CN110867593B - Composite diaphragm for flow battery and preparation method - Google Patents
Composite diaphragm for flow battery and preparation method Download PDFInfo
- Publication number
- CN110867593B CN110867593B CN201911197996.9A CN201911197996A CN110867593B CN 110867593 B CN110867593 B CN 110867593B CN 201911197996 A CN201911197996 A CN 201911197996A CN 110867593 B CN110867593 B CN 110867593B
- Authority
- CN
- China
- Prior art keywords
- ion exchange
- flow battery
- solution
- coating
- exchange solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 17
- 238000005342 ion exchange Methods 0.000 claims abstract description 57
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 238000000576 coating method Methods 0.000 claims abstract description 39
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 11
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 11
- 239000013543 active substance Substances 0.000 claims abstract description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 8
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 7
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000012982 microporous membrane Substances 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 12
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 238000000034 method Methods 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
- 230000001680 brushing effect Effects 0.000 claims description 4
- 239000003014 ion exchange membrane Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000004595 color masterbatch Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 18
- 239000004698 Polyethylene Substances 0.000 description 16
- 229920000573 polyethylene Polymers 0.000 description 16
- 239000012528 membrane Substances 0.000 description 13
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 4
- -1 Polyethylene Polymers 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 229940102001 zinc bromide Drugs 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising 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
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a composite diaphragm for a flow battery, which is obtained by coating an ion exchange layer on one side of a microporous diaphragm of a zinc-bromine flow battery, wherein the ion exchange layer is formed by coating an ion exchange solution added with a surfactant, the ion exchange solution is a perfluorinated sulfonic acid ion exchange solution, a sulfonated polysulfone ion exchange solution or a sulfonated polyether sulfone ion exchange solution, and the surfactant is an anionic surfactant; a method of making the composite separator is also disclosed. The composite diaphragm provided by the invention not only has better conductivity in the electrolyte, but also can effectively block free active substances in the electrolyte, prevent the self-discharge of the battery, improve the comprehensive performance of the flow battery and ensure the continuous and stable operation of the battery.
Description
Technical Field
The invention relates to the technical field of battery diaphragms, in particular to a composite diaphragm for a flow battery and a preparation method thereof.
Background
With the development of clean energy sources such as wind power generation, solar power generation and the like and the continuous rising of the energy production of power batteries, the demand of people for high-power, safe and reliable energy storage batteries is continuously increased, and the flow battery as a safe and stable high-power battery is continuously developed along with the trend and gradually occupies an important position in the field of energy storage batteries. The flow battery is a low-cost, high-efficiency and environment-friendly flow energy storage battery, has the advantages of high energy density and current efficiency, simple and easy operation of the device, long service life, low cost and the like, and is mainly applied to the fields of power grid peak shaving, power generation of renewable energy sources such as wind energy, solar energy and the like, electric vehicles and the like. The flow battery consists of bipolar plates, positive and negative electrodes, a diaphragm, electrolyte and the like. Through research and development of key materials of the battery, the cost of the battery can be effectively reduced, the efficiency of the battery is improved, and the service life and the performance of the battery are improved, so that the method has extremely important significance. The battery diaphragm is a key material in the flow battery and can separate the positive half battery from the negative half battery. The early flow batteries used proton exchange membranes, wherein Nafion series proton exchange membranes are widely used, although the barrier property of the Nafion series proton exchange membranes to active substances in electrolyte is high, and the mechanical properties of the Nafion series proton exchange membranes basically meet the use requirements of the flow batteries, most of the Nafion series proton exchange membranes are expensive in price and complex in process, and are not suitable for mass production and utilization. Therefore, a non-selective microporous separator has been developed, which is composed of a high molecular polymer material and other fillers, has an average pore diameter of about ten to several nanometers, and has a relatively good barrier effect against active materials in an electrolyte, but a small amount of free active materials in the electrolyte can diffuse through the microporous separator to a negative electrode to form self-discharge. While reducing pore size and porosity alone can reduce the battery self-discharge rate, it also increases the resistance of the separator in the electrolyte, thereby affecting voltage efficiency. At present, schemes for combining an ion exchange membrane and a microporous membrane are also studied, for example, technical schemes of flow cell membranes disclosed in CN 109546052A, CN 104269511A, and CN 102532575A, in which a layer of continuously compact ion exchange layer is completely covered on the surface of the microporous membrane, and the continuously compact ion exchange layer can block most of pores of the microporous membrane, increase the resistance of the membrane, and affect the voltage efficiency.
Disclosure of Invention
The invention aims to provide a composite diaphragm for a flow battery and a preparation method thereof, wherein the composite diaphragm not only has better conductivity in an electrolyte, but also can effectively block free active substances in the electrolyte, prevent the self-discharge of the battery, improve the comprehensive performance of the flow battery and ensure the continuous and stable operation of the battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the composite diaphragm for the flow battery is obtained by coating an ion exchange layer on one side of a microporous diaphragm of a zinc-bromine flow battery, wherein the ion exchange layer is formed by coating an ion exchange solution added with a surfactant, the ion exchange solution is a perfluorosulfonic acid ion exchange solution, a sulfonated polysulfone ion exchange solution or a sulfonated polyethersulfone ion exchange solution, and the surfactant is an anionic surfactant.
The zinc-bromine flow battery microporous membrane is prepared by mixing 10-35 parts by weight of silicon dioxide, 35-65 parts by weight of plasticizer, 10-40 parts by weight of PE raw material, 1-5 parts by weight of color master batch for absorbing 900-1000nm laser energy and 1-2 parts by weight of antioxidant.
The addition amount of the surfactant in the ion exchange solution is 0.08-0.12g/1ml solution.
The ion exchange solution is prepared by the following method:
adding 1 weight part of perfluorinated sulfonic acid resin, 1 weight part of sulfonated polysulfone resin or sulfonated polyether sulfone resin and 12.7-23.3 weight parts of high-boiling-point solvent into a high-pressure reaction kettle, stirring and heating to 200-250 ℃, keeping the pressure at 1-1.5MPa for 2-6h, then cooling to room temperature, discharging solution from the reaction kettle, precipitating and filtering to obtain filtrate, namely the ion exchange solution.
In the preparation process of the composite diaphragm for the flow battery and the ion exchange solution, the resin and the solvent are stirred and heated to 200 ℃ and the pressure is 1MPa, and the temperature is kept for 4 hours.
The high-boiling-point solvent is N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide.
In the composite diaphragm for the flow battery, the anionic surfactant is sodium dodecyl benzene sulfonate or an active agent containing sodium dodecyl benzene sulfonate; because the ion exchange solution contains sulfonic acid groups and the sodium dodecyl benzene sulfonate also contains sulfonic acid groups, the sodium dodecyl benzene sulfonate used as the surfactant can not introduce other groups, and is easy to obtain and low in cost.
The preparation method of the composite separator for the flow battery comprises the following steps:
A. cutting the microporous diaphragm;
B. adding a surfactant into the ion exchange solution, and uniformly stirring to obtain a coating solution;
C. coating the surface of one side of the microporous membrane cut in the step A with the coating solution prepared in the step B;
D. putting the coated microporous diaphragm into an oven for drying, taking out and cooling to room temperature;
E. repeating the steps C-D for 2-5 times to obtain the product.
Further, the preparation method of the composite diaphragm for the flow battery comprises the following steps:
A. cutting the microporous membrane into the actual required size;
B. adding a surfactant into the ion exchange solution, wherein the addition amount of the surfactant is 0.08-0.12g/1ml of solution, and uniformly stirring to obtain a coating solution;
C. coating the surface of one side of the microporous membrane cut in the step A with the coating solution prepared in the step B in an amount of 1.3-2.1ml/1dm 2 ；
D. Putting the coated microporous membrane into an oven, drying at 40-70 ℃ for 20-120min, taking out and cooling to room temperature;
E. repeating the step C-D for 3-4 times to obtain the product.
In the preparation method of the composite diaphragm for the flow battery, in the step C, the coating mode is spraying, brushing or rolling.
Compared with the prior art, the invention has the following advantages: the composite diaphragm has good conductivity in electrolyte, can effectively block free active substances in the electrolyte, prevents the occurrence of self-discharge of the battery, can improve the comprehensive performance of the flow battery, and ensures the continuous and stable operation of the battery. Compared with the traditional microporous diaphragm, the composite diaphragm effectively blocks active substances in the electrolyte, greatly reduces the self-discharge of the battery and improves the charge and discharge performance of the battery; compared with the ion exchange membrane, the membrane has high mechanical strength, is not easy to damage, prolongs the service life of the battery, and has comprehensive performance superior to that of the microporous membrane and the ion exchange membrane. The composite membrane of the invention has thin ion exchange layer, less resin consumption and reduced production cost.
The preparation method of the composite diaphragm is to make the ion exchange layer completely attached to the microporous diaphragm, various coating modes including roll coating, dip coating, spray coating and the like all aim at making the film layer complete, and the ion exchange layer has certain thickness so as to ensure the ion exchange function. According to the preparation method, the surfactant is added into the ion exchange solution, so that the solute of the ion exchange solution effectively enters the micropores of the microporous diaphragm, a tiny polymer is generated in the micropores, the polymer is a chain polymer, and the chain polymer extends in the electrolyte to form a polymer brush and block active substances in the electrolyte. If the dosage of the ion exchange solution is large, a complete and continuous film layer can be formed by one-time coating, but the film layer can cover the holes of the microporous diaphragm, so that the resistance of the composite diaphragm in the electrolyte is increased, and the voltage efficiency of the battery is reduced; if the coating amount is reduced, the number of ion exchange functional groups is reduced, so that the capability of blocking active substances in the electrolyte is reduced, and the self-discharge of the battery is caused, thereby reducing the coulomb efficiency. The invention uses a mode of multiple coating, the dosage of ion exchange solution coated once is less, the surfactant is added in the ion exchange solution, a continuous film layer can not be formed, the micro polymer generated in the micropore diaphragm hole is used for exchanging ions, the resistance can not be increased, the number of ion exchange active groups is further increased, the voltage loss is reduced, the charging and discharging efficiency of the battery is improved, and the continuous and stable operation of the battery is ensured.
Drawings
FIG. 1 is a cyclic voltammetry curve diagram of a zinc-bromine single flow battery with the composite membrane prepared by the invention;
FIG. 2 is a cyclic voltammogram of a Polyethylene (PE) microporous membrane for a zinc-bromine single flow battery;
Detailed Description
Example 1 of the invention: a preparation method of a composite diaphragm for a flow battery comprises the following steps:
A. cutting the zinc-bromine flow battery microporous membrane into 10cm multiplied by 10cm (the zinc-bromine flow battery microporous membrane is prepared by mixing 240g of silicon dioxide (the brand number of AEROSIL 200), 500g of plasticizer (special oil for PE separators), 240g of PE raw material (120 g of UHMWPE with 500 million molecular weight and 120g of HDPE with 20 million molecular weight), 10g of color master (such as plasblak un 2014) for absorbing laser energy of 900-1000nm and 10g of antioxidant);
B. adding 200g of perfluorosulfonic acid resin and 3800g of high-boiling-point solvent N, N-Dimethylformamide (DMF) into a high-pressure reaction kettle, stirring and heating to 200 ℃, keeping the temperature for 4 hours under the pressure of 1.0MPa, then cooling to room temperature, discharging the solution from the reaction kettle, and preparing perfluorosulfonic acid ion exchange solution through precipitation and filtration; measuring 10ml of perfluorinated sulfonic acid ion exchange solution, adding 1g of sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a coating solution;
C. brushing the coating solution prepared in the step B on one side of the microporous membrane cut in the step A, wherein the brushing amount is 1.7ml;
D. putting the coated microporous membrane into an oven, heating at 60 ℃ for 30min, taking out and cooling to room temperature;
E. repeating the steps C-D for 3 times to obtain the product.
The composite membrane prepared in the embodiment and used for the flow battery is assembled in a zinc-bromine single flow battery developed by the applicant to test the battery performance, and the test conditions are as follows: electrolyte concentration: the zinc bromide was 2.25M; the complexing agent MEP (N-methyl-N-ethyl-pyrrolidium bromide) is 0.8M, and the conductive supporting agent (potassium chloride) is 1M; the current density of charge and discharge is 15mA cm -2 Charging time 2h, electrode area 100cm -2 (ii) a The galvanic pile is formed by superposing four groups of sequentially arranged anodes, composite diaphragms and cathodes of the current collector. The cyclic voltammetry curve of the composite membrane zinc-bromine single flow battery is shown in fig. 1, after the battery is subjected to 100 normal charge and discharge cycles, the average coulombic efficiency of the battery is 91.2%, the average voltage efficiency of the battery is 84.8%, and the average energy efficiency of the battery is 77.3%.
As a comparison, a Polyethylene (PE) microporous separator (ZBMM 01 film, baodingboenghuitong New energy science and technology Co., ltd.) without an ion exchange layer was packedThe zinc bromide single flow battery prepared by the applicant is matched to test the battery performance, and the test conditions are as follows: electrolyte concentration: zinc bromide 2.25M; the complexing agent MEP (N-methyl-N-ethyl-pyrrolidium bromide) is 0.8M, and the conductive supporting agent (potassium chloride) is 1M; the current density of charge and discharge is 15mA cm -2 Charging time 2h, electrode area 100cm -2 (ii) a The galvanic pile is formed by overlapping four single batteries which are connected in series and consists of a positive end plate, a current collector, a negative end plate, four groups of positive electrodes, polyethylene (PE) microporous diaphragms and negative electrodes which are sequentially arranged, and the current collector. As shown in fig. 2, after the battery undergoes 16 normal charge and discharge cycles, the average coulombic efficiency of the battery is 86.2%, the average voltage efficiency of the battery is 84.2%, and the average energy efficiency of the battery is 72.5%.
The comparison result shows that after 100 times of normal charge-discharge cycles, the composite diaphragm provided by the invention is still superior to the battery using the PE microporous diaphragm after 16 times of normal charge-discharge cycles, so that the composite diaphragm provided by the invention has very obvious improvement on the charge-discharge performance and the service life of the battery.
Example 2: a preparation method of a composite diaphragm for a flow battery comprises the following steps:
A. the zinc-bromine flow battery microporous membrane is a ZBMM01 membrane produced by Baodingbeihuitong New energy science and technology Limited and cut into 10cm multiplied by 10cm;
B. adding 150g of perfluorosulfonic acid resin and 3500g of high-boiling-point solvent N, N-Dimethylformamide (DMF) into a high-pressure reaction kettle, stirring and heating to 200 ℃, keeping the temperature for 4 hours under the pressure of 1.0MPa, then cooling to room temperature, discharging the solution from the reaction kettle, and preparing perfluorosulfonic acid ion exchange solution through precipitation and filtration; measuring 10ml of perfluorinated sulfonic acid ion exchange solution, adding 1g of sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a coating solution;
C. rolling and coating the coating solution prepared in the step B on one side of the microporous membrane cut in the step A, wherein the rolling and coating amount is 1.5-1.7ml;
D. putting the coated microporous membrane into an oven, heating at 40 ℃ for 120min, taking out and cooling to room temperature;
E. repeating the steps C-D for 3 times to obtain the product.
Example 3: a preparation method of a composite diaphragm for a flow battery comprises the following steps:
A. cutting the microporous diaphragm of the zinc-bromine flow battery into 10cm multiplied by 10cm (the microporous diaphragm of the zinc-bromine flow battery is prepared by mixing 350g of silicon dioxide, 500g of plasticizer (special oil for PE separator), 100g of PE raw material (50 g of UHMWPE with 500 ten thousand molecular weight and 50g of HDPE with 15 ten thousand molecular weight), 30g of color master (such as Polyblack-2778) for absorbing laser energy of 900-1000nm and 20g of antioxidant);
B. adding 200g of sulfonated polysulfone resin and 3000g of high-boiling-point solvent N, N-dimethylacetamide (DMAc) into a high-pressure reaction kettle, stirring and heating to 200 ℃ and keeping the temperature under the pressure of 1.5MPa for 6 hours, then cooling to room temperature, discharging solution from the reaction kettle, and preparing sulfonated polysulfone ion exchange solution through precipitation and filtration; measuring 6ml of sulfonated polysulfone ion exchange solution, adding 0.72g of surfactant containing sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a coating solution;
C. spraying the coating solution prepared in the step B on one side of the microporous membrane cut in the step A, wherein the spraying amount is 1.3ml;
D. putting the coated microporous membrane into an oven, heating at 40 ℃ for 60min, taking out and cooling to room temperature;
E. repeating the steps C-D for 5 times to obtain the product.
Example 4: a preparation method of a composite diaphragm for a flow battery comprises the following steps:
A. cutting the zinc-bromine flow battery microporous membrane into 12cm multiplied by 15cm (the zinc-bromine flow battery microporous membrane is prepared by mixing 300g of silicon dioxide, 350g of plasticizer (PE separator special oil), 320g of PE raw material (UHMWPE 192g with 500 million molecular weight and HDPE 128g with 15 million molecular weight), 20g of color master (such as Polyblack-2778) for absorbing laser energy of 900-1000nm and 10g of antioxidant);
B. adding 200g of perfluorosulfonic acid resin and 3700g of high-boiling-point solvent N, N-Dimethylformamide (DMF) into a high-pressure reaction kettle, stirring and heating to 210 ℃, keeping the temperature under the pressure of 1.1MPa for 2 hours, cooling to room temperature, discharging solution from the reaction kettle, precipitating and filtering to prepare perfluorosulfonic acid ion exchange solution; measuring 20ml of perfluorinated sulfonic acid ion exchange solution, adding 1.6g of sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a coating solution;
C. rolling and coating the coating solution prepared in the step B on one side of the microporous membrane cut in the step A, wherein the rolling and coating amount is 3.8ml;
D. putting the coated microporous membrane into an oven, heating at 50 ℃ for 40min, taking out and cooling to room temperature;
E. repeating the steps C-D for 4 times to obtain the product.
Example 5: a preparation method of a composite diaphragm for a flow battery comprises the following steps:
A. the zinc-bromine flow battery microporous membrane is a ZBMM01 membrane produced by Baoding Baineng New energy science and technology Limited and cut into 10cm multiplied by 20cm;
B. adding 200g of sulfonated polyethersulfone resin and 3800g of high-boiling-point solvent dimethyl sulfoxide into a high-pressure reaction kettle, stirring and heating to 250 ℃ and keeping the temperature under the pressure of 1.2MPa for 5 hours, then cooling to room temperature, discharging the solution from the reaction kettle, and preparing sulfonated polyethersulfone ion exchange solution by precipitation and filtration; measuring 10ml of sulfonated polyether sulfone ion exchange solution, adding 0.8g of sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a coating solution;
C. spraying the coating solution prepared in the step B on one side of the microporous membrane cut in the step A, wherein the spraying amount is 3ml;
D. putting the coated microporous membrane into an oven, heating at 70 ℃ for 20min, taking out and cooling to room temperature;
E. repeating the steps A-D for 2 times to obtain the product.
Example 6: a preparation method of a composite diaphragm for a flow battery comprises the following steps:
A. cutting the zinc-bromine flow battery microporous membrane into 20cm multiplied by 30cm (the zinc-bromine flow battery microporous membrane is prepared by mixing 100g of silicon dioxide, 650g of plasticizer (30% DOP is added into special oil for PE separator), 180g of PE raw material (120 g of UHMWPE with molecular weight of 400 ten thousand and 60g of HDPE with molecular weight of 5 ten thousand), 50g of color master (such as Polyblack-2778) for absorbing laser energy of 900-1000nm and 20g of antioxidant);
B. adding 300g of sulfonated polyethersulfone resin and 3800g of high-boiling-point solvent dimethyl sulfoxide into a high-pressure reaction kettle, stirring and heating to 220 ℃ and keeping the temperature for 3 hours under the pressure of 1.0MPa, then cooling to room temperature, discharging the solution from the reaction kettle, and preparing sulfonated polyethersulfone ion exchange solution by precipitation and filtration; measuring 40ml of sulfonated polyether sulfone ion exchange solution, adding 4g of sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a coating solution;
C. spraying the coating solution prepared in the step B on one side of the microporous membrane cut in the step A, wherein the spraying amount is 9.6ml;
D. putting the coated microporous membrane into an oven, heating at 60 ℃ for 30min, taking out and cooling to room temperature;
E. repeating the steps A-D for 4 times to obtain the product.
Claims (6)
1. A composite separator for a flow battery, characterized by: the ion exchange membrane is obtained by coating an ion exchange layer on one side of a microporous membrane of a zinc-bromine flow battery, wherein the ion exchange layer is formed by coating an ion exchange solution added with a surfactant, the ion exchange solution is a perfluorinated sulfonic acid ion exchange solution, a sulfonated polysulfone ion exchange solution or a sulfonated polyether sulfone ion exchange solution, and the surfactant is an anionic surfactant; the addition amount of the surfactant in the ion exchange solution is 0.1-0.12g/1ml solution; the anionic surfactant is sodium dodecyl benzene sulfonate or an active agent containing sodium dodecyl benzene sulfonate; the ion exchange solution is prepared by the following method:
adding 1 weight part of perfluorinated sulfonic acid resin, 1 weight part of sulfonated polysulfone resin or sulfonated polyether sulfone resin and 15.0-23.3 weight parts of high-boiling-point solvent into a high-pressure reaction kettle, stirring and heating to 200-250 ℃, keeping the pressure at 1-1.5MPa for 2-6h, then cooling to room temperature, discharging the solution from the reaction kettle, precipitating and filtering to obtain filtrate, namely the ion exchange solution.
2. The composite separator for a flow battery as recited in claim 1, wherein: the microporous diaphragm of the zinc-bromine flow battery is prepared by mixing 10-35 parts by weight of silicon dioxide, 35-65 parts by weight of plasticizer, 10-40 parts by weight of PE raw material, 1-5 parts by weight of color master batch for absorbing 900-1000nm laser energy and 1-2 parts by weight of antioxidant.
3. The composite separator for a flow battery as recited in claim 1, wherein: in the preparation process of the ion exchange solution, the resin and the solvent are stirred and heated to 200 ℃ and the pressure is 1MPa, and the temperature is kept for 4 hours.
4. The composite separator for a flow battery as recited in claim 1, wherein: the high boiling point solvent is N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide.
5. The method of making a composite separator for a flow battery of any one of claims 1-4, comprising the steps of:
A. cutting the microporous membrane into the actual required size;
B. adding a surfactant into the ion exchange solution, wherein the addition amount of the surfactant is 0.1-0.12g/1ml of the solution, and uniformly stirring to obtain a coating solution;
C. coating the surface of one side of the microporous membrane cut in the step A with the coating solution prepared in the step B in an amount of 1.3-2.1ml/1dm 2 ；
D. Putting the coated microporous membrane into an oven, drying at 40-70 ℃ for 20-120min, taking out, and cooling to room temperature;
E. repeating the steps C-D for 2-5 times to obtain the product.
6. The method for preparing the composite separator for the flow battery according to claim 5, wherein: in the step C, the coating mode is spraying, brushing or rolling coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911197996.9A CN110867593B (en) | 2019-11-29 | 2019-11-29 | Composite diaphragm for flow battery and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911197996.9A CN110867593B (en) | 2019-11-29 | 2019-11-29 | Composite diaphragm for flow battery and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110867593A CN110867593A (en) | 2020-03-06 |
| CN110867593B true CN110867593B (en) | 2023-02-28 |
Family
ID=69657556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911197996.9A Active CN110867593B (en) | 2019-11-29 | 2019-11-29 | Composite diaphragm for flow battery and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110867593B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115651420B (en) * | 2022-10-19 | 2024-05-24 | 深圳圣安技术有限公司 | Perfluorosulfonic acid proton exchange membrane and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547551A (en) * | 1995-03-15 | 1996-08-20 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
| CN102237534A (en) * | 2010-04-28 | 2011-11-09 | 中国科学院金属研究所 | Perfluorinated sulfonic acid ion exchange membrane preparation process for vanadium redox battery |
| CN103618057A (en) * | 2013-11-26 | 2014-03-05 | 青海百能汇通新能源科技有限公司 | Zinc-bromine flow battery diaphragm applicable to laser welding, and preparation method thereof |
| CN105140543A (en) * | 2015-08-28 | 2015-12-09 | 中国东方电气集团有限公司 | Flow cell ion exchange membrane assembly, preparing method of flow cell ion exchange membrane assembly and flow cell comprising flow cell ion exchange membrane assembly |
| CN105161738A (en) * | 2015-10-08 | 2015-12-16 | 四川理工学院 | Composite membrane for vanadium batteries, continuous production method and application of composite membrane |
| WO2016064181A1 (en) * | 2014-10-21 | 2016-04-28 | 주식회사 엘지화학 | Method for reducing membrane permeability of vanadium ion, and vanadium redox battery comprising membrane prepared by same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10361035A1 (en) * | 2002-12-26 | 2004-07-29 | Tokuyama Corp., Shunan | Ion exchange membrane and manufacturing process therefor |
-
2019
- 2019-11-29 CN CN201911197996.9A patent/CN110867593B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547551A (en) * | 1995-03-15 | 1996-08-20 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
| CN102237534A (en) * | 2010-04-28 | 2011-11-09 | 中国科学院金属研究所 | Perfluorinated sulfonic acid ion exchange membrane preparation process for vanadium redox battery |
| CN103618057A (en) * | 2013-11-26 | 2014-03-05 | 青海百能汇通新能源科技有限公司 | Zinc-bromine flow battery diaphragm applicable to laser welding, and preparation method thereof |
| WO2016064181A1 (en) * | 2014-10-21 | 2016-04-28 | 주식회사 엘지화학 | Method for reducing membrane permeability of vanadium ion, and vanadium redox battery comprising membrane prepared by same |
| CN105140543A (en) * | 2015-08-28 | 2015-12-09 | 中国东方电气集团有限公司 | Flow cell ion exchange membrane assembly, preparing method of flow cell ion exchange membrane assembly and flow cell comprising flow cell ion exchange membrane assembly |
| CN105161738A (en) * | 2015-10-08 | 2015-12-16 | 四川理工学院 | Composite membrane for vanadium batteries, continuous production method and application of composite membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110867593A (en) | 2020-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105226222B (en) | Application of the porous septum of hydrophilic modification in flow battery | |
| CN105131289B (en) | A kind of novel sulfonated polybenzimidazoles copolymer, cross linking membrane, preparation method and applications | |
| CN101383404A (en) | Fluorine/hydrocarbon composite ion exchange film and preparation thereof | |
| US10854890B2 (en) | Cross-linked porous membrane from hydrolysis of ester-containing side chain and preparation method thereof | |
| CN104617247B (en) | Preparation method of tandem laminated lithium-sulfur battery | |
| CN102867929B (en) | Composite anion-exchange membrane, its preparation and application | |
| CN105161738A (en) | Composite membrane for vanadium batteries, continuous production method and application of composite membrane | |
| CN110350223B (en) | Nano intercalation internal selection SPEEK/GO/TiO2Preparation method of composite ion selective membrane | |
| CN109873188A (en) | Application of the cluster ion exchange membrane in alkaline system zinc-iron flow battery | |
| CN108649256A (en) | The preparation method and application of sulfonate polybenzimidazole proton exchange membrane | |
| CN116444848A (en) | Porous ion conducting membrane, preparation method thereof and application thereof in acidic water system organic flow battery | |
| CN110867593B (en) | Composite diaphragm for flow battery and preparation method | |
| JP2022517035A (en) | Aqueous hybrid supercapacitor | |
| CN110120532B (en) | Preparation method of composite membrane | |
| CN113036156B (en) | Gel electrolyte and zinc-bromine or zinc-iodine single flow battery | |
| CN102456904B (en) | Structure of liquid-flow energy storage cell | |
| CN110120540B (en) | Continuous preparation method of porous composite ionic membrane | |
| CN105226223B (en) | C bases porous composite film and its application | |
| KR102066239B1 (en) | Separator complex and redox flow battery | |
| Zaffou et al. | Vanadium redox flow batteries for electrical energy storage: challenges and opportunities | |
| CN107546399B (en) | Ion exchange membrane with main chain separated from ion exchange group and preparation and application thereof | |
| CN111718505B (en) | Sulfonated polyether-ether-ketone/polyvinylidene fluoride composite ion exchange membrane for all-vanadium redox flow battery and preparation method thereof | |
| CN111200145B (en) | Ion conduction membrane with double ion channels and preparation and application thereof | |
| CN108123155A (en) | A kind of preparation method of non-fluorine porous composite film used for all-vanadium redox flow battery | |
| CN111048813B (en) | Organic-inorganic composite membrane for iron-chromium flow battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220402 Address after: 210000 No. 109, zhuangpai Road, moling street, Jiangning District, Nanjing, Jiangsu Province (Jiangning Development Zone) Applicant after: Jiangsu HengAn Energy Storage Technology Co.,Ltd. Address before: Room 320, block B, Chuangye building, No. 8, Zhongguancun East Road, Haidong Industrial Park, Haidong City, Qinghai Province Applicant before: QINGHAI BAINENG HUITONG NEW ENERGY SCIENCE & TECHNOLOGY CO.,LTD. Applicant before: Qinghai baineng Huitong new energy technology Co.,Ltd. energy storage engineering technology branch |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A composite separator and preparation method for liquid flow batteries Granted publication date: 20230228 Pledgee: Bank of China Limited by Share Ltd. Nanjing Jiangning branch Pledgor: Jiangsu HengAn Energy Storage Technology Co.,Ltd. Registration number: Y2024980022116 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |