CN112151825A - Multilayer composite membrane for flow battery and preparation method thereof - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 239000002052 molecular layer Substances 0.000 claims abstract description 6
- 238000005191 phase separation Methods 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims description 18
- 239000004693 Polybenzimidazole Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 229920002480 polybenzimidazole Polymers 0.000 claims description 12
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
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- 239000002994 raw material Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 229920000831 ionic polymer Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 230000010220 ion permeability Effects 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
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
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- 230000035515 penetration Effects 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims description 2
- 230000002349 favourable effect Effects 0.000 claims description 2
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- 229920000642 polymer Polymers 0.000 claims description 2
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- 230000009466 transformation Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 abstract description 5
- 230000008020 evaporation Effects 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
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- 238000011161 development Methods 0.000 description 2
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- 239000002253 acid Substances 0.000 description 1
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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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
- H01M8/023—Porous and characterised by the material
- H01M8/0239—Organic resins; Organic polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0243—Composites in the form of mixtures
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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
- H01M8/18—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
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- B01D2325/00—Details relating to properties of membranes
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- B01D2325/025—Finger pores
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- B01D2325/026—Sponge structure
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Abstract
The invention relates to the technical field of redox flow batteries, in particular to a multilayer composite membrane for a flow battery and a preparation method thereof. The porous membrane prepared by the traditional non-solvent induced phase separation method (NIPS) is mostly composed of a thin dense layer and a finger-shaped microporous layer, and the ion selectivity is poor. The invention adjusts the technological parameters in the step of evaporating the solvent, specifically the evaporation time and temperature, by improving the NIPS method, and additionally introduces a layer of spongy nano-pore structure on the basis of the original asymmetric double-layer porous membrane to form a multilayer composite membrane with a nano-layer/micro-pore layer/compact layer structure. The multilayer composite membrane prepared by the invention has the advantages of strong ion selectivity, high proton conductivity, low cost, simple preparation method and the like, and is suitable for the field of redox flow batteries.
Description
Technical Field
The invention relates to the technical field of redox flow batteries, in particular to a multilayer composite membrane for a flow battery and a preparation method thereof.
Background
In order to solve the problems of instability and intermittence of renewable energy sources such as solar energy, wind energy and the like in the power generation grid connection process, the research and development of a safe, stable and efficient large-scale energy storage system are imperative. The Redox Flow Battery (RFB) is considered to be a large-scale energy storage technology with great application prospect due to the advantages of flexible design, high efficiency, long service life and the like. Among them, the Vanadium Redox Flow Battery (VRFB) based on the redox reaction between different valence Vanadium ions avoids the existence of cross contamination of electrolyte in the conventional flow battery, and has gained much attention.
The diaphragm is an important component of the flow battery and plays a role in separating the electrodes on two sides, preventing the mixing of positive and negative electrolytes and conducting the whole battery loop. This requires membranes that have both excellent ionic conductivity and selectivity, good stability, and low cost. Taking an all-vanadium flow battery as an example, the Nafion-series perfluorosulfonic acid membrane is most widely applied to the vanadium battery at present. The Nafion membrane has excellent proton conductivity and chemical stability, and shows higher energy efficiency and longer cycle life in battery performance. But the commercial development of the flow battery is severely limited due to high price and poor ion selectivity. Therefore, the development of high-performance low-cost battery separators is the key to the commercial application of flow batteries.
The all-vanadium redox flow battery developed at present replaces a diaphragm and is mainly divided into an ion exchange membrane and a porous nanofiltration membrane. The former relies on ion exchange groups on the membrane material to achieve selective conduction of ions, while the latter relies on differences in the pore sizes of the active species, charge carrier ions and porous membranes to achieve the purpose of ion separation and conduction. The latter is more promising since most ion exchange functional groups are unstable in strong acid, strongly oxidizing environments. The conventional method for preparing porous membranes in industry is a phase inversion method, which mainly uses a non-solvent induced phase separation method (NIPS), and the prepared porous membranes are mostly composed of a relatively thin dense layer and a finger-shaped microporous layer. Although the membrane has higher proton conductivity, the ion selectivity is lower, and better battery performance is difficult to achieve. How to give consideration to vanadium ion selectivity and proton conductivity, further improve the performance of the battery, reduce the cost, and have important significance for the commercialization of the vanadium flow battery.
Disclosure of Invention
The invention aims to provide a multilayer composite membrane for a flow battery and a preparation method thereof, wherein the multilayer composite membrane ensures higher proton conductivity, further improves ion selectivity, and simultaneously ensures that the preparation process is simple and easy to control and the preparation cost is low.
The technical scheme of the invention is as follows:
a multilayer composite membrane for a flow battery has a composite structure of a nano layer/a microporous layer/a compact layer, and specifically comprises a spongy nanopore layer, a finger-shaped microporous layer and an ultrathin compact layer from bottom to top in sequence; among them, the nano-layer and the dense layer provide higher ion selectivity, and the microporous layer provides higher ion conductivity.
The multilayer composite membrane for the flow battery has the advantages that the aperture of the spongy nanopore layer is 1-100 nm, and the thickness of the spongy nanopore layer is 1-500 mu m; the transverse aperture of the finger-shaped microporous layer is 2-10 mu m, and the thickness of the finger-shaped microporous layer is 1-500 mu m; the thickness of the ultrathin and compact layer is 0.1-10 mu m.
The multi-layer composite membrane for the flow battery is characterized in that the hole walls of the finger-shaped micro-hole layers are mutually communicated, so that a continuous channel is provided for the transmission of protons, and the surface resistance is 0.05-0.15 omega-cm2(ii) a The sponge-like nanopore layer has low pore wall connectivity, is favorable for blocking the penetration of vanadium ions, and has the following technical indexes of ion selectivity: the vanadium ion permeability is (1-10) x 10-6cm2h-1。
The multilayer composite membrane for the flow battery is prepared from one or more than two of ionic polymers or nonionic polymers as raw materials, wherein: the ionic polymer is Polybenzimidazole (PBI), sulfonated polyether ether ketone (SPEEK), Sulfonated Polyimide (SPI) and polyether sulfone (PES), and the non-ionic polymer is polyvinylidene fluoride (PVDF) and Polyacrylonitrile (PAN).
The preparation method of the multilayer composite membrane for the flow battery specifically comprises the following steps:
(1) dissolving raw materials of the multilayer composite film in an organic solvent, heating and dissolving at the temperature of 20-100 ℃, and preparing a casting solution with the mass percentage of 2-30 wt%;
(2) standing the casting solution obtained in the step (1) for defoaming, and carrying out ultrasonic treatment for 5-15 min before use;
(3) adopting a non-solvent induced phase separation method, casting the solution obtained in the step (2) on a flat and smooth glass plate, scraping out a certain thickness by using a scraper, placing the glass plate on a heating plate to volatilize the solvent, and then placing the whole body in a poor solvent of the film raw material resin for phase transformation to prepare a multilayer composite film;
(4) and (4) soaking and washing the multilayer composite membrane obtained in the step (3) in deionized water for at least 2 times, and storing in water for later use.
In the preparation method of the multilayer composite membrane for the flow battery, in the step (1), the used organic solvent is one or more than two of N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide and dichloromethane.
In the preparation method of the multilayer composite membrane for the flow battery, in the step (3), the poor solvent is water.
According to the preparation method of the multilayer composite membrane for the flow battery, in the step (3), the height of the scraper is controlled to be 50-500 mu m.
In the preparation method of the multilayer composite membrane for the flow battery, in the step (3), the solvent volatilization time is 1-30 min, and the heating plate temperature is 20-100 ℃.
The design idea of the invention is as follows:
the preparation of porous films is an effective means to reduce the resistance of the film. Conventional non-solvent induced phase separation (NIPS) methods are often applied to the preparation of porous films. The porous membrane prepared by the method mostly consists of a thin compact layer and a finger-shaped microporous layer, and has low resistance but poor ion selectivity. The invention adjusts the technological parameters in the step of evaporating the solvent, specifically the evaporation time and temperature, by improving the NIPS method, and additionally introduces a layer of spongy nano-pore structure on the basis of the original asymmetric double-layer porous membrane to integrally form the multilayer composite membrane with the nano-layer/micro-pore layer/compact layer structure. On the premise of not increasing the membrane resistance as much as possible, the ion selectivity of the membrane is greatly improved, so that the membrane with excellent battery performance is obtained.
The invention has the following advantages and beneficial effects:
1. according to the invention, through improving the process steps of the traditional NIPS method, after the casting solution is paved on a glass plate, the whole body is placed on a heating plate to evaporate the solvent, and a layer of spongy nanopore structure is additionally introduced on the basis of the original asymmetric double-layer porous membrane, so that the ion selectivity of the porous membrane is effectively improved, and the battery performance is further improved.
2. The invention adjusts the thickness of the finger-shaped microporous layer and the spongy nanoporous layer by adjusting the evaporation time and temperature, thereby regulating the ion selectivity and proton conductivity of the porous membrane. The preparation method is simple and flexible, can freely regulate and control the performance of the membrane according to requirements, and is suitable for industrial large-scale production.
3. The preparation method adopted by the invention only needs to use the membrane raw material resin, water and a cleaning solvent, does not need expensive instruments and various additives, and has the advantages of environment-friendly preparation process and low preparation cost.
4. The multilayer composite film prepared by the invention has wide selection of film raw materials, and can be ionic resin or nonionic resin.
Drawings
FIG. 1 is a schematic diagram of the preparation of a multilayer composite film according to example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the surface (a) and cross-section (b) of the multilayer composite film prepared in example 1.
Fig. 3 is a graph (a) comparing the sheet resistance and vanadium ion permeability of the multi-layer composite membrane prepared in example 1 with that of a control Nafion212 membrane (b). (b) In the figure, the abscissa Time represents Time (h) and the ordinate VO represents Time (h)2+concentration represents the concentration (mol L) of vanadium ions that have permeated-1)。
Fig. 4 is a graph comparing the performance of assembled cells of the two-layer membrane, multi-layer composite membrane prepared in example 1 and a control group Nafion 212.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The present invention will be described in further detail below by way of examples and figures.
Example 1:
as shown in fig. 1, the multilayer composite membrane for the flow battery is prepared by the following specific steps:
1. weighing 2g of Polybenzimidazole (PBI) into a glass bottle, adding 12ml of N, N-dimethylacetamide (DMAc), heating and stirring at 60 ℃ for dissolving for 12h, standing for 12h to obtain a 15 wt% PBI casting solution, and carrying out ultrasonic treatment for 10min before use.
2. And (2) adopting a non-solvent induced phase separation method, taking a clean glass plate, placing the glass plate on a flat experiment table, pouring 2ml of the casting solution obtained in the step (1) onto the glass plate, scraping the glass plate by using a scraper, setting the height of the scraper to be 200 mu m, immediately placing the glass plate on a heating plate, heating and drying the glass plate for 3min at the temperature of 60 ℃, and placing the whole body in deionized water for phase conversion after partial volatilization of the solvent to obtain the PBI multilayer composite membrane.
3. And (3) immersing the PBI multilayer composite membrane obtained in the step (2) in deionized water, repeatedly cleaning twice, thoroughly removing the solvent, and storing in water for later use.
The multilayer composite film of this example will be characterized structurally and in terms of properties as follows:
as shown in fig. 2(a), the surface SEM of the PBI multilayer composite membrane prepared in example 1 shows that the dense layer of the multilayer composite membrane exhibits a uniform and dense morphology. As shown in FIG. 2(b), the cross-sectional SEM image of the PBI multilayer composite membrane prepared comprises an ultrathin dense layer (thickness of 1.7 μm), a finger-shaped microporous layer (lateral pore size of 2-10 μm and thickness of 25.3 μm) and a sponge-shaped nanoporous layer (pore size of 10-100 nm and thickness of 23.0 μm) in this order from top to bottom, and the total thickness is about 50 μm. The pore walls of the finger-shaped microporous layers are highly communicated, so that a continuous channel is provided for the transmission of protons, and the pore walls of the sponge-shaped microporous layers are low in communication degree, so that the penetration of vanadium ions is blocked.
As shown in fig. 3, the sheet resistance and vanadium ion permeability of the prepared PBI multilayer composite membrane, the conventional two-layer porous membrane and the Nafion212 membrane are compared. As can be seen from FIG. 3(a), the incorporation of the nanoporous layer increases the sheet resistance (0.10. omega. cm) of the composite film to some extent2) But still the sheet resistance was less than that of the control commercial Nafion212 film (0.22. omega. cm)2) The multilayer composite membrane is shown to have higher proton conductivity than the Nafion membrane. As can be seen from FIG. 3(b), the vanadium ion permeability of the multilayer composite membrane (3.26X 10)-6cm2 h-1) Much lower than Nafion membrane (3.7X 10)-5cm2 h-1) And a conventional NIPS-prepared two-layer porous membrane (1.73X 10)-4cm2 h-1) It shows that it has excellent vanadium resistance.
As shown in fig. 4, the performance of the assembled battery of the prepared multi-layer composite membrane and the control group Nafion212 is compared. The multi-layer composite membrane has higher proton conductivity (compared with Nafion 212) and ion selectivity (compared with Nafion212 and a double-layer porous membrane), and shows outstanding energy efficiency in the vanadium flow battery (the multi-layer composite membrane: 90.08%; Nafion: 85.29%; the double-layer porous membrane: 75.81%).
Example 2:
the same procedure as in example 1, except that a mixture of sulfonated polyether ether ketone (SPEEK) and polyether sulfone (PES) was used as a membrane raw material resin in step 2.
Example 3:
the same procedure as in example 1, except that DMSO was used as the solvent in step 3.
Example 4:
the same procedure as in example 1 was conducted except that the doctor blade height used in step 3 was set to 250 μm.
Example 5:
the same procedure as in example 1 was repeated, except that the solvent evaporation time in step 3 was adjusted to 10 min.
The results of the examples show that the multilayer composite membrane prepared by the invention has the advantages of strong ion selectivity, high proton conductivity, low cost, simple preparation method and the like, and is suitable for the field of redox flow batteries.
Claims (9)
1. A multilayer composite membrane for a flow battery is characterized in that the multilayer composite membrane has a nano-layer/microporous layer/compact layer composite structure, and specifically comprises a spongy nanopore layer, a finger-shaped microporous layer and an ultrathin compact layer from bottom to top in sequence; among them, the nano-layer and the dense layer provide higher ion selectivity, and the microporous layer provides higher ion conductivity.
2. The multilayer composite film for the flow battery according to claim 1, wherein the aperture of the spongy nanoporous layer is 1 to 100nm, and the thickness is 1 to 500 μm; the transverse aperture of the finger-shaped microporous layer is 2-10 mu m, and the thickness of the finger-shaped microporous layer is 1-500 mu m; the thickness of the ultrathin and compact layer is 0.1-10 mu m.
3. The multilayer composite membrane for flow batteries according to claim 1, wherein the pore walls of the finger-shaped microporous layers are interconnected to provide continuous channels for proton transport, resulting in an area resistance of 0.05 to 0.15 Ω. cm2(ii) a The sponge-like nanopore layer has low pore wall connectivity, is favorable for blocking the penetration of vanadium ions, and has the following technical indexes of ion selectivity: the vanadium ion permeability is (1-10) x 10-6cm2 h-1。
4. The multilayer composite membrane for flow batteries according to claim 1, wherein the raw material of the multilayer composite membrane is selected from one or more of ionic polymers or nonionic polymers, wherein: the ionic polymer is Polybenzimidazole (PBI), sulfonated polyether ether ketone (SPEEK), Sulfonated Polyimide (SPI) and polyether sulfone (PES), and the non-ionic polymer is polyvinylidene fluoride (PVDF) and Polyacrylonitrile (PAN).
5. A method for preparing a multilayer composite membrane for a flow battery according to any one of claims 1 to 4, which comprises the following steps:
(1) dissolving raw materials of the multilayer composite film in an organic solvent, heating and dissolving at the temperature of 20-100 ℃, and preparing a casting solution with the mass percentage of 2-30 wt%;
(2) standing the casting solution obtained in the step (1) for defoaming, and carrying out ultrasonic treatment for 5-15 min before use;
(3) adopting a non-solvent induced phase separation method, casting the solution obtained in the step (2) on a flat and smooth glass plate, scraping out a certain thickness by using a scraper, placing the glass plate on a heating plate to volatilize the solvent, and then placing the whole body in a poor solvent of the film raw material resin for phase transformation to prepare a multilayer composite film;
(4) and (4) soaking and washing the multilayer composite membrane obtained in the step (3) in deionized water for at least 2 times, and storing in water for later use.
6. The method for preparing a multilayer composite membrane for a flow battery according to claim 5, wherein in the step (1), the organic solvent is one or more of N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide and dichloromethane.
7. The method for preparing a multilayer composite membrane for a flow battery according to claim 5, wherein the poor solvent used in the step (3) is water.
8. The method for preparing a multilayer composite membrane for a flow battery according to claim 5, wherein in the step (3), the height of the scraper is controlled to be 50-500 μm.
9. The method for preparing the multilayer composite membrane for the flow battery according to claim 5, wherein in the step (3), the solvent is volatilized for 1-30 min, and the temperature of the heating plate is 20-100 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113571767A (en) * | 2021-07-26 | 2021-10-29 | 欣旺达电动汽车电池有限公司 | Gel polymer electrolyte membrane, method for preparing the same, and polymer electrolyte battery |
| CN117638127A (en) * | 2024-01-26 | 2024-03-01 | 杭州德海艾科能源科技有限公司 | High-ion-selectivity mixed matrix porous diaphragm for vanadium battery and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055724A (en) * | 2011-10-19 | 2013-04-24 | 华东理工大学 | Method for preparing polysulfones polymer microporous membrane by counter-current thermally induced phase separation method |
| CN103682211A (en) * | 2012-09-06 | 2014-03-26 | 中国科学院大连化学物理研究所 | Application of porous diaphragm in flow energy storage battery |
| KR20150070064A (en) * | 2015-06-01 | 2015-06-24 | 서강대학교산학협력단 | Polybenzimidasole nano-composite membrane using phosphoric acid group-containing silsesquioxane, preparing method of the same, and fuel cell including the same |
| CN105226224A (en) * | 2014-07-03 | 2016-01-06 | 中国科学院大连化学物理研究所 | The application of a kind of porous ion conductive membranes in lithium-sulfur cell |
| CN110048148A (en) * | 2019-04-24 | 2019-07-23 | 东北大学 | Polybenzimidazole polymer porous electrolyte membrane preparation method for flow battery |
-
2020
- 2020-09-30 CN CN202011059061.7A patent/CN112151825A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055724A (en) * | 2011-10-19 | 2013-04-24 | 华东理工大学 | Method for preparing polysulfones polymer microporous membrane by counter-current thermally induced phase separation method |
| CN103682211A (en) * | 2012-09-06 | 2014-03-26 | 中国科学院大连化学物理研究所 | Application of porous diaphragm in flow energy storage battery |
| CN105226224A (en) * | 2014-07-03 | 2016-01-06 | 中国科学院大连化学物理研究所 | The application of a kind of porous ion conductive membranes in lithium-sulfur cell |
| KR20150070064A (en) * | 2015-06-01 | 2015-06-24 | 서강대학교산학협력단 | Polybenzimidasole nano-composite membrane using phosphoric acid group-containing silsesquioxane, preparing method of the same, and fuel cell including the same |
| CN110048148A (en) * | 2019-04-24 | 2019-07-23 | 东北大学 | Polybenzimidazole polymer porous electrolyte membrane preparation method for flow battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113571767A (en) * | 2021-07-26 | 2021-10-29 | 欣旺达电动汽车电池有限公司 | Gel polymer electrolyte membrane, method for preparing the same, and polymer electrolyte battery |
| CN117638127A (en) * | 2024-01-26 | 2024-03-01 | 杭州德海艾科能源科技有限公司 | High-ion-selectivity mixed matrix porous diaphragm for vanadium battery and preparation method thereof |
| CN117638127B (en) * | 2024-01-26 | 2024-04-26 | 杭州德海艾科能源科技有限公司 | High-ion-selectivity mixed matrix porous diaphragm for vanadium battery and preparation method thereof |
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