBs), in particular to a preparation method of a porous composite ionic membrane for all-vanadium redox flow batteries.
Background
The development of new energy sources such as wind energy, solar energy and the like is an important way for solving the problem of energy resource shortage and represents the future development direction of energy sources. However, due to time and region dependence, off-grid wind energy and solar energy power generation must use an energy storage system, otherwise, all-weather utilization is difficult. And the direct grid connection also needs to adopt an energy storage system to carry out peak load regulation and frequency modulation on the power grid, otherwise, the direct grid connection brings great impact on the power and the frequency of the power grid. Therefore, efficient, large-scale energy storage technology becomes the key core for its development and application.
The Vanadium battery (Vanadium redox flow battery/Vanadium redox flow battery) is based on VO2+/VO2 +And V2+/V3+The flow energy storage battery technology of the electric pair is characterized in that energy is stored in electrolyte. Compared with the traditional storage battery, the vanadium battery can be charged and discharged rapidly with large current, has low self-discharge rate, realizes large-capacity storage of energy, is an ideal energy storage form meeting the requirements of a smart grid and wind energy and solar power generation on large-scale energy storage, and provides conditions for developing the energy storage technology of the vanadium battery due to the rich vanadium resource advantages in China.
The all vanadium redox flow battery is H with V (II)/V (III) and V (IV)/V (V) redox couples2SO4The solution is respectively made into positive and negative half electricityThe cell electrolyte. H2SO4Is ionized into H+And SO4 2-Then H in the electrolyte+Sustained replacement of H in ion exchange membranes+And then enters into another electrolyte to complete the conducting process. VO in the battery positive electrolyte when discharging2 +The ions are reduced to VO2+Ion, V in negative electrode electrolyte2+The ions are oxidized to V3+Ions. When charging, the process is reversed.
The vanadium battery is developed to the present day, and reaches a more advanced level, but still has many key problems to be solved urgently, wherein the key material diaphragm is one of the two, the diaphragm in the vanadium battery has the functions of isolating positive and negative electrode electrolyte solutions and preventing the vanadium ions with different valence states from mutually permeating, the cross contamination of the positive and negative electrode electrolyte solutions is prevented, the ion selectivity is improved, protons can freely pass through, and the vanadium with different valence states has high selectivity. Until now, the diaphragm used by the all-vanadium redox flow battery is mainly a Nafion membrane produced by DuPont in America, the membrane forming process is a membrane extrusion method, and DuPont monopolizes many years in the field of the world perfluorinated ion membrane. The diaphragm is mainly prepared by a solution casting method at home, and a solution casting method is disclosed in the patent of Chinese patent application (publication number CN101316880A), but the solution casting method has the disadvantages of large solvent consumption, low production efficiency and serious environmental pollution. Although the Nafion membrane has good chemical stability and high proton conductivity, the membrane has the defects of high vanadium ion transmittance, poor dimensional stability and high price, so that the large-scale application of the Nafion membrane is limited to a certain extent. Therefore, the development of a high-production-efficiency, high-performance separator plays an important role in the commercial application of vanadium batteries.
Disclosure of Invention
The invention aims to provide a preparation method of a porous composite ionic membrane for an all-vanadium redox flow battery, which solves the problems of high vanadium ion transmittance of the currently used perfluorinated sulfonic acid proton exchange membrane, low production efficiency of a domestic diaphragm preparation process and the like.
The technical scheme of the invention is as follows:
a preparation method of a composite membrane comprises the steps of gel slurry preparation, extrusion, heat treatment, extraction and rolling, wherein perfluorosulfonic acid resin with good chemical stability is used as a membrane material main body, one or more than two polymers with different functions are mixed, the resin is dissolved by an organic solvent to obtain slurry, an additive is added, and the mixture is uniformly mixed to form a gel material; putting the gel material into an extruder for extrusion molding, putting the molded membrane into different temperature section environments, sequentially decreasing the temperature sections from high to low, putting the membrane subjected to gradient heat treatment into an extracting agent for extraction, taking out the membrane, washing the membrane by deionized water, and rolling by hot rollers to obtain the porous ion exchange composite membrane.
According to the preparation method of the composite membrane, polymers with different functions are polyvinylidene fluoride resin, polybenzimidazole resin, polysulfone resin and polyether sulfone resin, and the mass ratio of the polymer to the perfluorinated sulfonic acid resin is 1: 10 to 100.
According to the preparation method of the composite membrane, the additive is dibutyl phthalate DBP, polyvinyl alcohol PVA or polyvinyl pyrrolidone PVP, and the mass ratio of the additive to the perfluorinated sulfonic acid resin is 1: 30-200.
According to the preparation method of the composite film, the melt flow rate of the polymer is 2-35 g/min, and the polymer is dried for 24 hours at 70-130 ℃ before melting.
According to the preparation method of the composite membrane, the heat treatment drying tunnel adopts a mode of up-and-down electric heating or far infrared heating of a drying oven tunnel, and different temperature sections are between 60 ℃ and 200 ℃.
According to the preparation method of the composite membrane, the organic solvent is xylene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone, and the mass ratio of the organic solvent to the perfluorinated sulfonic acid resin is 1: 5 to 20.
In the preparation method of the composite membrane, the extracting agent is one or more than two mixed reagents of ethanol, methanol or deionized water.
According to the preparation method of the composite membrane, the average pore diameter of the non-fluorine porous ion exchange composite membrane is 5-200 nm, and the porosity of the porous ion exchange composite membrane is 30-80%.
According to the preparation method of the composite membrane, the total thickness of the porous ion exchange composite membrane is 50-200 microns, and preferably 70-180 microns.
The preparation method of the composite membrane comprises the steps of rolling the membrane washed by deionized water by a hot roller, rolling by a rolling machine and cutting into the required size.
The invention has the following advantages and beneficial effects:
1. the invention takes perfluorosulfonic acid resin with good chemical stability as a membrane material main body, mixes one or more than two polymers with different functions and additives, carries out gel extrusion molding to form an ion exchange membrane base membrane, enters the extruded ion exchange membrane into different temperature sections for heat treatment, then enters the membrane into an extracting agent for extraction, enters deionized water for washing the extracted membrane, and carries out hot-pressing and rolling on the washed membrane to obtain the porous ion exchange composite membrane. The composite membrane prepared by the method has the advantages of simple process, high production efficiency, continuous production and low price, and can be suitable for all-vanadium redox flow batteries (VRB).
2. The invention selects the perfluorosulfonic acid resin with good chemical stability as the main body of the membrane material, thereby ensuring the chemical stability of the membrane; other polymers are blended, so that the swelling of the membrane is reduced, and the vanadium ion permeation is reduced; in order to secure the conductivity of the film, the film is prepared as a porous film. Therefore, the composite membrane has good conductivity and good vanadium resistance, has the advantages of good ion selective permeability, good conductivity, mechanical property, chemical stability, greatly reduced cost and the like, and can be widely applied to the field of all-vanadium redox flow batteries.
Drawings
FIG. 1 is a process flow for preparing a composite membrane.
Detailed Description
In the specific implementation process, as shown in fig. 1, the process flow of the preparation method of the composite membrane of the invention is as follows, the preparation of slurry → extrusion molding → gradient heat treatment → extraction → hot roller rolling → porous composite ionic membrane, the process takes perfluorosulfonic acid resin with good chemical stability as the main body of the membrane material, one or more than two polymers with different functions are mixed, the resin is dissolved by organic solvent to obtain slurry, and the additive is added and mixed uniformly. Putting the gel material into an extruder for extrusion molding, putting the molded membrane into a plurality of temperature section environments, sequentially decreasing the temperature sections from high to low, putting the membrane subjected to gradient heat treatment into extract liquid for extraction, extracting the additive to form holes, finally washing the extracted membrane in deionized water, and rolling by using a hot roller to form the membrane to obtain the composite membrane. The continuous preparation process of the composite membrane is simple, the prepared membrane has low swelling, good dimensional stability, high mechanical strength, low vanadium ion permeability, good chemical and thermal stability, is suitable for all-vanadium redox flow batteries (VRB), is simple to operate, and has low requirements on equipment and operators.
The technical means of the present invention will be described in more detail below with reference to examples.
Example 1
Dissolving 10kg of perfluorosulfonic acid resin and 0.3kg of polyvinylidene fluoride (PVDF) resin in 100L of Dimethylacetamide (DMAC), wherein the melt flow rate of the polyvinylidene fluoride resin is 10-20 g/min, and drying the polyvinylidene fluoride resin for 24 hours at 90-110 ℃ before melting. Heating and stirring at 200 ℃ for dissolving for 5-8 hours to form gel, adding 200mL of dibutyl phthalate serving as an additive into the mixed solution, stirring for 1-3 hours, vibrating in an ultrasonic oscillator for 1-2 hours to thin the solution and expel micro bubbles in the solution, putting the gel material into an extruder, extruding and molding at 170-250 ℃ through a grinding tool, putting the film into three temperature sections of 180-200 ℃, 100-140 ℃ and 60-80 ℃, performing gradient heat treatment (the gradient heat treatment is used for regulating and controlling the volatilization speed of the solvent and the leaching speed of the extractant) which are gradually decreased from high to low, putting the film into the mixed solution of the extractant ethanol and deionized water for extraction after the heat treatment, taking out the film, washing the film with deionized water, putting the ion exchange film into a drying tunnel for drying at 70-90 ℃, and rolling the dried film under the heat pressure to obtain the porous composite film.
The relevant performance data for this example is as follows:
the thickness of the porous ion exchange composite membrane prepared by the embodiment is 100 micrometers, the average pore diameter of micropores is 80 nm-120 nm, the porosity is 55%, the coulombic efficiency of the battery is 95%, the voltage efficiency is 80%, and the energy efficiency is 76%.
Example 2
Dissolving 10kg of perfluorosulfonic acid resin and 0.3kg of polybenzimidazole resin in 100L of dimethyl sulfoxide, wherein the melt flow rate of the polybenzimidazole resin is 5-15 g/min, and the polybenzimidazole resin is dried for 24 hours at 80-100 ℃ before being melted. Heating and stirring at 200 ℃ for dissolving for 5-8 hours to form gel, adding 400mL of additive polyvinyl alcohol into the mixed solution, stirring for 1-3 hours, vibrating in an ultrasonic oscillator for 1-2 hours to refine the solution and expel micro bubbles in the solution, putting the gel material into an extruder, extruding and molding at 170-250 ℃ through a grinding tool, performing gradient heat treatment on the film at 180-200 ℃, 100-140 ℃ and 60-80 ℃ in a descending order, extracting the heat-treated film in a mixed solution of an extracting agent ethanol and deionized water, taking out the film, washing the ion exchange film in deionized water, drying the ion exchange film at 70-90 ℃ in a drying tunnel, and rolling the dried film under hot pressure to obtain the porous composite film.
The relevant performance data for this example are as follows:
the thickness of the porous ion exchange composite membrane prepared by the embodiment is 80 microns, the average pore diameter of micropores is 30 nm-50 nm, the porosity is 42%, the coulombic efficiency of the battery is 86%, the voltage efficiency is 84%, and the energy efficiency is 72%.
Example 3
Dissolving 10kg of perfluorinated sulfonic acid resin and 0.3kg of polysulfone resin in 100L of N-methyl pyrrolidone, wherein the melt flow rate of the polysulfone resin and the polyether sulfone resin is 20-30 g/min, and the polysulfone resin and the polyether sulfone resin are dried for 24 hours at 100-120 ℃ before melting. Heating and stirring at 200 ℃ for dissolving for 5-8 hours to form gel, adding 100mL of polyvinylpyrrolidone serving as an additive into the mixed solution, stirring for 1-3 hours, vibrating in an ultrasonic oscillator for 1-2 hours to refine the solution and expel micro bubbles in the solution, putting the gel material into an extruder, extruding and molding at 170-250 ℃ through a grinding tool, performing gradient heat treatment on the film at 180-200 ℃, 100-140 ℃ and 60-80 ℃ in a descending order, introducing the heat-treated film into the mixed solution of ethanol serving as an extracting agent and deionized water for extraction, taking out the film, washing the film with deionized water, introducing the ion exchange film into a drying tunnel, drying at 70-90 ℃, and rolling the dried film under hot pressure to obtain the porous composite film.
The relevant performance data for this example is as follows:
the thickness of the porous ion exchange composite membrane prepared by the embodiment is 120 microns, the average pore diameter of micropores is 130 nm-150 nm, the porosity is 68%, the coulombic efficiency of the battery is 97%, the voltage efficiency is 75%, and the energy efficiency is 72%.
The experimental result shows that the adjustment of the proportion of the resin and the additive has certain influence on the efficiency of the battery. With the increase of the amount of the additive, the porosity of the porous ion exchange composite membrane is increased, the pore diameter is increased, and the vanadium resistance of the porous ion exchange composite membrane is reduced, but the hydrogen ion conductivity is improved. The conductivity of the porous ion exchange composite membrane prepared by the invention meets the use requirement of the vanadium battery, has the advantages of good vanadium resistance, chemical stability, low price and the like, can be continuously produced, and is widely applied to the field of all-vanadium redox flow batteries.
Claims (7)
1. A preparation method of a porous ion exchange composite membrane for an all-vanadium redox flow battery is characterized by comprising the steps of gel slurry preparation, extrusion, heat treatment, extraction and rolling, wherein perfluorosulfonic acid resin with good chemical stability is used as a membrane material main body, one or more than two polymers with different functions are mixed, the resin is dissolved by an organic solvent to obtain slurry, an additive is added, and the mixture is uniformly mixed to form a gelatinous material; putting the gelatinous material into an extruder for extrusion molding, performing gradient heat treatment on the molded membrane in three temperature sections of 180-200 ℃, 100-140 ℃ and 60-80 ℃ in a descending order, extracting the membrane subjected to the gradient heat treatment in an extracting agent, taking out the membrane, washing the membrane in deionized water, and rolling by hot rollers to obtain a porous ion exchange composite membrane;
the polymer with different functions is polyvinylidene fluoride resin, polybenzimidazole resin, polysulfone resin and polyether sulfone resin, and the mass ratio of the polymer to the perfluorinated sulfonic acid resin is 1: 10 to 100 parts;
the additive is dibutyl phthalate DBP, polyvinyl alcohol PVA or polyvinyl pyrrolidone PVP, and the mass ratio of the additive to the perfluorinated sulfonic acid resin is 1: 30-200 parts of;
the organic solvent is xylene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone, and the mass ratio of the organic solvent to the perfluorinated sulfonic acid resin is 1: 5 to 20.
2. The method for preparing a porous ion exchange composite membrane for an all-vanadium redox flow battery according to claim 1, wherein the heat treatment drying tunnel adopts an oven tunnel up-down electric heating or far infrared heating mode.
3. The method for preparing the porous ion exchange composite membrane for the all-vanadium redox flow battery according to claim 1, wherein the extraction agent is one or a mixture of two or more of ethanol, methanol and deionized water.
4. The method for preparing a porous ion exchange composite membrane for an all-vanadium redox flow battery according to claim 1, wherein the average pore diameter of the porous ion exchange composite membrane is 5nm to 200nm, and the porosity of the porous ion exchange composite membrane is 30 to 80%.
5. The method for preparing a porous ion exchange composite membrane for an all-vanadium redox flow battery according to claim 1, wherein the total thickness of the porous ion exchange composite membrane is 50 to 200 μm.
6. The method for preparing a porous ion exchange composite membrane for an all-vanadium redox flow battery according to claim 1, wherein the total thickness of the porous ion exchange composite membrane is 70 to 180 μm.
7. The method for preparing a porous ion exchange composite membrane for an all-vanadium redox flow battery according to claim 1, wherein the membrane washed with deionized water is rolled by a hot roll, wound by a winder, and cut into a desired size.
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| CN1990527A (en) * | 2005-12-26 | 2007-07-04 | 北京化工大学 | Method for preparing perfluorinated sulfonic acid ionic membrane by gel extruding and flow-flattening film |
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| CN102881853A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院金属研究所 | Blending membrane for all-vanadium redox flow battery and preparation method for blending membrane |
| CN103087338A (en) * | 2013-01-18 | 2013-05-08 | 淮安科润膜材料有限公司 | Device and method for manufacturing composite perfluorinated ion exchange membrane for vanadium battery |
| KR20160064429A (en) * | 2014-11-28 | 2016-06-08 | 상명대학교 천안산학협력단 | Composite membranes for redox flow battery electrolyte and their fabrication method |
| CN104494157A (en) * | 2014-12-01 | 2015-04-08 | 深圳市星源材质科技股份有限公司 | Melt-spinning and cold-stretching preparation method of polyolefin microporous membrane and lithium battery membrane |
| CN110120540A (en) * | 2018-02-05 | 2019-08-13 | 中国科学院金属研究所 | A kind of continuous preparation method of porous composite ionic membrane |
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